WO1998035006A1 - Liquid cleaning composition - Google Patents

Liquid cleaning composition Download PDF

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Publication number
WO1998035006A1
WO1998035006A1 PCT/US1998/002462 US9802462W WO9835006A1 WO 1998035006 A1 WO1998035006 A1 WO 1998035006A1 US 9802462 W US9802462 W US 9802462W WO 9835006 A1 WO9835006 A1 WO 9835006A1
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alkyl
compositions
group
weight
composition
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PCT/US1998/002462
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French (fr)
Inventor
Stephen Wayne Heinzman
Barry Thomas Ingram
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The Procter & Gamble Company
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Priority claimed from GB9702731A external-priority patent/GB2321900A/en
Priority claimed from GB9726894A external-priority patent/GB2332443A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU61520/98A priority Critical patent/AU6152098A/en
Publication of WO1998035006A1 publication Critical patent/WO1998035006A1/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • the present invention relates liquid cleaning compositions comprising a polyamine cationic surfactant, containing at least one quaternary amine group and at least one primary, secondary or tertiary amine group.
  • the compositions preferably are in the form of aqueous or non-aqueous laundry, dish washing, shampoo or hard-surface cleaning compositions.
  • surfactants for use liquid cleaning compositions can be found in the literature, but the reality is that many such surfactants are chemicals which are not always suitable in such liquid compositions, because of certain properties they have (such as instability in acidic or basic environment, incompatibility with bleach, malodour problems, biodegradability problems).
  • One of the main problems encountered by the manufacturers of liquid cleaning compositions is that the majority of the surfactants know in the art are not sufficiently water-soluble or not sufficiently water-soluble by low temperatures. This leads to problems both during the manufacturing of the compositions and during use of the compositions. Introduction of functional groups to the surfactants to solubilise the surfactants in water can lead to reduction of the surface activity of the surfactant, which results in a reduction of the cleaning by these surfactants.
  • cationic surfactants are suggested to be usable in detergents.
  • One group of cationic surfactants which is widely studied is the group consisting of quaternary ammonium or imidazolinium compounds, which are often designed for speciality use.
  • US-A-4,228,042 discloses biodegradable cationic surfactants, including cationic ester surfactants for use in detergent compositions to provide greasy/oily soil removal.
  • US 3,567,729 discloses diquatemary ammonium compounds for use in detergents.
  • US 5,068,431 describes quaternary ammonium compounds, containing amphoteric amine oxide groups.
  • polyamine cationic compounds containing at least one cationically charged quaternary amine group and at least one primary, secondary or tertiary amine group (as described in copending application UK 9702731.2) are very good surfactants, suitable for use in liquid cleaning compositions, such as liquid laundry and dish washing compositions, hard-surface cleaners, (hair) shampoo compositions.
  • surfactants are found to be more biodegradable and to have a very low aquatic toxicity, relative to most quaternary amine compounds.
  • polyamine cationic surfactants It has been found that the stability of the polyamine cationic surfactants is not affected by changes of the pH. Furthermore, it has been found that, depending on their structure, most of the polyamine cationic compounds of the present invention and detergent compositions containing these polyamine cationic surfactants, are stable under standard storage and washing conditions.
  • certain polyamine cationic surfactants can be compatible with bleach, especially oxygen-based bleaches, and with certain bleach activators.
  • the present invention relates to liquid cleaning compositions comprising
  • the liquid cleaning composition of the invention can be any liquid cleaning composition which requires surfactancy.
  • Preferred examples are liquid aqueous or non-aqueous laundry or dish washing detergents, hard-surface cleaning compositions (hereinafter referred to as HSC compositions) and shampoo compositions.
  • the preferred level of incorporation of the surfactant in the liquid compositions will depend on the purpose of the composition, e.g. concentrated laundry or dish washing detergent compositions will usually comprise a higher level of these surfactants than diluted hard-surface cleaners.
  • the liquid compositions of the invention will generally comprise the polyamine cationic surfactant at a level of from 0.05% to 50% by weight of the composition, more preferably from 0.1% to 30% or even more preferably from 0.2% to 20% or even to 15% or 10% by weight. Highly preferred levels in, for example, concentrated liquid laundry or dish washing compositions are 0.2% to 10% by weight of the surfactant.
  • the liquid compositions also comprise additional ingredients, which can be essentially any ingredient known in the art to be useful in liquid cleaning compositions. Which additional ingredients are present in the compositions of the invention and also which are the preferred levels of these additional ingredients will again depend on the purpose of the composition.
  • the description herein of the various liquid compositions of the invention exemplifies preferred ingredients of those compositions, but is by no means meant to limit the invention thereto.
  • a cationic surfactant for use in the compositions of the present invention comprises at least one quaternized ammonium group and at least one primary, secondary or tertiary amine group, whereby not more than one linear or branched polyoxyalkylene group is present as substituent group.
  • Preferred cationic surfactant of the present invention are polyamine cationic surfactants of the general formula (I):
  • L is a linking unit, and each L is independently selected from the group consisting of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B, C or D units; x is a number from 0 to 10, y is a number from 0 to 10; and wherein the units A- and D- are each independently selected from
  • R ⁇ , R2, R3, R4, R5, Rg, R7 and Rg are independently selected from the group consisting of C1 -C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group and hydrogen, one of Rj, R2, R3, R4, R5, Rg, R7 or Rg can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or Rj and R2, Rjand R2 and R3, R4 and R5 or Rg and R7 form together with the nitrogen atom part of a ring structure; or R3 is not present and Rj or R2 is double bonded to the nitrogen; or R7 is not present and Rg is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; or, when x and y are 0, R !
  • M" is one or more counterions, and at least one A or D comprises a quaternized ammonium group in which none of Ri , R2 or R3 is hydrogen, or at least one B is present in which neither Rg nor R7 is hydrogen, and at least one A or D comprises a primary, secondary or tertiary amine group, or at least one C is present.
  • the units B-L and C-L are linked when both are present (i.e. when x and y do not equal 0), and they can be randomly present along the chain between the end units A- L and D.
  • the value of x+y is from 1 to 4.
  • x+y is greater than 1, at least one of present groups A, B, C or D is a secondary or primary ammonium group.
  • x 0 and y is a number from 1 to 4. Even more preferably, both x and y are 0.
  • the surfactant comprises only one quaternary group A or D.
  • Rg, R7 and/or Rg are each independently selected from a Cj-Cg, more preferably C1-C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyi group or, most preferably hydrogen.
  • R ⁇ is a C -Cj4 alkyl, (poly) hydroxyalkyi or alkoxy group or an aralkyl group, most preferably a 2-ethylhexyl group
  • R2 and R3 are each independently Ci - Cg, more preferably C1-C3 alkyl or hydroxyalkyi groups and preferably R4 and R5 (and Rg, R7 and Rg when present) are each independently Cj-Cg, more preferably C1-C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyi groups or, most preferably, hydrogen atoms.
  • R4 is preferably a Cg-Cj4 alkyl, (poly) hydroxyalkyi, alkoxy group or an aralkyl group, most preferably a 2-ethylhexyl group
  • R5 is preferably a C]-Cg, more preferably a -C3 alkyl, (poly) hydroxyalkyi group or hydrogen and
  • R ⁇ , R2 and R3 (and Rg, R7 and Rg when present) are each independently preferably Cj-Cg, more preferably C1-C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyi groups or aralkyl groups.
  • the ring structure is preferably a benzene ring structure, morpholino ring structure or a piperazino ring structure, or a subtituted benzene or substituted morpholino or substituted piperazino ring structure.
  • the ring structure is preferably a benzene ring structure, morpholino ring structure or a piperazino ring structure, or a substituted benzene or substituted morpholino or substituted piperazino ring structure.
  • L groups are independently preferably a Ci-Cg, more preferably a C2-C4 linear or branched alkyl, hydroxy alkyl, alkoxy or hydroxy alkoxy group. If x+y is 0, the 1 group is preferably a C 2 alkyl group. If group L comprises more than 2 carbon atoms, the surfactant preferably comprises at least one primary or secondary A, B, C or D group. Examples of preferred polyamine cationic surfactants of the present invention are:
  • Ri , R4, Rg and Rg are as described above;
  • R2, R3 and R5 are independently selected from the group consisting of methyl, ethyl, hydroxyethyl, hydroxypropyl, polyhydroxy propyl, ethoxy, propoxy or 2,3,4,5,6-penta hydroxy hexyl, and are most preferably methyl or hydroxyethyl groups;
  • Ri Q is a methyl or hydroxyethyl group;
  • L is as described above;
  • R ⁇ and/or R2 and/or R4 are most preferably a 2-ethylhexyl group.
  • a highly preferred cationic polyamine surfactant is of formula VI, as defined above, wherein R2 is a hydroxypropyl or hydroxyethyl group, R3 and RJO are methyl groups, L is C2-C3 alkyl group.
  • Highly preferred polyamine cationic surfactant are those of the formulas:
  • R is as described above, preferably a C2-C14, preferably Cg-Ci4 linear or branched alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group; particularly preferred R ⁇ groups are hydroxyalkyi groups, where the alkyl groups have 2 to 5 carbon atoms, especially hydroxyethyl and hydroxypropyl are preferred; particularly preferred alkyl R ⁇ groups have up to 9 carbon atoms, most preferably R ⁇ is a 2- ethylhexyl group; and R ⁇ is a C2-C14 alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group or a A or D unit as described above .
  • the anion M ⁇ is a counterion for the cationically charged polyamine surfactant. Therefore, the number of M" anions present will depend on the cationic charge of the polyamine surfactant, which depends on the groups A, B, C and D. The number of M" anions will be at least 1.
  • a preferred counterion is a halide anion, more preferably a sulphate anion.
  • Liquid cleaning compositions further comprise a solvent or a mixture of solvents.
  • the compositions can be aqueous or non-aqueous compositions.
  • the compositions contain from 1% to 99.9%, preferably from 5% to 90%, and most typically from 10% to 50% of solvents.
  • solvents and levels of incorporation thereof will depend on the precise nature of the cleaning compositions and the cleaning operation for which it is to be used.
  • low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, including the cationic surfactant of the invention, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used.
  • Liquid cleaning compositions additional ingredients
  • liquid compositions in accordance with the present invention of from 0.05% to 95% by weight of the composition, liquid cleaning composition additional ingredients.
  • additional ingredients and levels of incorporation thereof will depend on the precise nature of the cleaning compositions and the cleaning operation for which it is to be used.
  • Liquid laundry and dish washing cleaning compositions additional ingredients
  • the liquid compositions for use as laundry or dish washing cleaning compositions invention can comprise additional surfactants, herein also referred to as co- surfactants, preferably selected from: anionic surfactants, preferably selected from the group of alkyl alkoxylated sulfates, alkyl sulfates, and/or linear alkyl benzenesulfonate surfactants; cationic surfactants, preferably selected from quaternary ammonium surfactants; nonionic surfactants, preferably alkyl ethoxylates, alkyl polyglucosides, and/or amine or amine oxide surfactants; amphoteric surfactants, preferably selected from betaines and/or polycarboxylates (for example polyglycinates); and zwiterionic surfactants.
  • anionic surfactants preferably selected from the group of alkyl alkoxylated sulfates, alkyl sulfates, and/or linear alkyl benzenesulf
  • liquid laundry or dish washing compositions of the present invention typically comprise from 0.1% to35%, preferably from ⁇ .5% to 15%, by weight of co-surfactants.
  • Selected co-surfactants are further identified as follows.
  • Nonlimiting examples of anionic co-surfactants useful herein typically at levels from about 0.1% to about 50%, by weight, include the conventional C ⁇ j-Ci 8 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates (“AS”), the Cio-Cjg secondary (2,3) alkyl sulfates of the formula CH3(CH2) ⁇ (CHOSO 3 " M + ) CH3 and CH 3 (CH 2 ) y (CHOSO 3 " M + ) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the Ci n-C j alpha-sulfonated fatty acid esters, the Ci ⁇ -Ci sulfated alkyl polyglycosides, the Cjo-Ci
  • Ci2-C ⁇ betaines and sulfobetaines can also be included in the overall compositions.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Cio-Cjg soaps may be used.
  • Other conventional useful anionic co-surfactants are listed in standard texts.
  • alkyl alkoxylated sulfate surfactants useful herein are preferably water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyi group having a Cjo- 24 alkyl component, preferably a Cj2- C]g alkyl or hydroxyalkyi, more preferably C12-C15 alkyl or hydroxyalkyi, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C10-C24 alkyl or hydroxyalkyi group having a Cjo- 24 alkyl component, preferably a Cj
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include ethanol-, triethanol-, methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C12-C15 alkyl polyethoxylate (1.0) sulfate (Cj2- C 15 E(1.0)M), C12-C15 alkyl polyethoxylate (2.25) sulfate (C 12 -C 15 E(2.25)M), C 12-Cl5 alkyl polyethoxylate (3.0) sulfate (C12-C i5E(3.0)M), and C12-C15 alkyl polyethoxylate (4.0) sulfate (C]2-Ci5E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • alkyl sulfate surfactants useful herein are preferably water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyi having a C 1 Q-C 1 g alkyl component, more preferably a Cl2"Cl5 alkyl or hydroxyalkyi, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
  • R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyi having a C 1 Q-C 1 g alkyl component, more preferably a Cl2"Cl5 alkyl or hydroxyalkyi
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or am
  • methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • alkyl ester sulfonate surfactants including linear esters of C -C20 carboxyiic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • the preferred alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula : R 3 - CH(SO 3 M) - C(O) - OR 4 wherein R 3 is a C -C20 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a Cj-Cg hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt- forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R 3 is C ⁇ Q-C ⁇ alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R 3 is CiQ-Cjg alkyl.
  • anionic co-surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention.
  • These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-C22 primary of secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated Cl2"Clg monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-Cj2 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolygluco
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin. et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
  • the laundry or dish washing detergent compositions of the present invention typically comprise from 0.1% to 50%, preferably from 1% to 40% by weight of such anionic surfactants.
  • Nonlimiting examples of nonionic co-surfactants useful herein typically at levels from about 0.1% to about 50%, by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), Ci o-Cjg glycerol ethers, and the like.
  • AE alkoxylated alcohol
  • PFAA's polyhydroxy fatty acid amides
  • APG's alkyl polyglycosides
  • Ci o-Cjg glycerol ethers and the like.
  • condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the present invention.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C12-C15 primary alcohols containing 5- 10 moles of ethylene oxide per mole of alcohol.
  • nonionic surfactants of this type include: TergitolT 15-S-9 (the condensation product of Cj 1 -C15 linear alcohol with 9 moles ethylene oxide) and Tergitol ⁇ M 24-L-6 NMW (the condensation product of C ⁇ 2-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol ⁇ M 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23.3 (the condensation product of C12-C13 linear alcohol with 3 moles of ethylene oxide), NeodolTM 45.7 ( me condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide) and Neodol ⁇ M 45.5 ( he condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; Kyro ⁇ M EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The
  • HLB HLB
  • AE nonionic surfactants 8-17 and most preferred from 8-14.
  • Condensates with propylene oxide and butylene oxides may also be used.
  • Another class of preferred nonionic co-surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula.
  • Rl is H, or C 1.4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof
  • R ⁇ is C5.31 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • Rl is methyl
  • R ⁇ is a straight Cl 1-15 alkyl or C15.17 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • Typical examples include the C ⁇ -Cjg and C12-C14 N-methylglucamides. See U.S. 5.194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can also be used; see U.S. 5,489,393.
  • alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside).
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-. 3-. 4-. and/or 6- positions on the preceding saccharide units.
  • Preferred alkylpolyglycosides have the formula
  • R ⁇ is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyi, hydroxyalkylphenyl. and mixtures thereof in which the alkyl groups contain from about 10 to about 18, prelerabh from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 10 about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1 .3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position).
  • the additional glycosyl units can then be attached between their 1- position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
  • Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
  • Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include Igepal ⁇ M CO-630, marketed by the GAF Corporation; and TritonTM X-45, X-l 14, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the present invention.
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the commercially-available Pluronic ⁇ M surfactants, marketed by BASF.
  • nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 1 1,000.
  • this type of nonionic surfactant include certain of the commercially available Tetronic ⁇ M compounds, marketed by BASF.
  • compositions of the present invention may comprise amine oxide in accordance with the general formula I: Rl(EO) x (PO) y (BO) z N(O)(CH 2 R')2.qH2O (I).
  • the structure (I) provides one long-chain moiety Rl(EO) x (PO)y(BO) z and two short chain moieties, C ⁇ R'.
  • R' is preferably selected from hydrogen, methyl and -CH2OH.
  • Rl is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, Rl is a primary alkyl moiety.
  • Rl is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
  • Rl may be somewhat longer, having a chainlength in the range C12-C24.
  • amine oxides are illustrated by C 12- 14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,075,501 and 5,071,594, incorporated herein by reference.
  • the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, Rl is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy.
  • amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
  • amine oxides herein are solutions at ambient temperature.
  • Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • R' is H
  • R' is CH2OH, such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2- hydroxyethyl)amine oxide and oleylbis(2-hydroxyethyl)amine oxide, dodecyldimethylamine oxide dihydrate.
  • Preferred amines for use herein include amines according to the formula:
  • R ⁇ is a Cg-Cj2 alkyl group
  • n is from about 2 to about 4
  • X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are individually selected from H, C1-C4 alkyl, or (CH2-CH2-O(R5)) wherein R5 is H or methyl.
  • These preferred amines include the following: R 1 -(CH 2 ) 2 -NH 2
  • R ⁇ is a Cg-Ci 2 alkyl group and R5 is H or CH3.
  • the amine is described by the formula: Ri -C(O)-NH-(CH 2 )3-N(CH 3 )2 wherein R ⁇ is C -Cj2 alkyl.
  • Particularly preferred amines include those selected from the group consisting of octyl amine, hexyl amine, decyl amine. dodecyl amine, C -Cj2 bis(hydroxyethyl)amine, Cg-Ci 2 bis(hydroxyisopropyl)amine, and C -Ci2 amido- propyl dimethyl amine, and mixtures.
  • Nonhmiting examples of additional cationic co-surfactants useful herein typically at levels from 0.1% to 50%, by weight include the choline ester-type quats and alkoxylated quaternary ammonium (AQA) surfactant compounds, and the like.
  • AQA alkoxylated quaternary ammonium
  • Cationic co-surfactants useful as a component of the surfactant system is a cationic choline ester-type quat surfactant which are preferably water dispersible compounds having surfactant properties and comprise at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
  • Suitable cationic ester surfactants, including choline ester surfactants have for example been disclosed in U.S. Patents Nos. 4,228,042, 4,239,660 and 4,260,529.
  • these cationic ester surfactant are hydrolysable under the conditions of a laundry wash method.
  • AQA compounds alkoxylated quaternary ammonium surfactant compounds having the formula:
  • Rl is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms;
  • R ⁇ is an alkyl group containing from one to three carbon atoms, preferably methyl;
  • R 3 and R 4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl;
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and mixed ethoxy/propoxy; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably to about 4; preferably both p and q are 1.
  • ethoxy i.e., -CH2CH2O-
  • q is from 1 to about 30, preferably 1 to about 4, and most preferably to about 4; preferably both p and q are 1.
  • EP 2,084, published May 30, 1979, by The p -octer & Gamble Company which describes cationic co-surfactants of this type which are also useful herein..
  • the levels of the AQA surfactants used to prepare finished laundry or dish washing detergent compositions typically range from about 0.1% to about 5%, preferably from about 0.45% to about 2.5%, by weight.
  • the liquid cleaning compositions for laundry and dish washing preferably further comprise a builder system.
  • a builder system or mixed builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetra-acetate, metal ion sequestrants such as aminopoly-phosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylene phosphonic acid.
  • phosphate builders can also be used herein.
  • Most preferred laundry detergent compositions according to the present invention comprise citrate/fatty acid mixed builder systems.
  • Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R- CH(COOH)CH 2 (COOH) wherein R is CiO-20 al yl or alkenyl, preferably Ci2-16 > or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
  • Specific examples include lauryl succinate, myristyl succinate, palmityl succinate 2- dodecenylsuccinate, 2-tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
  • polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071, as well as maleates.
  • suitable fatty acid builders for use herein are saturated or unsaturated C J O-18 f attv ac ids, as well as the corresponding soaps.
  • Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • the preferred unsaturated fatty acid is oleic acid.
  • Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
  • Builders are normally included in amounts of from 0.5% to 50% by weight of the composition preferably from 3% to 30% and most usually from 5% to 15% by weight.
  • compositions of the present invention may further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits.
  • Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases or mixtures thereof.
  • a preferred combination is a composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with the lipolytic enzyme variant D96L at a level of from 50 LU to 8500 LU per liter wash solution.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
  • suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids.
  • suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo).
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991.
  • Said cellulases and/or peroxidases are normally incorporated in the composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Nordisk A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Also proteases described in our co-pending application USSN 08/136,797 can be included in the detergent composition of the invention. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • a preferred protease herein referred to as "Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for the amino acid residue at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions ⁇ equivalent to those selected from the group consisting of +99.
  • proteases are also described in PCT publications: WO 95/30010 published Novenber 9, 1995 by The Procter & Gamble Company; WO 95/3001 1 published Novenber 9, 1995 by The Procter & Gamble Company; WO 95/29979 published Novenber 9, 1995 by The Procter & Gamble Company.
  • Highly preferred enzymes that can be included in the detergent compositions of the present invention include lipases. It has been found that the cleaning performance on greasy soils is synergistically improved by using lipases.
  • Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from Amano Pharmaceutical Co.
  • Lipase P (Amano,” hereinafter referred to as "Amano-P".
  • lipases such as Ml Lipase® and Lipomax ® (Gist-Brocades).
  • Highly preferred lipases are the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826.
  • the Humicola lanuginosa strain DSM 4106 is used.
  • This enzyme is incorporated into the composition in accordance with the invention at a level of from 50 LU to 8500 LU per liter wash solution.
  • the variant D96L is present at a level of from 100 LU to 7500 LU per liter of wash solution. More preferably at a level of from 150 LU to 5000 LU per liter of wash solution.
  • D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 viz. wherein the native lipase ex Humicola lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L). According to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor).
  • the lipases and/or cutinases are normally incorporated in the composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Amylases (& and/or ⁇ ) can be included for removal of carbohydrate-based stains. Suitable amylases are Termamyl (Novo Nordisk), Fungamyl ⁇ and BAN ⁇ (Novo Nordisk).
  • Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents, especially improved oxidative stability as measured against a reference-point of TERMAMYL® in commercial use in 1993.
  • These preferred amylases herein share the characteristic of being "stability- enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g.. to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 11, measured versus the above- identified reference-point amylase.
  • oxidative stability e.g. to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10
  • thermal stability e.g., at common wash temperatures such as about 60°C
  • Stability can be measured using any of the art- disclosed technical tests. See, for example, references disclosed in WO 9402597. Stability-enhanced amylases can be obtained from Novo or from Genencor International. One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein.
  • Such preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B.
  • Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®. Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo.
  • Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo. Said enzymes are normally incorporated in the composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • enzyme oxidation scavengers which are described in Copending European Patent application 92870018.6 filed on January 31, 1992.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • detergent compositions may be employed, such as soil- suspending agents, soil-release polymers, bactericides, coloring agents, foam control agents, corrosion inhibitors and perfumes.
  • the liquid compositions according to the present invention are in "concentrated form"; in such case, the liquid detergent compositions according to the present invention will contain a lower amount of solvent, compared to conventional liquid detergents.
  • the level of solvent is then less than 50%, preferably less than 30% by weight of the detergent compositons.
  • the liquid compositions can also be adapted to be used as pre-treatment compositions, e.i. to be applied directly to soils and stains in a pretreatment step before washing the fabrics.
  • the detergent compositions of the present invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
  • Liquid detergent compositions herein especially those designed for fabric laundering, may also comprise a non-aqueous carrier medium as described in more detail hereinafter.
  • liquid cleaning compositions especially those designed for fabric laundering or dish washing, which comprise a non-aqueous carrier medium
  • non-aqueous carrier medium can be prepared according to the disclosures of U.S. Patents 4,753,570; 4,767.558; 4,772,413; 4,889,652; 4,892,673; GB-A- 2,158.838; GB-A-2,195,125; GB-A-2, 195,649; U.S. 4,988,462; U.S.
  • compositions can contain various particulate detersive ingredients (including the bleaching agents, as disclosed hereinabove) stably suspended therein.
  • non-aqueous compositions thus comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited references.
  • the cationic surfactant of the invention is incorporated in the compositions at the levels and in the manner described hereinabove for the manufacture of other laundry detergent compositions.
  • the liquid phase will generally comprise from 35% to 99.9% by weight of the detergent compositions herein. More preferably, the liquid phase will comprise from about 50% to 95% by weight of the compositions. Most preferably, the liquid phase will comprise from about 45% to 75% by weight of the compositions herein.
  • the liquid phase of the detergent compositions herein essentially contains relatively high concentrations of a certain type anionic surfactant combined with a certain type of nonaqueous, liquid diluent.
  • the anionic surfactant preferablyutilized as an essential component of the nonaqueous liquid phase is one selected from the alkali metal salts of alkylbenzene sulfonic acids in which the alkyl group contains from about 10 to 16 carbon atoms, in straight chain or branched chain configuration.
  • alkylbenzene sulfonic acids in which the alkyl group contains from about 10 to 16 carbon atoms, in straight chain or branched chain configuration.
  • LAS sodium and potassium linear straight chain alkylbenzene sulfonates
  • Sodum Cj i ⁇ Cj4 LAS is especially preferred.
  • the alkylbenzene sulfonate anionic surfactant will be dissolved in the nonaqueous liquid diluent which makes up the second component of the nonaqueous phase.
  • the alkylbenzene sulfonate anionic surfactant is generally present to the extent of from 30% to 65% by weight of the liquid phase. More preferably, the alkylbenzene sulfonate anionic surfactant will comprise from 35% to 50% by weight of the nonaqueous liquid phase of the compositions herein. Utilization of this anionic surfactant in these concentrations corresponds to an anionic surfactant concentration in the total composition of from 15% to 60% by weight, more preferably from 20% to 40% by weight, of the composition.
  • the anionic surfactant or the preferred, hereinbefore described, alkylbenzene sulfonate anionic surfactant is combined with a nonaqueous liquid diluent which contains two essential components. These two components are a liquid alcohol alkoxylate material and a nonaqueous, low-polarity organic solvent.
  • Such materials are themselves also nonionic surfactants.
  • Such materials correspond to the general formula:
  • Rl(C m H 2m O) n OH wherein Rl is a Cg - Ci g alkyl group, m is from 2 to 4, and n ranges from about 2 to
  • Rl is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
  • the alkoxylated fatty alcohols will be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
  • the alkoxylated fatty alcohol component of the liquid diluent will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15.
  • HLB hydrophilic-lipophilic balance
  • fatty alcohol alkoxylates useful as one of the components of the nonaqueous liquid diluent in the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company.
  • Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 1 1 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary Cj2 - C13 alcohol having about 9 moles of ethylene oxide and Neodol 91- 10, an ethoxylated Co. - C ⁇ ⁇ primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename.
  • Dobanol 91-5 is an ethoxylated C9-C1 ] fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
  • Suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Corporation.
  • the former is a mixed ethoxylation product of C ⁇ ⁇ to C15 linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
  • Alcohol ethoxylates useful in the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 1 1. Such products have also been commercially marketed by Shell Chemical Company.
  • the alcohol alkoxylate component which is preferably utilized as part of the liquid diluent in the nonaqueous compositions herein will generally be present to the extent of from 1% to 60% of the liquid phase composition. More preferably, the alcohol alkoxylate component will comprise 5% to 40% of the liquid phase. Most preferably, the essentially utilized alcohol alkoxylate component will comprise from 5% to 30% of the detergent composition liquid phase. Utilization of alcohol alkoxylate in these concentrations in the liquid phase corresponds to an alcohol alkoxylate concentration in the total composition of froml% to 60% by weight, more preferably from 2% to 40% by weight, and most preferably from 5% to 25% by weight, of the composition.
  • a second preferred component of the liquid diluent which forms part of the liquid phase of the detergent compositions herein comprises nonaqueous, low-polarity organic solvent(s).
  • solvent is used herein to connote the non-surface active carrier or diluent portion of the liquid phase of the composition. While some of the essential and/or optional components of the compositions herein may actually dissolve in the "solvent"-containing liquid phase, other components will be present as paniculate material dispersed within the "solvent"-containing liquid phase. Thus the term “solvent” is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto.
  • nonaqueous organic materials which are employed as solvents herein are those which are liquids of low polarity.
  • low-polarity liquids are those which have little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate.
  • relatively polar solvents such as ethanol should not be utilized.
  • Suitable types of low-polarity solvents useful in the nonaqueous liquid detergent compositions herein do include non-vicinal C4-C alkylene glycols, alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like.
  • a preferred type of nonaqueous, low-polarity solvent for use in the compositions herein comprises the non-vicinal C4-Cg branched or straight chain alkylene glycols.
  • Materials of this type include hexylene glycol (4-methyl-2,4-pentanediol), 1,6- hexanediol, 1,3-butylene glycol and 1,4-butylene glycol. Hexylene glycol is the most preferred.
  • nonaqueous, low-polarity solvent for use herein comprises the mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-Cg alkyl ethers.
  • the specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
  • Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred.
  • Compounds of the type have been commercially marketed under the tradenames Dowanol, Carbitol, and Cellosolve.
  • nonaqueous, low-polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs).
  • PEGs polyethylene glycols
  • Such materials are those having molecular weights of at least about 150.
  • PEGs of molecular weight ranging from about 200 to 600 are most preferred.
  • non-polar, nonaqueous solvent comprises lower molecular weight methyl esters.
  • methyl esters Such materials are those of the general formula: R!-C(O)-OCH3 wherein Rl ranges from 1 to about 18.
  • suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
  • the nonaqueous, low-polarity organic solvent(s) employed should, of course, be compatible and non-reactive with other composition components, e.g., bleach and/or activators, used in the liquid detergent compositions herein.
  • a solvent component will generally be utilized in an amount of from about 1% to 70% by weight of the liquid phase.
  • the nonaqueous, low-polarity organic solvent will comprise from 10% to 60% by weight of the liquid phase, most preferably from 20% to 50% by weight, of the liquid phase of the composition. Utilization of this organic solvent in these concentrations in the liquid phase corresponds to a solvent concentration in the total composition of from 1% to 50% by weight, more preferably from 5% to 40% by weight, and most preferably from 10% to 30% by weight, of the composition.
  • the ratio of alcohol alkoxylate to organic solvent within the liquid diluent can be used to vary the rheological properties of the detergent compositions eventually formed.
  • the weight ratio of alcohol alkoxylate to organic solvent will range from 50:1 to 1:50. More preferably, this ratio will range from 3:1 to 1 :3.
  • the amount of total liquid diluent in the nonaqueous liquid phase herein will be determined by the type and amounts of other composition components and by the desired composition properties.
  • the liquid diluent will comprise from 35% to 70% of the nonaqueous liquid phase of the compositions herein. More preferably, the liquid diluent will comprise from 50% to 65% of the nonaqueous liquid phase. This corresponds to a nonaqueous liquid diluent concentration in the total composition of from 15% to 70% by weight, more preferably from about 20% to 50% by weight, of the composition.
  • the nonaqueous compositions herein also essentially comprise froml% to 65% by weight, more preferably from 5% to 50% by weight, of a solid phase of particulate material which is dispersed and suspended within the liquid phase.
  • particulate material will range in size from 0.1 to 1500 microns. More preferably such material will range in size from 5 to 200 microns.
  • the particulate material utilized herein can comprise one or more types of composition components which in particulate form are substantially insoluble in the nonaqueous liquid phase of the composition.
  • the types of particulate materials which can be utilized are described in detail as follows:
  • nonaqueous liquid detergent compositions herein can be prepared by combining the components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form the phase stable compositions herein.
  • essential and certain preferred optional components will be combined in a particular order and under certain conditions.
  • an admixture of the alkylbenzene sulfonate anionic surfactant and the components of the nonaqueous diluent is formed by heating a combination of these materials to a temperature from about 30°C to 100°C.
  • the heated admixture formed as hereinbefore described is maintained under shear agitation at a temperature from about 40°C to 100°C for a period of from about 2 minutes to 20 hours.
  • a vacuum can be applied to the admixture at this point.
  • This second process step serves to completely dissolve the anionic surfactant in the nonaqueous liquid phase.
  • this liquid phase combination of materials is cooled to a temperature of from about 0°C to 35°C.
  • This cooling step serves to form a structured, surfactant-containing liquid base into which the particulate material of the detergent compositions herein can be added and dispersed.
  • Particulate material is added in a fourth process step by combining the particulate material with the liquid base which is maintained under conditions of shear agitation.
  • shear agitation is maintained, essentially all of any optional surfactants in solid particulate form can be added in the form of particles ranging in size from about 0.2 to 1,000 microns.
  • particles of substantially all of an organic builder e.g., citrate and/or fatty acid, and/or an alkalinity source, e.g., sodium carbonate
  • an organic builder e.g., citrate and/or fatty acid
  • an alkalinity source e.g., sodium carbonate
  • Other solid form optional ingredients can then be added to the composition at this point. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a uniform dispersion of insoluble solid phase particulates within the liquid phase.
  • bleaching agent can be added to the composition, again while the mixture is maintained under shear agitation.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning. These include oxygen bleaches as well as other bleaching agents such as percarboxylic acid bleaching agents and salts thereof.
  • Suitable examples of this latter class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.
  • peroxygen bleaching agents which include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, perborate bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, and persulfate bleach (e.g., OXONE, manufactured commercially by DuPont).
  • enzyme prills are incorporated, they are preferably added to the nonaqueous liquid matrix last.
  • agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from about 1 to 30 minutes.
  • PAS Salt of R, N + (CH 3 ) 2 R 2 , wherein R, is C 2 -C 3 hydroxyalkyi and R 2 is primary ethylene amine or primary propylene amine
  • PAS Salt of R, N + (CH 3 ) 2 R 2 wherein R, is C 5 -C 8 alkyl and
  • R 2 is primary ethylene amine or primary propylene amine
  • Nai2(A102SiO2)i2- 27H2O having a primary particle size in the range from 0.1 to 10 micrometers
  • Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • Silicate Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio)
  • Bismuth nitrate Bismuth nitrate salt PA30 Polyacrylic acid of average molecular weight approximately 8,000
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate.
  • PVNO Polyvinylpyridine N-oxide PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole
  • bleach-containing nonaqueous liquid laundry detergent is prepared having the composition as set forth in Table I. Table I
  • Protease enzyme 0.4 0-1.0 Citrate 4.3 3-6 PB1 3.4 2-7 NOBS 8.0 2-12 Carbonate 13.9 5-20 DTPA 0.9 0-1.5 Brightener 1 0.4 0-0.6 Silicone antifoam 0.1 0-0.3
  • the resulting composition is an anhydrous heavy duty liquid laundry detergent which provides excellent stain and soil removal performance when used in normal fabric laundering operations.
  • Example further illustrates the invention herein with respect to a hand dishwashing liquid.
  • Maxata issee®® pprrootteeaassee 0.50 0-1.0
  • Liquid detergent compositions are made according to the following.
  • liquid detergent compositions (A-D) are found to be very efficient in the removal of a wide range of stains and soils from fabrics under various usage conditions.
  • PAS/PAS j 2.0 1.0 0.5 7.0 4.0 1.3
  • Amylase (300KMU/g) 0.1 0.1 0.1 0.1 0.1 - 0.1
  • liquid detergent formulations are in accord with the invention (levels are given as parts per weight).
  • liquid detergent formulations were prepared in accord with the invention (levels are given in parts per weight):
  • liquid detergent compositions were prepared in accord with the invention (levels are given in parts per weight).
  • liquid cleaning compositions of the invention can be in the form of shampoo compositions, which can comprise any of the ingredients described above but which typically can comprise the following additional ingredients, described herein.
  • water soluble refers to any material that is sufficiently soluble in water to form a substantially clear solution to the naked eye at a concentration of 0.1% in water, i.e. distilled or equivalent, at 25°C.
  • the cationic surfactant is preferably present at a level of from 0.05% to 15%, more preferably from 0.2% to 10% by weight.
  • the shampoo compositions will comprise, in addition to the cationic surfactan, one or more co-surfactants selected from the group consisting of anionic surfactant, nonionic surfactant, amphoteric surfactant, zwitterionic surfactants, and mixtures thereof.
  • the shampoo compositions preferably comprise an anionic co-surfactant.
  • Surfactant mixture concentrations range from 5% to 50%, preferably from 8% to 30%, more preferably from 10% to 25%, by weight of the compositions.
  • the shampoo compositions preferably comprise an anionic co-surfactant, and preferably at concentrations of from 5% to 30%, more preferably from 7% to 25%, even more preferably from 8% to 20%, and most preferably from 9% to 18%, by weight of the composition.
  • Anionic surfactants for use in the shampoo compositions include alkyl and alkyl ether sulfates. These materials have the respective formulae ROSO3M and RO(C2H4O) x SO3M, wherein R is alkyl or alkenyl of from about 8 to about 30 carbon atoms, x is 1 to 10, and M is a cation such as ammonium, alkanolamines, such as triethanolamine, monovalent metals, such as sodium and potassium, and polyvalent metal cations, such as magnesium, and calcium.
  • the cation M, of the anionic surfactant should be chosen such that the anionic surfactant component is water soluble. Solubility will depend upon the particular anionic surfactants and cations chosen.
  • R has from about 12 to about 18 carbon atoms in both the alkyl and alkyl ether sulfates.
  • the alkyl ether sulfates are typically made as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms.
  • the alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil are preferred herein. Such alcohols are reacted with between about 0 and about 10, and especially about 3, molar proportions of ethylene oxide and the resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
  • alkyl ether sulfates which may be used in the shampoo compositions of the present invention are sodium and ammonium salts of coconut alkyl triethylene glycol ether sulfate: tallow alkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate.
  • Highly preferred alkyl ether sulfates are those comprising a mixture of individual compounds, said mixture having an average alkyl chain length of from about 10 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide.
  • Suitable anionic surfactants are the water-soluble salts of organic, sulfuric acid reaction products of the general formula [ Ri -SO3-M ] where R ⁇ is selected from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 10 to about 18, carbon atoms; and M is a cation, as previously described, subject to the same limitations regarding polyvalent metal cations as previously discussed.
  • surfactants are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-, and n-paraffins, having about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g., SO3, H2SO4, obtained according to known sulfonation methods, including bleaching and hydrolysis.
  • a sulfonating agent e.g., SO3, H2SO4
  • alkali metal and ammonium sulfonated C ⁇ rj-18 n-paraffins are preferred.
  • anionic surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil.
  • Other similar anionic surfactants are described in U.S. Patents 2,486,921; 2,486,922; and 2,396,278.
  • anionic surfactants suitable for use in the shampoo compositions are the succinnates, examples of which include disodium N-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetrasodium N-(l,2-dicarboxyethyl)-N-octadecylsulfosuccinnate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.
  • succinnates examples of which include disodium N-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetrasodium N-(l,2-dicarboxy
  • Suitable anionic surfactants include olefin sulfonates having about 10 to about 24 carbon atoms.
  • olefin sulfonates is used herein to mean compounds which can be produced by the sulfonation of alpha-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates.
  • the sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SO2, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO2, etc., when used in the gaseous form.
  • inert diluents for example by liquid SO2, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO2, etc., when used in the gaseous form.
  • the alpha-olefins from which the olefin sulfonates are derived are mono-olefins having about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms. Preferably, they are straight chain olefins.
  • the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
  • Another class of anionic surfactants suitable for use in the shampoo compositions are the beta-alkyloxy alkane sulfonates. These compounds have the following formula:
  • R is a straight chain alkyl group having from about 6 to about 20 carbon atoms
  • R2 is a lower alkyl group having from about 1 (preferred) to about 3 carbon atoms
  • M is a water-soluble cation as hereinbefore described.
  • Preferred anionic surfactants for use in the shampoo compositions include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate.
  • the surfactant of the shampoo compositions may comprise an amphoteric and/or zwitterionic surfactant. Concentrations of such surfactants will generally range from 0.5% to 20%, preferably from 1% to 10%, by weight of the shampoo compositions.
  • Amphoteric surfactants for use in the shampoo compositions include the derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical is straight or branched and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • an anionic water solubilizing group e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • Zwitterionic surfactants for use in the shampoo compositions include the derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals are straight or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • a these compounds is:
  • R contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety;
  • Y is selected from the group consisting of nitrogen,
  • R is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms
  • X is 1 when Y is a sulfur atom, and 2
  • Y when Y is a nitrogen or phosphorus atom; R is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
  • amphoteric and zwitterionic surfactants also include sultaines and amidosultaines. Sultaines and amidosultaines can be used as foam enhancing surfactants that are mild to the eye in partial replacement of anionic surfactants.
