WO2015065809A1 - Stable non-aqueous liquid compositions comprising a cationic polymer in particulate form - Google Patents

Stable non-aqueous liquid compositions comprising a cationic polymer in particulate form Download PDF

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Publication number
WO2015065809A1
WO2015065809A1 PCT/US2014/061992 US2014061992W WO2015065809A1 WO 2015065809 A1 WO2015065809 A1 WO 2015065809A1 US 2014061992 W US2014061992 W US 2014061992W WO 2015065809 A1 WO2015065809 A1 WO 2015065809A1
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Prior art keywords
aqueous liquid
alkyl
liquid composition
cationic polymer
composition according
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PCT/US2014/061992
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French (fr)
Inventor
Anne OBERLIN
Jorg THEUERKAUF
Samuel November
Karel Jozef Maria Depoot
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Dow Global Technologies Llc
Rohm And Haas Company
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Publication of WO2015065809A1 publication Critical patent/WO2015065809A1/en

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004Non aqueous liquid compositions comprising insoluble particles
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707Polyethers, e.g. polyalkyleneoxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines or polyalkyleneimines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • the present invention relates to stable non-aqueous liquid compositions that deliver good fabric care benefit.
  • the invention also relates to a process for stably suspending cationic polymers in non-aqueous liquid compositions.
  • Cationic polymers are known in the Art for providing improved fabric care, particularly softness and better fabric feel. Therefore, there is a desire to add these polymers to liquid compositions, including compact compositions, and unit dose liquid laundry articles.
  • WO 2007/107215 discloses a process whereby, a cationic cellulosic polymer is initially dissolved in water and optionally, a solvent.
  • cationic polymers can complex with the encapsulating water-soluble or dispersible film, which are generally anionically charged. This leads to reduced film solubility.
  • WO2011/163371 discloses non-aqueous liquid compositions comprising a cationic polymer in particulate form, for unit dose articles and other uses.
  • a non-aqueous liquid composition comprising: a cationic polymer in particulate form; and polypropylene glycol.
  • the present invention also provides for a process for preparing the non-aqueous liquid composition, characterized in that the process comprises the steps of: providing a cationic polymer dispersion by combining the cationic polymer with the polypropylene glycol; and combining the cationic polymer dispersion with a non-aqueous liquid feed.
  • the present invention solves the problem of providing dispersions of particulate cationic polymers which have improved stability, in addition to improved compatibility with water-soluble or dispersible films.
  • Polypropylene glycol in the non-aqueous composition has surprisingly been found to improve the stability of the cationic polymer in particulate form, in the non-aqueous composition.
  • the polypropylene glycol improves the distribution of the cationic polymer particles in the nonaqueous composition, and inhibits cakes or clumps from forming.
  • polypropylene glycol to disperse the cationic polymer particles, highly viscous polymer premixes are avoided.
  • a further consequence is that, since the cationic polymer particles remain well suspended and less swollen, they are easier to process and dose.
  • Flowable refers to a liquid having a viscosity of less than 3000 mPa*s at 20°C, and a shear rate of 20 s "1 .
  • the viscosity is in the range of from 100 to 2000 mPa*s, more preferably from 500 to 1500 mPa*s, at 20 °C at a shear rate of 20 s "1 .
  • Non-aqueous liquid compositions are:
  • non-aqueous liquid composition refers to any liquid composition comprising less than 20 %, preferably less than 15 %, more preferably less than 12 %, most preferably less than 8% by weight of water. For instance, containing no additional water beyond what is entrained with other constituent ingredients.
  • liquid also includes viscous forms such as gels and pastes.
  • the non-aqueous liquid may include other solids or gases in suitably subdivided form, but excludes forms which are non-liquid overall, such as tablets or granules.
  • the non-aqueous composition of the present invention may also comprise from 2% to 40 %, more preferably from 5 % to 25 % by weight of additional non-aqueous solvents.
  • additional non-aqueous solvent refers to any organic solvent which contains no amino functional groups, not including polypropylene glycol.
  • Preferred additional non-aqueous solvents include monohydric alcohols; dihydric alcohols;
  • polyhydric alcohols polyhydric alcohols; glycerol; glycols including dipropylene glycol, and polyalkylene glycols such as polyethylene glycol, with the exception of polypropylene glycol; and mixtures thereof.
  • More preferred additional non-aqueous solvents include monohydric alcohols, dihydric alcohols, polyhydric alcohols, glycerol, and mixtures thereof. Highly preferred are mixtures of such solvents, especially mixtures of two or more of the following: lower aliphatic alcohols such as ethanol, propanol, butanol, isopropanol; diols such as 1,2-propanediol or 1,3 -propanediol; and glycerol.
  • non-aqueous liquid compositions of the present invention may include embodiments in which propanediols are used but methanol and ethanol are not used.
  • additional non-aqueous solvents are liquid at ambient temperature and pressure (i.e. 21°C and 1 atmosphere), and comprise carbon, hydrogen and oxygen. Additional non-aqueous solvents may be present when preparing a premix, or in the final non-aqueous composition.
  • the non-aqueous liquid compositions of the present invention may comprise from 0.01 % to 30 %, preferably from 0.05 % to 25 %, more preferably from 0.1 % to 10 % by weight of the cationic polymer in particulate form. That is, the cationic polymer is insoluble in the non-aqueous liquid composition, or does not fully dissolve in the non-aqueous liquid composition.
  • the cationic polymer has a solubility of less than 50wt%, preferably less than 25wt%, more preferably less than 15wt%, even more preferably less than 10wt% most preferably less than 5wt% in the nonaqueous liquid composition, when added at the desired level, at a temperature of 20°C.
  • the cationic polymer particles preferably have a volume based D90 diameter of less than 300 microns, preferably less than 200 microns, more preferably less than 150 microns.
  • the volume based D90 diameter is defined as 90% of the particles having a volume smaller than the volume of a sphere having the diameter D90.
  • the method for measuring the particle size is given in the Test Methods.
  • the cationic polymer particles are preferably as small as possible. Having smaller particles result in faster dissolution, particularly at lower temperatures, making such particles particularly suitable for providing fabric care benefit during low temperature fabric treatments.
  • Suitable particulate forms include solids that are completely free of water and/or other solvent, but also includes solids that are partially hydrated and/or solvated.
  • the cationic polymer preferably has a cationic charge density of from 0.005 to 23, more preferably from 0.01 to 12, most preferably from 0.1 to 7 milliequivalents/g, at the pH of the non-aqueous liquid composition.
  • the charge density is calculated by dividing the number of net charges per repeating unit by the molecular weight of the repeating unit.
  • the positive charges could be located on the backbone of the polymer and/or the side chains of polymer.
  • cationic polymer also includes amphoteric polymers that have a net cationic charge at the pH of the non-aqueous composition.
  • suitable cationic polymers are polysaccharides, proteins and synthetic polymers.
  • Cationic polysaccharides include cationic cellulose derivatives, cationic guar gum derivatives, chitosan and derivatives, and cationic starches.
  • Suitable cationic polysaccharides include cationically modified cellulose, particularly cationic hydroxyethylcellulose and cationic hydroxypropylcellulose.
  • Preferred cationic celluloses for use herein include those which may or may not be hydrophobically-modified, including those having hydrophobic substituent groups, having a molecular weight of from 50,000 to 2,000,000, more preferably from 100,000 to 1,000,000, and most preferably from 200,000 to 800,000.
  • Preferred hydrophobic substituent groups are alkyl substitutions. Alkyl substitution on the anhydroglucose rings of the polymer may range from 0.01% to 10% per glucose unit, preferably from 0.03% to 5%, more preferably from 0.05% to 2% per glucose unit, of the polymeric material.
  • n is an integer from 20 to 10,000
  • R 4 is H, and R 1 , R 2 , R 3 are each independently selected from the group consisting of: H; Ci- C 32 alkyl; Ci-C 32 substituted alkyl, C5-C 32 or C6-C 32 aryl, C5-C 32 or C6-C 32 substituted aryl or C6-Q
  • R 1 , R 2 , R 3 are each independently selected from the group consisting of: H,
  • n is an integer selected from 0 to 10 and
  • Rx is selected from the group consisting of:
  • a " is a suitable anion.
  • a " is selected from the group consisting of: CI “ , Br “ , ⁇ , methylsulfate, ethylsulfate, toluene sulfonate, carboxylate, and phosphate;
  • each R 5 is independently selected from the group consisting of: H; Ci-C 32 alkyl; Ci-C 32 substituted alkyl, C5-C32 or C6-C 32 aryl, C5-C32 or C6-C 32 substituted aryl, C6-C 32 alkylaryl, C6-C 32 substituted alkylaryl, and OH.
  • each R 5 is selected from the group consisting of: H, Ci-C 32 alkyl, and Ci-C 32 substituted alkyl. More preferably, R 5 is selected from the group consisting of H, methyl, and ethyl.
  • Each R 6 is independently selected from the group consisting of: H, Ci-C 32 alkyl, Ci-C 32 substituted alkyl, Cs-C 32 or C6-C 32 aryl, Cs-C 32 or C6-C 32 substituted aryl, C6-C 32 alkylaryl, and Ce- C 32 substituted alkylaryl.
  • each R 6 is selected from the group consisting of: H, Ci-C 32 alkyl, and Ci-C 32 substituted alkyl.
  • Each T is independently selected from the group: H, v
  • each v in said polysaccharide is an integer from 1 to 10.
  • v is an integer from 1 to 5.
  • the sum of all v indices in each Rx in said polysaccharide is an integer from 1 to 30, more
  • the cationic cellulose may be lightly cross-linked with a dialdehyde, such as glyoxyl, to prevent forming lumps, nodules or other agglomerations when added to water at ambient temperatures.
  • a dialdehyde such as glyoxyl
  • the cationic cellulose ethers of Structural Formula I likewise include those which are commercially available and further include materials which can be prepared by conventional chemical modification of commercially available materials.
  • Commercially available cellulose ethers of the Structural Formula I type include those with the UNO name Polyquaternium 10, such as those sold under the trade names: UCARE Polymer JR 30M, JR 400, JR 125, LR 400 and LK 400 polymers; Polyquaternium 67 such as those sold under the trade name Softcat SKTM, all of which are marketed by The Dow Chemical Company, Midland, Michigan; and Polyquaternium 4 such as those sold under the trade name: Celquat H200 and Celquat L-200, available from National Starch and Chemical Company, Bridgewater, NJ.
  • polysaccharides include hydroxyethyl cellulose or hydoxypropylcellulose quaternized with glycidyl Ci 2 -C 2 2 alkyl dimethyl ammonium chloride.
  • suitable polysaccharides include the polymers with the INCI names
  • Polyquaternium 24 such as those sold under the trade name QUATRISOFT polymer LM- 200 by Amerchol Corporation, Edison, New Jersey . Cationic starches described by D. B. Solarek in Modified Starches, Properties and Uses published by CRC Press (1986) and in U.S. Pat. No.
  • Suitable cationic galactomannans include cationic guar gums or cationic locust bean gum.
  • An example of a cationic guar gum is a quaternary ammonium derivative of Hydroxypropyl Guar such as those sold under the trade name: Jaguar C13 and Jaguar Excel available from Rhodia, Inc of Cranbury NJ and N-Hance by Aqualon, Wilmington, DE.
  • a synthetic cationic polymer may also be useful as the cationic polymer.
  • Synthetic polymers include synthetic addition polymers of the general structure:
  • each R 1 may be independently: hydrogen, C 1 -C 12 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, -OR a> or -C(0)OR a wherein R a may be selected from the group consisting of: hydrogen, C 1 -C24 alkyl, and combinations thereof.
