WO2016192905A1 - Laundry detergent composition - Google Patents

Laundry detergent composition Download PDF

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Publication number
WO2016192905A1
WO2016192905A1 PCT/EP2016/059313 EP2016059313W WO2016192905A1 WO 2016192905 A1 WO2016192905 A1 WO 2016192905A1 EP 2016059313 W EP2016059313 W EP 2016059313W WO 2016192905 A1 WO2016192905 A1 WO 2016192905A1
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WO
WIPO (PCT)
Prior art keywords
laundry detergent
detergent composition
composition according
alkoxylated
surfactant
Prior art date
Application number
PCT/EP2016/059313
Other languages
French (fr)
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
Dietmar Andreas LANG
Original Assignee
Unilever Plc
Unilever N.V.
Conopco, Inc., D/B/A Unilever
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Plc, Unilever N.V., Conopco, Inc., D/B/A Unilever filed Critical Unilever Plc
Priority to BR112017025607-0A priority Critical patent/BR112017025607B1/en
Priority to CN201680026582.8A priority patent/CN107835851B/en
Priority to EP16718686.5A priority patent/EP3303536B1/en
Publication of WO2016192905A1 publication Critical patent/WO2016192905A1/en

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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D2111/12—

Definitions

  • the present Invention provides and enzymatic and dispersant formulation for use in domestic laundry.
  • Laundry detergent formulations containing a high fraction of anionic surfactant relative to non-ionic surfactant are ubiquitous.
  • Protease enzymes are used in laundry detergent formulations to remove protein containing stains from fabrics.
  • WO2013/087286 discloses liquids formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
  • WO 02/36727 discloses a detergent composition comprising a detersive surfactant, a metallo protease and a calcium ion.
  • US 2005/107281 discloses ether carboxylic acids based on alkoxylated
  • styrylphenols their preparation, and to their use as surface-active additives.
  • US2004/087458 discloses a composition comprising a surfactant blend of nonionic and anionic surfactants useful for the removal of oligomer deposits from polyester fibers and polyester processing equipment.
  • the composition of the present invention includes a surfactant blend of an ethoxylated sorbitan ester and at least one additional nonionic or anionic surfactant.
  • GB 2007692 discloses anti-soiling and anti-redesposition compositions which can be used in detergency.
  • the present invention provides a laundry detergent composition comprising:
  • a surfactant other than an alkoxylated di or tri aryl phenol dispersant, selected from: anionic and non-ionic surfactants, preferably from 6 to 30 wt%, more preferably 8 to 20 wt%, wherein the weight fraction of non- ionic surfactant anionic surfactant is from 0 to 0.3, preferably 0 to 0.15, most preferably 0.05 to 0.12;
  • alkoxylation is ethoxylation, preferably of the structure:
  • Ri is selected from H and aryl groups, X is selected from ethoxy or propoxy groups; n is from 6 to 70, T is selected from H, SO3 " ; COO " and PO3 2" , most preferably H. Most preferably Ri is styryl and n is from 12 to 20.
  • the protease is a serine protease, more preferably a subtilase type serine proteases, most preferably a subtilisin subtilase type serine protease.
  • the wt% of anionic surfactants are calculated as the sodium salt.
  • the wt% of a charged alkoxylated di or tri aryl phenol, is calculated as the sodium salt.
  • the present invention provides a domestic method of treating a textile, the method comprising the steps of:
  • the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt% of phosphate.
  • powder laundry detergent formulations are predominantly carbonate built. Powders, should preferably give an in use pH of 9.5-1 1 .
  • the laundry detergent is an aqueous liquid laundry detergent, preferably with a pH of from 7 to 9.
  • Protease enzymes hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains.
  • proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http://merops.sanqer.ac.uk/). Serine proteases are preferred. Subtilase type serine proteases are more preferred. The term "subtilases" refers to a sub-group of serine protease according to Siezen et al., Protein Engng. 4 (1991 ) 719-737 and Siezen et al. Protein Science 6 (1997) 501 -523.
  • Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate.
  • the subtilases may be divided into 6 sub-divisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.
  • subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B.
  • amyloliquefaciens Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in (WO93/18140).
  • Other useful proteases may be those described in W092/175177, WO01/016285, WO02/026024 and WO02/016547.
  • trypsin-like proteases are trypsin (e.g.