  • Sultaines including amidosultaines, include for example, cocodimethylpropylsultaine, stearyldimethylpropylsultaine, lauryl-bis-(2-hydroxyethyl) propylsultaine and the like; and the amidosultaines such as cocoamidodimethylpropylsultaine, stearylamidododimethylpropylsultaine, laurylamidobis-(2-hydroxyethyl) propylsultaine, and the like.
  • amidohydroxysultaines such as the Cl2"C ⁇ g hydrocarbyl amidopropyl hydroxysultaines, especially C12-C14 hydrocarbyl amido propyl hydroxysultaines, e.g., laurylamidopropyl hydroxysultaine and cocamidopropyl hydroxysultaine.
  • C12-C14 hydrocarbyl amido propyl hydroxysultaines e.g., laurylamidopropyl hydroxysultaine and cocamidopropyl hydroxysultaine.
  • Other sultaines are described in U.S. Patent 3,950,417, which descriptions are incorporated herein by reference.
  • amphoteric surfactants are the aminoalkanoates of the formula
  • R-N [(CH 2 ) m COOM] 2 and mixtures thereof; wherein n and m are numbers from 1 to 4, R is Cg - C22 alkyl or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium.
  • suitable aminoalkanoates include n-alkylamino-propionates and n-alkyliminodipropionates, specific examples of which include N-lauryl- -beta-amino propionic acid or salts thereof, and N-lauryl-beta-imino-dipropionic acid or salts thereof, and mixtures thereof.
  • amphoteric surfactants include those represented by the formula :
  • Rl is Cg - C22 alkyl or alkenyl. preferably C ⁇ -Cj
  • R 2 is hydrogen or CH CO 2 M
  • R 3 is CH 2 CH 2 OH or CH2CH 2 OCH 2 CH 2 COOM
  • R 4 is hydrogen, CH 2 CH 2 OH, or CH2CH2OCH2CH2COOM
  • Z is CO M or CH CO M
  • n is 2 or 3, preferably 2
  • M is hydrogen or a cation, such as alkali metal (e.g., lithium, sodium, potassium), alkaline earth metal (beryllium, magnesium, calcium, strontium, barium), or ammonium.
  • This type of surfactant is sometimes classified as an imidazoline-type amphoteric surfactant, although it should be recognized that it does not necessarily have to be derived, directly or indirectly, through an imidazoline intermediate.
  • Suitable materials of this type are marketed under the trade name MIRANOL and are understood to comprise a complex mixture of species, and can exist in protonated and non-protonated species depending upon pH with respect to species that can have a hydrogen at R 2 . All such variations and species are meant to be encompassed by the above formula.
  • surfactants of the above formula are monocarboxylates and dicarboxylates.
  • examples of these materials include cocoamphocarboxypropionate, cocoamphocarboxypropionic acid, cocoamphocarboxyglycinate (alternately referred to as cocoamphodiacetate), and cocoamphoacetate.
  • MIRANOL C2M CONC. N.P. MIRANOL C2M CONC. O.P.
  • MIRANOL C2M SF MIRANOL CM SPECIAL (Miranol, Inc.); ALKATERIC 2CIB (Alkaril Chemicals); AMPHOTERGE W-2 (Lonza, Inc.); MONATERIC CDX-38, MONATERIC CSH-32 (Mona Industries); REWOTERIC AM-2C (Rewo Chemical Group); and SCHERCOTERIC MS-2 (Scher Chemicals).
  • Betaine surfactants (zwitterionic) suitable for use in the shampoo compositions are those represented by the formula:
  • Ri is a member selected from the group consisting of
  • R2 is lower alkyl or hydroxyalkyi
  • R3 is lower alkyl or hydroxyalkyi
  • R4 is a member selected from the group consisting of hydrogen and lower alkyl
  • R5 is higher alkyl or alkenyl
  • Y is lower alkyl, preferably methyl; m is an integer from 2 to 7, preferably from 2 to 3; n is the integer 1 or 0;
  • M is hydrogen or a cation, as previously described, such as an alkali metal, alkaline earth metal, or ammonium.
  • lower alkyl or "hydroxyalkyi” means straight or branch chained, saturated, aliphatic hydrocarbon radicals and substituted hydrocarbon radicals having from one to about three carbon atoms such as, for example, methyl, ethyl, propyl, isopropyl, hydroxypropyl, hydroxyethyl, and the like.
  • higher alkyl or alkenyl means straight or branch chained saturated (i.e., “higher alkyl") and unsaturated (i.e., “higher alkenyl”) aliphatic hydrocarbon radicals having from about eight to about 20 carbon atoms such as, for example, lauryl, cetyl, stearyl, oleyl, and the like. It should be understood that the term “higher alkyl or alkenyl” includes mixtures of radicals which may contain one or more intermediate linkages such as ether or polyether linkages or non-functional substitutents such as hydroxyl or halogen radicals wherein the radical remains of hydrophobic character.
  • surfactant betaines of the above formula wherein n is zero which are useful herein include the alkylbetaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryl dimethyl-alpha-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, lauryl-bis-(2-hydroxyethyl)carboxymethylbetaine, stearyl-bis-(2-hy- droxypropyl)carboxymethylbetaine, oleyl- dimethyl-gamma-carboxypropylbetaine, lauryl-bix-(2-hydroxypropyl)- alpha-carboxyethylbetaine, etc.
  • alkylbetaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryl dimethyl-alpha-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, lau
  • the sulfobetaines may be represented by cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryl-bis-(2-hydroxyethyl)sulfopropylbetaine, and the like.
  • amido betaines and amidosulfo betaines useful in the shampoo compositions include the amidocarboxybetaines, such as cocoamidodimethylcarboxymethylbetaine, laurylamidodi- methylcarboxymethylbetaine, cetylamidodimethylcarboxymethylbetaine, laurylamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, cocoamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, etc.
  • amidocarboxybetaines such as cocoamidodimethylcarboxymethylbetaine, laurylamidodi- methylcarboxymethylbetaine, cetylamidodimethylcarboxymethylbetaine, laurylamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, cocoamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, etc.
  • amido sulfobetaines may be represented by cocoamidodimethylsulfopropylbetaine, stearylamidodimethylsulfopropylbetaine, lauryl- amido-bis-(2-hydroxyethyl)-sulfopropylbetaine, and the like.
  • the shampoo compositions may comprise a nonionic surfactant as the detersive surfactant component therein.
  • Nonionic surfactants include those compounds produced by condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • Preferred nonionic surfactants for use in the shampoo compositions include the following:
  • polyethylene oxide condensates of alkyl phenols e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 20 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to from about 10 to about 60 moles of ethylene oxide per mole of alkyl phenol;
  • ethylene oxide e.g., a coconut alcohol ethylene oxide condensate having from about 10 to about 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from about 10 to about 14 carbon atoms
  • Rl contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to about 1 glyceryl moiety
  • R 2 and R 3 contain from about 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals;
  • R contains an alkyl, alkenyl or monohyd ⁇ alkyl radical ranging from about 8 to about 18 carbon atoms in chain length, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety and R * and R" are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms;
  • long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of from about 1 to about 3 carbon atoms (usually methyl) and one long hydrophobic chain which include alkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals containing from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety;
  • alkyl polysaccharide (APS) surfactants e.g. alkyl polyglycosides
  • alkyl polysaccharide (APS) surfactants e.g. alkyl polyglycosides
  • alkyl polysaccharide (APS) surfactants having a hydrophobic group with about 6 to about 30 carbon atoms and polysaccharide (e.g., polyglycoside) as the hydrophilic group; optionally, there can be a polyalkylene-oxide group joining the hydrophobic and hydrophilic moieties; and the alkyl group (i.e., the hydrophobic moiety) can be saturated or unsaturated, branched or unbranched, and unsubstituted or substituted (e.g., with hydroxy or cyclic rings); and
  • polyethylene glycol (PEG) glyceryl fatty esters such as those of the formula R(O)OCH 2 CH(OH)CH (OCH 2 CH 2 ) n OH wherein n is from about 5 to about 200, preferably from about 20 to about 100, and R is an aliphatic hydrocarbyl having from about 8 to about 20 carbon atoms.
  • the shampoo compositions preferably also comprise a silicone hair conditioning agent at concentrations effective to provide hair conditioning benefits. Such concentrations range from 0 .05% to 10%, preferably from 0.1% to 8%, more preferably from 0.1% to 5%, most preferably from 0.2% to 3%, by weight of the shampoo compositions.
  • the silicone hair conditioning agents for use in the shampoo compositions are insoluble in the shampoo compositions, and are preferably nonvolatile. Typically it will be intermixed in the shampoo composition so as to be in the form of a separate, discontinuous phase of dispersed, insoluble particles, also referred to as droplets. These droplets are suspended with a suspending agent described hereinafter.
  • the silicone hair conditioning agent phase will comprise a silicone fluid hair conditioning agent such as a silicone fluid and can also comprise other ingredients, such as a silicone resin to enhance silicone fluid deposition efficiency or enhance glossiness of the hair (especially when high refractive index (e.g. above about 1.46) silicone conditioning agents are used (e.g. highly phenylated silicones).
  • nonvolatile refers to silicone material with little or no significant vapor pressure under ambient conditions, as is understood by those in the art. Boiling point under one atmosphere (atm) will preferably be at least about 250°C, more preferably at least about 275°C, most preferably at least about 300°C. Vapor pressure is preferably about 0.2mm HG at 25°C or less, preferably about 0.1mm HG at 25°C or less.
  • the silicone hair conditioning agent phase may comprise volatile silicone, nonvolatile silicone, or mixtures thereof. Typically, if volatile silicones are present, it will be incidental to their use as a solvent or carrier for commercially available forms of nonvolatile silicone materials ingredients, such as silicone gums and resins.
  • the silicone hair conditioning agents for use in the shampoo compositions preferably have a viscosity of from about 20 to about 2,000,000 centistokes, more preferably from about 1 ,000 to about 1 ,800,000 centistokes, even more preferably from about 50,000 to about 1,500,000 centistokes, most preferably from about 100,000 to about 1,500,000 centistokes, at 25°C.
  • the viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970.
  • Silicone fluid for use in the shampoo compositions includes silicone oil which are flowable silicone materials with a viscosity of less than 1 ,000,000 centistokes, preferably between about 5 and 1 ,000,000 centistokes, more preferably between about 10 and about 100,000 centistokes, at 25°C.
  • Suitable silicone oils include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof.
  • Other insoluble, nonvolatile silicone fluids having hair conditioning properties can also be used.
  • Silicone resins can be included in the silicone conditioning agent. These resins are highly crosslinked polymeric siloxane systems. The crosslinking is introduced through the incorporation of trifunctional and tetrafunctional silanes with mono functional or difunctional, or both, silanes during manufacture of the silicone resin. As is well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of crosslinking) such that they dry down to a rigid, or hard, film are considered to be silicone resins.
  • the ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material.
  • Silicone materials which have at least about 1.1 oxygen atoms per silicon atom will generally be silicone resins herein.
  • the ratio of oxygemsilicon atoms is at least about 1.2: 1.0.
  • Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-substituted silanes being most commonly utilized.
  • Preferred resins are offered by General Electric as GE SS4230 and SS4267.
  • Commercially available silicone resins will generally be supplied in a dissolved form in a low viscosity volatile or nonvolatile silicone fluid.
  • the silicone resins for use herein should be supplied and incorporated into the present compositions in such dissolved form, as will be readily apparent to those skilled in the art.
  • the shampoo compositions may further comprise selected polyalkylene glycols in amounts effective to enhance lather performance and enhance spreadability of the shampoo compositions on hair. Effective concentrations of the selected polyethylene glycols range from 0.025% to 1.5%, preferably from 0.05% to 1%, more preferably from 0.1% to 0.5%, by weight of the shampoo compositions.
  • polyalkylene glycols suitable for use in the shampoo compositions are characterized by the general formula:
  • R is hydrogen, methyl or mixtures thereof, preferably hydrogen, and n is an integer having an average value of from about 1,500 to about 25,000, preferably from about 2,500 to about 20,000, and more preferably from about 3,500 to about 15,000.
  • R is hydrogen
  • these materials are polymers of ethylene oxide, which are also known as polyethylene oxides, polyoxyethylenes, and polyethylene glycols.
  • R is methyl
  • these materials are polymers of propylene oxide, which are also known as polypropylene oxides, polyoxypropylenes, and polypropylene glycols.
  • R is methyl, it is also understood that various positional isomers of the resulting polymers can exist.
  • suitable polyethylene glycol polymers include PEG-2M wherein R equals hydrogen and n has an average value of about 2,000 (PEG 2-M is also known as Polyox WSR® N-10, which is available from Union Carbide and as PEG-2,000); PEG-5M wherein R is hydrogen and n has an average value of about 5,000 (PEG 5-M is also known as Polyox WSR® N-35 and Polyox WSR® N-80, both available from Union Carbide and as PEG-5,000 and Polyethylene Glycol 300,000); PEG-7M wherein R is hydrogen and n has an average value of about 7,000 (PEG 7-M is also known as Polyox WSR® N-750 available from Union Carbide); PEG-9M wherein R is hydrogen and n has an average value of about 9,000 (PEG 9- M is also known as Polyox WSR® N-3333 available from Union Carbide); and PEG- 14 M wherein R is hydrogen and n has an average value of about 14,000 (PEG 14 M where
  • the shampoo compositions may further comprise a suspending agent at concentrations effective for suspending the silicone hair conditioning agent in dispersed form in the shampoo compositions. Such concentrations range from 0.1% 1 10%, preferably from 0.3% to 5.0%, by weight of the shampoo compositions.
  • Suitable suspending agents include acyl derivatives, long chain amine oxides, and mixtures thereof. When used in the shampoo compositions, these suspending agents are present in crystalline form. These suspending agents are described in U.S. Patent 4,741,855, which description is incorporated herein by reference. These preferred suspending agents include ethylene glycol esters of fatty acids preferably having from about 16 to about 22 carbon atoms. More preferred are the ethylene glycol stearates, both mono and distearate, but particularly the distearate containing less than about 7% of the mono stearate.
  • suspending agents include alkanol amides of fatty acids, preferably having from about 16 to about 22 carbon atoms, more preferably about 16 to 18 carbon atoms, preferred examples of which include stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanol- amide and stearic monoethanolamide stearate.
  • long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmi- tate, etc.); glyceryl esters (e.g., glyceryl distearate) and long chain esters of long chain alkanol amides (e.g., stearamide diethanolamide distearate, stearamide monoethanolamide stearate).
  • Long chain acyl derivatives, ethylene glycol esters of long chain carboxyiic acids, long chain amine oxides, and alkanol amides of long chain carboxyiic acids in addition to the preferred materials listed above may be used as suspending agents.
  • suspending agents with long chain hydrocarbyls having C -C22 chains may be used.
  • acyl derivatives suitable for use as suspending agents include N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na and K salts), particularly N,N-di(hydrogenated) Ci g, Ci g and tallow amido benzoic acid species of this family, which are commercially available from Stepan Company (Northfield, Illinois, USA).
  • Suitable long chain amine oxides for use as suspending agents include alkyl (Cjg-C22) dimethyl amine oxides, e.g., stearyl dimethyl amine oxide
  • suspending agents include xanthan gum at concentrations ranging from 0.3% t3%, preferably from 0.4% to 1.2%, by weight of the shampoo compositions.
  • xanthan gum as a suspending agent in silicone containing shampoo compositions is described, for example, in U.S. Patent 4,788,006, which description is incorporated herein by reference.
  • Combinations of long chain acyl derivatives and xanthan gum may also be used as a suspending agent in the shampoo compositions. Such combinations are described in U.S. Patent 4,704,272, which description is incorporated herein by reference.
  • suspending agents include carboxyvinyl polymers. Preferred among these polymers are the copolymers of acrylic acid crosslinked with polyallylsucrose as described in U.S. Patent 2,798,053, which description is incorporated herein by reference. Examples of these polymers include Carbopol 934, 940, 941, and 956, available from B. F. Goodrich Company .
  • Preferred carboxyvinyl polymers have a molecular weight of at least about 750,000; more preferred are carboxyvinyl polymers having a molecular weight of at least about 1,250,000; most preferred are carboxyvinyl polymers having a molecular weight of at least about 3,000,000.
  • suspending agents include primary amines having a fatty alkyl moiety having at least about 16 carbon atoms, examples of which include palmitamine or stearamine, and secondary amines having two fatty alkyl moieties each having at least about 12 carbon atoms, examples of which include dipalmitoylamine or di(hydrogenated tallow)amine. Still other suitable suspending agents include di(hydrogenated tallow)phthalic acid amide, and crosslinked maleic anhydride- methyl vinyl ether copolymer.
  • suspending agents may be used in the shampoo compositions, including those that can impart a gel-like viscosity to the composition, such as water soluble or colloidally water soluble polymers like cellulose ethers (e.g., methylcellulose, hydroxybutyl methylcellulose, hyroxypropylcellulose, hydroxypropyl methylcellulose, hydroxyethyl ethylcellulose and hydorxethylcellulose), guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch and starch derivatives, and other thickeners, viscosity modifiers, gelling agents, etc. Mixtures of these materials can also be used.
  • water soluble or colloidally water soluble polymers like cellulose ethers (e.g., methylcellulose, hydroxybutyl methylcellulose, hyroxypropylcellulose, hydroxypropyl methylcellulose, hydroxyethyl ethylcellulose and
  • the shampoo compositions can comprise from 20% to 99.9%, preferably from 50% to 94.8%, more preferably from 60% to 85%, by weight of water.
  • the shampoo compostions of the present invention may further comprise water soluble cationic polymeric conditioning agents, hydrocarbon conditioning agents, cationic surfactants, and mixtures thereof.
  • Additional cationic surfactants for use as hair conditioning agents in the shampoo compositions will typically contain quaternary nitrogen moieties.
  • suitable cationic surfactants are described in following documents, all of which are incorporated by reference herein in their entirety: M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers, (North American edition 1979); Schwartz, et al., Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; U.S. Patent 3,155,591; U. S. Patent 3,929,678; U. S. Patent 3,959,461 and U. S. Patent 4,387,090.
  • optional materials include foam boosters, preservatives, • thickeners, cosurfactants, dyes, perfumes, solvents, styling polymers, anti-static agents, anti-dandruff aids, and pediculocides, pH adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate, etc.; perfumes; and dyes.
  • Optional antidandruff agents include particulate antidandruff agents such as pyridinethione salts, selenium compounds such as selenium disulfide, and soluble antidandruff agents.
  • Dimethicone is a 40(gum)/60(fluid) weight ratio blend of SE-76 dimethicone gum available from General Electric Silicones Division and a dimethicone fluid having a viscosity of 350 centistokes.
  • HSC compositions Hard-surface cleaning compositions
  • the liquid cleaning composition of the invention can be in the form of a compositon suitable for the cleaning of a hard-surface are liquid compositions.
  • the HSC compositions preferably comprise the cationic surfactant at a level of from
  • the liquid compositions of the present invention are preferably but not necessarily formulated as aqueous compositions, i.e. whereby the solvent of the compositions of the invention comprises water.
  • Aqueous compositions typically comprise from 50% to 99.9% by weight of the total composition of water, preferably from 60% to 95%, and more preferably from 80% to 95%.
  • the liquid compositions herein may be formulated in the full pH range of 0 to 14, preferably 1 to 13.
  • the compositions herein are formulated in a neutral to highly alkaline pH range from 7 to 13. preferably from 9 to 1 1 and more preferably from 9.5 to 11.
  • the pH of the compositions herein can be adjusted by any of the means well-known to those skilled in the art such as acidifying agents like organic or inorganic acids, or alkalinising agents like NaOH, KOH, K2CO3, Na2CO3 and the like.
  • Preferred organic acids for use herein have a pk of less than 6.
  • Suitable organic acids are selected from the group consisting of citric acid, lactic acid, glycolic acid, succinic acid, glutaric acid and adipic acid and mixtures thereof.
  • a mixture of said acids may be commercially available from BASF under the trade name Sokalan® DCS.
  • liquid compositions may comprise a variety of optional ingredients, including the ingredients described herein before,depending on the technical benefit aimed for and the surface treated.
  • Suitable ingredients for use herein include surfactants, builders, chelants, polymers, solvents, buffers, bactericides, hydrotropes, colorants, stabilisers, radical scavengers, bleaches, bleach activators, suds controlling agents like fatty acids, enzymes, soil suspenders, dye transfer agents, brighteners, anti dusting agents, dispersants, dye transfer inhibitors, pigments, dyes and/or perfumes.