  • R 1 is preferably: hydrogen, C 1 -C 4 alkyl, or -OR a, or - C(0)OR a ;
  • each R 2 may be independently selected from the group consisting of: hydrogen, hydroxyl, halogen, C 1 -C 12 alkyl, -OR a> substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic, heterocyclic, and combinations thereof.
  • R 2 is preferably selected from the group consisting of: hydrogen, C 1 -C 4 alkyl, and combinations thereof.
  • Each Z may be independently: hydrogen, halogen; linear or branched Ci-C 30 alkyl, nitrilo, N(R 3 ) 2 - C(0)N(R 3 ) 2 ; -NHCHO (formamide); -OR 3 , -0(CH 2 ) n N(R 3 ) 2 , -0(CH 2 ) n N + (R 3 ) 3 X - C(0)OR 4 ; - C(0)N-(R 3 ) 2; -C(0)0(CH 2 ) n N(R 3 ) 2 , -C(0)0(CH 2 ) n N + (R 3 ) 3 X ⁇ -OCO(CH 2 ) n N(R 3 ) 2 , -
  • R 3 may be independently selected from the group consisting of: hydrogen, C 1 -C24 alkyl, C 2 -C 8 hydroxyalkyl, benzyl, substituted benzyl, and combinations thereof;
  • X may be a water soluble anion
  • n may be from 1 to 6.
  • R 5 may be independently selected from the group consisting of: hydrogen, C 1 -C6 alkyl, and combinations thereof.
  • Z from Structural Formula ⁇ , may also be selected from the group consisting of: non- aromatic nitrogen heterocycles containing a quaternary ammonium ion, heterocycles containing an N-oxide moiety, aromatic nitrogens containing heterocycles wherein one or more or the nitrogen atoms may be quaternized; aromatic nitrogen-containing heterocycles wherein at least one nitrogen may be an N-oxide, and combinations thereof.
  • Non-limiting examples of addition polymerizing monomers comprising a heterocyclic Z unit includes l-vinyl-2-pyrrolidinone, 1-vinylimidazole, quaternized vinyl imidazole, 2-vinyl-l,3-dioxolane, 4-vinyl-l-cyclohexenel,2-epoxide, and 2- vinylpyridine, 2-vinylpyridine N-oxide, 4-vinylpyridine 4-vinylpyridine N-oxide.
  • a non-limiting example of a Z unit which can be made to form a cationic charge in situ may be the -NHCHO unit, formamide.
  • the formulator can prepare a polymer, or co-polymer, comprising formamide units some of which are subsequently hydrolyzed to form vinyl amine equivalents.
  • the polymers or co-polymers may also contain one or more cyclic polymer units derived from cyclically polymerizing monomers.
  • An example of a cyclically polymerizing monomer is dimethyl diallyl ammonium having the formula:
  • Suitable copolymers may be made from one or more cationic monomers selected from the group consisting of ⁇ , ⁇ -dialkylaminoalkyl methacrylate, ⁇ , ⁇ -dialkylaminoalkyl acrylate, N,N- dialkylaminoalkyl acrylamide, ⁇ , ⁇ -dialkylaminoalkylmethacrylamide , quaternized N,N- dialkylaminoalkyl methacrylate, quaternized ⁇ , ⁇ -dialkylaminoalkyl acrylate, quaternized N,N- dialkylaminoalkyl acrylamide, quaternized ⁇ , ⁇ -dialkylaminoalkylmethacrylamide, vinylamine and its derivatives, allylamine and its derivatives, vinyl imidazole, quaternized vinyl imidazole and diallyl dialkyl ammonium chloride and combinations thereof, and optionally a second monomer selected from the group consisting of acrylamide, ⁇ , ⁇ -dialkyl
  • the synthetic polymers are: poly(acrylamide-co- diallyldimethylammonium chloride), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride), poly(acrylamide-co-N,N-dimethyl aminoethyl methacrylate), poly(acrylamide-co-N,N- dimethyl aminoethyl methacrylate), poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co-dimethyl aminoethyl methacrylate),
  • suitable synthetic polymers are Polyquaternium-1, Polyquaternium-5, Polyquaternium-6, Polyquaternium-7, Polyquaternium-8, Polyquaternium-l l, Polyquaternium-14, Polyquaternium-22, Polyquaternium-28, Polyquaternium-30, Polyquaternium-32 and Polyquaternium-33.
  • Other cationic polymers include polyethyleneamine and its derivatives and polyamidoamine-epichlorohydrin (PAE) Resins.
  • the polyethylene derivative may be an amide derivative of polyetheylenimine sold under the trade name Lupasol SK. Also included are alkoxylated polyethylenimine; alkyl polyethyleneimine and quaternized polyethyleneimine. These polymers are described in Wet Strength resins and their applications edited by L. L. Chan, TAPPI Press (1994).
  • the weight-average molecular weight of the polymer will generally be from 10,000 to 5,000,000, or from 100,000 to 200,000, or from 200,000 to 1,500,000 Dal tons, as determined by size exclusion chromatography relative to polyethylene oxide standards with RI detection.
  • the mobile phase used is a solution of 20% methanol in 0.4M MEA, 0.1 M NaN0 3 , 3% acetic acid on a Waters Linear Ultrahdyrogel column, 2 in series.
  • the non-aqueous composition of the present invention comprises polypropylene glycol.
  • the non-aqueous liquid composition may comprise from 0.05 % to 98 %, preferably from 0.5 % to 75 %, more preferably from 3 % to 68 % by weight of polypropylene glycol.
  • polypropylene glycol greatly improves the physical stability of the cationic polymer particulates in the non-aqueous composition. It is believed that the polypropylene glycol inhibits the agglomeration of the cationic polymer particles, by limiting the solvation, and hence swelling of the particles.
  • the particles are less swollen, they are less visible, even when they deposit on a water-soluble film which is used to form a unit-dose article. Furthermore, even when they do deposit on such water-soluble films, they are less able to interact with the water-soluble film, since they are less solvated. As a result, there is less impact on the dissolution of the water- soluble film, such as during a wash cycle.
  • the polypropylene glycol has a molecular weight of from 208 g/mol to 4000 g/mol, more preferably from 208 g/mol to 2000 g/mol, even more preferably from 250 g/mol to 700 g/mol.
  • Suitable spacer particles may have an volume based D90 diameter of less than 5 microns, preferably from 0.1 microns to 1 micron.
  • the spacer particles may be polymeric or non-polymeric. Suitable non-polymeric spacer particles include mica. Suitable polymeric spacer particles include those comprising a polymer and/or a copolymer. Preferably, the spacer particles are anionically charged, such as those comprising a polyacrylate polymer or copolymer. It is believed that the anionic charge attracts the spacer particle to the cationic polymer particles.
  • the non-aqueous composition of the present invention may comprise from 0.1 % to 30 %, preferably from 0.5 percent to 15 % by weight of the spacer particles.
  • any present agglomerates of the cationic polymer particles may also be weakened by the presence of soluble cations and/or polyvalent anions. While polyvalent cations, particularly those having the charges derived from different charged groups are preferred, even monovalent cations have been shown to provide a benefit. It is believed that the cations form bilayers that are able to reduce the attraction between the cationic polymer particles.
  • Suitable single species polyvalent cations include the cations of magnesium and calcium.
  • Suitable cationic surfactants are preferably water-soluble, but can also be water-dispersible or water-insoluble. Such cationic surfactants have at least one quaternized nitrogen and at least one long-chain hydrocarbyl group. Compounds comprising two, three or even four long-chain hydrocarbyl groups are also included. Examples include
  • alkyltrimethylammonium salts such as C12 alkyltrimethylammonium chloride, or their hydroxyalkyl substituted analogues.
  • the present invention may comprise from 1% or more by weight of the cationic surfactant.
  • Amphoteric surfactants particularly those that have a net cationic charge at the pH of the non-aqueous composition, are also useful cations for the present invention.
  • Suitable polyvalent anions include: Citric Acid; Diethylene triamine pentaacetic acid (DTP A); 1- hydroxyethane 1,1-diphosphonic acid (HEDP); Maleic acid; Polyacrylates; Polyacrylic/maleic acid copolymers; succinic acid, and mixtures thereof.
  • the non-aqueous composition may comprise from 0.1 % to 30 %, preferably from 0.5 to 15 % by weight of the cation and/or polyvalent anion.
  • the non-aqueous liquid compositions of the present invention may include conventional laundry detergent ingredients selected from the group consisting of: anionic and nonionic surfactants; additional surfactants; enzymes; enzyme stabilizers; cleaning polymers, including: amphiphilic alkoxylated grease cleaning polymers, clay soil cleaning polymers, soil release polymers, and soil suspending polymers; bleaching systems; optical brighteners; hueing dyes; particulate material; perfume and other odour control agents; hydrotropes; suds suppressors; fabric care benefit agents; pH adjusting agents; dye transfer inhibiting agents; preservatives; non-fabric substantive dyes and mixtures thereof.
  • cleaning polymers including: amphiphilic alkoxylated grease cleaning polymers, clay soil cleaning polymers, soil release polymers, and soil suspending polymers; bleaching systems; optical brighteners; hueing dyes; particulate material; perfume and other odour control agents; hydrotropes; suds suppressors; fabric care benefit agents; pH adjusting agents; dye transfer inhibiting
  • Non-aqueous liquid compositions of the present invention may comprise from 1 % to 70%, preferably from 10% to 50%, and more preferably from 15% to 45% by weight of an anionic and/or nonionic surfactant.
  • the non-aqueous liquid compositions of the present invention preferably comprise from 1 to 70 %, more preferably from 5 to 50 % by weight of one or more anionic surfactants.
  • Preferred anionic surfactant are selected from the group consisting of: CI 1 -CI 8 alkyl benzene sulfonates, C10-C20 branched-chain and random alkyl sulfates, C10-C18 alkyl ethoxy sulfates, mid-chain branched alkyl sulfates, mid-chain branched alkyl alkoxy sulfates, C10-C18 alkyl alkoxy carboxylates comprising 1-5 ethoxy units, modified alkylbenzene sulfonate, C12-C20 methyl ester sulfonate, C10-C18 alpha-olefin sulfonate, C6-C20 sulfosuccinates, fatty acids, and mixtures thereof.
  • compositions of the present invention preferably comprise at least one sulphonic acid surfactant, such as a linear alkyl benzene sulphonic acid, or the water- soluble salt forms.
  • Anionic sulfonate or sulfonic acid surfactants suitable for use herein include the acid and salt forms of linear or branched C5-C20, more preferably C10-C16, most preferably CI 1-C13 alkylbenzene sulfonates, C5-C20 alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C5-C20 sulfonated polycarboxylic acids, and mixtures thereof.
  • the aforementioned surfactants can vary widely in their 2-phenyl isomer content.
  • Anionic sulphate salts suitable for use in compositions of the invention include: primary and secondary alkyl sulphates, having a linear or branched alkyl or alkenyl moiety having from 9 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms; beta-branched alkyl sulphate surfactants; and mixtures thereof.
  • Mid-chain branched alkyl sulphates or sulfonates are also suitable anionic surfactants for use in the compositions of the invention.
  • Preferred are the C5-C22, preferably C10-C20 mid-chain branched alkyl primary sulphates.
  • a suitable average total number of carbon atoms for the alkyl moieties is preferably within the range of from 14.5 to 17.5.
  • Preferred mono-methyl-branched primary alkyl sulphates are selected from the group consisting of the 3-methyl to 13-methyl pentadecanol sulphates, the corresponding hexadecanol sulphates, and mixtures thereof. Dimethyl derivatives or other biodegradable alkyl sulphates having light branching can similarly be used.
  • Other suitable anionic surfactants for use herein include fatty methyl ester sulphonates and/or alkyl ethoxy sulphates (AES) and/or alkyl polyalkoxylated carboxylates (AEC).
