WO2009087033A1 - Granules - Google Patents
Granules Download PDFInfo
- Publication number
- WO2009087033A1 WO2009087033A1 PCT/EP2008/067794 EP2008067794W WO2009087033A1 WO 2009087033 A1 WO2009087033 A1 WO 2009087033A1 EP 2008067794 W EP2008067794 W EP 2008067794W WO 2009087033 A1 WO2009087033 A1 WO 2009087033A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dyes
- violet
- sokalan
- silica
- binder
- Prior art date
Links
Classifications
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0034—Fixed on a solid conventional detergent ingredient
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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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0084—Antioxidants; Free-radical scavengers
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
-
- 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
- C11D3/40—Dyes ; Pigments
-
- 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
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
Definitions
- the present invention relates to the reduction in migration of actives from granules.
- Powder detergents for clothes washing are formulated at high pH and often contain percarbonate or perborate as a bleach.
- high performance organic chemicals such as anti-oxidants, shading dyes and shading pigments may be added to the formulation. These compounds are frequently chemically unstable to high pH and bleach, so that on storage they are destroyed. To prevent this, they may be segregated from the formulation, by adding them to the formulation in separate post-dosed granules.
- An acidic polymer may be added to the granule used to increase stability as described in WO2007/039042 (Unilever) .
- non-ionic surfactants in such granules, to initially mix the HPOCs in and to aid dispersion and delivery of the ingredients in the wash, as described in WO2006/053598 (Unilever) . This is especially the case when the HPOCs are hydrophobic materials.
- the non-ionic containing granules leach non-ionic over the whole formulation, again exposing the HPOCs to high pH and bleach.
- the problem is particularly severe in powder detergent formulations that contain high levels of non-ionic surfactant.
- the leaching from the granule can also lead to powder discolouration, especially for dyes and pigments.
- the present invention provides a granule comprising:
- the non-ionic surfactant having the HPOC mixed therein is in contact with the silica and coated with the binder .
- High performance organic chemicals are organic chemicals added to the formulation at low levels, preferably between 0.00001 to 0.5 wt% to give benefits beyond detergency to the user .
- the HPOC is limited to an anti-oxidant, a shading dyes, a shading pigment or mixtures thereof.
- the HPOC is most preferably a dye.
- Dyes preferably selected from the groups of basic dye, acid dyes, direct dyes, hydrophobic dyes selected from solvent dyes and disperse dyes.
- Dyes may be selected from those listed in the colour index
- Blue and violet thiazolium mono-azo dyes may also be used as described in WO 2007/084729.
- the granule contains 0.01 to 1.0 wt% of a shading dye for fabric whiteness.
- the shading dye is preferably selected from:
- Direct dyes Direct violet and direct blue dyes are preferred.
- the dye are bis or tris - azo dyes.
- the carcinogenic benzidene based dyes are not preferred.
- the direct dye is a direct violet of the following structure
- Ri is hydrogen or alkyl
- R2 is hydrogen, alkyl or substituted or unsubstituted aryl, preferably phenyl
- R3 and R4 are independently hydrogen or alkyl
- n is 0, 1 or 2, preferably 1 or 2.
- Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.
- the direct dye may be covalently linked to a photobleach, for example as described in WO2006/024612.
- Cotton substantive acid dyes give benefits to cotton containing garments.
- Preferred dyes and mixes of dyes are blue or violet.
- Preferred acid dyes are:
- R a , R b , R c and R d are selected from: H, an branched or linear Cl to C7-alkyl chain, benzyl a phenyl, and a naphthyl; the dye is substituted with at least one SC>3 ⁇ or -COO ⁇ group; the B ring does not carry a negatively charged group or salt thereof; and the A ring may further substituted to form a naphthyl; the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F, and NO 2 .
- Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
- the composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores .
- Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
- Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
- Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton. Preferably the reactive group is hydrolysed or the dye has been reactive group has been reacted with an organic species such as a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the colour index.