  • proteases are the variants described in: W092/19729, WO96/034946, WO98/201 15, WO98/201 16, WO99/01 1768, WO01/44452, WO03/006602, WO04/03186, WO04/041979, WO07/006305, W01 1/036263, W01 1/036264, especially the variants with substitutions in one or more of the following positions: 3, 4, 9, 15, 27, 36, 57, 68, 76, 87, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 104, 106, 1 18, 120, 123, 128, 129, 130, 160, 167, 170, 194, 195, 199, 205, 206, 217, 218, 222, 224, 232, 235, 236, 245, 248, 252 and 274 using the BPN'
  • subtilase variants may comprise the mutations: S3T, V4I, S9R, A15T, K27R, * 36D, V68A, N76D, N87S,R, * 97E, A98S, S99G,D,A, S99AD, S101 G,M,R S103A, V104I,Y,N, S106A, G1 18V,R, H120D,N, N123S, S128L, P129Q, S130A, G160D, Y167A, R170S, A194P, G195E, V199M, V205I, L217D, N218D, M222S, A232V, K235L, Q236H, Q245R, N252K, T274A (using BPN' numbering).
  • protease is a subtilisins (EC 3.4.21 .62).
  • subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in (WO93/18140).
  • the subsilisin is derived from Bacillus, preferably Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and
  • subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
  • suitable commercially available protease enzymes include those sold under the trade names names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra,
  • Maxatase® Maxacal®, Maxapem®, Purafect®, Purafect Prime®, PreferenzTm, Purafect MA®, Purafect Ox®, Purafect OxP®, Puramax®, Properase®, EffectenzTm, FN2®, FN3® , FN4®, Excellase®,
  • BLAP Henkel/ Kemira
  • BLAP R BLAP with S3T + V4I + V199M + V205I + L217D
  • BLAP X BLAP with S3T + V4I + V205I
  • BLAP F49 BLAP with S3T + V4I + A194P + V199M + V205I + L217D
  • alkoxylated di or tri aryl phenol dispersants are not included as surfactants.
  • the alkoxylated di or tri aryl phenol is preferably uncharged.
  • the alkoxylation is ethoxylation, most preferably with from 6 to 70 (CH2CH2O) units.
  • R-i is selected from H and aryl groups, X is selected from ethoxy or propoxy groups; n is from 6 to 70, T is selected from H, SO3 " ; COO " and PO3 2" , most preferably H. Most preferably Ri is styryl and n is from 12 to 20.
  • a most preferred structure is:
  • n is selected from: 10; 1 1 ; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21 ; 22; 23; 24; 25; 26; 27; 28; 29; 30; 31 ; 32; 33; 34; 35; 36; 37; 38; 39; 40; 41 ; 42; 43; 44; 45; 46; 47; 48; 49; 50; 51 ; 52; 53; and, 54;, preferably 12; 13; 14; 15; 16; 17; 18; 19; 20
  • the laundry composition comprises anionic charged surfactant (which includes a mixture of the same).
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cie alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C9 to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to Ci5 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the anionic surfactant is preferably selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates; soaps; alkyl (preferably methyl) ester sulphonates, and mixtures thereof.
  • the most preferred anionic surfactants are selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates and mixtures thereof.
  • the alkyl ether sulphate is a C12-C14 n-alkyl ether sulphate with an average of 1 to 3EO (ethoxylate) units.
  • Sodium lauryl ether sulphate is particularly preferred (SLES).
  • the linear alkyl benzene sulphonate is a sodium C11 to C15 alkyl benzene sulphonates.
  • the alkyl sulphates is a linear or branched sodium C12 to C18 alkyl sulphates.
  • Sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyl sulphate).
  • the level of anionic surfactant in the laundry composition is preferably from (i) 5 to 50 wt% negatively charged surfactant, preferably the level of negatively charged surfactant is from 6 to 30 wt%, more preferably 8 to 20 wt%.
  • anionic surfactant Preferably two or more anionic surfactant are present, preferably linear alkyl benzene sulphonate together with an alkyl ether sulphate.
  • Non-ionic surfactant may be present in the surfactant mix.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids or amides, especially ethylene oxide either alone or with propylene oxide.
  • Preferred nonionic detergent compounds are the condensation products of aliphatic Cs to Cie primary or secondary linear or branched alcohols with ethylene oxide.
  • the alkyl ethoxylated non-ionic surfactant is a Cs to Cie primary alcohol with an average ethoxylation of 7EO to 9EO units.
  • Builder materials may be selected from 1 ) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • calcium sequestrant builder materials examples include alkali metal
  • polyphosphates such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
  • precipitating builder materials examples include sodium orthophosphate and sodium carbonate.
  • Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in
  • the composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below. Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
  • a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
  • Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
  • Zeolite and carbonate are preferred builders for powder detergents.