  • Any fatty acid is suitable for use herein, including but not limited to lauric, myristic, palmitic stearic, oleic, linoleic, linolenic acid, and mixtures thereof.
  • the fatty acid is preferably selected from those which are flowable at less than 30°C.
  • Naturally obtainable fatty acids which are usually complex mixtures, are also suitable (such as tallow, coconut, and palm kernel fatty acids).
  • a preferred fatty acid is palm kernel fatty acid.
  • such fatty acids provide a builder benefit, and after neutralization, a detergency benefit.
  • the amount of fatty acid can be in the range of from 0.1% to 30%, preferably from 1% to 20%, more preferably from 3 to 15%, by weight of the composition.
  • anionic surfactants can be used, for example mixtures of
  • alkylbenzenesulphonates and AES.
  • the anionic surfactants are typically present in the form of their salts with alkanolamines or alkali metals such as sodium and potassium.
  • the anionic surfactants are neutralized with alkanolamines, such as monoethanolamine or triethanolamine, and are fully soluble in the nonaqueous liquid composition.
  • the non-aqueous liquid compositions of the present invention may include from 1 to 70 %, preferably from 5 to 50 % by weight of a nonionic surfactant.
  • Suitable nonionic surfactants include, but are not limited to C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates, C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed
  • Alkylpolysaccharides such as disclosed in U.S. Pat. 4,565,647 are also useful nonionic surfactants for compositions of the invention.
  • alkyl polyglucoside surfactants are also useful nonionic surfactants for compositions of the invention.
  • suitable nonionic surfactants include those of the formula Rl(OC 2 H 4 ) n OH, wherein Rl is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to 80.
  • the nonionic surfactants may be condensation products of C12-C15 alcohols with from 5 to 20 moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol condensed with 6.5 moles of ethylene oxide per mole of alcohol.
  • Additional suitable nonionic surfactants include polyhydroxy fatty acid amides of the formula: wherein R is a C9-C17 alkyl or alkenyl, Rl is a methyl group and Z is glycidyl derived from a reduced sugar or alkoxylated derivative thereof. Examples are N-methyl N-l-deoxyglucityl cocoamide and N-methyl N-l-deoxyglucityl oleamide.
  • the non-aqueous liquid compositions of the present invention may comprise additional surfactant selected from the group consisting: anionic, cationic, nonionic, amphoteric and/or zwitterionic surfactants and mixtures thereof.
  • Amphoteric detersive surfactants suitable for use in the composition include those surfactants broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic group such as carboxy, sulphonate, sulphate, phosphate, or phosphonate.
  • Suitable amphoteric detersive surfactants for use in the present invention include, but are not limited to: cocoamphoacetate, cocoamphodiacetate,
  • Zwitterionic detersive surfactants suitable for use in non-aqueous liquid compositions are well known in the art, and include those surfactants broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulphonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic group such as carboxy, sulfonate, sulphate, phosphate or phosphonate. Zwitterionics such as betaines are also suitable for this invention.
  • amine oxide surfactants having the formula: R(EO) x (PO) y (BO) z N(0)(CH 2 R') 2 .qH20 are also useful in compositions of the present invention.
  • R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is more preferably C12-C16 primary alkyl.
  • R' is a short-chain moiety preferably selected from hydrogen, methyl and -CH 2 OH.
  • EO is ethyleneoxy
  • PO propyleneneoxy
  • BO is butyleneoxy.
  • Amine oxide surfactants are illustrated by C12-C14 alkyldimethyl amine oxide.
  • Non-limiting examples of other anionic, zwitterionic, amphoteric or optional additional surfactants suitable for use in the compositions are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co., and U.S. Pat. Nos. 3,929,678, 2,658,072; 2,438,091 ; 2,528,378.
  • the non-aqueous liquid compositions of the present invention may comprise from 0.0001 % to 8 % by weight of a detersive enzyme which provides cleaning performance and/or fabric care benefits. Such compositions preferably have a composition pH of from 6 to 10.5.
  • Suitable enzymes can be selected from the group consisting of: lipase, protease, amylase, cellulase, mannanase, pectate lyase, xyloglucanase, and mixtures thereof.
  • a preferred enzyme combination comprises a cocktail of conventional detersive enzymes such as lipase, protease, cellulase and amylase. Detersive enzymes are described in greater detail in U.S. Patent No. 6,579,839.
  • Enzyme Stabilizers Enzymes can be stabilized using any known stabilizer system such as calcium and/or magnesium compounds, boron compounds and substituted boric acids, aromatic borate esters, peptides and peptide derivatives, polyols, low molecular weight carboxylates, relatively hydrophobic organic compounds [e.g.
  • esters dialkyl glycol ethers, alcohols or alcohol alkoxylates], alkyl ether carboxylate in addition to a calcium ion source, benzamidine hypochlorite, lower aliphatic alcohols and carboxylic acids, N,N-bis(carboxymethyl) serine salts, (meth)acrylic acid-(meth)acrylic acid ester copolymer and PEG; lignin compound, polyamide oligomer, glycolic acid or its salts, poly hexamethylene biguanide or N,N-bis-3-amino-propyl- dodecyl amine or salt, sorbitol, and mixtures thereof.
  • the non-aqueous composition may comprise from 1 % to 15 %, more preferably from 2 % to 7 %, by weight of a fabric care benefit agent.
  • Fabric care benefit agent refers to any material that can provide fabric care benefits.
  • Non-limiting examples of fabric care benefits include, but are not limited to: fabric softening, colour protection, colour restoration, pill/fuzz reduction, anti-abrasion and anti- wrinkling.
  • Non-limiting examples of fabric care benefit agents include: silicone derivatives, such as polydimethylsiloxane and amino- functional silicones; oily sugar derivatives; dispersible poly olefins; polymer latexes; cationic surfactants and combinations thereof.
  • the non-aqueous liquid compositions herein may contain from 0.01 % to 20 %, preferably from 0.05 % to 15 %, more preferably from 0.1 % to 10 % by weight of cleaning polymers, that provide for broad-range soil cleaning of surfaces and fabrics. Any suitable cleaning polymer may be of use.
  • Useful cleaning polymers are described in US 2009/0124528A1.
  • Non-limiting examples of useful categories of cleaning polymers include: amphiphilic alkoxylated grease cleaning polymers; clay soil cleaning polymers; soil release polymers; and soil suspending polymers.
  • Other anionic polymers, useful for improving soil cleaning include: non-silicone- containing polymers of natural origin, but also of synthetic origin.
  • Suitable anionic non-silicone- containing polymers may be selected from the group consisting of xanthan gum, anionic starch, carboxymethyl guar, carboxymethyl hydroxypropyl guar, carboxy methyl cellulose and ester modified carboxymethyl cellulose, N-carboxyalkyl chitosan, N-carboxyalkyl chitosan amides, pectin, carrageenan gum, chondroitin sulfate, galactomanans, hyaluronic acid-, and alginic acid- based polymers, and derivatives thereof and mixtures thereof.
  • the anionic non- silicone-containing polymer maybe selected from carboxymethyl guar, carboxymethyl hydroxypropyl guar, carboxymethyl cellulose and xanthan gum, and derivatives and mixtures thereof.
  • Preferred anionic non-silicone-containing polymers include those commercially available from CPKelco, sold under the tradename of Kelzan® RD and from Aqualon, sold under the tradename of Galactosol® SP722S, Galactosol® 60H3FD, and Galactosol® 70H4FD.
  • Optical brighteners These are also known as fluorescent whitening agents for textiles. Preferred levels are from 0.001 % to 2 % by weight of the non-aqueous liquid composition. Suitable brighteners are disclosed in EP 68669 IB and include hydrophobic as well as hydrophilic types. Brightener 49 is preferred for use in the present invention.
  • Hueing dyes or fabric shading dyes are useful laundering adjuncts in nonaqueous liquid compositions. Suitable dyes include blue and/or violet dyes having a hueing or shading effect. See, for example, WO 2009/087524 Al , WO2009/087034A1 and references therein. Recent developments that are suitable for the present invention include sulfonated phthalocyanine dyes having a zinc or aluminium central atom.
  • the non-aqueous liquid compositions herein may comprise from 0.00003 % to 0.1 %, preferably from 0.00008 % to 0.05 % by weight of the fabric hueing dye.
  • the non-aqueous composition may include additional particulate material such as clays, suds suppressors, encapsulated oxidation-sensitive and/or thermally sensitive ingredients such as perfumes (perfume microcapsules), bleaches and enzymes; or aesthetic adjuncts such as pearlescent agents including mica, pigment particles, or the like. Suitable levels are from 0.0001 % to 10 %, or from 0.1 % to 5 % by weight of the non-aqueous composition.
  • the non-aqueous composition comprises a free and/or micro-encapsulated perfume. If present, the free perfume is typically incorporated at a level from 0.001 % to 10 %, preferably from 0.01 % to 5 %, more preferably from 0.1 % to 3 % by weight of the non-aqueous composition.
  • the perfume microcapsule is formed by at least partially surrounding the perfume raw materials with a wall material.
  • the microcapsule wall material comprises: melamine crosslinked with formaldehyde, polyurea, urea crosslinked with formaldehyde or urea crosslinked with gluteraldehyde.
  • Suitable perfume microcapsules and perfume nanocapsules include those described in the following references: US 2003215417 Al ; US 2003216488 Al ; US 2003158344 Al ; US 2003165692 Al ; US 2004071742 Al; US 2004071746 Al; US 2004072719 Al ; US 2004072720 Al; EP 1393706 Al ; US 2003203829 Al ; US 2003195133 Al ; US 2004087477 Al; US 20040106536 Al ; US 6645479; US 6200949; US 4882220; US 4917920; US 4514461 ; US RE 32713; US 4234627.
  • the non-aqueous composition comprises odour control agents such as uncomplexed cyclodextrin, as described in US 5,942,217.
  • odour control agents such as uncomplexed cyclodextrin, as described in US 5,942,217.
  • suitable odour control agents include those described in: US 5,968,404, US 5,955,093, US 6,106,738, US 5,942,217, and US 6,033,679.
  • Hydrotropes The non-aqueous liquid composition of the present invention typically comprises a hydrotrope in an effective amount, preferably up to 15%, more preferably from 1 % to 10 %, most preferably from 3 % to 6 % by weight, so that the compositions are readily dispersed in water.
  • Suitable hydrotropes for use herein include anionic-type hydrotropes, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium and ammonium toluene sulfonate, sodium potassium and ammonium cumene sulfonate, and mixtures thereof, as disclosed in US 3,915,903.
  • the non-aqueous liquid compositions of the present invention may comprise from 0.6 % to 25 %, preferably from 1 % to 20 %, more preferably from 2 % to 7 % by weight of the multivalent water-soluble organic builder and/or chelants.
  • Water-soluble organic builders provide a wide range of benefits including sequestration of calcium and magnesium (improving cleaning in hard water), provision of alkalinity, transition metal ion complexation, metal oxide colloid stabilisation, and provision of substantial surface charge for peptisation and suspension of other soils.
  • Chelants may selectively bind transition metals (such as iron, copper and manganese) which impact stain removal and the stability of bleach ingredients, such as organic bleach catalysts, in the wash solution.