- Shading photo-bleaches are dyes which form reactive bleach species on exposure to light. They are best used in combination with other shading dyes and pigments to give a blue or violet colour.
- the photo-bleach molecule absorbs light and attains an electronical excited state, PB*.
- This electronically excited state is quenched by triplet oxygen, 3 O 2 , in the surroundings to form singlet 1 O 2 .
- Singlet oxygen is a highly reactive bleach.
- Suitable Shading photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or Al-Zl where Zl is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion.
- the phthalocyanine has 1-4 SO3X groups covalently bonded to it where X is an alkali metal or ammonium ion.
- X alkali metal or ammonium ion
- Xanthene type dyes are preferred, particularly based on the structure :
- the dye may be substituted by halogens and other elements/groups.
- Particularly preferred examples are Food Red 14 and Rose Bengal, Phloxin B, Eosin Y.
- Basic dyes are organic dyes that carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the colour index. Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141.
- Pigments are coloured particles preferably with an average particle size in the range of 0.01 to 0.1 micron size, which are practically insoluble in aqueous medium that contain surfactants.
- Preferred pigments are blue or violet.
- Pigments may be selected from the blue and blue pigments listed in the colour index. Inorganic pigments such as pigment blue 29 or pigment pigment violet 15 may be used, however organic pigments are preferred.
- Preferred organic pigments are pigment violet 1, 1:1, 1:2, 2, 3, 5:1, 13, 19, 23, 25, 27, 31, 32, 37, 39, 42, 44, 50 and Pigment blue 1, 2, 9, 10, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 19, 24:1, 25, 56, 60, 61, 62, 66, 75, 79 and 80.
- More preferred pigments are pigment violet 3, 13, 23, 27, 37, 39, pigment blue 14, 25, 66 and 75.
- pigment violet 23 The most preferred is pigment violet 23.
- ANTIOXIDANT One class of anti-oxidants suitable for use in the present invention is alkylated phenols having the general formula:
- RJx wherein R is C1-C22 linear or branched alkyl, preferably methyl or branched C3-C6 alkyl; C3-C6 alkoxy, preferably methoxy; Rl is a C3-C6 branched alkyl, preferably tert- butyl; x is 1 or 2.
- Hindered phenolic compounds are preferred as antioxidant.
- Another class of anti-oxidants suitable for use in the present invention is a benzofuran or benzopyran derivative having the formula:
- Rl and R2 are each independently alkyl or Rl and R2 can be taken together to form a C5-C6 cyclic hydrocarbyl moiety;
- B is absent or CH2 ;
- R4 is C1-C6 alkyl;
- R5 is hydrogen or -C(O)R3 wherein R3 is hydrogen or C1-C19 alkyl;
- R6 is C1-C6 alkyl;
- R7 is hydrogen or C1-C6 alkyl;
- X is - CH2OH, or -CH2A wherein A is a nitrogen comprising unit, phenyl, or substituted phenyl.
- Preferred nitrogen comprising A units include amino, pyrrolidino, piperidino, morpholino, piperazino, and mixtures thereof.
- antioxidants are found as follows. A derivative of ⁇ -tocopherol, beta-tocopherol, gamma- tocopherol, delta-tocophero, and alkyl esters of gallic acid, especially octyl gallate and dodecyl gallate.
- suitable antioxidants are the class of hindered amine light stabilisers (HALS), particularly those based 2,2,6, 6-tetramethylpipiridines .
- Non-limiting examples of anti-oxidants suitable for use in the present invention include phenols inter alia 2,6-di- tert-butylphenol, 2, 6-di-tert-butyl-4-methylphenol, mixtures of 2 and 3- tert-butyl-4-methoxyphenol .
- Mixtures of antioxidants may be use and in particular mixtures that have synergic antioxidant effects as found in, for example, WO02/072746.
- Preferred non-ionic surfactants are, for example, polyethoxylated alcohols, ethoxylated alkyl phenols, anhydrosorbitols, and alkoxylated anhydrosorbitol esters.