  • the composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w.
  • Aluminosilicates are materials having the general formula:
  • the preferred sodium aluminosilicates contain 1 .5-3.5 S1O2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • the ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1 .
  • phosphate builders may be used.
  • 'phosphate' embraces diphosphate, triphosphate, and phosphonate species.
  • Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
  • the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt% of phosphate.
  • the powder laundry detergent formulation is carbonate built.
  • the composition preferably comprises a fluorescent agent (optical brightener).
  • Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %.
  • Preferred classes of fluorescer are: Di- styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di- sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1 ,2-d]triazole, disodium 4,4'- bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5-triazin-2-yl)]amino ⁇ stilbene- 2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1 ,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.
  • the aqueous solution used in the method has a fluorescer present.
  • a fluorescer is present in the aqueous solution used in the method it is preferably in the range from 0.0001 g/l to 0.1 g/l, preferably 0.001 to 0.02 g/l.
  • the composition comprises a perfume.
  • the perfume is preferably in the range from 0.001 to 3 wt %, most preferably 0.1 to 1 wt %.
  • CTFA Cosmetic, Toiletry and Fragrance
  • compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
  • top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender,
  • Perfume and top note may be used to cue the whiteness benefit of the invention.
  • the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
  • a peroxygen bleach e.g., sodium percarbonate, sodium perborate, and peracid.
  • the composition may comprise one or more further polymers.
  • suitable polymers are carboxymethylcellulose, poly (ethylene glycol), polyvinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • Polymers present to prevent dye deposition for example poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole), are preferably absent from the formulation.
  • One or more further enzymes are preferred present in a laundry composition of the invention and when practicing a method of the invention.
  • the level of each enzyme in the laundry composition of the invention is from 0.0001 wt% to 0.1 wt% protein.
  • the further enzyme is preferably selected from: amylases lipases; and, cellulases.
  • Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
  • Shading Dyes are preferably present in the formulation at a level from 0.002 to 0.2wt%.
  • Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zurich, 2003) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003).
  • Shading Dyes for use in laundry detergents preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700nm) of greater than 5000 L mol "1 cm -1 , preferably greater than 10000 L mol "1 cm -1 .
  • the dyes are blue or violet in colour.
  • Preferred shading dye chromophores are azo, azine, anthraquinone, and
  • triphenylmethane preferably carry a net anionic charged or are uncharged.
  • Azine preferably carry a net anionic or cationic charge.
  • Blue or violet shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. In this regard the dye gives a blue or violet colour to a white cloth with a hue angle of 240 to 345, more preferably 250 to 320, most preferably 250 to 280.
  • the white cloth used in this test is bleached non-mercerised woven cotton sheeting.
  • Shading dyes are discussed in WO2005/003274, WO2006/032327(Unilever), WO 2006/032397 (Unilever), WO2006/045275 (Unilever), WO06/027086 (Unilever), WO 2008/017570 (Unilever), WO 2008/141880 (Unilever), WO2009/132870
  • WO 2010/102861 Unilever
  • WO 2010/148624 Unilever
  • WO2008/087497 P&G
  • WO201 1/01 1799 P&G
  • WO2012/054820 P&G
  • WO2013/142495 P&G
  • WO2013/151970 P&G
  • Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes.
  • Bis-azo dyes are preferably sulphonated bis-azo dyes.
  • Preferred examples of sulphonated bis-azo compounds are direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , Direct Violet 66, direct violet 99 and alkoxylated versions thereof.
  • Alkoxylated bis-azo dyes are discussed in WO2012/054058 and WO2010/151906.
  • An example of an alkoxylated bis-azo dye is :
  • Azine dye are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS- No 72749-80-5, acid blue 59, and the phenazine dye selected from:
  • X3 is selected from: -H; -F; -Chb; -C2H5; -OCH3; and, -OC2H5;
  • X4 is selected from: -H; -CH 3 ; -C2H5; -OCH3; and, -OC2H5;
  • Y2 is selected from: -OH; -OCH2CH2OH; -CH(OH)CH 2 OH; -OC(O)CH 3 ; and, C(O)OCH 3 .
  • the shading dye is present in the composition in range from 0.0001 to 0.5 wt %, preferably 0.001 to 0.1 wt%. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class. As stated above the shading dye is a blue or violet shading dye.
  • the shading dye is most preferably a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine.
  • the alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation.
  • 80 to 95 mol% of the N-H groups in the polyethylene imine are replaced with iso-propyl alcohol groups by propoxylation.