  • the multivalent water-soluble organic builder and/or chelants of the present invention are selected from the group consisting of: MEA citrate, citric acid, aminoalkylenepoly(alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates, and nitrilotrimethylene, phosphonates, diethylene triamine penta (methylene phosphonic acid) (DTPMP), ethylene diamine tetra(methylene phosphonic acid) (DDTMP), hexamethylene diamine tetra(methylene phosphonic acid), hydroxy- ethylene 1,1 diphosphonic acid (HEDP), hydroxyethane dimethylene phosphonic acid, ethylene diamine di-succinic acid (EDDS), ethylene diamine tetraacetic acid (EDTA),
  • DTPMP di
  • HEDTA hydroxyethylethylenediamine triacetate
  • NTA nitrilotriacetate
  • MGDA methylglycinediacetate
  • IDS iminodisuccinate
  • HIDS hydroxyethyliminodisuccinate
  • HEIDA hydroxyethyliminodiacetate
  • GLDA glycine diacetate
  • DTP A diethylene triamine pentaacetic acid
  • External structuring system The physical stability of the cationic polymer particulates in the non-aqueous liquid composition can be further improved if the non-aqueous liquid composition also comprises an external structurant.
  • An external structuring system is a compound or mixture of compounds which provide either a sufficient yield stress or low shear viscosity to stabilize the nonaqueous liquid compositions independently from, or extrinsic from, the structuring effect of any detersive surfactants in the composition.
  • the non-aqueous liquid composition may comprise from 0.01 % to 10 %, preferably from 0.1 % to 4 % by weight of an external structuring system, on an active basis.
  • Suitable external structuring systems include non-polymeric crystalline, hydroxy- functional structurants, polymeric structurants, or mixtures thereof.
  • the external structurant system imparts a high shear viscosity at 20 s "1 , at 20°C, of from 1 to 3000 cps, and a viscosity at low shear (at 0.05 s "1 at 20°C) of greater than 5000 cps.
  • the viscosity is measured using an AR 550 rheometer, from TA instruments, using a plate steel spindle with a 40 mm diameter and a gap size of 1000 ⁇ .
  • the high shear viscosity at 20s "1 can be obtained from a logarithmic shear rate sweep from 0.1s "1 to 1200s "1 in 3 minutes time at 20°C.
  • the low shear viscosity is measured over a period of 3 minutes at a fixed shear rate ("Peak Hold") of 0.05 s "1 at 20°C.
  • the external structuring system may comprise a non-polymeric crystalline, hydroxyl functional structurant.
  • Such non-polymeric crystalline, hydroxyl functional structurants generally comprise a crystallisable glyceride which can be pre-emulsified to aid dispersion into the final nonaqueous composition.
  • Preferred crystallisable glycerides include hydrogenated castor oil or "HCO", and derivatives thereof, provided that it is capable of crystallizing in the non-aqueous composition.
  • suitable external structuring systems may comprise a naturally derived and/or synthetic polymeric structurant.
  • Suitable naturally derived polymeric structurants include: hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof.
  • Suitable polysaccharide derivatives include: pectine, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof.
  • suitable synthetic polymeric structurants include: polycarboxylates, polyacrylates, hydrophobically modified ethoxylated urethanes (HEUR), hydrophobically modified alkali swellable emulsions (HASE), and mixtures thereof.
  • Preferred polymeric structurants can be selected from the group consisting of:
  • HEUR hydrophobically-modified ethoxylated urethanes
  • HASE hydrophobically modified alkali swellable emulsion
  • HEUR and HASE polymeric structurants are typically used for structuring in aqueous compositions.
  • such polymers have been found to be particularly effective for suspending the cationic polymer, in particulate form, in the non-aqueous composition.
  • HEUR polymeric structurants are water-soluble polymers, having hydrophobic end-groups, comprising blocks of ethylene glycol units, propylene glycol units, and mixtures thereof, in addition to ure thane units.
  • the HEUR polymeric structurants preferably has a backbone comprising one or more polyoxyalkylene segments greater than 10 oxyalkylene units in length.
  • the HEUR polymeric structurant is preferably a hydrophobically modified polyurethane polyether comprising the reaction product of a dialkylamino alkanol with a multi-functional isocyanate, a polyether diol, and optionally a polyether triol.
  • the polyether diol has a weight average molecular weight between 2,000 and 12,000, preferably between 6,000 and 10,000
  • Preferred HEUR olymeric structurants can have the following structure:
  • R is an alkyl chain, preferably a C6-C24 alkyl chain, more preferably a C12-C18 alkyl chain, n is preferably from 25 to 400, preferably from 50 to 250, more preferably from 75 to 180, X can be any suitable linking group.
  • Suitable HEUR polymeric structurants can have a molecular weight of from 1,000 to 1,000,000, more preferably from 15,000 to 50,000 g/mol.
  • An example of a suitable HEUR polymeric structurant is ACUSOLTM 880, sold by DOW.
  • HEUR polymeric structurants thicken via an associative mechanism, wherein the hydrophobic parts of HEUR polymers build up associations with other hydrophobes present in the composition, such as the cationic polymers in particulate form.
  • HASE polymers are typically synthesized by free-radical emulsion polymerization of varying mixtures of hydrophilic monomers such as acrylic acid, methacrylic acid, or maleic anhydride, lipophilic monomers such as ethyl acrylate, butyl acrylate, or methyl methacrylate, and associative monomers such as long chain alkyl (C8 to C22) acrylates or styrenic derivatives.
  • hydrophilic monomers such as acrylic acid, methacrylic acid, or maleic anhydride
  • lipophilic monomers such as ethyl acrylate, butyl acrylate, or methyl methacrylate
  • associative monomers such as long chain alkyl (C8 to C22) acrylates or styrenic derivatives.
  • Preferred HASE polymeric structurants can have the following structure:
  • R is preferably H or an alkyl group.
  • R is preferably a C1-C6 alkyl group, more preferably a CI to C2 alkyl group.
  • R is preferably a CI alkyl group.
  • Ri is preferably H or an alkyl group.
  • R is preferably a C1-C6 alkyl group, more preferably a CI to C2 alkyl group.
  • Ri is preferably a CI alkyl group.
  • R 2 is any suitable hydrophobic group, such as a C4-C24 alkyl group, more preferably a C8-C20 alkyl group.
  • R 2 can also be alkoxylated.
  • R 2 is ethoxylated, propoxylated, and combinations thereof. More preferably R 2 is ethoxylated.
  • R 2 can be alkoxylated to a degree of from 1 to 60, preferably from 10 to 50.
  • R 3 is preferably H or an alkyl group.
  • R 3 is preferably a C1-C6 alkyl group, more preferably a CI to C3 alkyl group.
  • R 3 is preferably a C2 alkyl group.
  • the repeating units comprising R, R 1; R 2 , and R 3 can be in any suitable order, or even randomly distributed through the polymer chain.
  • Suitable HASE polymeric structurants can have a molecular weight of from 50,000 to 500,000 g/mol, preferably from 80,000 to 400,000 g/mol, more preferably from 100,000 to 300,000 g/mol.
  • the ratio of x:y can be from 1:20 to 20: 1, preferably from 1: 10 to 10: 1, more preferably from 1:5 to 5: 1.
  • the ratio of x:w can be from 1:20 to 20: 1, preferably from 1: 10 to 10: 1, more preferably from 1:5 to 5: 1.
  • the ratio of x:z can be from 1: 1 to 500: 1, preferably from 2: 1 to 250: 1, more preferably from 25 : 1 to 75 : 1.
  • HASE polymeric structurants are ACUSOLTM 801S, ACUSOLTM805S, ACUSOLTM 820, ACUSOLTM 823, sold by DOW.
  • HASE polymeric structurants are believed to structure by a combination of polyelectrolytic chain expansion and through association of the hydrophobe groups, present in the HASE polymeric structurant, with other hydrophobes present in the composition, such as the cationic polymers in particulate form.
  • the non-aqueous liquid composition can comprise further structurants, such as hydrogenated castor oil.
  • Non-aqueous liquid compositions of the present invention may be comprised in unit dose articles, having at least one liquid filled compartment.
  • a liquid-filled compartment refers to a partition of the unit dose article comprising a liquid capable of wetting a fabric e.g., clothing.
  • Such unit dose articles comprise, in single, easy to use dosage form: a cationic polymer in particulate form, stably suspended in a non-aqueous composition which further comprises polypropylene glycol, encapsulated in a water-soluble or dispersible film.
  • the unit dose article can be of any form, shape and material which is suitable for holding the non-aqueous composition, i.e. without allowing the release of the non-aqueous composition, and any additional component, from the unit dose article prior to contact of the unit dose article with water.
  • the exact execution will depend, for example, on the type and amount of the compositions in the unit dose article, the number of compartments in the unit dose article, and on the characteristics required from the unit dose article to hold, protect and deliver or release the compositions or components.
  • the unit dose article comprises a water-soluble or dispersible film which fully encloses at least one inner volume, comprising the non-aqueous composition.
  • the unit dose article may optionally comprise additional compartments comprising non-aqueous liquid and/or solid components. Alternatively, any additional solid component may be suspended in a liquid-filled compartment.
  • a multi-compartment unit dose form may be desirable for such reasons as: separating chemically incompatible ingredients; or where it is desirable for a portion of the ingredients to be released into the wash earlier or later.
  • any compartment which comprises a liquid component also comprises an air bubble.
  • the air bubble may have a volume of less than 50%, preferably less than 40%, more preferably less than 30%, more preferably less than 20%, most preferably less than 10% of the volume space of said compartment. Without being bound by theory, it is believed that the presence of the air bubble increases the tolerance of the unit dose article to the movement of the liquid component within the compartment, thus reducing the risk of the liquid component leaking from the compartment.
  • Water-soluble or dispersible film typically has a solubility of at least 50%, preferably at least 75%, more preferably at least 95%.
  • the method for determining water-solubility of the film is given in the Test Methods.
  • the water-soluble or dispersible film typically has a dissolution time of less than 100 seconds, preferably less than 85 seconds, more preferably less than 75 seconds, most preferably less than 60 seconds.
  • the method for determining the dissolution time of the film is given in the Test Methods.
  • Preferred films are polymeric materials, preferably polymers which are formed into a film or sheet.
  • the film can be obtained by casting, blow -moulding, extrusion or blow extrusion of the polymer material, as known in the art.
  • the water-soluble or dispersible film comprises: polymers, copolymers or derivatives thereof, including polyvinyl alcohols (PVA), polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum gum and carrageenan.
  • PVA polyvinyl alcohols
  • polyvinyl pyrrolidone polyalkylene oxides
  • the water-soluble or dispersible film comprises: polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates.
  • the water-soluble or dispersible film comprises: polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC).
  • HPMC hydroxypropyl methyl cellulose
  • the level of polymer or copolymer in the film is at least 60 % by weight.
  • the polymer or copolymer preferably has a weight average molecular weight of from 1000 to 1,000,000, more preferably from 10,000 to 300,000, even more preferably form 15,000 to 200,000, and most preferably from 20,000 to 150,000.
  • Copolymers and mixtures of polymers can also be used. This may in particular be beneficial to control the mechanical and/or dissolution properties of the compartments or unit dose article, depending on the application thereof and the required needs. For example, it may be preferred that a mixture of polymers is present in the film, whereby one polymer material has a higher water- solubility than another polymer material, and/or one polymer material has a higher mechanical strength than another polymer material. Using copolymers and mixtures of polymers can have other benefits, including improved long-term resiliency of the water-soluble or dispersible film to the detergent ingredients.
  • US 6,787,512 discloses polyvinyl alcohol copolymer films comprising a hydrolyzed copolymer of vinyl acetate and a second sulfonic acid monomer, for improved resiliency against detergent ingredients.
  • An example of such a film is sold by Monosol of Merrillville, Indiana, US, under the brand name: M8900.
  • M8900 Monosol of Merrillville, Indiana, US, under the brand name: M8900.
  • a mixture of polymers is used, having different weight average molecular weights, for example a mixture of polyvinyl alcohol or a copolymer thereof, of a weight average molecular weight of from 10,000 to 40,000, and of another polyvinyl alcohol or copolymer, with a weight average molecular weight of from 100,000 to 300,000.