  • the liquid compositions preferably comprise a surfactant, or mixtures thereof.
  • Said surfactant may be present in the compositions in amounts of from 0.1% to 50% by weight of the total composition, preferably of from 0.1% to 20% and more preferably of from 1% to 10%.
  • Surfactants are desired herein as they further contribute to the cleaning performance and/or gloss benefit of the compositions of the present invention.
  • Surfactants to be used herein include nonionic surfactants, anionic surfactants, additional cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.
  • nonionic surfactants are the nonionic surfactants.
  • Suitable nonionic surfactants are the nonionic surfactants descibed herein before.
  • Highly suitable nonionic surfactants for use herein include a class of compounds which may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be branched or linear aliphatic (e.g. Guerbet or secondary alcohols) or alkyl aromatic in nature.
  • a well-known class of nonionic synthetic detergents is made available on the market under the trade name "Pluronic".
  • nonionic synthetic detergents include : (i) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • the alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, and nonane;
  • Particularly preferred surfactants include also the anionic surfactants, including the anionic surfactants described herein before. Suitable anionic surfactants for use herein include alkali metal (e.g., sodium or potassium) fatty acids, or soaps thereof, containing from about 8 to about 24, preferably from about 10 to about 20 carbon atoms.
  • the fatty acids including those used in making the soaps can be obtained from natural sources such as, for instance, plant or animal -derived glycerides (e.g., palm oil, coconut oil, babassu oil, soybean oil. castor oil, tallow, whale oil, fish oil, tallow, grease, lard and mixtures thereof).
  • the fatty acids can also be synthetically prepared (e.g., by oxidation of petroleum stocks or by the Fischer-Tropsch process).
  • Alkali metal soaps can be made by direct saponification of fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps.
  • tallow is used herein in connection with fatty acid mixtures which typically have an approximate carbon chain length distribution of 2.5% C14, 29% C16, 23% C18, 2% palmitoleic, 41.5% oleic and 3% linoleic (the first three fatty acids listed are saturated). Other mixtures with similar distribution, such as the fatty acids derived from various animal tallows and lard, are also included within the term tallow.
  • the tallow can also be hardened (i.e., hydrogenated) to convert part or all of the unsaturated fatty acid moieties to saturated fatty acid moieties.
  • coconut refers to fatty acid mixtures which typically have an approximate carbon chain length distribution of about 8% C8, 7% ClO, 48% C12, 17% C14, 9% C16, 2% C18, 7% oleic, and 2% linoleic (the first six fatty acids listed being saturated).
  • Other sources having similar carbon chain length distribution such as palm kernel oil and babassu oil are included with the term coconut oil.
  • Suitable zwitterionic detergents to be used herein comprise the betaine and betaine- like surfactants, described herein before
  • Amphoteric and ampholytic detergents which can be either cationic or anionic depending upon the pH of the system are represented by detergents such as dodecylbeta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids such as those produced according to the teaching of U.S. Pat. No. 2,438,091, and the products sold under the trade name "Miranol", and described in U.S. Pat. No. 2,528,378, said patents being incorporated herein by reference.
  • detergents such as dodecylbeta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids such as those produced according to
  • Suitable perfumes to be used herein include materials which provide an olfactory aesthetic benefit and/or cover any "chemical" odor that the product may have.
  • the main function of a small fraction of the highly volatile, low boiling (having low boiling points), perfume components in these perfumes is to improve the fragrance odor of the product itself, rather than impacting on the subsequent odor of the surface being cleaned.
  • perfume components in these perfumes provide a fresh and clean impression to the surfaces, and it is desirable that these ingredients be deposited and present on the dry surface.
  • Perfume ingredients can be readily solubilized in the compositions, for instance by the nonionic detergent surfactants.
  • the perfume ingredients and compositions suitable to be used herein are the conventional ones known in the art. Selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations.
  • Suitable perfume compounds and compositions can be found in the art including U.S. Pat. Nos. : 4,145,184, Brain and Cummins, issued March 20, 1979; 4,209,417, Whyte, issued June 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1, 1979, all of said patents being incorporated herein by reference.
  • Chelating agents can preferred ingrwedients of HSC compositions. They can be incorporated in the compositions herein in amounts ranging from 0.0% to 10.0% by weight of the total composition, preferably 0.1% to 5.0%.
  • Suitable phosphonate chelating agents to be used herein may include alkali metal ethane 1 -hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP).
  • the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
  • Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1 -hydroxy diphosphonate (HEDP).
  • DTPMP diethylene triamine penta methylene phosphonate
  • HEDP ethane 1 -hydroxy diphosphonate
  • Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®-
  • Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy -3,5-disulfobenzene.
  • a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
  • Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins.
  • Ethylenediamine N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
  • Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol- diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS® and methyl glycine di-acetic acid (MGDA).
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • carboxylate chelating agents to be used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
  • compositions herein may further comprises other polymeric compounds like other carboxylate-containing polymer, or mixtures thereof, up to a level of 20%, by weight of the total compositon, preferably 0.01% to 5%.
  • suitable carboxylate- containing polymer include those described herein before.
  • carboxylate- containing polymer it is meant herein a polymer or copolymer comprising at least a monomeric unit which contains at least a carboxylate functionality.
  • Any carboxylate-containing polymer known to those skilled in the art can be employed according to the present invention such as homo- or co-polymeric polycarboxylic acids or their salts including polyacrylates and polymers and copolymers of maleic anhydride or/and acrylic acid and the like, or mixtures thereof
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 1 ,000,000, more preferably from about 10,000 to 150,000 and most preferably from about 20,000 to 100,000.
  • Water- soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl. U.S. Patent 3,308,067, issued March 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred carboxylate- containing polymer.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1 :1, more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982. Particularly preferred is a copolymer of maleic / acrylic acid with an average molecular weight of about 70,000. Such copolymers are commercially available from BASF under the trade name SOKALAN CP5.
  • carboxylate-containing polymers to be used herein include cellulose derivatives such as carboxymethylcellulose.
  • carboxymethylcellulose may be used as a salt with conventional cation such as sodium, potassium, amines or substituted amines.
  • compositions may further comprise a divalent counterion, or mixtures thereof.
  • All divalent ions known to those skilled in the art may be used herein.
  • Preferred divalent ions to be used herein are calcium, zinc, cadmium, nickel, copper, cobalt, zirconium, chromium and/or magnesium and more preferred are calcium, zinc and/or magnesium.
  • Said divalent ions may be added in the form of salts for example as chloride, acetate, sulphate, formate and/or nitrate or as a complex metal salt.
  • calcium may be added in the form of calcium chloride, magnesium as magnesium acetate or magnesium sulphate and zinc as zinc chloride.
  • the liquid HSC compositions may also comprises a builder or a mixture thereof, as an optional ingredeint.
  • Suitable builders for use herein include polycarboxylates and polyphosphates, and salts thereof.
  • the compositions of the present invention comprise up to 20.0 % by weight of the total composition of a builder or mixtures thereof, preferably from 0.1% to 10.0% , and more preferably from 0.5% to 5.0%.
  • Suitable polyphosphonates for use herein are the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates.
  • the most preferred builder for use herein is citrate.
  • compositions according to the present invention may further comprise a suds controlling agent such as 2-alkyl alkanol, or mixtures thereof, as a preferred optional ingredient.
  • a suds controlling agent such as 2-alkyl alkanol, or mixtures thereof, as a preferred optional ingredient.
  • Particularly suitable to be used in the present invention are the 2-alkyl alkanols having an alkyl chain comprising from 6 to 16 carbon atoms, preferably from 8 to 12 and a terminal hydroxy group, said alkyl chain being substituted in the ⁇ position by an alkyl chain comprising from 1 to 10 carbon atoms, preferably from 2 to 8 and more preferably 3 to 6.
  • compositions herein may comprise up to 2% by weight of the total composition of a 2-alkyl alkanol, or mixtures thereof, preferably from 0.1% to 1.5% and most preferably from 0.1% to 0.8%.
  • liquid compositions herein may also comprise a bleaching component. Any bleach known to those skilled in the art may be suitable to be used herein including any peroxygen bleach as well as a chlorine releasing component.
  • compositions of the present invention comprise a solvent or a mixtures thereof.
  • Solvents to be used herein include all those known to the those skilled in the art of hard-surfaces cleaner compositions. Suitable solvents for use herein include ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms, glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C6-C16 glycol ethers and mixtures thereof.
  • Suitable glycols to be used herein are according to the formula HO-CR1R2-OH wherein Rl and R2 are independently H or a C2-C10 saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic. Suitable glycols to be used herein are dodecaneglycol and/or propanediol.
  • Suitable alkoxylated glycols to be used herein are according to the formula R-(A)n- Rl-OH wherein R is H, OH, a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein Rl is H or a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, and A is an alkoxy group preferably ethoxy, methoxy, and or propoxy and n is from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated glycols to be used herein are methoxy octadecanol and/or ethoxyethoxyethanol.
  • Suitable alkoxylated aromatic alcohols to be used herein are according to the formula R (A) n -OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated aromatic alcohols are benzoxyethanol and/or benzoxypropanol.
  • Suitable aromatic alcohols to be used herein are according to the formula R-OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
  • R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
  • a suitable aromatic alcohol to be used herein is benzyl alcohol.
  • Suitable aliphatic branched alcohols to be used herein are according to the formula R-OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12.
  • Particularly suitable aliphatic branched alcohols to be used herein include 2-ethylbutanol and/or 2-methylbutanol.
  • Suitable alkoxylated aliphatic branched alcohols to be used herein are according to the formula R (A) n -OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and or 2-methylbutoxyethanol.
  • Suitable alkoxylated linear C1-C5 alcohols to be used herein are according to the formula R (A) n -OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated aliphatic linear C1-C5 alcohols are butoxy propoxy propanol (n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol or mixtures thereof. Butoxy propoxy propanol is commercially available under the trade name n-BPP® from Dow chemical.
  • Suitable linear C1-C5 alcohols to be used herein are according to the formula R-OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4.
  • Suitable linear C1-C5 alcohols are methanol, ethanol, propanol or mixtures thereof.
  • Suitable solvents include butyl diglycol ether (BDGE), butyltriglycol ether, ter amilic alcohol and the like. Particularly preferred solvents to be used herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.
  • BDGE butyl diglycol ether
  • ter amilic alcohol ter amilic alcohol
  • Particularly preferred solvents to be used herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.
  • the solvent present in the HSC compositions comprise a mixture of water with up to 20% by weight of the total composition of any of the ethers, alcohols and/or glycols described above, preferably from 0.5% to 10% by weight and more preferably from 1% to 8%.
  • compositions were made by mixing the listed ingredients in the listed proportions. All proportions are % by weight of the total composition. Excellent first and next-time cleaning performance and good gloss were delivered to the hard-surfaces cleaned with these compositions both under neat and diluted conditions, e.g. at a dilution level of 50:1 to 200:1 (wate ⁇ composition).
  • compositions (weight%):
  • Dobanol® 23-3 1.3 3.2 - - 1.3 - -
  • PVP K60® is a vinylpyrrolidone homopolymer (average molecular weight of
  • Polyquat 11® is a quaternized copolymers of vinyl pyrrolidone and dimethyl aminoethylmethacrylate commercially available from BASF.
  • PEG DME-2000® is dimethyl polyethylene glycol (MW 2000) commercially available from Hoescht.
  • Jeffamine® ED-2001 is a capped polyethylene glycol commercially available from
  • MME PEG (2000) is monomethyl ether polyethylene glycol (MW 2000) which was obtained from Fluka Chemie AG.
  • Isofol 12® is 2-butyl octanol
  • Dobanol® 23-3 is a C12-C13 EO 3 nonionic surfactant commercially available from
  • C8-AS is octyl sulphate available from Albright and Wilson, under the tradename
  • AO21 is a C12-14 EO21 alcohol ethoxylate.
  • Isalchem® AS is a branched alcohol alkyl sulphate commercially available from

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Abstract

The present invention relates to liquid cleaning compositions comprising a polyamine cationic surfactant, containing at least one quaternary amine group and at least one primary, secondary or tertiary amine group. The compositions preferably are in the form of aqueous or non-aqueous laundry, dishwashing, shampoo or hard-surface cleaning compositions.

Description

Liquid cleaning composition
Technical field
The present invention relates liquid cleaning compositions comprising a polyamine cationic surfactant, containing at least one quaternary amine group and at least one primary, secondary or tertiary amine group. The compositions preferably are in the form of aqueous or non-aqueous laundry, dish washing, shampoo or hard-surface cleaning compositions.
Background to the invention
The satisfactory removal of greasy soils, stains or substances, generally having a high proportion of triglycerides or fatty acids, is a challenge faced by the formulator of cleaning compositions. Surfactant components have traditionally been employed in cleaning products, such as liquid cleaning compositions, to facilitate the removal of such greasy soils/stains. In particular, surfactant systems comprising cationic surfactants have been described for use in greasy soil/stain removal.
A wide selection of surfactants for use liquid cleaning compositions can be found in the literature, but the reality is that many such surfactants are chemicals which are not always suitable in such liquid compositions, because of certain properties they have (such as instability in acidic or basic environment, incompatibility with bleach, malodour problems, biodegradability problems). One of the main problems encountered by the manufacturers of liquid cleaning compositions, is that the majority of the surfactants know in the art are not sufficiently water-soluble or not sufficiently water-soluble by low temperatures. This leads to problems both during the manufacturing of the compositions and during use of the compositions. Introduction of functional groups to the surfactants to solubilise the surfactants in water can lead to reduction of the surface activity of the surfactant, which results in a reduction of the cleaning by these surfactants.
Thus, the challenge to the manufacturer seeking improved performance has been increased by these various factors.
A variety of cationic surfactants are suggested to be usable in detergents. One group of cationic surfactants which is widely studied is the group consisting of quaternary ammonium or imidazolinium compounds, which are often designed for speciality use. US-A-4,228,042 discloses biodegradable cationic surfactants, including cationic ester surfactants for use in detergent compositions to provide greasy/oily soil removal. For example, US 3,567,729 discloses diquatemary ammonium compounds for use in detergents. For example, US 5,068,431 describes quaternary ammonium compounds, containing amphoteric amine oxide groups.
The Applicants have now found that certain polyamine cationic compounds, containing at least one cationically charged quaternary amine group and at least one primary, secondary or tertiary amine group (as described in copending application UK 9702731.2) are very good surfactants, suitable for use in liquid cleaning compositions, such as liquid laundry and dish washing compositions, hard-surface cleaners, (hair) shampoo compositions.
These compounds have been found to be sufficiently water-soluble, even under cold water conditions, and to be very surface active. This results in a improved cleaning performance and improved ease of formulation of the liquid compositions. In particular, it has been found that these compounds are very surface active under alkaline washing conditions, and it has been found that they give excellent cleaning performance benefits. This is believed to be due to the compounds containing both a positively charged group and a neutral, more hydrophobic group.
Furthermore, several examples of these surfactants are found to be more biodegradable and to have a very low aquatic toxicity, relative to most quaternary amine compounds.
It has been found that the stability of the polyamine cationic surfactants is not affected by changes of the pH. Furthermore, it has been found that, depending on their structure, most of the polyamine cationic compounds of the present invention and detergent compositions containing these polyamine cationic surfactants, are stable under standard storage and washing conditions.
Furthermore, it has been found that in liquid compositions or components thereof, certain polyamine cationic surfactants can be compatible with bleach, especially oxygen-based bleaches, and with certain bleach activators.
All documents cited in the present description are, in relevant part, incorporated herein by reference.
Summary of the Invention
The present invention relates to liquid cleaning compositions comprising
a) from 0.05% to 50% by weight of a polyamine cationic surfactants, containing at least one quaternary amine group and at least one primary, secondary or tertiary amine group;
b) from 1% to 99.9% by weight of a solvent;
c) from 0.05% to 95% by weight of liquid cleaning composition additional ingredients.
Detailed description of the invention
The liquid cleaning composition of the invention can be any liquid cleaning composition which requires surfactancy. Preferred examples are liquid aqueous or non-aqueous laundry or dish washing detergents, hard-surface cleaning compositions (hereinafter referred to as HSC compositions) and shampoo compositions.
The preferred level of incorporation of the surfactant in the liquid compositions will depend on the purpose of the composition, e.g. concentrated laundry or dish washing detergent compositions will usually comprise a higher level of these surfactants than diluted hard-surface cleaners. The liquid compositions of the inventionwill generally comprise the polyamine cationic surfactant at a level of from 0.05% to 50% by weight of the composition, more preferably from 0.1% to 30% or even more preferably from 0.2% to 20% or even to 15% or 10% by weight. Highly preferred levels in, for example, concentrated liquid laundry or dish washing compositions are 0.2% to 10% by weight of the surfactant.
The liquid compositions also comprise additional ingredients, which can be essentially any ingredient known in the art to be useful in liquid cleaning compositions. Which additional ingredients are present in the compositions of the invention and also which are the preferred levels of these additional ingredients will again depend on the purpose of the composition. The description herein of the various liquid compositions of the invention exemplifies preferred ingredients of those compositions, but is by no means meant to limit the invention thereto.
Cationic surfactant
A cationic surfactant for use in the compositions of the present invention comprises at least one quaternized ammonium group and at least one primary, secondary or tertiary amine group, whereby not more than one linear or branched polyoxyalkylene group is present as substituent group.
Preferred cationic surfactant of the present invention are polyamine cationic surfactants of the general formula (I):
Figure imgf000006_0001
wherein L is a linking unit, and each L is independently selected from the group consisting of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B, C or D units; x is a number from 0 to 10, y is a number from 0 to 10; and wherein the units A- and D- are each independently selected from
Ϊ —
Figure imgf000006_0002
R^ R, R θ
B— = N- and
M"
R 7
— C — = N-
R8
wherein R\, R2, R3, R4, R5, Rg, R7 and Rg are independently selected from the group consisting of C1 -C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group and hydrogen, one of Rj, R2, R3, R4, R5, Rg, R7 or Rg can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or Rj and R2, Rjand R2 and R3, R4 and R5 or Rg and R7 form together with the nitrogen atom part of a ring structure; or R3 is not present and Rj or R2 is double bonded to the nitrogen; or R7 is not present and Rg is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; or, when x and y are 0, R! or R2 or R3 and > or R5 form together with the nitrogen atoms of A and D part of a ring structure; M" is one or more counterions, and at least one A or D comprises a quaternized ammonium group in which none of Ri , R2 or R3 is hydrogen, or at least one B is present in which neither Rg nor R7 is hydrogen, and at least one A or D comprises a primary, secondary or tertiary amine group, or at least one C is present.
The units B-L and C-L are linked when both are present (i.e. when x and y do not equal 0), and they can be randomly present along the chain between the end units A- L and D.
Preferably, the value of x+y is from 1 to 4. Preferably, when x+y is greater than 1, at least one of present groups A, B, C or D is a secondary or primary ammonium group.
More preferably, x=0 and y is a number from 1 to 4. Even more preferably, both x and y are 0.
If x+y does not equal 0, it is preferred that the surfactant comprises only one quaternary group A or D. Preferably Rg, R7 and/or Rg are each independently selected from a Cj-Cg, more preferably C1-C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyi group or, most preferably hydrogen.
Preferably, R\ is a C -Cj4 alkyl, (poly) hydroxyalkyi or alkoxy group or an aralkyl group, most preferably a 2-ethylhexyl group, R2 and R3 are each independently Ci - Cg, more preferably C1-C3 alkyl or hydroxyalkyi groups and preferably R4 and R5 (and Rg, R7 and Rg when present) are each independently Cj-Cg, more preferably C1-C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyi groups or, most preferably, hydrogen atoms.
In a further preferred alternative, R4 is preferably a Cg-Cj4 alkyl, (poly) hydroxyalkyi, alkoxy group or an aralkyl group, most preferably a 2-ethylhexyl group R5 is preferably a C]-Cg, more preferably a -C3 alkyl, (poly) hydroxyalkyi group or hydrogen and R\ , R2 and R3 (and Rg, R7 and Rg when present) are each independently preferably Cj-Cg, more preferably C1-C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyi groups or aralkyl groups.
When Ri and R2, R\ and R2 and R3, R4 and R5 or Rg and R7 form together with the nitrogen atom part of a ring structure, the ring structure is preferably a benzene ring structure, morpholino ring structure or a piperazino ring structure, or a subtituted benzene or substituted morpholino or substituted piperazino ring structure.