  • the polyethylene imine before reaction with the dye and the propoxylation has a molecular weight of 600 to 1800.
  • An example structure of a preferred reactive anthraquinone covalently attached to a propoxylated polyethylene imine is:
  • Preferred reactive anthraquinone dyes are: Reactive blue 1 ; Reactive blue 2;
  • Reactive blue 4 Reactive blue 5; Reactive blue 6; Reactive blue 12; Reactive blue 16; reactive blue 19; Reactive blue 24 ; Reactive blue 27; Reactive blue 29; Reactive blue 36; Reactive blue 44; Reactive blue 46 ; Reactive blue 47; reactive blue 49; Reactive blue 50; Reactive blue 53; Reactive blue 55; Reactive blue 61 ; Reactive blue 66; Reactive blue 68; Reactive blue 69; Reactive blue 74; Reactive blue 86; Reactive blue 93; Reactive blue 94; Reactive blue101 ; Reactive blue103; Reactive bluel 14; Reactive blue1 17; Reactive blue125; Reactive blue141 ; Reactive blue142; Reactive blue 145; Reactive blue 149; Reactive blue 155; Reactive blue 164;
  • Reactive blue 166 Reactive blue 177; Reactive blue 181 ; Reactive blue 185; Reactive blue 188; Reactive blue 189; Reactive blue 206; Reactive blue 208;
  • Reactive blue 262 Reactive blue 263; and Reactive blue 172.
  • the dyes are listed according to Colour Index (Society of Dyers and
  • An aqueous liquid laundry detergent was prepared of the following formulation:
  • the formulation was used to wash eight 5x5cm EMPA 1 17 stain monitor

Abstract

The present invention provides an enzymatic and dispersant formulation for use in domestic laundry comprising (i) from 5 to 50 wt% of surfactant, other than an alkoxylated di or tri aryl phenol dispersant, selected from anionic and non-ionic surfactants, wherein the weight fraction of non-ionic surfactant/anionic surfactant is from 0 to 0.3, (ii) from 0.5 to 20 wt% of an alkoxylated di or tri aryl phenol dispersant, and (iii) from 0.0005 to 0.2 wt% protease enzyme. Domestic method of treating a textile comprising (i) treating a textile with from 1 g/L of an aqueous solution of the detergent composition and (ii) allowing said aqueous detergent solution to remain in contact with the textile for 10 minutes to 2 days, then rinsing and drying the textile.

Description

LAUNDRY DETERGENT COMPOSITION
Field of Invention
The present Invention provides and enzymatic and dispersant formulation for use in domestic laundry.
Background of Invention
Laundry detergent formulations containing a high fraction of anionic surfactant relative to non-ionic surfactant are ubiquitous. Protease enzymes are used in laundry detergent formulations to remove protein containing stains from fabrics.
WO2013/087286 (Unilever) discloses liquids formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
WO 02/36727 discloses a detergent composition comprising a detersive surfactant, a metallo protease and a calcium ion. US 2005/107281 discloses ether carboxylic acids based on alkoxylated
styrylphenols, their preparation, and to their use as surface-active additives.
US2004/087458 discloses a composition comprising a surfactant blend of nonionic and anionic surfactants useful for the removal of oligomer deposits from polyester fibers and polyester processing equipment. The composition of the present invention includes a surfactant blend of an ethoxylated sorbitan ester and at least one additional nonionic or anionic surfactant. GB 2007692 discloses anti-soiling and anti-redesposition compositions which can be used in detergency.
There is a need to increase stain removal in laundry formulations containing a high fraction of anionic surfactant relative to non-ionic surfactant.
Summary of the Invention Surprisingly the combination of a protease with an alkoxylated di or tri aryl phenol, provides enhanced stain removal.
In one aspect the present invention provides a laundry detergent composition comprising:
(i) from 5 to 50 wt% of a surfactant, other than an alkoxylated di or tri aryl phenol dispersant, selected from: anionic and non-ionic surfactants, preferably from 6 to 30 wt%, more preferably 8 to 20 wt%, wherein the weight fraction of non- ionic surfactant anionic surfactant is from 0 to 0.3, preferably 0 to 0.15, most preferably 0.05 to 0.12;
(ii) from 0.5 to 20 wt%, preferably 1 .5 to 10 wt%, most preferably 2.5 to 5 wt% of an alkoxylated di or tri aryl phenol, preferably the alkoxylated di or tri aryl phenol is uncharged. Preferably the alkoxylation is ethoxylation, preferably of the structure:
Figure imgf000004_0001
wherein Ri, is selected from H and aryl groups, X is selected from ethoxy or propoxy groups; n is from 6 to 70, T is selected from H, SO3"; COO" and PO32", most preferably H. Most preferably Ri is styryl and n is from 12 to 20.