  • polymer blend compositions for example comprising hydrolytically degradable and water-soluble polymer blends such as polylactide and polyvinyl alcohol, achieved by the mixing of polylactide and polyvinyl alcohol, typically comprising 1 to 35 % by weight polylactide and from 65 % to 99 % by weight of polyvinyl alcohol.
  • the polymer present in the film may be from 60% to 98% hydrolysed, more preferably from 80% to 90%, to improve the dissolution/dispersion of the film material.
  • the water-soluble or dispersible film herein may comprise additive ingredients other than the polymer or copolymer material.
  • plasticisers such as glycerol, ethylene glycol, diethyleneglycol, propylene glycol, sorbitol and mixtures thereof;
  • water-soluble films include polyvinyl alcohol and partially hydrolysed polyvinyl acetate, alginates, cellulose ethers such as
  • the present invention also provides for a preferred process of making a non-aqueous composition of the present invention, comprising the steps of (i) providing a cationic polymer dispersion by combining the cationic polymer with the polypropylene glycol and (ii) combining the cationic polymer dispersion with a non-aqueous liquid feed.
  • the cationic polymer dispersion comprises from 1 % to 35 %, more preferably from 10 % to 25 % by weight of the cationic polymer. Since the cationic polymer is in particulate form, the viscosity of the cationic polymer dispersion remains low and it can be easily incorporated into the non-aqueous liquid feed by typical mixing methods.
  • the non-aqueous feed may comprise some or all of the remaining ingredients, including anionic and/or nonionic surfactants.
  • the process may include a step of forming an external structurant premix, and combining the external structurant premix with the cationic polymer dispersion, or the non-aqueous feed, or the combined cationic polymer dispersion/non-aqueous feed.
  • the external structurant premix comprises a structurant selected from hydrogenated castor oil, hydophobically modified ethoxylated urethanes, hydrophobically modified alkali swellable emulsions, and mixture thereof. More preferably, the external structurant premix comprises a structurant selected from hydophobically modified ethoxylated urethanes, hydrophobically modified alkali swellable emulsions, and mixture thereof.
  • the non-aqueous liquid composition can be comprised in a unit dose article.
  • a unit dose article can be prepared according to methods known in the art. For instance, the water-soluble or dispersible film is cut to an appropriate size, and then folded to form the necessary number and size of compartments. The edges are then sealed using any suitable technology, for example heat sealing, wet sealing or pressure sealing.
  • a sealing source is brought into contact with said film, and heat or pressure is applied to seal the film material.
  • the water soluble or dispersible film is typically introduced to a mould and a vacuum applied so that said film is flush with the inner surface of the mould, thus forming an indent or niche in said film material.
  • vacuum-forming Another suitable method is thermo-forming.
  • Thermo-forming typically involves the step of forming a water-soluble or dispersible film in a mould under application of heat, which allows said film to deform and take on the shape of the mould.
  • a first piece of film material can be vacuum pulled into the mould so that said first piece of film material is flush with the inner walls of the mould.
  • a second piece of film material can then be positioned such that it completely overlaps with the first piece of film material.
  • the first piece of film material and second piece of film material are sealed together.
  • the first and second pieces of water-soluble or dispersible film can be made of the same material or can be different materials.
  • a piece of water-soluble or dispersible film material is folded at least twice, or at least three pieces of film material are used, or at least two pieces of film material are used wherein at least one piece of film material is folded at least once.
  • the third piece of film material, or a folded piece of film material creates a barrier layer that, when the film materials are sealed together, divides the internal volume of the unit dose article into two or more compartments.
  • a multi-compartment unit dose article may also be prepared by fitting a first piece of film material into a mould. A composition, or component thereof, can then be poured into the mould. A pre-formed compartment can then be placed over the mould containing the composition, or component thereof. The pre-formed compartment also preferably contains a composition, or component thereof. The pre-formed compartment and said first piece of water-soluble or dispersible film material are sealed together to form the multi -compartment unit dose article.
  • the Occhio Flow Cell FC200-S (Angleur, Belgium) is used to measure the particle size distribution.
  • the sample containing the particles to be analysed is diluted to 1 % by weight, using DPG (dipropylene glycol), to ensure single particle detection. 2 ml of the diluted sample is analysed according to the instructions provided with the device.
  • the film is cut and mounted into a folding frame slide mount for 24 mm by 36 mm diapositive film, without glass (part number 94.000.07, supplied by Else, The Netherlands, however plastic folding frames from other suppliers may be used).
  • a standard 600 ml glass beaker is filled with 500 ml of city water at 10°C and agitated using a magnetic stirring rod such that the bottom of the vortex is at the height of the 400 ml graduation mark on the beaker.
  • the slide mount is clipped to a vertical bar and suspended into the water, with the 36 mm side horizontal, along the diameter of the beaker, such that the edge of the slide mount is 5 mm from the beaker side, and the top of the slide mount is at the height of the 400 ml graduation mark.
  • the stop watch is started immediately the slide mount is placed in the water, and stopped when the film fully dissolves. This time is recorded as the "film dissolution time".
  • Cationically modified hydroxyethyl cellulose (LK400, ex-DOW), having a weight average molecular weight of 400,000 g/mol and 0.5% nitrogen substitution, was dispersed in the following dispersants: PPG400, PEG200 (comparative), 1,2-propanediol (comparative), and glycerol
  • the cationically modified hydroxyethyl cellulose dispersed in PEG200 swelled to a volume of 240% more than the volume of the cationically modified hydroxyethyl cellulose dispersed in PPG400.
  • the cationically modified hydroxyethyl cellulose dispersed in 1,2-propanediol swelled to a volume of 420% more than the volume of the cationically modified hydroxyethyl cellulose dispersed in PPG400.
  • the cationically modified hydroxyethyl cellulose dispersed in glycerol had fully dissolved after 1 week.
  • Cationically modified hydroxyethyl cellulose (LR400, ex-DOW), having a weight average molecular weight of 400,000 g/mol and 1 % nitrogen substitution, was dispersed in the following dispersants: PPG400, PEG200 (comparative), 1,2-propanediol (comparative), and glycerol (comparative), to form a 4wt% dispersion of the cationically modified hydroxyethyl cellulose.
  • the dispersions were left at room temperature for 1 week. In order to measure the difference in swelling, the height of the sediment, consisting of the swollen cationically modified hydroxyethyl cellulose, was measured.
  • the cationically modified hydroxyethyl cellulose dispersed in PEG200 swelled to a volume of 266% more than the volume of the cationically modified hydroxyethyl cellulose dispersed in PPG400.
  • the cationically modified hydroxyethyl cellulose dispersed in 1,2-propanediol, and cationically modified hydroxyethyl cellulose dispersed in glycerol had both fully dissolved after 1 week.
  • Examples 1 to 7 are compositions comprising a cationic polymer in particulate form, in a non-aqueous composition comprising polypropylene glycol:
  • non-aqueous liquid compositions of examples 1 to 7 can also be encapsulated in a water- soluble film (such as M8630, supplied by Monosol), to form stable liquid-comprising unit dose articles of the present invention.
  • a water- soluble film such as M8630, supplied by Monosol

Abstract

The need for a stable, compact composition providing improved fabric care benefit, that is also convenient to use, can be met by incorporating a cationic polymer into a non-aqueous composition, using polypropylene glycol. Such compositions have good physical stability, with little or no clumping of the cationic polymer in particulate form.

Description

STABLE NON-AQUEOUS LIQUID COMPOSITIONS COMPRISING A CATIONIC POLYMER IN PARTICULATE FORM
CROSS-REFERENCE TO RELATED APPLICATION
This application claims benefit of priority from European Patent Application Number
EP13190513.5, filed October 28, 2013, which application is incorporated by reference herein in its entirety.
FIELD OF THE INVENTION
The present invention relates to stable non-aqueous liquid compositions that deliver good fabric care benefit. The invention also relates to a process for stably suspending cationic polymers in non-aqueous liquid compositions.
BACKGROUND OF THE INVENTION
Today' s consumers desire an easy to use laundry product with improved fabric care benefits, including: improved softness, reduced fabric wrinkles, less mechanical damage during washing, less pills/fuzz, and less colour transfer or fading. Cationic polymers are known in the Art for providing improved fabric care, particularly softness and better fabric feel. Therefore, there is a desire to add these polymers to liquid compositions, including compact compositions, and unit dose liquid laundry articles.
As liquid laundry compositions become more and more compact, it is desirable to reduce or eliminate those ingredients that do not improve performance, including water. However, certain ingredients, such as cationic polymers are difficult to solubilise when little or no water is present. Also, these ingredients increase the composition viscosity to unacceptable levels at low water concentrations. Various means have been attempted to overcome this problem. Pre-dissolving the cationic polymer with low amounts of water leads to very viscous premixes that are difficult to process. WO 2007/107215 discloses a process whereby, a cationic cellulosic polymer is initially dissolved in water and optionally, a solvent. In addition, it has been discovered that for unit dose articles, cationic polymers can complex with the encapsulating water-soluble or dispersible film, which are generally anionically charged. This leads to reduced film solubility. WO2011/163371 discloses non-aqueous liquid compositions comprising a cationic polymer in particulate form, for unit dose articles and other uses.
However, a need remains for improved stability of dispersions of cationic polymers in nonaqueous compositions, in addition for improved compatibility with water-soluble or dispersible films. SUMMARY OF THE INVENTION
According to the present invention, there is provided a non-aqueous liquid composition comprising: a cationic polymer in particulate form; and polypropylene glycol.
The present invention also provides for a process for preparing the non-aqueous liquid composition, characterized in that the process comprises the steps of: providing a cationic polymer dispersion by combining the cationic polymer with the polypropylene glycol; and combining the cationic polymer dispersion with a non-aqueous liquid feed.
DETAILED DESCRIPTION OF THE INVENTION
The present invention solves the problem of providing dispersions of particulate cationic polymers which have improved stability, in addition to improved compatibility with water-soluble or dispersible films.
Polypropylene glycol in the non-aqueous composition, has surprisingly been found to improve the stability of the cationic polymer in particulate form, in the non-aqueous composition. The polypropylene glycol improves the distribution of the cationic polymer particles in the nonaqueous composition, and inhibits cakes or clumps from forming. By using polypropylene glycol to disperse the cationic polymer particles, highly viscous polymer premixes are avoided. A further consequence is that, since the cationic polymer particles remain well suspended and less swollen, they are easier to process and dose.
All percentages, ratios and proportions used herein are by weight percent of the non-aqueous liquid composition. When referring to unit dose articles, all percentages, ratios and proportions used herein are by weight percent of the contents of the unit dose compartment. That is, excluding the weight of the encapsulating material. For multi -compartment unit dose articles, percentages, ratios and proportions used herein, are by weight percent of the contents of the individual unit dose compartment, unless otherwise specified.
"Flowable", as defined herein, refers to a liquid having a viscosity of less than 3000 mPa*s at 20°C, and a shear rate of 20 s"1. Preferably, the viscosity is in the range of from 100 to 2000 mPa*s, more preferably from 500 to 1500 mPa*s, at 20 °C at a shear rate of 20 s"1.