When x+y is 0 and Ri or R2 or R3 and R or R5 form together with the nitrogen atoms of group A and D part of a ring structure, the ring structure is preferably a benzene ring structure, morpholino ring structure or a piperazino ring structure, or a substituted benzene or substituted morpholino or substituted piperazino ring structure.
L groups are independently preferably a Ci-Cg, more preferably a C2-C4 linear or branched alkyl, hydroxy alkyl, alkoxy or hydroxy alkoxy group. If x+y is 0, the 1 group is preferably a C2 alkyl group. If group L comprises more than 2 carbon atoms, the surfactant preferably comprises at least one primary or secondary A, B, C or D group. Examples of preferred polyamine cationic surfactants of the present invention are:
R^
Figure imgf000009_0001
R,
R^
Figure imgf000009_0002
R^ CH-
Figure imgf000009_0003
R*
R 10 -N NH θ ■2 (γ)
M"
R-
Figure imgf000009_0004
R-: R,
Figure imgf000010_0001
R. R 8 R.
wherein Ri , R4, Rg and Rg are as described above; R2, R3 and R5 are independently selected from the group consisting of methyl, ethyl, hydroxyethyl, hydroxypropyl, polyhydroxy propyl, ethoxy, propoxy or 2,3,4,5,6-penta hydroxy hexyl, and are most preferably methyl or hydroxyethyl groups; Ri Q is a methyl or hydroxyethyl group; L is as described above; R\ and/or R2 and/or R4 are most preferably a 2-ethylhexyl group.
A highly preferred cationic polyamine surfactant is of formula VI, as defined above, wherein R2 is a hydroxypropyl or hydroxyethyl group, R3 and RJO are methyl groups, L is C2-C3 alkyl group.
Highly preferred polyamine cationic surfactant are those of the formulas:
NT ° rVT /
Θ — N— CH2 CH2 — NH2 or CH3 — N— CH2 CH2 CH
CH3 CH3 Rll
or
CH
M" 3
Rl ^~ CH2 CH2 CH2 ^2
CH3
wherein R is as described above, preferably a C2-C14, preferably Cg-Ci4 linear or branched alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group; particularly preferred R\ groups are hydroxyalkyi groups, where the alkyl groups have 2 to 5 carbon atoms, especially hydroxyethyl and hydroxypropyl are preferred; particularly preferred alkyl R\ groups have up to 9 carbon atoms, most preferably R\ is a 2- ethylhexyl group; and R \ is a C2-C14 alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group or a A or D unit as described above .
The anion M~ is a counterion for the cationically charged polyamine surfactant. Therefore, the number of M" anions present will depend on the cationic charge of the polyamine surfactant, which depends on the groups A, B, C and D. The number of M" anions will be at least 1. A preferred counterion is a halide anion, more preferably a sulphate anion.
Solvents
Liquid cleaning compositions further comprise a solvent or a mixture of solvents. The compositions can be aqueous or non-aqueous compositions. The compositions contain from 1% to 99.9%, preferably from 5% to 90%, and most typically from 10% to 50% of solvents.
The precise nature of these solvents, and levels of incorporation thereof will depend on the precise nature of the cleaning compositions and the cleaning operation for which it is to be used. Typically, besides water, low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, including the cationic surfactant of the invention, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used.
Liquid cleaning compositions additional ingredients
The liquid compositions in accordance with the present invention of from 0.05% to 95% by weight of the composition, liquid cleaning composition additional ingredients. The precise nature of these additional ingredients, and levels of incorporation thereof will depend on the precise nature of the cleaning compositions and the cleaning operation for which it is to be used.
Liquid laundry and dish washing cleaning compositions: additional ingredients
Co-surfactants
The liquid compositions for use as laundry or dish washing cleaning compositions invention can comprise additional surfactants, herein also referred to as co- surfactants, preferably selected from: anionic surfactants, preferably selected from the group of alkyl alkoxylated sulfates, alkyl sulfates, and/or linear alkyl benzenesulfonate surfactants; cationic surfactants, preferably selected from quaternary ammonium surfactants; nonionic surfactants, preferably alkyl ethoxylates, alkyl polyglucosides, and/or amine or amine oxide surfactants; amphoteric surfactants, preferably selected from betaines and/or polycarboxylates (for example polyglycinates); and zwiterionic surfactants.
A wide range of these co-surfactants can be used in the cleaning compositions of the present invention. A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these co-surfactants, is given in US Patent 3,664,961 issued to Norris on May 23, 1972. Amphoteric surfactants are also described in detail in
"Amphoteric Surfactants. Second Edition", E.G. Lomax, Editor (published 19 , by
Marcel Dekker, Inc.)
The liquid laundry or dish washing compositions of the present invention typically comprise from 0.1% to35%, preferably fromθ.5% to 15%, by weight of co- surfactants. Selected co-surfactants are further identified as follows.
Anionic Co-surfactants:
Nonlimiting examples of anionic co-surfactants useful herein, typically at levels from about 0.1% to about 50%, by weight, include the conventional C\ j-Ci 8 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates ("AS"), the Cio-Cjg secondary (2,3) alkyl sulfates of the formula CH3(CH2)χ(CHOSO3 "M+) CH3 and CH3 (CH2)y(CHOSO3 "M+) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the Ci n-Cj alpha-sulfonated fatty acid esters, the Ci ø-Ci sulfated alkyl polyglycosides, the Cjo-Ci alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates), and C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates). The Ci2-Cι betaines and sulfobetaines ("sultaines"), ClO"Cl8 amine oxides, and the like, can also be included in the overall compositions. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Cio-Cjg soaps may be used. Other conventional useful anionic co-surfactants are listed in standard texts. The alkyl alkoxylated sulfate surfactants useful herein are preferably water soluble salts or acids of the formula RO(A)mSO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyi group having a Cjo- 24 alkyl component, preferably a Cj2- C]g alkyl or hydroxyalkyi, more preferably C12-C15 alkyl or hydroxyalkyi, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include ethanol-, triethanol-, methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C12-C15 alkyl polyethoxylate (1.0) sulfate (Cj2- C15E(1.0)M), C12-C15 alkyl polyethoxylate (2.25) sulfate (C12-C15E(2.25)M), C12-Cl5 alkyl polyethoxylate (3.0) sulfate (C12-C i5E(3.0)M), and C12-C15 alkyl polyethoxylate (4.0) sulfate (C]2-Ci5E(4.0)M), wherein M is conveniently selected from sodium and potassium.
The alkyl sulfate surfactants useful herein are preferably water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyi having a C 1 Q-C 1 g alkyl component, more preferably a Cl2"Cl5 alkyl or hydroxyalkyi, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
Other suitable anionic surfactants that can be used are alkyl ester sulfonate surfactants including linear esters of C -C20 carboxyiic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula : R3 - CH(SO3M) - C(O) - OR4 wherein R3 is a C -C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a Cj-Cg hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt- forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R3 is C\Q-C\ alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is CiQ-Cjg alkyl.
Other anionic co-surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-C22 primary of secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated Cl2"Clg monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-Cj2 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2θ)j - CH2COO-M+ wherein R is a C -C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin. et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
When included therein, the laundry or dish washing detergent compositions of the present invention typically comprise from 0.1% to 50%, preferably from 1% to 40% by weight of such anionic surfactants.
Nonionic Co-surfactants:
Nonlimiting examples of nonionic co-surfactants useful herein typically at levels from about 0.1% to about 50%, by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), Ci o-Cjg glycerol ethers, and the like.
More specifically, the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the present invention. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 1 to about 10 moles, preferably 2 to 7, most preferably 2 to 5, of ethylene oxide per mole of alcohol. Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C12-C15 primary alcohols containing 5- 10 moles of ethylene oxide per mole of alcohol.
Examples of commercially available nonionic surfactants of this type include: TergitolT 15-S-9 (the condensation product of Cj 1 -C15 linear alcohol with 9 moles ethylene oxide) and TergitolτM 24-L-6 NMW (the condensation product of Cι 2-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolτM 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23.3 (the condensation product of C12-C13 linear alcohol with 3 moles of ethylene oxide), NeodolTM 45.7 (me condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide) and NeodolτM 45.5 ( he condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; KyroτM EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company; and Genapol LA O3O or O5O (the condensation product of C\ 2-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. The preferred range of HLB in these AE nonionic surfactants is from 8-17 and most preferred from 8-14. Condensates with propylene oxide and butylene oxides may also be used. Another class of preferred nonionic co-surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula.
R? — C — N — Z ,
O R wherein Rl is H, or C 1.4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R^ is C5.31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, Rl is methyl, R^ is a straight Cl 1-15 alkyl or C15.17 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction. Typical examples include the C^-Cjg and C12-C14 N-methylglucamides. See U.S. 5.194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can also be used; see U.S. 5,489,393.
Also useful as a nonionic co-surfactant in the present invention are the alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-. 3-. 4-. and/or 6- positions on the preceding saccharide units.
Preferred alkylpolyglycosides have the formula
R2θ(CnH2nO)t(glycosyl)x
wherein R^ is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyi, hydroxyalkylphenyl. and mixtures thereof in which the alkyl groups contain from about 10 to about 18, prelerabh from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 10 about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1 .3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position). The additional glycosyl units can then be attached between their 1- position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position. Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Igepal^M CO-630, marketed by the GAF Corporation; and Triton™ X-45, X-l 14, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially-available PluronicτM surfactants, marketed by BASF.
Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 1 1,000. Examples of this type of nonionic surfactant include certain of the commercially available TetronicτM compounds, marketed by BASF.
Also preferred nonionics are amine oxide surfactants. The compositions of the present invention may comprise amine oxide in accordance with the general formula I: Rl(EO)x(PO)y(BO)zN(O)(CH2R')2.qH2O (I).
In general, it can be seen that the structure (I) provides one long-chain moiety Rl(EO)x(PO)y(BO)z and two short chain moieties, C^R'. R' is preferably selected from hydrogen, methyl and -CH2OH. In general Rl is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, Rl is a primary alkyl moiety. When x+y+z = 0, Rl is a hydrocarbyl moiety having chainlength of from about 8 to about 18. When x+y+z is different from 0, Rl may be somewhat longer, having a chainlength in the range C12-C24. The general formula also encompasses amine oxides wherein x+y+z = 0, R\ = Cg-Ci g, R' = H and q = 0-2, preferably 2. These amine oxides are illustrated by C 12- 14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,075,501 and 5,071,594, incorporated herein by reference.
The invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, Rl is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Such amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
Highly preferred amine oxides herein are solutions at ambient temperature. Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
Whereas in certain of the preferred embodiments R' is H, there is some latitude with respect to having R' slightly larger than H. Specifically, the invention further encompasses embodiments wherein R' is CH2OH, such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2- hydroxyethyl)amine oxide and oleylbis(2-hydroxyethyl)amine oxide, dodecyldimethylamine oxide dihydrate.
Preferred amines for use herein include amines according to the formula:
R1-X-(CH2)n-N(R3)(R4)
wherein R\ is a Cg-Cj2 alkyl group; n is from about 2 to about 4, X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are individually selected from H, C1-C4 alkyl, or (CH2-CH2-O(R5)) wherein R5 is H or methyl.
These preferred amines include the following: R1-(CH2)2-NH2
Rl-O-(CH2)3-NH2
R1-C(O)-NH-(CH2)3-N(CH3)2
R1-N[CH2-CH(OH)-R5]2
wherein R\ is a Cg-Ci 2 alkyl group and R5 is H or CH3.
In a highly preferred embodiment, the amine is described by the formula: Ri -C(O)-NH-(CH2)3-N(CH3)2 wherein R\ is C -Cj2 alkyl.
Particularly preferred amines include those selected from the group consisting of octyl amine, hexyl amine, decyl amine. dodecyl amine, C -Cj2 bis(hydroxyethyl)amine, Cg-Ci 2 bis(hydroxyisopropyl)amine, and C -Ci2 amido- propyl dimethyl amine, and mixtures.
Cationic Co-surfactants:
Nonhmiting examples of additional cationic co-surfactants useful herein typically at levels from 0.1% to 50%, by weight include the choline ester-type quats and alkoxylated quaternary ammonium (AQA) surfactant compounds, and the like.
Cationic co-surfactants useful as a component of the surfactant system is a cationic choline ester-type quat surfactant which are preferably water dispersible compounds having surfactant properties and comprise at least one ester (i.e. -COO-) linkage and at least one cationically charged group. Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in U.S. Patents Nos. 4,228,042, 4,239,660 and 4,260,529.
In a preferred aspect these cationic ester surfactant are hydrolysable under the conditions of a laundry wash method.
Cationic co-surfactants useful herein also include alkoxylated quaternary ammonium (AQA) surfactant compounds (referred to hereinafter as "AQA compounds") having the formula:
Figure imgf000020_0001
wherein Rl is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R^ is an alkyl group containing from one to three carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl; X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and mixed ethoxy/propoxy; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably to about 4; preferably both p and q are 1. See also: EP 2,084, published May 30, 1979, by The p-octer & Gamble Company, which describes cationic co-surfactants of this type which are also useful herein.. The levels of the AQA surfactants used to prepare finished laundry or dish washing detergent compositions typically range from about 0.1% to about 5%, preferably from about 0.45% to about 2.5%, by weight.
Further additional ingredients
The liquid cleaning compositions for laundry and dish washing preferably further comprise a builder system. Any conventional builder system or mixed builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetra-acetate, metal ion sequestrants such as aminopoly-phosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylene phosphonic acid. Though less preferred for obvious environmental reasons, phosphate builders can also be used herein. Most preferred laundry detergent compositions according to the present invention comprise citrate/fatty acid mixed builder systems.
Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R- CH(COOH)CH2(COOH) wherein R is CiO-20 al yl or alkenyl, preferably Ci2-16> or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examples include lauryl succinate, myristyl succinate, palmityl succinate 2- dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071, as well as maleates.
Especially for the liquid execution herein, suitable fatty acid builders for use herein are saturated or unsaturated C J O-18 fattv acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
Builders are normally included in amounts of from 0.5% to 50% by weight of the composition preferably from 3% to 30% and most usually from 5% to 15% by weight.
Preferred compositions of the present invention may further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits. Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases or mixtures thereof.
A preferred combination is a composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with the lipolytic enzyme variant D96L at a level of from 50 LU to 8500 LU per liter wash solution.
The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo).
Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991.
Said cellulases and/or peroxidases are normally incorporated in the composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Nordisk A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Also proteases described in our co-pending application USSN 08/136,797 can be included in the detergent composition of the invention. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
A preferred protease herein referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for the amino acid residue at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions ■equivalent to those selected from the group consisting of +99. +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO 95/10615 published April 20, 1995 by Genencor International.
Useful proteases are also described in PCT publications: WO 95/30010 published Novenber 9, 1995 by The Procter & Gamble Company; WO 95/3001 1 published Novenber 9, 1995 by The Procter & Gamble Company; WO 95/29979 published Novenber 9, 1995 by The Procter & Gamble Company.
Highly preferred enzymes that can be included in the detergent compositions of the present invention include lipases. It has been found that the cleaning performance on greasy soils is synergistically improved by using lipases. Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P". Further suitable lipases are lipases such as Ml Lipase® and Lipomax ® (Gist-Brocades). Highly preferred lipases are the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826. Preferably the Humicola lanuginosa strain DSM 4106 is used. This enzyme is incorporated into the composition in accordance with the invention at a level of from 50 LU to 8500 LU per liter wash solution. Preferably the variant D96L is present at a level of from 100 LU to 7500 LU per liter of wash solution. More preferably at a level of from 150 LU to 5000 LU per liter of wash solution.
By D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 viz. wherein the native lipase ex Humicola lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L). According to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor).
The lipases and/or cutinases are normally incorporated in the composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
Amylases (& and/or β) can be included for removal of carbohydrate-based stains. Suitable amylases are Termamyl (Novo Nordisk), Fungamyl^ and BAN^ (Novo Nordisk).
Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents, especially improved oxidative stability as measured against a reference-point of TERMAMYL® in commercial use in 1993. These preferred amylases herein share the characteristic of being "stability- enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g.. to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 11, measured versus the above- identified reference-point amylase. Stability can be measured using any of the art- disclosed technical tests. See, for example, references disclosed in WO 9402597. Stability-enhanced amylases can be obtained from Novo or from Genencor International. One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus α-amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein. Such preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b) stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha- Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B. licheniformis NOB 8061. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®. Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo. Said enzymes are normally incorporated in the composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent application 92870018.6 filed on January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
Other components used in detergent compositions may be employed, such as soil- suspending agents, soil-release polymers, bactericides, coloring agents, foam control agents, corrosion inhibitors and perfumes.
Preferably, the liquid compositions according to the present invention are in "concentrated form"; in such case, the liquid detergent compositions according to the present invention will contain a lower amount of solvent, compared to conventional liquid detergents. The level of solvent is then less than 50%, preferably less than 30% by weight of the detergent compositons. These concentrated products provide advantages to the consumer, who has a product which can be used in lower amounts and to the producer, who has lower shipping costs.
The liquid compositions can also be adapted to be used as pre-treatment compositions, e.i. to be applied directly to soils and stains in a pretreatment step before washing the fabrics.
The detergent compositions of the present invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
Solvent for liquid laundry and dish washing compositions
As described above, a variety of solvents, including water, can be used in the liquid compositons of the invention. Liquid detergent compositions herein, especially those designed for fabric laundering, may also comprise a non-aqueous carrier medium as described in more detail hereinafter.
Non-aqueous Liquid Compositions
The manufacture of liquid cleaning compositions, especially those designed for fabric laundering or dish washing, which comprise a non-aqueous carrier medium can be conducted in the manner disclosed in more detail hereinafter. In an alternate mode, such non-aqueous compositions can be prepared according to the disclosures of U.S. Patents 4,753,570; 4,767.558; 4,772,413; 4,889,652; 4,892,673; GB-A- 2,158.838; GB-A-2,195,125; GB-A-2, 195,649; U.S. 4,988,462; U.S. 5,266,233; EP- A-225,654 (6/16/87); EP-A-510,762 (10/28/92); EP-A-540,089 (5/5/93); EP-A- 540,090 (5/5/93); U.S. 4,615,820; EP-A-565,017 (10/13/93); EP-A-030,096 (6/10/81), incorporated herein by reference. Such compositions can contain various particulate detersive ingredients (including the bleaching agents, as disclosed hereinabove) stably suspended therein. Such non-aqueous compositions thus comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited references. The cationic surfactant of the invention is incorporated in the compositions at the levels and in the manner described hereinabove for the manufacture of other laundry detergent compositions.
Liquid Phase:
The liquid phase will generally comprise from 35% to 99.9% by weight of the detergent compositions herein. More preferably, the liquid phase will comprise from about 50% to 95% by weight of the compositions. Most preferably, the liquid phase will comprise from about 45% to 75% by weight of the compositions herein. The liquid phase of the detergent compositions herein essentially contains relatively high concentrations of a certain type anionic surfactant combined with a certain type of nonaqueous, liquid diluent.
Anionic Surfactant
The anionic surfactant preferablyutilized as an essential component of the nonaqueous liquid phase is one selected from the alkali metal salts of alkylbenzene sulfonic acids in which the alkyl group contains from about 10 to 16 carbon atoms, in straight chain or branched chain configuration. (See U.S. Patents 2,220,099 and 2,477,383, incorporated herein by reference.) Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates (LAS) in which the average number of carbon atoms in the alkyl group is from about 1 1 to 14. Sodum Cj i~Cj4 LAS is especially preferred.
The alkylbenzene sulfonate anionic surfactant will be dissolved in the nonaqueous liquid diluent which makes up the second component of the nonaqueous phase. To form the structured liquid phase required for suitable phase stability and acceptable rheology, the alkylbenzene sulfonate anionic surfactant is generally present to the extent of from 30% to 65% by weight of the liquid phase. More preferably, the alkylbenzene sulfonate anionic surfactant will comprise from 35% to 50% by weight of the nonaqueous liquid phase of the compositions herein. Utilization of this anionic surfactant in these concentrations corresponds to an anionic surfactant concentration in the total composition of from 15% to 60% by weight, more preferably from 20% to 40% by weight, of the composition.
Nonaqueous Liquid Diluent
To form the liquid phase of the cleaning compositions, the anionic surfactant or the preferred, hereinbefore described, alkylbenzene sulfonate anionic surfactant is combined with a nonaqueous liquid diluent which contains two essential components. These two components are a liquid alcohol alkoxylate material and a nonaqueous, low-polarity organic solvent.