(iii) from 0.0005 to 0.2wt% of a protease enzyme, preferably from 0.002 to
0.02wt%. Preferably the protease is a serine protease, more preferably a subtilase type serine proteases, most preferably a subtilisin subtilase type serine protease.
The wt% of anionic surfactants are calculated as the sodium salt. The wt% of a charged alkoxylated di or tri aryl phenol, is calculated as the sodium salt.
In a further aspect the present invention provides a domestic method of treating a textile, the method comprising the steps of:
(i) treating a textile with from 1 g/L of an aqueous solution of the laundry detergent composition as defined in any one of the preceding claims; and,
(ii) allowing said aqueous laundry detergent solution to remain in contact with the textile for 10 minutes to 2 days then rinsing and drying the textile. Detailed Description of the Invention Detergent format
Preferably the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt% of phosphate. Preferably powder laundry detergent formulations are predominantly carbonate built. Powders, should preferably give an in use pH of 9.5-1 1 .
Most preferably the laundry detergent is an aqueous liquid laundry detergent, preferably with a pH of from 7 to 9.
Protease
Protease enzymes hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains.
Examples of suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http://merops.sanqer.ac.uk/). Serine proteases are preferred. Subtilase type serine proteases are more preferred. The term "subtilases" refers to a sub-group of serine protease according to Siezen et al., Protein Engng. 4 (1991 ) 719-737 and Siezen et al. Protein Science 6 (1997) 501 -523. Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate. The subtilases may be divided into 6 sub-divisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family. Examples of subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in (WO93/18140). Other useful proteases may be those described in W092/175177, WO01/016285, WO02/026024 and WO02/016547. Examples of trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO89/06270, W094/25583 and WO05/040372, and the chymotrypsin proteases derived from Cellumonas described in WO05/052161 and WO05/052146. Further Examples of useful proteases are the variants described in: W092/19729, WO96/034946, WO98/201 15, WO98/201 16, WO99/01 1768, WO01/44452, WO03/006602, WO04/03186, WO04/041979, WO07/006305, W01 1/036263, W01 1/036264, especially the variants with substitutions in one or more of the following positions: 3, 4, 9, 15, 27, 36, 57, 68, 76, 87, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 104, 106, 1 18, 120, 123, 128, 129, 130, 160, 167, 170, 194, 195, 199, 205, 206, 217, 218, 222, 224, 232, 235, 236, 245, 248, 252 and 274 using the BPN'
numbering. More preferred the subtilase variants may comprise the mutations: S3T, V4I, S9R, A15T, K27R, *36D, V68A, N76D, N87S,R, *97E, A98S, S99G,D,A, S99AD, S101 G,M,R S103A, V104I,Y,N, S106A, G1 18V,R, H120D,N, N123S, S128L, P129Q, S130A, G160D, Y167A, R170S, A194P, G195E, V199M, V205I, L217D, N218D, M222S, A232V, K235L, Q236H, Q245R, N252K, T274A (using BPN' numbering).
Most preferably the protease is a subtilisins (EC 3.4.21 .62).
Examples of subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in (WO93/18140). Preferably the subsilisin is derived from Bacillus, preferably Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and
Bacillus gibsonii as described in US 6,312,936 B I, US 5,679,630, US 4,760,025, US7,262,042 and WO09/021867. Most preferably the subtilisin is derived from Bacillus gibsonii or Bacillus Lentus. Suitable commercially available protease enzymes include those sold under the trade names names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra,
Neutrase®, Everlase® and Esperase® all could be sold as Ultra® or Evity®
(Novozymes A S),
Those sold under the tradename Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3® , FN4®, Excellase® and Purafect OXP® by Genencor International.
Those sold under the tradename Maxatase®, Maxacal®, Maxapem®, Purafect®, Purafect Prime®, PreferenzTm, Purafect MA®, Purafect Ox®, Purafect OxP®, Puramax®, Properase®, EffectenzTm, FN2®, FN3® , FN4®, Excellase®,
Opticlean® and Optimase® (Danisco/DuPont), Axapem™ (Gist-Brocases N.V.), Those available from Henkel/ Kemira, namely BLAP (sequence shown in Figure 29 of US 5,352,604 with the following mutations S99D + SIOI R + S103A + V104I + G159S, hereinafter referred to as BLAP), BLAP R (BLAP with S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V205I + L217D) - all from Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin with mutations A230V + S256G + S259N) from Kao.