Non-aqueous liquid compositions:
As used herein, "non-aqueous liquid composition" refers to any liquid composition comprising less than 20 %, preferably less than 15 %, more preferably less than 12 %, most preferably less than 8% by weight of water. For instance, containing no additional water beyond what is entrained with other constituent ingredients. The term liquid also includes viscous forms such as gels and pastes. The non-aqueous liquid may include other solids or gases in suitably subdivided form, but excludes forms which are non-liquid overall, such as tablets or granules. The non-aqueous composition of the present invention may also comprise from 2% to 40 %, more preferably from 5 % to 25 % by weight of additional non-aqueous solvents. That is, in addition to the polypropylene glycol. As used herein, "additional non-aqueous solvent" refers to any organic solvent which contains no amino functional groups, not including polypropylene glycol. Preferred additional non-aqueous solvents include monohydric alcohols; dihydric alcohols;
polyhydric alcohols; glycerol; glycols including dipropylene glycol, and polyalkylene glycols such as polyethylene glycol, with the exception of polypropylene glycol; and mixtures thereof. More preferred additional non-aqueous solvents include monohydric alcohols, dihydric alcohols, polyhydric alcohols, glycerol, and mixtures thereof. Highly preferred are mixtures of such solvents, especially mixtures of two or more of the following: lower aliphatic alcohols such as ethanol, propanol, butanol, isopropanol; diols such as 1,2-propanediol or 1,3 -propanediol; and glycerol. Also preferred are propanediol and mixtures thereof with diethylene glycol, where the mixture contains no methanol or ethanol. Thus embodiments of non-aqueous liquid compositions of the present invention may include embodiments in which propanediols are used but methanol and ethanol are not used.
Preferable additional non-aqueous solvents are liquid at ambient temperature and pressure (i.e. 21°C and 1 atmosphere), and comprise carbon, hydrogen and oxygen. Additional non-aqueous solvents may be present when preparing a premix, or in the final non-aqueous composition. Cationic polymer in particulate form:
The non-aqueous liquid compositions of the present invention may comprise from 0.01 % to 30 %, preferably from 0.05 % to 25 %, more preferably from 0.1 % to 10 % by weight of the cationic polymer in particulate form. That is, the cationic polymer is insoluble in the non-aqueous liquid composition, or does not fully dissolve in the non-aqueous liquid composition. Preferably, the cationic polymer has a solubility of less than 50wt%, preferably less than 25wt%, more preferably less than 15wt%, even more preferably less than 10wt% most preferably less than 5wt% in the nonaqueous liquid composition, when added at the desired level, at a temperature of 20°C.
The cationic polymer particles preferably have a volume based D90 diameter of less than 300 microns, preferably less than 200 microns, more preferably less than 150 microns. The volume based D90 diameter is defined as 90% of the particles having a volume smaller than the volume of a sphere having the diameter D90. The method for measuring the particle size is given in the Test Methods. The cationic polymer particles are preferably as small as possible. Having smaller particles result in faster dissolution, particularly at lower temperatures, making such particles particularly suitable for providing fabric care benefit during low temperature fabric treatments.
Suitable particulate forms include solids that are completely free of water and/or other solvent, but also includes solids that are partially hydrated and/or solvated. The cationic polymer preferably has a cationic charge density of from 0.005 to 23, more preferably from 0.01 to 12, most preferably from 0.1 to 7 milliequivalents/g, at the pH of the non-aqueous liquid composition. The charge density is calculated by dividing the number of net charges per repeating unit by the molecular weight of the repeating unit. The positive charges could be located on the backbone of the polymer and/or the side chains of polymer.
The term "cationic polymer" also includes amphoteric polymers that have a net cationic charge at the pH of the non-aqueous composition. Non-limiting examples of suitable cationic polymers are polysaccharides, proteins and synthetic polymers. Cationic polysaccharides include cationic cellulose derivatives, cationic guar gum derivatives, chitosan and derivatives, and cationic starches. Suitable cationic polysaccharides include cationically modified cellulose, particularly cationic hydroxyethylcellulose and cationic hydroxypropylcellulose. Preferred cationic celluloses for use herein include those which may or may not be hydrophobically-modified, including those having hydrophobic substituent groups, having a molecular weight of from 50,000 to 2,000,000, more preferably from 100,000 to 1,000,000, and most preferably from 200,000 to 800,000. Preferred hydrophobic substituent groups are alkyl substitutions. Alkyl substitution on the anhydroglucose rings of the polymer may range from 0.01% to 10% per glucose unit, preferably from 0.03% to 5%, more preferably from 0.05% to 2% per glucose unit, of the polymeric material.
These cationic materials have repeating substituted anhydroglucose units that correspond to the general Structural Formula I as follows:
Figure imgf000005_0001
Structural Formula I
wherein:
m is an integer from 20 to 10,000
Each R4 is H, and R1, R2, R3 are each independently selected from the group consisting of: H; Ci- C32 alkyl; Ci-C32 substituted alkyl, C5-C32 or C6-C32 aryl, C5-C32 or C6-C32 substituted aryl or C6-Q
alkylaryl, or C6-C32 substituted alkylaryl,
Figure imgf000005_0002
Preferably, R1, R2, R3 are each independently selected from the group consisting of: H,
Figure imgf000006_0001
, C1-C4 alkyl, and combinations thereof;
n is an integer selected from 0 to 10 and
Rx is selected from the group consisting of:
OT R6 OH R,
I a l I a | 6
CH— CH-C¾ N— R6 A" _CH_CH_CH- N— R6 A
H, , and , and combinations thereof.
wherein A" is a suitable anion. Preferably, A" is selected from the group consisting of: CI", Br", Γ, methylsulfate, ethylsulfate, toluene sulfonate, carboxylate, and phosphate;
each R5 is independently selected from the group consisting of: H; Ci-C32 alkyl; Ci-C32 substituted alkyl, C5-C32 or C6-C32 aryl, C5-C32 or C6-C32 substituted aryl, C6-C32 alkylaryl, C6-C32 substituted alkylaryl, and OH. Preferably, each R5 is selected from the group consisting of: H, Ci-C32 alkyl, and Ci-C32 substituted alkyl. More preferably, R5 is selected from the group consisting of H, methyl, and ethyl.
Each R6 is independently selected from the group consisting of: H, Ci-C32 alkyl, Ci-C32 substituted alkyl, Cs-C32 or C6-C32 aryl, Cs-C32 or C6-C32 substituted aryl, C6-C32 alkylaryl, and Ce- C32 substituted alkylaryl. Preferably, each R6 is selected from the group consisting of: H, Ci-C32 alkyl, and Ci-C32 substituted alkyl.
OT
-^CH2— CH-CH2-0^-R5
Each T is independently selected from the group: H, v
R2°T OH CH2OH
- CH— CH2AND _CH2_CH_CH2_R5; CH_CH2_R5.
wherein each v in said polysaccharide is an integer from 1 to 10. Preferably, v is an integer from 1 to 5. The sum of all v indices in each Rx in said polysaccharide is an integer from 1 to 30, more
OT
_ _ l
preferably from 1 to 20, even more preferably from 1 to 10. In the last CH2 CH CH2 O R5;
Figure imgf000006_0002
2-R5group in a chairi; T is always an H.
The cationic cellulose may be lightly cross-linked with a dialdehyde, such as glyoxyl, to prevent forming lumps, nodules or other agglomerations when added to water at ambient temperatures.
The cationic cellulose ethers of Structural Formula I likewise include those which are commercially available and further include materials which can be prepared by conventional chemical modification of commercially available materials. Commercially available cellulose ethers of the Structural Formula I type include those with the UNO name Polyquaternium 10, such as those sold under the trade names: UCARE Polymer JR 30M, JR 400, JR 125, LR 400 and LK 400 polymers; Polyquaternium 67 such as those sold under the trade name Softcat SK™, all of which are marketed by The Dow Chemical Company, Midland, Michigan; and Polyquaternium 4 such as those sold under the trade name: Celquat H200 and Celquat L-200, available from National Starch and Chemical Company, Bridgewater, NJ. Other suitable polysaccharides include hydroxyethyl cellulose or hydoxypropylcellulose quaternized with glycidyl Ci2-C22 alkyl dimethyl ammonium chloride. Examples of such polysaccharides include the polymers with the INCI names
Polyquaternium 24 such as those sold under the trade name QUATRISOFT polymer LM- 200 by Amerchol Corporation, Edison, New Jersey . Cationic starches described by D. B. Solarek in Modified Starches, Properties and Uses published by CRC Press (1986) and in U.S. Pat. No.
7,135,451, col. 2, line 33 - col. 4, line 67. Suitable cationic galactomannans include cationic guar gums or cationic locust bean gum. An example of a cationic guar gum is a quaternary ammonium derivative of Hydroxypropyl Guar such as those sold under the trade name: Jaguar C13 and Jaguar Excel available from Rhodia, Inc of Cranbury NJ and N-Hance by Aqualon, Wilmington, DE.
A synthetic cationic polymer may also be useful as the cationic polymer. Synthetic polymers include synthetic addition polymers of the general structure:
Figure imgf000007_0001
Structural Formula II
wherein each R1 may be independently: hydrogen, C1-C12 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, -ORa> or -C(0)ORa wherein Ra may be selected from the group consisting of: hydrogen, C1-C24 alkyl, and combinations thereof. R1 is preferably: hydrogen, C1-C4 alkyl, or -ORa, or - C(0)ORa;
wherein each R2 may be independently selected from the group consisting of: hydrogen, hydroxyl, halogen, C1-C12 alkyl, -ORa> substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic, heterocyclic, and combinations thereof. R2 is preferably selected from the group consisting of: hydrogen, C1-C4 alkyl, and combinations thereof.
Each Z may be independently: hydrogen, halogen; linear or branched Ci-C30 alkyl, nitrilo, N(R3)2 - C(0)N(R3)2; -NHCHO (formamide); -OR3, -0(CH2)nN(R3)2, -0(CH2)nN+(R3)3X - C(0)OR4; - C(0)N-(R3)2; -C(0)0(CH2)nN(R3)2, -C(0)0(CH2)nN+(R3)3X \ -OCO(CH2)nN(R3)2, -
OCO(CH2)nN+(R3)3X \ -C(0)NH-(CH2)nN(R3)2, -C(0)NH(CH2)nN+(R3)3X \ -(CH2)nN(R3)2, - (CH2)nN+(R3)3X \ Each R3 may be independently selected from the group consisting of: hydrogen, C1-C24 alkyl, C2-C8 hydroxyalkyl, benzyl, substituted benzyl, and combinations thereof;
be independently selected from the group consisting of: hydrogen, C1-C24 alkyl,
Figure imgf000008_0001
and combinations thereof .
X may be a water soluble anion, n may be from 1 to 6.
R5 may be independently selected from the group consisting of: hydrogen, C1-C6 alkyl, and combinations thereof.
Z, from Structural Formula Π, may also be selected from the group consisting of: non- aromatic nitrogen heterocycles containing a quaternary ammonium ion, heterocycles containing an N-oxide moiety, aromatic nitrogens containing heterocycles wherein one or more or the nitrogen atoms may be quaternized; aromatic nitrogen-containing heterocycles wherein at least one nitrogen may be an N-oxide, and combinations thereof. Non-limiting examples of addition polymerizing monomers comprising a heterocyclic Z unit includes l-vinyl-2-pyrrolidinone, 1-vinylimidazole, quaternized vinyl imidazole, 2-vinyl-l,3-dioxolane, 4-vinyl-l-cyclohexenel,2-epoxide, and 2- vinylpyridine, 2-vinylpyridine N-oxide, 4-vinylpyridine 4-vinylpyridine N-oxide.
A non-limiting example of a Z unit which can be made to form a cationic charge in situ, may be the -NHCHO unit, formamide. The formulator can prepare a polymer, or co-polymer, comprising formamide units some of which are subsequently hydrolyzed to form vinyl amine equivalents.