- An example of a preferred nonionic surfactant is a polyethoxylated alcohol manufactured and marketed by the Shell Chemical Company under the trademark "Neodol”.
- Neodol 25-7 which is a mixture of 12 to 15 carbon chain length alcohols with about 7 ethylene oxide groups per molecule; Neodol 23-65, a C12-13 mixture with about 6.5 moles of ethylene oxide; Neodol 25-9, a C12-13 mixture with about 9 moles of ethylene oxide; and Neodol 45-7, a C14-15 mixture with about seven moles of ethylene oxide.
- nonionic surfactants useful in the present invention include trimethyl nonyl polyethylene glycol ethers such as those, manufactured and marketed by Union Carbide Corporation under the Trademark Tergitol, octyl phenoxy polyethoxy ethanols sold by Rohm and Haas under the Trademark Triton, and polyoxyethylene alcohols, such as Brij 76 and Brij 97, trademarked products of Atlas Chemical Co.
- the hydrophilic lipophilic balance (HLB) is preferably below about 13, and more preferably below 10.
- the silica has a pore volume of from 0.2 to 2.5 ml/g, most preferably 1.2 to 2 ml/g.
- the pore volume is measured by mercury intrusion porosimetry or water saturation method at 293K.
- the water saturation method is preferred; here a known weight of the silica is slowly mixed with a known volume of water, such that excess water is present.
- the container is sealed and left till the silica becomes fully saturated (i.e. all pores are filled) .
- the excess water is then removed and the volume measured. Pore volume is then given by the equation:
- the pore volume served to provide cavities into which the non-ionic/HPOC migrates during application.
- the silica has an average particle size, APS, from 0.1 to 100 microns, preferably 1 to 15 microns. Preferably this is as measured by a laser diffraction particle size analyser, preferably a Malvern HP with 100mm lens .
- the silica is a neutral or acidic silica.
- the silica is amorphous.
- the silica is without a wax surface treatment. This permits ready delivery of the HPOCs to the wash medium.
- a binder is a material used to bind together two or more other materials in mixtures. Its two principal properties are adhesion and cohesion .
- the binder is other than a non- ionic surfactant. Binders are standard in the art of laundry detergent granules, examples of which are: Sokalan® CP45, Sokalan® CP5, ethylene glycol, surfactants, anionic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrylates, citric acid and mixtures thereof.
- the binder has a melting point above 30 0 C.
- the binder is selected from the group consisting of a polyacrylate, polyethylene glycol, and polyacrylate/maleate copolymer.
- the binder may serve as a coating agent and a cogranulent for the silica particles.
- Suitable polymers for use herein are water-soluble.
- water-soluble it is meant herein that the polymers have a solubility greater than 5 g/1 at 20 0 C in demineralised water .
- the binder is preferably an acidic polymer.
- an acidic polymer it is meant herein that a 1% solution of said polymers has a pH of less than 7, preferably less than 5.5.
- Suitable polymers for use herein have a molecular weight in the range of from 1000 to 280,000, preferably from 1500 to 150, 000.
- Suitable polymers which meet the above criteria and are therefore particularly useful in the present invention, include those having the following empirical formula I
- the proportion of M being H in such polymers is preferably such as to ensure that the polymer is sufficiently acidic to meet the acidity criteria as hereinbefore defined.
- Polymers according to formula I are known in the field of laundry detergents, and are typically used as chelating agents, as for instance in GB-A-I, 597, 756.
- Preferred polycarboxylate polymers fall into several categories.
- a first category belongs to the class of copolymeric polycarboxylate polymers which, formally at least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C1-C4 alkyl acrylic acid as second monomer.