Alcohol Alkoxylates
One preferred component of the liquid diluent used to form the compositions herein comprises an alkoxylated fatty alcohol material. Such materials are themselves also nonionic surfactants. Such materials correspond to the general formula:
Rl(CmH2mO)nOH wherein Rl is a Cg - Ci g alkyl group, m is from 2 to 4, and n ranges from about 2 to
12. Preferably Rl is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms. Preferably also the alkoxylated fatty alcohols will be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
The alkoxylated fatty alcohol component of the liquid diluent will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15.
Examples of fatty alcohol alkoxylates useful as one of the components of the nonaqueous liquid diluent in the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 1 1 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary Cj2 - C13 alcohol having about 9 moles of ethylene oxide and Neodol 91- 10, an ethoxylated Co. - C\ \ primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename. Dobanol 91-5 is an ethoxylated C9-C1 ] fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Corporation. The former is a mixed ethoxylation product of C\ \ to C15 linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
Other types of alcohol ethoxylates useful in the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 1 1. Such products have also been commercially marketed by Shell Chemical Company.
The alcohol alkoxylate component which is preferably utilized as part of the liquid diluent in the nonaqueous compositions herein will generally be present to the extent of from 1% to 60% of the liquid phase composition. More preferably, the alcohol alkoxylate component will comprise 5% to 40% of the liquid phase. Most preferably, the essentially utilized alcohol alkoxylate component will comprise from 5% to 30% of the detergent composition liquid phase. Utilization of alcohol alkoxylate in these concentrations in the liquid phase corresponds to an alcohol alkoxylate concentration in the total composition of froml% to 60% by weight, more preferably from 2% to 40% by weight, and most preferably from 5% to 25% by weight, of the composition. Nonaqueous Low-Polarity Organic Solvent
A second preferred component of the liquid diluent which forms part of the liquid phase of the detergent compositions herein comprises nonaqueous, low-polarity organic solvent(s). The term "solvent" is used herein to connote the non-surface active carrier or diluent portion of the liquid phase of the composition. While some of the essential and/or optional components of the compositions herein may actually dissolve in the "solvent"-containing liquid phase, other components will be present as paniculate material dispersed within the "solvent"-containing liquid phase. Thus the term "solvent" is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto.
The nonaqueous organic materials which are employed as solvents herein are those which are liquids of low polarity. For purposes of this invention, "low-polarity" liquids are those which have little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate. Thus relatively polar solvents such as ethanol should not be utilized. Suitable types of low-polarity solvents useful in the nonaqueous liquid detergent compositions herein do include non-vicinal C4-C alkylene glycols, alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like.
A preferred type of nonaqueous, low-polarity solvent for use in the compositions herein comprises the non-vicinal C4-Cg branched or straight chain alkylene glycols. Materials of this type include hexylene glycol (4-methyl-2,4-pentanediol), 1,6- hexanediol, 1,3-butylene glycol and 1,4-butylene glycol. Hexylene glycol is the most preferred.
Another preferred type of nonaqueous, low-polarity solvent for use herein comprises the mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-Cg alkyl ethers. The specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred. Compounds of the type have been commercially marketed under the tradenames Dowanol, Carbitol, and Cellosolve. Another preferred type of nonaqueous, low-polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs). Such materials are those having molecular weights of at least about 150. PEGs of molecular weight ranging from about 200 to 600 are most preferred.
Yet another preferred type of non-polar, nonaqueous solvent comprises lower molecular weight methyl esters. Such materials are those of the general formula: R!-C(O)-OCH3 wherein Rl ranges from 1 to about 18. Examples of suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
The nonaqueous, low-polarity organic solvent(s) employed should, of course, be compatible and non-reactive with other composition components, e.g., bleach and/or activators, used in the liquid detergent compositions herein. Such a solvent component will generally be utilized in an amount of from about 1% to 70% by weight of the liquid phase. More preferably, the nonaqueous, low-polarity organic solvent will comprise from 10% to 60% by weight of the liquid phase, most preferably from 20% to 50% by weight, of the liquid phase of the composition. Utilization of this organic solvent in these concentrations in the liquid phase corresponds to a solvent concentration in the total composition of from 1% to 50% by weight, more preferably from 5% to 40% by weight, and most preferably from 10% to 30% by weight, of the composition.
Alcohol Alkoxylate To Solvent Ratio
The ratio of alcohol alkoxylate to organic solvent within the liquid diluent can be used to vary the rheological properties of the detergent compositions eventually formed. Generally, the weight ratio of alcohol alkoxylate to organic solvent will range from 50:1 to 1:50. More preferably, this ratio will range from 3:1 to 1 :3.
Liquid Diluent Concentration
As with the concentration of the anionic surfactant mixture or the preferred alkylbenzene sulfonate anionic surfactant mixture, the amount of total liquid diluent in the nonaqueous liquid phase herein will be determined by the type and amounts of other composition components and by the desired composition properties. Generally, the liquid diluent will comprise from 35% to 70% of the nonaqueous liquid phase of the compositions herein. More preferably, the liquid diluent will comprise from 50% to 65% of the nonaqueous liquid phase. This corresponds to a nonaqueous liquid diluent concentration in the total composition of from 15% to 70% by weight, more preferably from about 20% to 50% by weight, of the composition.
Solid Phase:
The nonaqueous compositions herein also essentially comprise froml% to 65% by weight, more preferably from 5% to 50% by weight, of a solid phase of particulate material which is dispersed and suspended within the liquid phase. Generally such particulate material will range in size from 0.1 to 1500 microns. More preferably such material will range in size from 5 to 200 microns.
The particulate material utilized herein can comprise one or more types of composition components which in particulate form are substantially insoluble in the nonaqueous liquid phase of the composition. The types of particulate materials which can be utilized are described in detail as follows:
Composition Preparation and Use:
The nonaqueous liquid detergent compositions herein can be prepared by combining the components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form the phase stable compositions herein. In a typical process for preparing such compositions, essential and certain preferred optional components will be combined in a particular order and under certain conditions.
In the first step of such a typical preparation process, an admixture of the alkylbenzene sulfonate anionic surfactant and the components of the nonaqueous diluent is formed by heating a combination of these materials to a temperature from about 30°C to 100°C. In a second process step, the heated admixture formed as hereinbefore described is maintained under shear agitation at a temperature from about 40°C to 100°C for a period of from about 2 minutes to 20 hours. Optionally, a vacuum can be applied to the admixture at this point. This second process step serves to completely dissolve the anionic surfactant in the nonaqueous liquid phase. In a third process step, this liquid phase combination of materials is cooled to a temperature of from about 0°C to 35°C. This cooling step serves to form a structured, surfactant-containing liquid base into which the particulate material of the detergent compositions herein can be added and dispersed. Particulate material is added in a fourth process step by combining the particulate material with the liquid base which is maintained under conditions of shear agitation. When more than one type of particulate material is to be added, it is preferred that a certain order of addition be observed. For example, while shear agitation is maintained, essentially all of any optional surfactants in solid particulate form can be added in the form of particles ranging in size from about 0.2 to 1,000 microns. After addition of any optional surfactant particles, particles of substantially all of an organic builder, e.g., citrate and/or fatty acid, and/or an alkalinity source, e.g., sodium carbonate, can be added while continuing to maintain this admixture of composition components under shear agitation. Other solid form optional ingredients can then be added to the composition at this point. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a uniform dispersion of insoluble solid phase particulates within the liquid phase.
After some or all of the foregoing solid materials have been added to this agitated mixture, particles of bleaching agent can be added to the composition, again while the mixture is maintained under shear agitation. By adding the bleaching agent material last, or after all or most of the other components, and especially after alkalinity source particles, have been added, desirable stability benefits for the bleach can be realized. The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning. These include oxygen bleaches as well as other bleaching agents such as percarboxylic acid bleaching agents and salts thereof. Suitable examples of this latter class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al. Preferred are peroxygen bleaching agents, which include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, perborate bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, and persulfate bleach (e.g., OXONE, manufactured commercially by DuPont).
If enzyme prills are incorporated, they are preferably added to the nonaqueous liquid matrix last. As a final process step, after addition of all of the particulate material, agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from about 1 to 30 minutes.
In the following Examples, the abbreviations for the various ingredients used for the compositions have the following meanings.
LAS Sodium linear C \ 2 alkyl benzene sulfonate
TAS Sodium tallow alkyl sulfate
C45AS Sodium C14-C15 linear alkyl sulfate
C25AS Sodium C12- 15 linear alkyl sulfate
CxyEzS Sodium C 1 X-C 1 v branched alkyl sulfate condensed with z moles of ethylene oxide
CxyFA Cιx-Ciy fatty acid
C45E7 A C14.15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide
CxyEz A Cι x_ι y branched primary alcohol condensed with an average of z moles of ethylene oxide
C24 N-Me Glucamide: Cl2"Cl4 N-methyl glucamide
CxAPA : Alkyl amido propyl amine
PAS : Salt of R, N+ (CH3)2 R2, wherein R, is C2-C3 hydroxyalkyi and R2 is primary ethylene amine or primary propylene amine
PAS, Salt of R, N+ (CH3)2 R2 wherein R, is C5-C8 alkyl and
R2 is primary ethylene amine or primary propylene amine
PAS2 Salt of 2-ethylhexyl, methyl, hydroxethyl-ammonium di(C C4 alkyl) ethylene amine PAS3 Salt of 2-ethylhexyl, methyl, hydroxethyl-ammonium di (C C alkyl) propylene amine
QAS R2.N+(CH3)2(C2H4OH) with R2 = C12 - C1 Soap Sodium linear alkyl carboxylate derived from an
80/20 mixture of tallow and coconut oils.
CFAA Ci2-C Coco alkyl N-methyl glucamide TFAA Ci g-C j alkyl N-methyl glucamide TPKFA C12-C14 topped whole cut fatty acids STPP Anhydrous sodium tripolyphosphate Zeolite A Hydrated Sodium Aluminosilicate of formula
Nai2(A102SiO2)i2- 27H2O having a primary particle size in the range from 0.1 to 10 micrometers
NaSKS-6 Crystalline layered silicate of formula δ -Na2Si2O5
Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200μm and 900μm
Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm
Silicate Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio)
Metasilicate Sodium metasilicate (SiO2:Na2O ratio = 1.0) Sodium sulfate Anhydrous sodium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425μm and 850 μm
MA AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000.
CMC Sodium carboxymethyl cellulose
Protease Proteolytic enzyme of activity 4KNPU/g sold by
NOVO Industries A/S under the tradename
Savinase
Alcalase Proteolytic enzyme of activity 3AU/g sold by
NOVO Industries A/S Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename
Carezyme
Amylase Amylolytic enzyme of activity 60KNU/g sold by
NOVO Industries A/S under the tradename
Termamyl 60T
BSA Amylotic enzyme sold under the tradename Duramyl by Novo Industries A/S (approx 1% enzyme activity) Lipase Lipolytic enzyme of activity lOOkLU/g sold by
NOVO Industries A/S under the tradename
Lipolase
Endolase Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A S
PB4 Sodium perborate tetrahydrate of nominal formula
NaBO .3H O.H2θ2 PB1 Anhydrous sodium perborate bleach of nominal formula NaBθ2-H2θ2
Percarbonate Sodium Percarbonate of nominal formula
2Na2Cθ3.3H2θ2
NaDCC Sodium dichloroisocyanurate NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.
TAED Tetraacetylethylenediamine DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the
Trade name Dequest 2060
BTA Benzotriazole
BzP Benzoyl Peroxide
Paraffin Paraffin oil sold under the tradename Winog 70 by
Winershall
Bismuth nitrate Bismuth nitrate salt PA30 Polyacrylic acid of average molecular weight approximately 8,000
Terpolymer Terpolymer of average molecular weight approx.
7,000, comprising acrylic:maleic:ethylacrylic acid monomer units at a weight ratio of 60:20:20
480N Random copolymer of 3:7 acrylic/methacrylic acid, average molecular weight about 3,500
MEA Monoethanolamine
PG Propanediol
EtOH Ethanol
PAAC Pentaamine acetate cobalt (III) salt
Photoactivated Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer
Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP 1,1 -hydroxy ethane diphosphonic acid 33
PVNO Polyvinylpyridine N-oxide PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole
SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone
SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
Silicone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.
NaOH Solution of sodium hydroxide KOH Solution of potassium hydroxide DTPA Diethylene triamine pentaacetic acid NaTS Sodium toluene sulfonic acid
EXAMPLE 1
A non-limiting example of bleach-containing nonaqueous liquid laundry detergent is prepared having the composition as set forth in Table I. Table I
Component Wt. % Range (% wt.) Liquid Phase LAS 25.3 18-35 C24 E5 13.6 10-20
Hexylene glycol 27.3 20-30 Perfume 0.4 0-1.0 C18 SADS* 2.0 1-3.0 PAS/PAS! 1.2 0.2-4.0 Solids
Protease enzyme 0.4 0-1.0 Citrate 4.3 3-6 PB1 3.4 2-7 NOBS 8.0 2-12 Carbonate 13.9 5-20 DTPA 0.9 0-1.5 Brightener 1 0.4 0-0.6 Silicone antifoam 0.1 0-0.3
Minors Balance
*C18 Alkyl 1,4 disulfate prepared from maleic anhydride and C14 alpha olefin according to the method of Synthesis Examples I or II.
The resulting composition is an anhydrous heavy duty liquid laundry detergent which provides excellent stain and soil removal performance when used in normal fabric laundering operations. EXAMPLE 2
The following Example further illustrates the invention herein with respect to a hand dishwashing liquid.
Ingredi eenntt % (wt. Range (% wO
C14 SA \DDSS** 2.0 0.15-3
Ammo nniiuumm CCi122--i133 aallkkyyll < sulfate 7.0 2-35
Figure imgf000038_0001
C12-C 1144 eetthhooxxyy ((11)) ssuullffaattee 20.5 5-35
Coconu itt aammiinnee ooxxiiddee 2.6 2-5
Betaine ;//TTeettrroonniicc 770044®® 0.87-0.10 0-2 (mix)
Alcoho >1l EEtthhooxxyyllaattee CCggEEjj \\ 5.0 2-10
Ammo nniiuumm xxyylleennee ssuullffoonnate 4.0 1-6
Ethano 1l 4.0 0-7
Ammo nniiuumm cciittrraattee 0.06 0-1.0
Magne ssiiuumm cchhllooririddee 3.3 0-4.0
Calcium τι cchhllooririddee 2.5 0-4.0
Ammo nniiuumm ssuullffaattee 0.08 0-4.0
Hydrog >eenn ppeerrooxxiiddee 200 ppm 0-300 ppm
Perfum ιee 0.18 0-0.5
Maxata issee®® pprrootteeaassee 0.50 0-1.0
Water a anndd mmiinnoorrss Balance —
*C14 Alkyl 1,4 disulfate prepared according to the method of Synthesis Examples I or II.
EXAMPLE 3
Liquid detergent compositions are made according to the following.
% by weight of the detergent compositions
Figure imgf000038_0002
Figure imgf000039_0001
*C18 Alkyl 1,4 disulfate prepared from maleic anhydride and C14 alpha olefin according to the method of Synthesis Examples I or II.
The above liquid detergent compositions (A-D) are found to be very efficient in the removal of a wide range of stains and soils from fabrics under various usage conditions.
EXAMPLES 4-9
The following are heavy duty liquid laundry detergent compositions according to the present invention. Example #: 4 5 6 7 8 9
C18 SADS* 6.5 6.5 6.5 6.5 6.5 6.5
C25 AS 10 8.0 - - 5.0 5.0
C35AE3S/C25AE3S 2.0 9.0 - - 7.0 7.0
C24 N-Me Glucamide 6.0 5.0 4.5 3.7 4.0 4.0
C35 E7 6.0 1.0 - - - -
C25 AE2.5S - - 12.0 12.0 - -
C23 E9 - - 2.0 1.0 5.0 5.0
PAS/PAS j 2.0 1.0 0.5 7.0 4.0 1.3
C10 APA - 1.5 - 2.0 - 2.5
C24 Fatty Acid 7.5 1.1 2.0 4.0 5.0 5.0
C48 Fatty Acid 3.0 3.5 - - - -
Citric Acid 1.0 3.5 3.0 3.0 3.0 3.0
Protease (34 g/#) 0.6 0.6 0.9 0.9 1.2 1.2
Lipolase (lOOKLU/g) 0.1 0.1 0.1 0.1 0.2 0.2
Amylase (300KMU/g) 0.1 0.1 0.1 0.1 - 0.1
Carezyme (5000 0.03 0.03 0.05 0.05 0.2 0.2
CEVU/g)
Endo A (5000 CEVU/g) 0.1 0.1 - - - -
Brightener 0.1 0.1 - - - -
Boric Acid 3.0 3.0 3.5 3.5 4.0 4.0
MEA 8.0 4.0 1.0 1.5 7.0 7.0
NaOH 1.0 4.0 3.0 2.5 1.0 1.0
PG 12.0 12.0 7.5 7.5 7.0 7.0
EtOH 1.0 1.0 3.5 3.5 6.0 6.0
Na TS - - 2.5 2.5 - -
Minors
Minors — Balance-
Example 10
The following liquid detergent formulations are in accord with the invention (levels are given as parts per weight).
Figure imgf000040_0001
Figure imgf000041_0001
Example 11
The following liquid detergent formulations were prepared in accord with the invention (levels are given in parts per weight):
Figure imgf000041_0002
Figure imgf000042_0001
Example 12
The following liquid detergent compositions were prepared in accord with the invention (levels are given in parts per weight).
Figure imgf000043_0001
Shampoo compositions
The liquid cleaning compositions of the invention can be in the form of shampoo compositions, which can comprise any of the ingredients described above but which typically can comprise the following additional ingredients, described herein. As used herein, "water soluble" refers to any material that is sufficiently soluble in water to form a substantially clear solution to the naked eye at a concentration of 0.1% in water, i.e. distilled or equivalent, at 25°C.
The cationic surfactant is preferably present at a level of from 0.05% to 15%, more preferably from 0.2% to 10% by weight.
Co-Surfactant
The shampoo compositions will comprise, in addition to the cationic surfactan, one or more co-surfactants selected from the group consisting of anionic surfactant, nonionic surfactant, amphoteric surfactant, zwitterionic surfactants, and mixtures thereof. The shampoo compositions preferably comprise an anionic co-surfactant. Surfactant mixture concentrations range from 5% to 50%, preferably from 8% to 30%, more preferably from 10% to 25%, by weight of the compositions.
Anionic surfactant
The shampoo compositions preferably comprise an anionic co-surfactant, and preferably at concentrations of from 5% to 30%, more preferably from 7% to 25%, even more preferably from 8% to 20%, and most preferably from 9% to 18%, by weight of the composition.
Anionic surfactants for use in the shampoo compositions include alkyl and alkyl ether sulfates. These materials have the respective formulae ROSO3M and RO(C2H4O)xSO3M, wherein R is alkyl or alkenyl of from about 8 to about 30 carbon atoms, x is 1 to 10, and M is a cation such as ammonium, alkanolamines, such as triethanolamine, monovalent metals, such as sodium and potassium, and polyvalent metal cations, such as magnesium, and calcium. The cation M, of the anionic surfactant should be chosen such that the anionic surfactant component is water soluble. Solubility will depend upon the particular anionic surfactants and cations chosen.
Preferably, R has from about 12 to about 18 carbon atoms in both the alkyl and alkyl ether sulfates. The alkyl ether sulfates are typically made as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms. The alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil are preferred herein. Such alcohols are reacted with between about 0 and about 10, and especially about 3, molar proportions of ethylene oxide and the resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
Specific examples of alkyl ether sulfates which may be used in the shampoo compositions of the present invention are sodium and ammonium salts of coconut alkyl triethylene glycol ether sulfate: tallow alkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate. Highly preferred alkyl ether sulfates are those comprising a mixture of individual compounds, said mixture having an average alkyl chain length of from about 10 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide.
Other suitable anionic surfactants are the water-soluble salts of organic, sulfuric acid reaction products of the general formula [ Ri -SO3-M ] where R^ is selected from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 10 to about 18, carbon atoms; and M is a cation, as previously described, subject to the same limitations regarding polyvalent metal cations as previously discussed. Examples of such surfactants are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-, and n-paraffins, having about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g., SO3, H2SO4, obtained according to known sulfonation methods, including bleaching and hydrolysis. Preferred are alkali metal and ammonium sulfonated Cι rj-18 n-paraffins.
Still other suitable anionic surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil. Other similar anionic surfactants are described in U.S. Patents 2,486,921; 2,486,922; and 2,396,278.