The polymers or co-polymers may also contain one or more cyclic polymer units derived from cyclically polymerizing monomers. An example of a cyclically polymerizing monomer is dimethyl diallyl ammonium having the formula:
Figure imgf000008_0002
Suitable copolymers may be made from one or more cationic monomers selected from the group consisting of Ν,Ν-dialkylaminoalkyl methacrylate, Ν,Ν-dialkylaminoalkyl acrylate, N,N- dialkylaminoalkyl acrylamide, Ν,Ν-dialkylaminoalkylmethacrylamide , quaternized N,N- dialkylaminoalkyl methacrylate, quaternized Ν,Ν-dialkylaminoalkyl acrylate, quaternized N,N- dialkylaminoalkyl acrylamide, quaternized Ν,Ν-dialkylaminoalkylmethacrylamide, vinylamine and its derivatives, allylamine and its derivatives, vinyl imidazole, quaternized vinyl imidazole and diallyl dialkyl ammonium chloride and combinations thereof, and optionally a second monomer selected from the group consisting of acrylamide, Ν,Ν-dialkyl acrylamide, methacrylamide, N,N- dialkylmethacrylamide, C1-C12 alkyl acrylate, C1-C12 hydroxyalkyl acrylate, polyalkylene glyol acrylate, C1-C12 alkyl methacrylate, C1-C12 hydroxyalkyl methacrylate, , polyalkylene glycol methacrylate, vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ether, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole and derivatives, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethane sulfonic acid (AMPS) and their salts, and combinations thereof. The polymer may optionally be cross-linked. Suitable crosslinking monomers include ethylene glycoldiacrylate, divinylbenzene, butadiene.
In certain embodiments, the synthetic polymers are: poly(acrylamide-co- diallyldimethylammonium chloride), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride), poly(acrylamide-co-N,N-dimethyl aminoethyl methacrylate), poly(acrylamide-co-N,N- dimethyl aminoethyl methacrylate), poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co-dimethyl aminoethyl methacrylate),
poly(hydroxpropylacrylate-co-methacrylamidopropyltrimethylammonium chloride),
poly(acrylamide-co-diallyldimethylammonium chloride-co-acrylic acid), poly(acrylamide- methacrylamidopropyltrimethyl ammonium chloride-co-acrylic acid). Examples of other suitable synthetic polymers are Polyquaternium-1, Polyquaternium-5, Polyquaternium-6, Polyquaternium-7, Polyquaternium-8, Polyquaternium-l l, Polyquaternium-14, Polyquaternium-22, Polyquaternium-28, Polyquaternium-30, Polyquaternium-32 and Polyquaternium-33. Other cationic polymers include polyethyleneamine and its derivatives and polyamidoamine-epichlorohydrin (PAE) Resins. In one aspect, the polyethylene derivative may be an amide derivative of polyetheylenimine sold under the trade name Lupasol SK. Also included are alkoxylated polyethylenimine; alkyl polyethyleneimine and quaternized polyethyleneimine. These polymers are described in Wet Strength resins and their applications edited by L. L. Chan, TAPPI Press (1994). The weight-average molecular weight of the polymer will generally be from 10,000 to 5,000,000, or from 100,000 to 200,000, or from 200,000 to 1,500,000 Dal tons, as determined by size exclusion chromatography relative to polyethylene oxide standards with RI detection. The mobile phase used is a solution of 20% methanol in 0.4M MEA, 0.1 M NaN03, 3% acetic acid on a Waters Linear Ultrahdyrogel column, 2 in series.
Columns and detectors are kept at 40°C. Flow is set to 0.5 mL/min.
Polypropylene glycol:
The non-aqueous composition of the present invention comprises polypropylene glycol. The non-aqueous liquid composition may comprise from 0.05 % to 98 %, preferably from 0.5 % to 75 %, more preferably from 3 % to 68 % by weight of polypropylene glycol. Surprisingly, it has been found that polypropylene glycol greatly improves the physical stability of the cationic polymer particulates in the non-aqueous composition. It is believed that the polypropylene glycol inhibits the agglomeration of the cationic polymer particles, by limiting the solvation, and hence swelling of the particles. Moreover, since the particles are less swollen, they are less visible, even when they deposit on a water-soluble film which is used to form a unit-dose article. Furthermore, even when they do deposit on such water-soluble films, they are less able to interact with the water-soluble film, since they are less solvated. As a result, there is less impact on the dissolution of the water- soluble film, such as during a wash cycle.
Any agglomerates that may form over time, are easily redistributed by gentle shaking. Preferably, the polypropylene glycol has a molecular weight of from 208 g/mol to 4000 g/mol, more preferably from 208 g/mol to 2000 g/mol, even more preferably from 250 g/mol to 700 g/mol.
The strength of any agglomerates that may form is further reduced by adding spacer particles. Suitable spacer particles may have an volume based D90 diameter of less than 5 microns, preferably from 0.1 microns to 1 micron. The spacer particles may be polymeric or non-polymeric. Suitable non-polymeric spacer particles include mica. Suitable polymeric spacer particles include those comprising a polymer and/or a copolymer. Preferably, the spacer particles are anionically charged, such as those comprising a polyacrylate polymer or copolymer. It is believed that the anionic charge attracts the spacer particle to the cationic polymer particles. The non-aqueous composition of the present invention may comprise from 0.1 % to 30 %, preferably from 0.5 percent to 15 % by weight of the spacer particles.
Any present agglomerates of the cationic polymer particles may also be weakened by the presence of soluble cations and/or polyvalent anions. While polyvalent cations, particularly those having the charges derived from different charged groups are preferred, even monovalent cations have been shown to provide a benefit. It is believed that the cations form bilayers that are able to reduce the attraction between the cationic polymer particles. Suitable single species polyvalent cations include the cations of magnesium and calcium. Suitable cationic surfactants are preferably water-soluble, but can also be water-dispersible or water-insoluble. Such cationic surfactants have at least one quaternized nitrogen and at least one long-chain hydrocarbyl group. Compounds comprising two, three or even four long-chain hydrocarbyl groups are also included. Examples include
alkyltrimethylammonium salts, such as C12 alkyltrimethylammonium chloride, or their hydroxyalkyl substituted analogues. The present invention may comprise from 1% or more by weight of the cationic surfactant. Amphoteric surfactants, particularly those that have a net cationic charge at the pH of the non-aqueous composition, are also useful cations for the present invention. Suitable polyvalent anions include: Citric Acid; Diethylene triamine pentaacetic acid (DTP A); 1- hydroxyethane 1,1-diphosphonic acid (HEDP); Maleic acid; Polyacrylates; Polyacrylic/maleic acid copolymers; succinic acid, and mixtures thereof. The non-aqueous composition may comprise from 0.1 % to 30 %, preferably from 0.5 to 15 % by weight of the cation and/or polyvalent anion.
Laundering adjuncts:
The non-aqueous liquid compositions of the present invention may include conventional laundry detergent ingredients selected from the group consisting of: anionic and nonionic surfactants; additional surfactants; enzymes; enzyme stabilizers; cleaning polymers, including: amphiphilic alkoxylated grease cleaning polymers, clay soil cleaning polymers, soil release polymers, and soil suspending polymers; bleaching systems; optical brighteners; hueing dyes; particulate material; perfume and other odour control agents; hydrotropes; suds suppressors; fabric care benefit agents; pH adjusting agents; dye transfer inhibiting agents; preservatives; non-fabric substantive dyes and mixtures thereof. Some of the optional ingredients which can be used are described in greater detail as follows:
Anionic and nonionic surfactants: Non-aqueous liquid compositions of the present invention may comprise from 1 % to 70%, preferably from 10% to 50%, and more preferably from 15% to 45% by weight of an anionic and/or nonionic surfactant.
The non-aqueous liquid compositions of the present invention preferably comprise from 1 to 70 %, more preferably from 5 to 50 % by weight of one or more anionic surfactants. Preferred anionic surfactant are selected from the group consisting of: CI 1 -CI 8 alkyl benzene sulfonates, C10-C20 branched-chain and random alkyl sulfates, C10-C18 alkyl ethoxy sulfates, mid-chain branched alkyl sulfates, mid-chain branched alkyl alkoxy sulfates, C10-C18 alkyl alkoxy carboxylates comprising 1-5 ethoxy units, modified alkylbenzene sulfonate, C12-C20 methyl ester sulfonate, C10-C18 alpha-olefin sulfonate, C6-C20 sulfosuccinates, fatty acids, and mixtures thereof. However, by nature, every anionic surfactant known in the art of detergent compositions may be used, such as those disclosed in "Surfactant Science Series", Vol. 7, edited by W. M.
Linfield, Marcel Dekker. However, the compositions of the present invention preferably comprise at least one sulphonic acid surfactant, such as a linear alkyl benzene sulphonic acid, or the water- soluble salt forms.
Anionic sulfonate or sulfonic acid surfactants suitable for use herein include the acid and salt forms of linear or branched C5-C20, more preferably C10-C16, most preferably CI 1-C13 alkylbenzene sulfonates, C5-C20 alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C5-C20 sulfonated polycarboxylic acids, and mixtures thereof. The aforementioned surfactants can vary widely in their 2-phenyl isomer content. Anionic sulphate salts suitable for use in compositions of the invention include: primary and secondary alkyl sulphates, having a linear or branched alkyl or alkenyl moiety having from 9 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms; beta-branched alkyl sulphate surfactants; and mixtures thereof. Mid-chain branched alkyl sulphates or sulfonates are also suitable anionic surfactants for use in the compositions of the invention. Preferred are the C5-C22, preferably C10-C20 mid-chain branched alkyl primary sulphates. When mixtures are used, a suitable average total number of carbon atoms for the alkyl moieties is preferably within the range of from 14.5 to 17.5. Preferred mono-methyl-branched primary alkyl sulphates are selected from the group consisting of the 3-methyl to 13-methyl pentadecanol sulphates, the corresponding hexadecanol sulphates, and mixtures thereof. Dimethyl derivatives or other biodegradable alkyl sulphates having light branching can similarly be used. Other suitable anionic surfactants for use herein include fatty methyl ester sulphonates and/or alkyl ethoxy sulphates (AES) and/or alkyl polyalkoxylated carboxylates (AEC).
Any fatty acid is suitable for use herein, including but not limited to lauric, myristic, palmitic stearic, oleic, linoleic, linolenic acid, and mixtures thereof. The fatty acid is preferably selected from those which are flowable at less than 30°C. Naturally obtainable fatty acids, which are usually complex mixtures, are also suitable (such as tallow, coconut, and palm kernel fatty acids). A preferred fatty acid is palm kernel fatty acid. Furthermore, such fatty acids provide a builder benefit, and after neutralization, a detergency benefit. The amount of fatty acid can be in the range of from 0.1% to 30%, preferably from 1% to 20%, more preferably from 3 to 15%, by weight of the composition.
Mixtures of anionic surfactants can be used, for example mixtures of
alkylbenzenesulphonates and AES.
The anionic surfactants are typically present in the form of their salts with alkanolamines or alkali metals such as sodium and potassium. Preferably, the anionic surfactants are neutralized with alkanolamines, such as monoethanolamine or triethanolamine, and are fully soluble in the nonaqueous liquid composition.
The non-aqueous liquid compositions of the present invention may include from 1 to 70 %, preferably from 5 to 50 % by weight of a nonionic surfactant. Suitable nonionic surfactants include, but are not limited to C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates, C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed
ethoxy lates/propoxylates), block alkylene oxide condensate of C6-C12 alkyl phenols, alkylene oxide condensates of C8-C22 alkanols and ethylene oxide/propylene oxide block polymers (Pluronic®-BASF Corp.), glycereth cocoate, alkyl polyglucosides, as well as semi polar nonionics (e.g., amine oxides and phosphine oxides). An extensive disclosure of suitable nonionic surfactants can be found in U.S. Pat. 3,929,678.