Alkoxylated di or tri aryl phenol
In the context of the current invention the alkoxylated di or tri aryl phenol dispersants are not included as surfactants.
The alkoxylated di or tri aryl phenol is preferably uncharged. Preferably the alkoxylation is ethoxylation, most preferably with from 6 to 70 (CH2CH2O) units.
Preferably it is a triarylphenol ethoxylate. Preferably of the structure:
Figure imgf000008_0001
wherein R-i, is selected from H and aryl groups, X is selected from ethoxy or propoxy groups; n is from 6 to 70, T is selected from H, SO3"; COO" and PO32", most preferably H. Most preferably Ri is styryl and n is from 12 to 20.
A most preferred structure is:
Figure imgf000008_0002
wherein n is selected from: 10; 1 1 ; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21 ; 22; 23; 24; 25; 26; 27; 28; 29; 30; 31 ; 32; 33; 34; 35; 36; 37; 38; 39; 40; 41 ; 42; 43; 44; 45; 46; 47; 48; 49; 50; 51 ; 52; 53; and, 54;, preferably 12; 13; 14; 15; 16; 17; 18; 19; 20
Surfactants
The laundry composition comprises anionic charged surfactant (which includes a mixture of the same).
Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cie alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C9 to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to Ci5 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The anionic surfactant is preferably selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates; soaps; alkyl (preferably methyl) ester sulphonates, and mixtures thereof.
The most preferred anionic surfactants are selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates and mixtures thereof. Preferably the alkyl ether sulphate is a C12-C14 n-alkyl ether sulphate with an average of 1 to 3EO (ethoxylate) units. Sodium lauryl ether sulphate is particularly preferred (SLES). Preferably the linear alkyl benzene sulphonate is a sodium C11 to C15 alkyl benzene sulphonates. Preferably the alkyl sulphates is a linear or branched sodium C12 to C18 alkyl sulphates. Sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyl sulphate).
The level of anionic surfactant in the laundry composition is preferably from (i) 5 to 50 wt% negatively charged surfactant, preferably the level of negatively charged surfactant is from 6 to 30 wt%, more preferably 8 to 20 wt%.
Preferably two or more anionic surfactant are present, preferably linear alkyl benzene sulphonate together with an alkyl ether sulphate. Non-ionic surfactant may be present in the surfactant mix. Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids or amides, especially ethylene oxide either alone or with propylene oxide. Preferred nonionic detergent compounds are the condensation products of aliphatic Cs to Cie primary or secondary linear or branched alcohols with ethylene oxide.
Preferably the alkyl ethoxylated non-ionic surfactant is a Cs to Cie primary alcohol with an average ethoxylation of 7EO to 9EO units.
Builders or Complexing Agents
Builder materials may be selected from 1 ) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
Examples of calcium sequestrant builder materials include alkali metal
polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.
Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in
EP-A-0,384,070. The composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below. Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate) are preferred builders for powder detergents.
The composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w. Aluminosilicates are materials having the general formula:
0.8-1 .5 M20. AI2O3. 0.8-6 SiO2 where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1 .5-3.5 S1O2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. The ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1 .
Alternatively, or additionally to the aluminosilicate builders, phosphate builders may be used. In this art the term 'phosphate' embraces diphosphate, triphosphate, and phosphonate species. Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
Preferably the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt% of phosphate. Preferably the powder laundry detergent formulation is carbonate built. Fluorescent Agent
The composition preferably comprises a fluorescent agent (optical brightener).
Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %. Preferred classes of fluorescer are: Di- styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di- sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade
Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1 ,2-d]triazole, disodium 4,4'- bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5-triazin-2-yl)]amino}stilbene- 2-2' disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1 ,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.
It is preferred that the aqueous solution used in the method has a fluorescer present. When a fluorescer is present in the aqueous solution used in the method it is preferably in the range from 0.0001 g/l to 0.1 g/l, preferably 0.001 to 0.02 g/l.
Perfume
Preferably the composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt %, most preferably 0.1 to 1 wt %. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance
Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
It is commonplace for a plurality of perfume components to be present in a
formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
In perfume mixtures preferably 15 to 25 wt% are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender,
dihydromyrcenol, rose oxide and cis-3-hexanol.
Perfume and top note may be used to cue the whiteness benefit of the invention.
It is preferred that the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
Polymers
The composition may comprise one or more further polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), polyvinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
Polymers present to prevent dye deposition, for example poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole), are preferably absent from the formulation.