Other anionic surfactants suitable for use in the shampoo compositions are the succinnates, examples of which include disodium N-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetrasodium N-(l,2-dicarboxyethyl)-N-octadecylsulfosuccinnate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.
Other suitable anionic surfactants include olefin sulfonates having about 10 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds which can be produced by the sulfonation of alpha-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates. The sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SO2, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO2, etc., when used in the gaseous form.
The alpha-olefins from which the olefin sulfonates are derived are mono-olefins having about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms. Preferably, they are straight chain olefins.
In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
A specific alpha-olefin sulfonate mixture of the above type is described more fully in the U.S. Patent 3,332,880, which description is incorporated herein by reference.
Another class of anionic surfactants suitable for use in the shampoo compositions are the beta-alkyloxy alkane sulfonates. These compounds have the following formula:
Figure imgf000046_0001
where R is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R2 is a lower alkyl group having from about 1 (preferred) to about 3 carbon atoms, and M is a water-soluble cation as hereinbefore described.
Many other anionic surfactants suitable for use in the shampoo compositions are described in McCutcheon's. Emulsifiers and Detergents. 1989 Annual, published by M. C. Publishing Co., and in U.S. Patent 3,929,678, which descriptions are incorporated herein by reference.
Preferred anionic surfactants for use in the shampoo compositions include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate. lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, and sodium dodecyl benzene sulfonate.
Amphoteric and zwitterionic surfactants
The surfactant of the shampoo compositions may comprise an amphoteric and/or zwitterionic surfactant. Concentrations of such surfactants will generally range from 0.5% to 20%, preferably from 1% to 10%, by weight of the shampoo compositions.
Amphoteric surfactants for use in the shampoo compositions include the derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical is straight or branched and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
Zwitterionic surfactants for use in the shampoo compositions include the derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals are straight or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A these compounds is:
Figure imgf000047_0001
2 where R contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety; Y is selected from the group consisting of nitrogen,
3 phosphorus, and sulfur atoms; R is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom, and 2
4 when Y is a nitrogen or phosphorus atom; R is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups. Examples of amphoteric and zwitterionic surfactants also include sultaines and amidosultaines. Sultaines and amidosultaines can be used as foam enhancing surfactants that are mild to the eye in partial replacement of anionic surfactants. Sultaines, including amidosultaines, include for example, cocodimethylpropylsultaine, stearyldimethylpropylsultaine, lauryl-bis-(2-hydroxyethyl) propylsultaine and the like; and the amidosultaines such as cocoamidodimethylpropylsultaine, stearylamidododimethylpropylsultaine, laurylamidobis-(2-hydroxyethyl) propylsultaine, and the like. Preferred are amidohydroxysultaines such as the Cl2"Cι g hydrocarbyl amidopropyl hydroxysultaines, especially C12-C14 hydrocarbyl amido propyl hydroxysultaines, e.g., laurylamidopropyl hydroxysultaine and cocamidopropyl hydroxysultaine. Other sultaines are described in U.S. Patent 3,950,417, which descriptions are incorporated herein by reference.
Other suitable amphoteric surfactants are the aminoalkanoates of the formula
R-NH(CH2)nCOOM, the iminodialkanoates of the formula
R-N[(CH2)mCOOM]2 and mixtures thereof; wherein n and m are numbers from 1 to 4, R is Cg - C22 alkyl or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium.
Examples of suitable aminoalkanoates include n-alkylamino-propionates and n-alkyliminodipropionates, specific examples of which include N-lauryl- -beta-amino propionic acid or salts thereof, and N-lauryl-beta-imino-dipropionic acid or salts thereof, and mixtures thereof.
Other suitable amphoteric surfactants include those represented by the formula :
Figure imgf000048_0001
wherein Rl is Cg - C22 alkyl or alkenyl. preferably C^-Cj , R2 is hydrogen or CH CO2M, R3 is CH2CH2OH or CH2CH2OCH2CH2COOM, R4 is hydrogen, CH2CH2OH, or CH2CH2OCH2CH2COOM. Z is CO M or CH CO M, n is 2 or 3, preferably 2, M is hydrogen or a cation, such as alkali metal (e.g., lithium, sodium, potassium), alkaline earth metal (beryllium, magnesium, calcium, strontium, barium), or ammonium. This type of surfactant is sometimes classified as an imidazoline-type amphoteric surfactant, although it should be recognized that it does not necessarily have to be derived, directly or indirectly, through an imidazoline intermediate.
Suitable materials of this type are marketed under the trade name MIRANOL and are understood to comprise a complex mixture of species, and can exist in protonated and non-protonated species depending upon pH with respect to species that can have a hydrogen at R2. All such variations and species are meant to be encompassed by the above formula.
Examples of surfactants of the above formula are monocarboxylates and dicarboxylates. Examples of these materials include cocoamphocarboxypropionate, cocoamphocarboxypropionic acid, cocoamphocarboxyglycinate (alternately referred to as cocoamphodiacetate), and cocoamphoacetate.
Commercial amphoteric surfactants include those sold under the trade names MIRANOL C2M CONC. N.P., MIRANOL C2M CONC. O.P., MIRANOL C2M SF, MIRANOL CM SPECIAL (Miranol, Inc.); ALKATERIC 2CIB (Alkaril Chemicals); AMPHOTERGE W-2 (Lonza, Inc.); MONATERIC CDX-38, MONATERIC CSH-32 (Mona Industries); REWOTERIC AM-2C (Rewo Chemical Group); and SCHERCOTERIC MS-2 (Scher Chemicals).
Betaine surfactants (zwitterionic) suitable for use in the shampoo compositions are those represented by the formula:
Figure imgf000049_0001
wherein:
Ri is a member selected from the group consisting of
COOM and CH(OH)-CH2SO M
R2 is lower alkyl or hydroxyalkyi; R3 is lower alkyl or hydroxyalkyi;
R4 is a member selected from the group consisting of hydrogen and lower alkyl;
R5 is higher alkyl or alkenyl;
Y is lower alkyl, preferably methyl; m is an integer from 2 to 7, preferably from 2 to 3; n is the integer 1 or 0;
M is hydrogen or a cation, as previously described, such as an alkali metal, alkaline earth metal, or ammonium.
The term "lower alkyl" or "hydroxyalkyi" means straight or branch chained, saturated, aliphatic hydrocarbon radicals and substituted hydrocarbon radicals having from one to about three carbon atoms such as, for example, methyl, ethyl, propyl, isopropyl, hydroxypropyl, hydroxyethyl, and the like. The term "higher alkyl or alkenyl" means straight or branch chained saturated (i.e., "higher alkyl") and unsaturated (i.e., "higher alkenyl") aliphatic hydrocarbon radicals having from about eight to about 20 carbon atoms such as, for example, lauryl, cetyl, stearyl, oleyl, and the like. It should be understood that the term "higher alkyl or alkenyl" includes mixtures of radicals which may contain one or more intermediate linkages such as ether or polyether linkages or non-functional substitutents such as hydroxyl or halogen radicals wherein the radical remains of hydrophobic character.
Examples of surfactant betaines of the above formula wherein n is zero which are useful herein include the alkylbetaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryl dimethyl-alpha-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, lauryl-bis-(2-hydroxyethyl)carboxymethylbetaine, stearyl-bis-(2-hy- droxypropyl)carboxymethylbetaine, oleyl- dimethyl-gamma-carboxypropylbetaine, lauryl-bix-(2-hydroxypropyl)- alpha-carboxyethylbetaine, etc. The sulfobetaines may be represented by cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryl-bis-(2-hydroxyethyl)sulfopropylbetaine, and the like.
Specific examples of amido betaines and amidosulfo betaines useful in the shampoo compositions include the amidocarboxybetaines, such as cocoamidodimethylcarboxymethylbetaine, laurylamidodi- methylcarboxymethylbetaine, cetylamidodimethylcarboxymethylbetaine, laurylamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, cocoamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, etc. The amido sulfobetaines may be represented by cocoamidodimethylsulfopropylbetaine, stearylamidodimethylsulfopropylbetaine, lauryl- amido-bis-(2-hydroxyethyl)-sulfopropylbetaine, and the like.
Nonionic surfactant
The shampoo compositions may comprise a nonionic surfactant as the detersive surfactant component therein. Nonionic surfactants include those compounds produced by condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
Preferred nonionic surfactants for use in the shampoo compositions include the following:
(1) polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 20 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to from about 10 to about 60 moles of ethylene oxide per mole of alkyl phenol;
(2) those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products;
(3) condensation products of aliphatic alcohols having from about 8 to about 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from about 10 to about 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from about 10 to about 14 carbon atoms;
(4) long chain tertiary amine oxides of the formula [ RI R2R3N - O ] where Rl contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to about 1 glyceryl moiety, and R2 and R3 contain from about 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals;
(5) long.chain tertiary phosphine oxides of the formula [RR'R' - O] where R contains an alkyl, alkenyl or monohydπ alkyl radical ranging from about 8 to about 18 carbon atoms in chain length, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety and R* and R" are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms;
(6) long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of from about 1 to about 3 carbon atoms (usually methyl) and one long hydrophobic chain which include alkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals containing from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety;
(7) alkyl polysaccharide (APS) surfactants (e.g. alkyl polyglycosides), examples of which are described in U.S. Patent 4,565,647, which description is incorporated herein by reference, and which discloses APS surfactants having a hydrophobic group with about 6 to about 30 carbon atoms and polysaccharide (e.g., polyglycoside) as the hydrophilic group; optionally, there can be a polyalkylene-oxide group joining the hydrophobic and hydrophilic moieties; and the alkyl group (i.e., the hydrophobic moiety) can be saturated or unsaturated, branched or unbranched, and unsubstituted or substituted (e.g., with hydroxy or cyclic rings); and
( 8 ) polyethylene glycol (PEG) glyceryl fatty esters, such as those of the formula R(O)OCH2CH(OH)CH (OCH2CH2)nOH wherein n is from about 5 to about 200, preferably from about 20 to about 100, and R is an aliphatic hydrocarbyl having from about 8 to about 20 carbon atoms.
Silicone Hair Conditioning Agent
The shampoo compositions preferably also comprise a silicone hair conditioning agent at concentrations effective to provide hair conditioning benefits. Such concentrations range from 0 .05% to 10%, preferably from 0.1% to 8%, more preferably from 0.1% to 5%, most preferably from 0.2% to 3%, by weight of the shampoo compositions.
The silicone hair conditioning agents for use in the shampoo compositions are insoluble in the shampoo compositions, and are preferably nonvolatile. Typically it will be intermixed in the shampoo composition so as to be in the form of a separate, discontinuous phase of dispersed, insoluble particles, also referred to as droplets. These droplets are suspended with a suspending agent described hereinafter. The silicone hair conditioning agent phase will comprise a silicone fluid hair conditioning agent such as a silicone fluid and can also comprise other ingredients, such as a silicone resin to enhance silicone fluid deposition efficiency or enhance glossiness of the hair (especially when high refractive index (e.g. above about 1.46) silicone conditioning agents are used (e.g. highly phenylated silicones).
As used herein, "nonvolatile" refers to silicone material with little or no significant vapor pressure under ambient conditions, as is understood by those in the art. Boiling point under one atmosphere (atm) will preferably be at least about 250°C, more preferably at least about 275°C, most preferably at least about 300°C. Vapor pressure is preferably about 0.2mm HG at 25°C or less, preferably about 0.1mm HG at 25°C or less.
The silicone hair conditioning agent phase may comprise volatile silicone, nonvolatile silicone, or mixtures thereof. Typically, if volatile silicones are present, it will be incidental to their use as a solvent or carrier for commercially available forms of nonvolatile silicone materials ingredients, such as silicone gums and resins.
The silicone hair conditioning agents for use in the shampoo compositions preferably have a viscosity of from about 20 to about 2,000,000 centistokes, more preferably from about 1 ,000 to about 1 ,800,000 centistokes, even more preferably from about 50,000 to about 1,500,000 centistokes, most preferably from about 100,000 to about 1,500,000 centistokes, at 25°C. The viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970.
Silicone fluid for use in the shampoo compositions includes silicone oil which are flowable silicone materials with a viscosity of less than 1 ,000,000 centistokes, preferably between about 5 and 1 ,000,000 centistokes, more preferably between about 10 and about 100,000 centistokes, at 25°C. Suitable silicone oils include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof. Other insoluble, nonvolatile silicone fluids having hair conditioning properties can also be used.
References disclosing examples of some suitable silicone fluids for use in the shampoo compositions include U.S. Patent 2.826,551, U.S. Patent 3,964,500, U.S. Patent 4,364,837, British Patent 849.433. and Silicon Compounds. Petrarch Systems, Inc. (1984), all of which are incorporated herein by reference.
Silicone resins can be included in the silicone conditioning agent. These resins are highly crosslinked polymeric siloxane systems. The crosslinking is introduced through the incorporation of trifunctional and tetrafunctional silanes with mono functional or difunctional, or both, silanes during manufacture of the silicone resin. As is well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of crosslinking) such that they dry down to a rigid, or hard, film are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. Silicone materials which have at least about 1.1 oxygen atoms per silicon atom will generally be silicone resins herein. Preferably, the ratio of oxygemsilicon atoms is at least about 1.2: 1.0. Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-substituted silanes being most commonly utilized. Preferred resins are offered by General Electric as GE SS4230 and SS4267. Commercially available silicone resins will generally be supplied in a dissolved form in a low viscosity volatile or nonvolatile silicone fluid. The silicone resins for use herein should be supplied and incorporated into the present compositions in such dissolved form, as will be readily apparent to those skilled in the art.
Background material on silicones including sections discussing silicone fluids, gums, and resins, as well as manufacture of silicones, can be found in Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition, pp 204-308, John Wiley & Sons, Inc., 1989, incorporated herein by reference.
Polyalkylene Glycol
The shampoo compositions may further comprise selected polyalkylene glycols in amounts effective to enhance lather performance and enhance spreadability of the shampoo compositions on hair. Effective concentrations of the selected polyethylene glycols range from 0.025% to 1.5%, preferably from 0.05% to 1%, more preferably from 0.1% to 0.5%, by weight of the shampoo compositions.
For example, polyalkylene glycols suitable for use in the shampoo compositions are characterized by the general formula:
H(OCH2CH)n— OH R wherein R is hydrogen, methyl or mixtures thereof, preferably hydrogen, and n is an integer having an average value of from about 1,500 to about 25,000, preferably from about 2,500 to about 20,000, and more preferably from about 3,500 to about 15,000. When R is hydrogen, these materials are polymers of ethylene oxide, which are also known as polyethylene oxides, polyoxyethylenes, and polyethylene glycols. When R is methyl, these materials are polymers of propylene oxide, which are also known as polypropylene oxides, polyoxypropylenes, and polypropylene glycols. When R is methyl, it is also understood that various positional isomers of the resulting polymers can exist.
Specific examples of suitable polyethylene glycol polymers include PEG-2M wherein R equals hydrogen and n has an average value of about 2,000 (PEG 2-M is also known as Polyox WSR® N-10, which is available from Union Carbide and as PEG-2,000); PEG-5M wherein R is hydrogen and n has an average value of about 5,000 (PEG 5-M is also known as Polyox WSR® N-35 and Polyox WSR® N-80, both available from Union Carbide and as PEG-5,000 and Polyethylene Glycol 300,000); PEG-7M wherein R is hydrogen and n has an average value of about 7,000 (PEG 7-M is also known as Polyox WSR® N-750 available from Union Carbide); PEG-9M wherein R is hydrogen and n has an average value of about 9,000 (PEG 9- M is also known as Polyox WSR® N-3333 available from Union Carbide); and PEG- 14 M wherein R is hydrogen and n has an average value of about 14,000 (PEG 14-M is also known as Polyox WSR® N-3000 available from Union Carbide). Suitable polyalkylene polymers include polypropylene glycols and mixed polyethylene/polypropylene glycols. Suspending Agent
The shampoo compositions may further comprise a suspending agent at concentrations effective for suspending the silicone hair conditioning agent in dispersed form in the shampoo compositions. Such concentrations range from 0.1% 1 10%, preferably from 0.3% to 5.0%, by weight of the shampoo compositions.
Suitable suspending agents include acyl derivatives, long chain amine oxides, and mixtures thereof. When used in the shampoo compositions, these suspending agents are present in crystalline form. These suspending agents are described in U.S. Patent 4,741,855, which description is incorporated herein by reference. These preferred suspending agents include ethylene glycol esters of fatty acids preferably having from about 16 to about 22 carbon atoms. More preferred are the ethylene glycol stearates, both mono and distearate, but particularly the distearate containing less than about 7% of the mono stearate. Other suitable suspending agents include alkanol amides of fatty acids, preferably having from about 16 to about 22 carbon atoms, more preferably about 16 to 18 carbon atoms, preferred examples of which include stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanol- amide and stearic monoethanolamide stearate. Other long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmi- tate, etc.); glyceryl esters (e.g., glyceryl distearate) and long chain esters of long chain alkanol amides (e.g., stearamide diethanolamide distearate, stearamide monoethanolamide stearate). Long chain acyl derivatives, ethylene glycol esters of long chain carboxyiic acids, long chain amine oxides, and alkanol amides of long chain carboxyiic acids in addition to the preferred materials listed above may be used as suspending agents. For example, it is contemplated that suspending agents with long chain hydrocarbyls having C -C22 chains may be used.
Other long chain acyl derivatives suitable for use as suspending agents include N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na and K salts), particularly N,N-di(hydrogenated) Ci g, Ci g and tallow amido benzoic acid species of this family, which are commercially available from Stepan Company (Northfield, Illinois, USA).
Examples of suitable long chain amine oxides for use as suspending agents include alkyl (Cjg-C22) dimethyl amine oxides, e.g., stearyl dimethyl amine oxide
Other suitable suspending agents include xanthan gum at concentrations ranging from 0.3% t3%, preferably from 0.4% to 1.2%, by weight of the shampoo compositions. The use of xanthan gum as a suspending agent in silicone containing shampoo compositions is described, for example, in U.S. Patent 4,788,006, which description is incorporated herein by reference. Combinations of long chain acyl derivatives and xanthan gum may also be used as a suspending agent in the shampoo compositions. Such combinations are described in U.S. Patent 4,704,272, which description is incorporated herein by reference.
Other suitable suspending agents include carboxyvinyl polymers. Preferred among these polymers are the copolymers of acrylic acid crosslinked with polyallylsucrose as described in U.S. Patent 2,798,053, which description is incorporated herein by reference. Examples of these polymers include Carbopol 934, 940, 941, and 956, available from B. F. Goodrich Company .
Preferred carboxyvinyl polymers have a molecular weight of at least about 750,000; more preferred are carboxyvinyl polymers having a molecular weight of at least about 1,250,000; most preferred are carboxyvinyl polymers having a molecular weight of at least about 3,000,000.
Other suitable suspending agents include primary amines having a fatty alkyl moiety having at least about 16 carbon atoms, examples of which include palmitamine or stearamine, and secondary amines having two fatty alkyl moieties each having at least about 12 carbon atoms, examples of which include dipalmitoylamine or di(hydrogenated tallow)amine. Still other suitable suspending agents include di(hydrogenated tallow)phthalic acid amide, and crosslinked maleic anhydride- methyl vinyl ether copolymer.
Other suitable suspending agents may be used in the shampoo compositions, including those that can impart a gel-like viscosity to the composition, such as water soluble or colloidally water soluble polymers like cellulose ethers (e.g., methylcellulose, hydroxybutyl methylcellulose, hyroxypropylcellulose, hydroxypropyl methylcellulose, hydroxyethyl ethylcellulose and hydorxethylcellulose), guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch and starch derivatives, and other thickeners, viscosity modifiers, gelling agents, etc. Mixtures of these materials can also be used.
Water The shampoo compositions can comprise from 20% to 99.9%, preferably from 50% to 94.8%, more preferably from 60% to 85%, by weight of water.
Additional Hair Conditioning Agents
The shampoo compostions of the present invention may further comprise water soluble cationic polymeric conditioning agents, hydrocarbon conditioning agents, cationic surfactants, and mixtures thereof.
Additional cationic Surfactants
Additional cationic surfactants for use as hair conditioning agents in the shampoo compositions will typically contain quaternary nitrogen moieties. Examples of suitable cationic surfactants are described in following documents, all of which are incorporated by reference herein in their entirety: M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers, (North American edition 1979); Schwartz, et al., Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; U.S. Patent 3,155,591; U. S. Patent 3,929,678; U. S. Patent 3,959,461 and U. S. Patent 4,387,090.