- preferred polycarboxylate polymers of this type are those in which X is CHO, R3 is H or Cl-4 alkyl, especially methyl, p is from about 0.1 to about 1.9, preferably from about 0.2 to about 1.5, n averages from about 10 to about 1500, preferably from about 50 to about 1000, more preferably from 100 to 800, especially from 120 to 400 and Y comprises monomer units of formula II
- Such polymers are available from BASF under the trade name Sokalan® CP5 (neutralised form) and Sokajan® CP45 (acidic form) .
- Binder materials are commercially readily available.
- the water soluble polymers of the Sokalan® type sold by BASF® are preferred.
- the granule is preferably of the size from 250 to 1400 microns.
- the granule size is as determined by passing through a mesh sieve. Preferably the size is in the range...
- the dye solvent violet 13 was mixed in non-ionic surfactant (7EO) to form a 0.5 wt% solution.
- the non-ionic was added to the carrier in a high shear mixer. Following this the binder was added to granulate the mixture. There resultant granules were dried in an oven at 353K finally sieved to give granules in the size range 500 to 1000 microns.
- the granules had the following composition. All percentages refer to weight.
- Granule 5 71% bentonite 17 12% CP5 Gasil 230 is a neutral silica with an APS of 3.6 microns and a pore volume of 1.6 ml/g.
- Gasil 200DF is an acidic silica with an APS of 4.3 microns and a pore volume of 0.4 ml/g.
- Gasil 200TP is similar to Gasil 200DF.
- Formulation (1) surfactant system: 18% sodium LAS. Builder system: 28% Sodium tripolyphosphate, sodium carbonate and sodium disilicate. Bleach system: none. Remainder sodium sulphate .
- Formulation (2) surfactant system: 7% sodium LAS, 3% non- ionic (7EO) .
- Builder system 45% Sodium tripolyphosphate, sodium carbonate, sodium disilicate.
- Bleach system none. Remainder sodium sulphate.
- Formulation (3) surfactant system: 10% sodium LAS, 5% non- ionic (7EO) .
- Builder system 35% zeolite 4A, sodium carbonate, Bleach systems 16% sodium percarbonate and TAED. Remainder sodium sulphate.
- Granule 1 the silica granule with high level of CP5 gave the best overall performance.
- Performance test showed that some dye was also destroyed in formulation (3) with time, this was least with granule (2) with the acidic binder CP13.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0821868-4A BRPI0821868A2 (en) | 2008-01-10 | 2008-12-17 | Granule |
EP08870061A EP2245133B1 (en) | 2008-01-10 | 2008-12-17 | Granules |
CN2008801248651A CN101910396B (en) | 2008-01-10 | 2008-12-17 | Granules |
ES08870061T ES2388018T3 (en) | 2008-01-10 | 2008-12-17 | Granules |
ZA2010/03971A ZA201003971B (en) | 2008-01-10 | 2010-06-03 | Granules |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08150143 | 2008-01-10 | ||
EP08150143.9 | 2008-01-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009087033A1 true WO2009087033A1 (en) | 2009-07-16 |
Family
ID=39490983
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2008/067794 WO2009087033A1 (en) | 2008-01-10 | 2008-12-17 | Granules |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP2245133B1 (en) |
CN (1) | CN101910396B (en) |
AR (1) | AR070132A1 (en) |
BR (1) | BRPI0821868A2 (en) |
CL (1) | CL2009000033A1 (en) |
ES (1) | ES2388018T3 (en) |
WO (1) | WO2009087033A1 (en) |
ZA (1) | ZA201003971B (en) |
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Also Published As
Publication number | Publication date |
---|---|
CN101910396B (en) | 2012-10-17 |
EP2245133B1 (en) | 2012-05-23 |
AR070132A1 (en) | 2010-03-17 |
ES2388018T3 (en) | 2012-10-05 |
ZA201003971B (en) | 2011-09-28 |
BRPI0821868A2 (en) | 2015-07-28 |
CL2009000033A1 (en) | 2009-10-23 |
CN101910396A (en) | 2010-12-08 |
EP2245133A1 (en) | 2010-11-03 |
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