Further Enzymes
One or more further enzymes are preferred present in a laundry composition of the invention and when practicing a method of the invention. Preferably the level of each enzyme in the laundry composition of the invention is from 0.0001 wt% to 0.1 wt% protein.
The further enzyme is preferably selected from: amylases lipases; and, cellulases. Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
Shading Dyes Shading dyes are preferably present in the formulation at a level from 0.002 to 0.2wt%.
Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zurich, 2003) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003).
Shading Dyes for use in laundry detergents preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700nm) of greater than 5000 L mol"1 cm-1, preferably greater than 10000 L mol"1 cm-1. The dyes are blue or violet in colour.
Preferred shading dye chromophores are azo, azine, anthraquinone, and
triphenylmethane. Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged. Azine preferably carry a net anionic or cationic charge. Blue or violet shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. In this regard the dye gives a blue or violet colour to a white cloth with a hue angle of 240 to 345, more preferably 250 to 320, most preferably 250 to 280. The white cloth used in this test is bleached non-mercerised woven cotton sheeting.
Shading dyes are discussed in WO2005/003274, WO2006/032327(Unilever), WO 2006/032397 (Unilever), WO2006/045275 (Unilever), WO06/027086 (Unilever), WO 2008/017570 (Unilever), WO 2008/141880 (Unilever), WO2009/132870
(Unilever), WO 2009/141 173 (Unilever), WO 2010/099997 (Unilever),
WO 2010/102861 (Unilever), WO 2010/148624 (Unilever), WO2008/087497 (P&G), WO201 1/01 1799 (P&G), WO2012/054820 (P&G), WO2013/142495 (P&G), and WO2013/151970 (P&G).
Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes. The mono-azo dyes are preferably alkoxylated and are preferably uncharged or anionically charged at pH=7. Alkoxylated thiophene dyes are discussed in WO/2013/142495 and WO/2008/087497. Preferred examples of thiophene dyes are shown below:
Figure imgf000016_0001
Figure imgf000016_0002
Figure imgf000016_0003
Bis-azo dyes are preferably sulphonated bis-azo dyes. Preferred examples of sulphonated bis-azo compounds are direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , Direct Violet 66, direct violet 99 and alkoxylated versions thereof.
Alkoxylated bis-azo dyes are discussed in WO2012/054058 and WO2010/151906. An example of an alkoxylated bis-azo dye is :
Figure imgf000016_0004
Azine dye are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS- No 72749-80-5, acid blue 59, and the phenazine dye selected from:
Figure imgf000017_0001
wherein: X3 is selected from: -H; -F; -Chb; -C2H5; -OCH3; and, -OC2H5;
X4 is selected from: -H; -CH3; -C2H5; -OCH3; and, -OC2H5;
Y2 is selected from: -OH; -OCH2CH2OH; -CH(OH)CH2OH; -OC(O)CH3; and, C(O)OCH3.
The shading dye is present is present in the composition in range from 0.0001 to 0.5 wt %, preferably 0.001 to 0.1 wt%. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class. As stated above the shading dye is a blue or violet shading dye.
A mixture of shading dyes may be used. The shading dye is most preferably a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine. The alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation. Preferably 80 to 95 mol% of the N-H groups in the polyethylene imine are replaced with iso-propyl alcohol groups by propoxylation. Preferably the polyethylene imine before reaction with the dye and the propoxylation has a molecular weight of 600 to 1800. An example structure of a preferred reactive anthraquinone covalently attached to a propoxylated polyethylene imine is:
Figure imgf000018_0001
(Structure I).
Preferred reactive anthraquinone dyes are: Reactive blue 1 ; Reactive blue 2;
Reactive blue 4; Reactive blue 5; Reactive blue 6; Reactive blue 12; Reactive blue 16; reactive blue 19; Reactive blue 24 ; Reactive blue 27; Reactive blue 29; Reactive blue 36; Reactive blue 44; Reactive blue 46 ; Reactive blue 47; reactive blue 49; Reactive blue 50; Reactive blue 53; Reactive blue 55; Reactive blue 61 ; Reactive blue 66; Reactive blue 68; Reactive blue 69; Reactive blue 74; Reactive blue 86; Reactive blue 93; Reactive blue 94; Reactive blue101 ; Reactive blue103; Reactive bluel 14; Reactive blue1 17; Reactive blue125; Reactive blue141 ; Reactive blue142; Reactive blue 145; Reactive blue 149; Reactive blue 155; Reactive blue 164;
Reactive blue 166; Reactive blue 177; Reactive blue 181 ; Reactive blue 185; Reactive blue 188; Reactive blue 189; Reactive blue 206; Reactive blue 208;
Reactive blue 246; Reactive blue 247; Reactive blue 258; Reactive blue 261 ;
Reactive blue 262; Reactive blue 263; and Reactive blue 172. The dyes are listed according to Colour Index (Society of Dyers and
Colou sts/American Association of Textile Chemists and Colorists) classification.