Further additiona, optional materials include foam boosters, preservatives, •thickeners, cosurfactants, dyes, perfumes, solvents, styling polymers, anti-static agents, anti-dandruff aids, and pediculocides, pH adjusting agents such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate, etc.; perfumes; and dyes. Optional antidandruff agents include particulate antidandruff agents such as pyridinethione salts, selenium compounds such as selenium disulfide, and soluble antidandruff agents.
Example Number
Component 10 11 12 13 14
Ammonium laureth-2 sulfate 5 3 2 10 8
Ammonium lauryl sulfate 5 5 4 5 8
C_ SADS* 0.6 1 4 5 7
Cocamide MEA 0 0.68 0.68 0.8 0
PAS 1.0 - - - 2.0
PAS2 - 6.0 0.7 3.0 -
PEG 14M 0.1 0.35 0.5 0.1 0 Cocamidopropylbetain 2.5 2.5 0 0 1.5
Cetylalcohol 0.42 0.42 0.42 0.5 0.5
Stearylalcohol 0.18 0.18 0.18 0.2 0.18
Ethyl glycol disterate 1.5 1.5 1.5 1.5 1.5
Dimethicone 1.75 1.75 1.75 1.75 1.75
Perfume solution 0.45 0.45 0.45 0.45 0.45
DMDM hydantoin 0.37 0.37 0.37 0.37 0.37
Color solutio (ppm) 64 64 64 64 64
Water and minors q.s. to 100% —
1. Dimethicone is a 40(gum)/60(fluid) weight ratio blend of SE-76 dimethicone gum available from General Electric Silicones Division and a dimethicone fluid having a viscosity of 350 centistokes.
*C Alkyl 1,4 disulfate prepared from maleic anhydride and C alpha olefin according to the method of Synthesis Examples I or II.
Hard-surface cleaning compositions (HSC compositions)
The liquid cleaning composition of the invention can be in the form of a compositon suitable for the cleaning of a hard-surface are liquid compositions.
The HSC compositions preferably comprise the cationic surfactant at a level of from
0.05% to 20%, more preferably from 0.3% to 15%, most preferably from 1.0% to
8% by weight.
The liquid compositions of the present invention are preferably but not necessarily formulated as aqueous compositions, i.e. whereby the solvent of the compositions of the invention comprises water. Aqueous compositions typically comprise from 50% to 99.9% by weight of the total composition of water, preferably from 60% to 95%, and more preferably from 80% to 95%.
The liquid compositions herein may be formulated in the full pH range of 0 to 14, preferably 1 to 13. Typically, the compositions herein are formulated in a neutral to highly alkaline pH range from 7 to 13. preferably from 9 to 1 1 and more preferably from 9.5 to 11. The pH of the compositions herein can be adjusted by any of the means well-known to those skilled in the art such as acidifying agents like organic or inorganic acids, or alkalinising agents like NaOH, KOH, K2CO3, Na2CO3 and the like. Preferred organic acids for use herein have a pk of less than 6. Suitable organic acids are selected from the group consisting of citric acid, lactic acid, glycolic acid, succinic acid, glutaric acid and adipic acid and mixtures thereof. A mixture of said acids may be commercially available from BASF under the trade name Sokalan® DCS.
Additioanl ingredient for HSC compositions:
The liquid compositions may comprise a variety of optional ingredients, including the ingredients described herein before,depending on the technical benefit aimed for and the surface treated.
Suitable ingredients for use herein include surfactants, builders, chelants, polymers, solvents, buffers, bactericides, hydrotropes, colorants, stabilisers, radical scavengers, bleaches, bleach activators, suds controlling agents like fatty acids, enzymes, soil suspenders, dye transfer agents, brighteners, anti dusting agents, dispersants, dye transfer inhibitors, pigments, dyes and/or perfumes.
The liquid compositions preferably comprise a surfactant, or mixtures thereof. Said surfactant may be present in the compositions in amounts of from 0.1% to 50% by weight of the total composition, preferably of from 0.1% to 20% and more preferably of from 1% to 10%.
Surfactants are desired herein as they further contribute to the cleaning performance and/or gloss benefit of the compositions of the present invention. Surfactants to be used herein include nonionic surfactants, anionic surfactants, additional cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.
Particularly preferred surfactants are the nonionic surfactants. Suitable nonionic surfactants are the nonionic surfactants descibed herein before. Highly suitable nonionic surfactants for use herein include a class of compounds which may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be branched or linear aliphatic (e.g. Guerbet or secondary alcohols) or alkyl aromatic in nature. For example, a well-known class of nonionic synthetic detergents is made available on the market under the trade name "Pluronic".
Other suitable nonionic synthetic detergents include : (i) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, and nonane;
(ii) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. Examples are compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5000 to about 1 1000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2500 to 3000;
(iii) The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms;
(iv) Trialkyl amine oxides and trialkyl phosphine oxides wherein one alkyl group ranges from 10 to 18 carbon atoms and t o alkyl groups range from 1 to 3 carbon atoms; the alkyl groups can contain hydroxy substituents; specific examples are dodecyl di(2-hydroxyethyl)amine oxide and tetradecyl dimethyl phosphine oxide.Particularly preferred surfactants include also the anionic surfactants, including the anionic surfactants described herein before. Suitable anionic surfactants for use herein include alkali metal (e.g., sodium or potassium) fatty acids, or soaps thereof, containing from about 8 to about 24, preferably from about 10 to about 20 carbon atoms.
The fatty acids including those used in making the soaps can be obtained from natural sources such as, for instance, plant or animal -derived glycerides (e.g., palm oil, coconut oil, babassu oil, soybean oil. castor oil, tallow, whale oil, fish oil, tallow, grease, lard and mixtures thereof). The fatty acids can also be synthetically prepared (e.g., by oxidation of petroleum stocks or by the Fischer-Tropsch process). Alkali metal soaps can be made by direct saponification of fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps.
The term "tallow" is used herein in connection with fatty acid mixtures which typically have an approximate carbon chain length distribution of 2.5% C14, 29% C16, 23% C18, 2% palmitoleic, 41.5% oleic and 3% linoleic (the first three fatty acids listed are saturated). Other mixtures with similar distribution, such as the fatty acids derived from various animal tallows and lard, are also included within the term tallow. The tallow can also be hardened (i.e., hydrogenated) to convert part or all of the unsaturated fatty acid moieties to saturated fatty acid moieties. When the term "coconut" is used herein it refers to fatty acid mixtures which typically have an approximate carbon chain length distribution of about 8% C8, 7% ClO, 48% C12, 17% C14, 9% C16, 2% C18, 7% oleic, and 2% linoleic (the first six fatty acids listed being saturated). Other sources having similar carbon chain length distribution such as palm kernel oil and babassu oil are included with the term coconut oil.
Suitable zwitterionic detergents to be used herein comprise the betaine and betaine- like surfactants, described herein before
Amphoteric and ampholytic detergents which can be either cationic or anionic depending upon the pH of the system are represented by detergents such as dodecylbeta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids such as those produced according to the teaching of U.S. Pat. No. 2,438,091, and the products sold under the trade name "Miranol", and described in U.S. Pat. No. 2,528,378, said patents being incorporated herein by reference. Suitable perfumes to be used herein include materials which provide an olfactory aesthetic benefit and/or cover any "chemical" odor that the product may have. The main function of a small fraction of the highly volatile, low boiling (having low boiling points), perfume components in these perfumes is to improve the fragrance odor of the product itself, rather than impacting on the subsequent odor of the surface being cleaned. However, some of the less volatile, high boiling perfume ingredients provide a fresh and clean impression to the surfaces, and it is desirable that these ingredients be deposited and present on the dry surface. Perfume ingredients can be readily solubilized in the compositions, for instance by the nonionic detergent surfactants.The perfume ingredients and compositions suitable to be used herein are the conventional ones known in the art. Selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations.
Suitable perfume compounds and compositions can be found in the art including U.S. Pat. Nos. : 4,145,184, Brain and Cummins, issued March 20, 1979; 4,209,417, Whyte, issued June 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1, 1979, all of said patents being incorporated herein by reference. Chelating agents can preferred ingrwedients of HSC compositions. They can be incorporated in the compositions herein in amounts ranging from 0.0% to 10.0% by weight of the total composition, preferably 0.1% to 5.0%.
Suitable phosphonate chelating agents to be used herein may include alkali metal ethane 1 -hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP). The phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities. Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1 -hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®-
Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy -3,5-disulfobenzene.
A preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof. Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins. Ethylenediamine N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol- diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms. Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS® and methyl glycine di-acetic acid (MGDA).
Further carboxylate chelating agents to be used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
The compositions herein may further comprises other polymeric compounds like other carboxylate-containing polymer, or mixtures thereof, up to a level of 20%, by weight of the total compositon, preferably 0.01% to 5%. Suitable carboxylate- containing polymer include those described herein before. By "carboxylate- containing polymer" it is meant herein a polymer or copolymer comprising at least a monomeric unit which contains at least a carboxylate functionality. Any carboxylate-containing polymer known to those skilled in the art can be employed according to the present invention such as homo- or co-polymeric polycarboxylic acids or their salts including polyacrylates and polymers and copolymers of maleic anhydride or/and acrylic acid and the like, or mixtures thereof
Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 1 ,000,000, more preferably from about 10,000 to 150,000 and most preferably from about 20,000 to 100,000. Water- soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl. U.S. Patent 3,308,067, issued March 7, 1967. Acrylic/maleic-based copolymers may also be used as a preferred carboxylate- containing polymer. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1 :1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982. Particularly preferred is a copolymer of maleic / acrylic acid with an average molecular weight of about 70,000. Such copolymers are commercially available from BASF under the trade name SOKALAN CP5.
Other suitable carboxylate-containing polymers to be used herein include cellulose derivatives such as carboxymethylcellulose. For example carboxymethylcellulose may be used as a salt with conventional cation such as sodium, potassium, amines or substituted amines.
The compositions may further comprise a divalent counterion, or mixtures thereof. All divalent ions known to those skilled in the art may be used herein. Preferred divalent ions to be used herein are calcium, zinc, cadmium, nickel, copper, cobalt, zirconium, chromium and/or magnesium and more preferred are calcium, zinc and/or magnesium. Said divalent ions may be added in the form of salts for example as chloride, acetate, sulphate, formate and/or nitrate or as a complex metal salt. For example, calcium may be added in the form of calcium chloride, magnesium as magnesium acetate or magnesium sulphate and zinc as zinc chloride.
The liquid HSC compositions may also comprises a builder or a mixture thereof, as an optional ingredeint. Suitable builders for use herein include polycarboxylates and polyphosphates, and salts thereof. Typically, the compositions of the present invention comprise up to 20.0 % by weight of the total composition of a builder or mixtures thereof, preferably from 0.1% to 10.0% , and more preferably from 0.5% to 5.0%.
Suitable polyphosphonates for use herein are the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates. The most preferred builder for use herein is citrate.
The compositions according to the present invention may further comprise a suds controlling agent such as 2-alkyl alkanol, or mixtures thereof, as a preferred optional ingredient. Particularly suitable to be used in the present invention are the 2-alkyl alkanols having an alkyl chain comprising from 6 to 16 carbon atoms, preferably from 8 to 12 and a terminal hydroxy group, said alkyl chain being substituted in the α position by an alkyl chain comprising from 1 to 10 carbon atoms, preferably from 2 to 8 and more preferably 3 to 6. Such suitable compounds are commercially available, for instance, in the Isofol® series such as Isofol® 12 (2-butyl octanol) or Isofol® 16 (2-hexyl decanol). Typically, the compositions herein may comprise up to 2% by weight of the total composition of a 2-alkyl alkanol, or mixtures thereof, preferably from 0.1% to 1.5% and most preferably from 0.1% to 0.8%.
The liquid compositions herein may also comprise a bleaching component. Any bleach known to those skilled in the art may be suitable to be used herein including any peroxygen bleach as well as a chlorine releasing component.
Solvent
The compositions of the present invention comprise a solvent or a mixtures thereof. Solvents to be used herein include all those known to the those skilled in the art of hard-surfaces cleaner compositions. Suitable solvents for use herein include ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms, glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C6-C16 glycol ethers and mixtures thereof.
Suitable glycols to be used herein are according to the formula HO-CR1R2-OH wherein Rl and R2 are independently H or a C2-C10 saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic. Suitable glycols to be used herein are dodecaneglycol and/or propanediol. Suitable alkoxylated glycols to be used herein are according to the formula R-(A)n- Rl-OH wherein R is H, OH, a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein Rl is H or a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, and A is an alkoxy group preferably ethoxy, methoxy, and or propoxy and n is from 1 to 5, preferably 1 to 2. Suitable alkoxylated glycols to be used herein are methoxy octadecanol and/or ethoxyethoxyethanol.
Suitable alkoxylated aromatic alcohols to be used herein are according to the formula R (A)n-OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2. Suitable alkoxylated aromatic alcohols are benzoxyethanol and/or benzoxypropanol.
Suitable aromatic alcohols to be used herein are according to the formula R-OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10. For example a suitable aromatic alcohol to be used herein is benzyl alcohol.
Suitable aliphatic branched alcohols to be used herein are according to the formula R-OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12. Particularly suitable aliphatic branched alcohols to be used herein include 2-ethylbutanol and/or 2-methylbutanol.
Suitable alkoxylated aliphatic branched alcohols to be used herein are according to the formula R (A)n-OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2. Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and or 2-methylbutoxyethanol.
Suitable alkoxylated linear C1-C5 alcohols to be used herein are according to the formula R (A)n-OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2. Suitable alkoxylated aliphatic linear C1-C5 alcohols are butoxy propoxy propanol (n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol or mixtures thereof. Butoxy propoxy propanol is commercially available under the trade name n-BPP® from Dow chemical.
Suitable linear C1-C5 alcohols to be used herein are according to the formula R-OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4. Suitable linear C1-C5 alcohols are methanol, ethanol, propanol or mixtures thereof.
Other suitable solvents include butyl diglycol ether (BDGE), butyltriglycol ether, ter amilic alcohol and the like. Particularly preferred solvents to be used herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.
Typically, the solvent present in the HSC compositions comprise a mixture of water with up to 20% by weight of the total composition of any of the ethers, alcohols and/or glycols described above, preferably from 0.5% to 10% by weight and more preferably from 1% to 8%.
The present invention will be further illustrated by the following examples.
Examples
The following compositions wer made by mixing the listed ingredients in the listed proportions. All proportions are % by weight of the total composition. Excellent first and next-time cleaning performance and good gloss were delivered to the hard-surfaces cleaned with these compositions both under neat and diluted conditions, e.g. at a dilution level of 50:1 to 200:1 (wateπcomposition).
Compositions (weight%):
Figure imgf000069_0001
G H I J K L M
Surfactants
C 9-1 1 EO5 - - 2.5 2.4 - 2.5 0.030
C12J4 EO5 - - 2.5 3.6 - 2.5 0.030
C7-9 EO6 3.2 8 - - 3.2 - -
Dobanol® 23-3 1.3 3.2 - - 1.3 - -
PAS 0.9 4.8 - 1.0 0.9 2.0 -
PAS, - - 2.0 - - - 1.0
NaLAS 0.9 _ 0.8 _ 0.9 0.8 0.009
NaC ocyl sulfate 1.2 3.0 1.5 1.5 1.2 1.5 0.018
C8-AS 0.8 2.0 - - 0.8 - -
Isalchem® AS - - - 0.6 - - -
Buffer
Na2CO3 1.0 2.0 0.2 0.6 1.0 0.2 0.002
Citrate - - 0.75 0.5 - 0.75 0.009
Caustic - - 0.5 0.3 - 0.5 0.006
Suds control
Fatty Acid 0.4 0.8 0.4 0.6 0.4 0.4 0.005
Isofol 12® 0.3 - 0.3 0.3 0.3 0.3 0.004
Polvmers
PEG DME-2000® 0.5 0.75 0.5 - - - 0.006
PVP K60® - 0.5 0.5 - - 0.5 0.006
Polyquat 11® 0.5 - - 0.5 0.5 - -
MME PEG (2000) - - - 0.5 - 0.5 -
PEG (2000) - - - - 0.5 - -
Minors and water — . -- up to 100% —
PH 10.7 10.75 9.5 9.5 10.75 9.5 8.5
PVP K60® is a vinylpyrrolidone homopolymer (average molecular weight of
160,000), commercially available from ISP Corporation, New York, NY and
Montreal, Canada.
Polyquat 11® is a quaternized copolymers of vinyl pyrrolidone and dimethyl aminoethylmethacrylate commercially available from BASF.
PEG DME-2000® is dimethyl polyethylene glycol (MW 2000) commercially available from Hoescht.
Jeffamine® ED-2001 is a capped polyethylene glycol commercially available from
Huntsman. PEG (2000) is polyethylene glycol (MW 2000).
MME PEG (2000) is monomethyl ether polyethylene glycol (MW 2000) which was obtained from Fluka Chemie AG.
Isofol 12® is 2-butyl octanol
Dobanol® 23-3 is a C12-C13 EO 3 nonionic surfactant commercially available from
SHELL.
C8-AS is octyl sulphate available from Albright and Wilson, under the tradename
Empimin® LV 33.
AO21 is a C12-14 EO21 alcohol ethoxylate.
Isalchem® AS is a branched alcohol alkyl sulphate commercially available from
Enichem.

Claims

70What is claimed is:
1. A liquid cleaning compositions comprising
a) from 0.05% to 50% by weight of a polyamine cationic surfactants, containing at least one quaternary amine group and at least one primary, secondary or tertiary amine group;
b) from 1% to 99.9% by weight of a solvent;
c ) from 0.05% to 95% by weight of liquid cleaning composition additional ingredients.
2. A composition or component according to claim 1 wherein the cationic surfactant is a polyamine cationic surfactant of the general formula:
Figure imgf000072_0001
wherein L is a linking unit, and each L is independently selected from the group consisting of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B, C or D units; x is a number from 0 to 10, y is a number from 0 to 10; and wherein the units A- and D- are each independently selected from
R, R,
╬ÿ
R2-N- and ΓÇóN
M"
R, R. R, ╬╕
B = N ; and
M"
R 7
C - = - N-
R8
wherein R\, R2, R3, R4, R5, Rg, R7 and Rg are independently selected from the group consisting of C1-C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyi, (poly) hydroxy alkenyl, alkoxy group and hydrogen, one of Ri , R2, R3, R4, R5, Rg, R7 or Rg can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or R\ and R2, Rjand R2 and R3, R4 and R5 or Rg and R7 form, together with the nitrogen atom part of a ring structure; or R3 is not present and R\ or R2 is double bonded to the nitrogen; or R7 is not present and Rg is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; or, when x and y are 0, Ri or R2 or R3 and j or R5 form together with the nitrogen atoms of A and D part of a ring structure; M" is one or more counterions, and at least one A or D comprises a quatemized ammonium group in which none of R\ , R2 or R3 is hydrogen, or at least one B is present in which neither Rg nor R7 is hydrogen, and at least one A or D comprises a primary, secondary or tertiary amine group, or at least one C is present.
3. A composition or component according to claim 2 comprising a polyamine cationic surfactant wherein x=0 and y=0.
4. A composition or component according to claim 2 or 3 comprising a polyamine cationic surfactant wherein R4 and R5 are, independently from each other, Ci -Cg alkyl or (poly) hydroxyalkyi group or hydrogen atom.
5. A composition or component according to any of claims 2 to 4 comprising a polyamine cationic surfactant, wherein L is a C2-C4 linear or branched alkyl or hydroxyalkyi group.
6. A composition according to any preceding claim in the form of an aqueous or nonaqueous laundry or dishwashing compositions, comprising the cationic surfactant at a level of from 0.2% to 10% by weight.
7. A composition according to claim 6 wherein the amount of solvent is up to 50% by weight of the composition.
8. A composition according to any of claims 1 to 5 in the form of a shampoo composition, comprising the cationic surfactant at a level of from 0.2% to 10% by weight.
9. A composition according to any of claims 1 to 5 in the form of a hard-surface cleaning composition, comprising the cationic surfactant at a level of from 0.3% to 15% by weight.
PCT/US1998/002462 1997-02-11 1998-02-11 Liquid cleaning composition WO1998035006A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU61520/98A AU6152098A (en) 1997-02-11 1998-02-11 Liquid cleaning composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9702731.2 1997-02-11
GB9702731A GB2321900A (en) 1997-02-11 1997-02-11 Cationic surfactants
GB9726894A GB2332443A (en) 1997-12-20 1997-12-20 Liquid cleaning composition
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