Experimental
Example 1
An aqueous liquid laundry detergent was prepared of the following formulation:
Figure imgf000019_0001
The formulation was used to wash eight 5x5cm EMPA 1 17 stain monitor
(blood/milk/ink stain on polycotton) in a tergotometer set at 200rpm. A 20 minute wash was conducted in 800ml of 26° French Hard water at 35°C, with 2.3g/L of the formulation. To simulate oily soil (6.7 g) of an SBL2004 soil strip (ex Warwick Equest) was added to the wash liquor.
Once the wash had been completed the cotton monitors were rinsed once in 400ml clean water, removed dried and the colour measured on a reflectometer and expressed as the CIE L*a*b* values. Equivalent Formulations but with the addition of 8.7wt% an alkoxylated tri aryl phenol: polyethylene glycol mono(2,4,6-tris(1 -phenylethyl)phenyl) ether with different levels of ethoxylation (16 and 54EO). Experiments were repeated with and without the addition of a subtilisin serine protease ((EC no. 232-752-2) to the wash liquor. (Alcalase® ex Novozymes). The enzyme was added to give 0.0043wt% pure active protein to the formulation.
95% confidence limits are also given calculated from the standard deviation on the measurements from the 8 monitors.
Figure imgf000020_0001
Inclusion of the protease and the alkoxylated aryl phenol to the formulation increases the stain removal as seen by higher L* values. The best stain removal is seen with the combination of protease and the alkoxylated aryl phenol.

Claims

1 . A laundry detergent composition comprising:
(i) from 5 to 50 wt% of a surfactant, other than an alkoxylated di or tri aryl phenol dispersant, selected from: anionic and non-ionic surfactants, wherein the weight fraction of non-ionic surfactant/anionic surfactant is from 0 to 0.3;
(ii) from 0.5 to 20 wt% of an alkoxylated di or tri aryl phenol dispersant; and,
(iii) from 0.0005 to 0.2 wt% of a protease enzyme.
2. A laundry detergent composition according to claim 1 , wherein the anionic
surfactant is selected from: linear alkyi benzene sulphonates; alkyi sulphates; alkyi ether sulphates; and mixtures thereof, and the non-ionic surfactant selected from: alkyi ethers with 7 to 9 ethoxy groups.
3. A laundry detergent composition according to claim 1 or 2, wherein the
protease is a serine protease.
4. A laundry detergent composition according to claim 3, wherein the protease is a subtilase type serine protease.
5. A laundry detergent composition according to claim 3 or 4, wherein the
protease is present from 0.002 to 0.02 wt%.
6. A laundry detergent composition according to any preceding claim, wherein the composition is an aqueous laundry liquid detergent.
7. A laundry detergent composition according to any preceding claim, wherein the alkoxylated di or tri aryl phenol dispersant is uncharged and the alkoxylation is ethoxylation.
8. A laundry detergent composition according to any preceding claim, wherein the alkoxylated di or tri aryl phenol dispersant is of the structure:
Figure imgf000022_0001
wherein R-i, is selected from H and styryl groups, X is selected from ethoxy or propoxy groups; n is from 6 to 70, T is selected from H, SO3"; COO" and PO32".
A laundry detergent composition according to any preceding claim, wherein the anionic and non-ionic surfactants is/are present in the range from 8 to 20 wt%.
A laundry detergent composition according to any preceding claim, wherein the weight fraction of non-ionic surfactant/anionic surfactant is from 0.05 to 0.12.
A laundry detergent composition according to any preceding claim, wherein the alkoxylated di or tri aryl phenol dispersant is present in the range 1 .5 to 10 wt%.
A domestic method of treating a textile, the method comprising the steps of:
(i) treating a textile with from 1 g/L of an aqueous solution of the laundry
detergent composition as defined in any one of the preceding claims; and,
(ii) allowing said aqueous laundry detergent solution to remain in contact with the textile for 10 minutes to 2 days then rinsing and drying the textile.
PCT/EP2016/059313 2015-06-02 2016-04-26 Laundry detergent composition WO2016192905A1 (en)

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