Alkylpolysaccharides such as disclosed in U.S. Pat. 4,565,647 are also useful nonionic surfactants for compositions of the invention. Also suitable are alkyl polyglucoside surfactants. In some embodiments, suitable nonionic surfactants include those of the formula Rl(OC2H4)nOH, wherein Rl is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to 80. In some embodiments, the nonionic surfactants may be condensation products of C12-C15 alcohols with from 5 to 20 moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol condensed with 6.5 moles of ethylene oxide per mole of alcohol. Additional suitable nonionic surfactants include polyhydroxy fatty acid amides of the formula:
Figure imgf000012_0001
wherein R is a C9-C17 alkyl or alkenyl, Rl is a methyl group and Z is glycidyl derived from a reduced sugar or alkoxylated derivative thereof. Examples are N-methyl N-l-deoxyglucityl cocoamide and N-methyl N-l-deoxyglucityl oleamide.
Additional Surfactants: The non-aqueous liquid compositions of the present invention may comprise additional surfactant selected from the group consisting: anionic, cationic, nonionic, amphoteric and/or zwitterionic surfactants and mixtures thereof.
Amphoteric detersive surfactants suitable for use in the composition include those surfactants broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic group such as carboxy, sulphonate, sulphate, phosphate, or phosphonate. Suitable amphoteric detersive surfactants for use in the present invention include, but are not limited to: cocoamphoacetate, cocoamphodiacetate,
lauroamphoacetate, lauroamphodiacetate, and mixtures thereof.
Zwitterionic detersive surfactants suitable for use in non-aqueous liquid compositions are well known in the art, and include those surfactants broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulphonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic group such as carboxy, sulfonate, sulphate, phosphate or phosphonate. Zwitterionics such as betaines are also suitable for this invention. Furthermore, amine oxide surfactants having the formula: R(EO)x(PO)y(BO)zN(0)(CH2R')2.qH20 are also useful in compositions of the present invention. R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is more preferably C12-C16 primary alkyl. R' is a short-chain moiety preferably selected from hydrogen, methyl and -CH2OH. When x+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated by C12-C14 alkyldimethyl amine oxide.
Non-limiting examples of other anionic, zwitterionic, amphoteric or optional additional surfactants suitable for use in the compositions are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co., and U.S. Pat. Nos. 3,929,678, 2,658,072; 2,438,091 ; 2,528,378.
Enzymes: The non-aqueous liquid compositions of the present invention may comprise from 0.0001 % to 8 % by weight of a detersive enzyme which provides cleaning performance and/or fabric care benefits. Such compositions preferably have a composition pH of from 6 to 10.5.
Suitable enzymes can be selected from the group consisting of: lipase, protease, amylase, cellulase, mannanase, pectate lyase, xyloglucanase, and mixtures thereof. A preferred enzyme combination comprises a cocktail of conventional detersive enzymes such as lipase, protease, cellulase and amylase. Detersive enzymes are described in greater detail in U.S. Patent No. 6,579,839.
Enzyme Stabilizers: Enzymes can be stabilized using any known stabilizer system such as calcium and/or magnesium compounds, boron compounds and substituted boric acids, aromatic borate esters, peptides and peptide derivatives, polyols, low molecular weight carboxylates, relatively hydrophobic organic compounds [e.g. certain esters, dialkyl glycol ethers, alcohols or alcohol alkoxylates], alkyl ether carboxylate in addition to a calcium ion source, benzamidine hypochlorite, lower aliphatic alcohols and carboxylic acids, N,N-bis(carboxymethyl) serine salts, (meth)acrylic acid-(meth)acrylic acid ester copolymer and PEG; lignin compound, polyamide oligomer, glycolic acid or its salts, poly hexamethylene biguanide or N,N-bis-3-amino-propyl- dodecyl amine or salt, sorbitol, and mixtures thereof.
Fabric Care Benefit Agents: The non-aqueous composition may comprise from 1 % to 15 %, more preferably from 2 % to 7 %, by weight of a fabric care benefit agent. "Fabric care benefit agent", as used herein, refers to any material that can provide fabric care benefits. Non-limiting examples of fabric care benefits include, but are not limited to: fabric softening, colour protection, colour restoration, pill/fuzz reduction, anti-abrasion and anti- wrinkling. Non-limiting examples of fabric care benefit agents include: silicone derivatives, such as polydimethylsiloxane and amino- functional silicones; oily sugar derivatives; dispersible poly olefins; polymer latexes; cationic surfactants and combinations thereof.
Cleaning Polymers: The non-aqueous liquid compositions herein, may contain from 0.01 % to 20 %, preferably from 0.05 % to 15 %, more preferably from 0.1 % to 10 % by weight of cleaning polymers, that provide for broad-range soil cleaning of surfaces and fabrics. Any suitable cleaning polymer may be of use. Useful cleaning polymers are described in US 2009/0124528A1. Non-limiting examples of useful categories of cleaning polymers include: amphiphilic alkoxylated grease cleaning polymers; clay soil cleaning polymers; soil release polymers; and soil suspending polymers. Other anionic polymers, useful for improving soil cleaning include: non-silicone- containing polymers of natural origin, but also of synthetic origin. Suitable anionic non-silicone- containing polymers may be selected from the group consisting of xanthan gum, anionic starch, carboxymethyl guar, carboxymethyl hydroxypropyl guar, carboxy methyl cellulose and ester modified carboxymethyl cellulose, N-carboxyalkyl chitosan, N-carboxyalkyl chitosan amides, pectin, carrageenan gum, chondroitin sulfate, galactomanans, hyaluronic acid-, and alginic acid- based polymers, and derivatives thereof and mixtures thereof. More preferably, the anionic non- silicone-containing polymer maybe selected from carboxymethyl guar, carboxymethyl hydroxypropyl guar, carboxymethyl cellulose and xanthan gum, and derivatives and mixtures thereof. Preferred anionic non-silicone-containing polymers include those commercially available from CPKelco, sold under the tradename of Kelzan® RD and from Aqualon, sold under the tradename of Galactosol® SP722S, Galactosol® 60H3FD, and Galactosol® 70H4FD.
Optical brighteners: These are also known as fluorescent whitening agents for textiles. Preferred levels are from 0.001 % to 2 % by weight of the non-aqueous liquid composition. Suitable brighteners are disclosed in EP 68669 IB and include hydrophobic as well as hydrophilic types. Brightener 49 is preferred for use in the present invention.
Hueing dyes: Hueing dyes or fabric shading dyes are useful laundering adjuncts in nonaqueous liquid compositions. Suitable dyes include blue and/or violet dyes having a hueing or shading effect. See, for example, WO 2009/087524 Al , WO2009/087034A1 and references therein. Recent developments that are suitable for the present invention include sulfonated phthalocyanine dyes having a zinc or aluminium central atom. The non-aqueous liquid compositions herein may comprise from 0.00003 % to 0.1 %, preferably from 0.00008 % to 0.05 % by weight of the fabric hueing dye.
Particulate material: The non-aqueous composition may include additional particulate material such as clays, suds suppressors, encapsulated oxidation-sensitive and/or thermally sensitive ingredients such as perfumes (perfume microcapsules), bleaches and enzymes; or aesthetic adjuncts such as pearlescent agents including mica, pigment particles, or the like. Suitable levels are from 0.0001 % to 10 %, or from 0.1 % to 5 % by weight of the non-aqueous composition.
Perfume and other odour control agents: In preferred embodiments, the non-aqueous composition comprises a free and/or micro-encapsulated perfume. If present, the free perfume is typically incorporated at a level from 0.001 % to 10 %, preferably from 0.01 % to 5 %, more preferably from 0.1 % to 3 % by weight of the non-aqueous composition.
If present, the perfume microcapsule is formed by at least partially surrounding the perfume raw materials with a wall material. Preferably, the microcapsule wall material comprises: melamine crosslinked with formaldehyde, polyurea, urea crosslinked with formaldehyde or urea crosslinked with gluteraldehyde. Suitable perfume microcapsules and perfume nanocapsules include those described in the following references: US 2003215417 Al ; US 2003216488 Al ; US 2003158344 Al ; US 2003165692 Al ; US 2004071742 Al; US 2004071746 Al; US 2004072719 Al ; US 2004072720 Al; EP 1393706 Al ; US 2003203829 Al ; US 2003195133 Al ; US 2004087477 Al; US 20040106536 Al ; US 6645479; US 6200949; US 4882220; US 4917920; US 4514461 ; US RE 32713; US 4234627.
In other embodiments, the non-aqueous composition comprises odour control agents such as uncomplexed cyclodextrin, as described in US 5,942,217. Other suitable odour control agents include those described in: US 5,968,404, US 5,955,093, US 6,106,738, US 5,942,217, and US 6,033,679. Hydrotropes: The non-aqueous liquid composition of the present invention typically comprises a hydrotrope in an effective amount, preferably up to 15%, more preferably from 1 % to 10 %, most preferably from 3 % to 6 % by weight, so that the compositions are readily dispersed in water. Suitable hydrotropes for use herein include anionic-type hydrotropes, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium and ammonium toluene sulfonate, sodium potassium and ammonium cumene sulfonate, and mixtures thereof, as disclosed in US 3,915,903.
Multivalent water-soluble organic builder and/or chelant: The non-aqueous liquid compositions of the present invention may comprise from 0.6 % to 25 %, preferably from 1 % to 20 %, more preferably from 2 % to 7 % by weight of the multivalent water-soluble organic builder and/or chelants. Water-soluble organic builders provide a wide range of benefits including sequestration of calcium and magnesium (improving cleaning in hard water), provision of alkalinity, transition metal ion complexation, metal oxide colloid stabilisation, and provision of substantial surface charge for peptisation and suspension of other soils. Chelants may selectively bind transition metals (such as iron, copper and manganese) which impact stain removal and the stability of bleach ingredients, such as organic bleach catalysts, in the wash solution. Preferably, the multivalent water-soluble organic builder and/or chelants of the present invention are selected from the group consisting of: MEA citrate, citric acid, aminoalkylenepoly(alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates, and nitrilotrimethylene, phosphonates, diethylene triamine penta (methylene phosphonic acid) (DTPMP), ethylene diamine tetra(methylene phosphonic acid) (DDTMP), hexamethylene diamine tetra(methylene phosphonic acid), hydroxy- ethylene 1,1 diphosphonic acid (HEDP), hydroxyethane dimethylene phosphonic acid, ethylene diamine di-succinic acid (EDDS), ethylene diamine tetraacetic acid (EDTA),
hydroxyethylethylenediamine triacetate (HEDTA), nitrilotriacetate (NTA), methylglycinediacetate (MGDA), iminodisuccinate (IDS), hydroxyethyliminodisuccinate (HIDS),
hydroxyethyliminodiacetate (HEIDA), glycine diacetate (GLDA), diethylene triamine pentaacetic acid (DTP A), and mixtures thereof.
External structuring system: The physical stability of the cationic polymer particulates in the non-aqueous liquid composition can be further improved if the non-aqueous liquid composition also comprises an external structurant. An external structuring system is a compound or mixture of compounds which provide either a sufficient yield stress or low shear viscosity to stabilize the nonaqueous liquid compositions independently from, or extrinsic from, the structuring effect of any detersive surfactants in the composition. The non-aqueous liquid composition may comprise from 0.01 % to 10 %, preferably from 0.1 % to 4 % by weight of an external structuring system, on an active basis. Suitable external structuring systems include non-polymeric crystalline, hydroxy- functional structurants, polymeric structurants, or mixtures thereof. Preferably, the external structurant system imparts a high shear viscosity at 20 s"1, at 20°C, of from 1 to 3000 cps, and a viscosity at low shear (at 0.05 s"1 at 20°C) of greater than 5000 cps. The viscosity is measured using an AR 550 rheometer, from TA instruments, using a plate steel spindle with a 40 mm diameter and a gap size of 1000 μηι. The high shear viscosity at 20s"1 can be obtained from a logarithmic shear rate sweep from 0.1s"1 to 1200s"1 in 3 minutes time at 20°C. The low shear viscosity is measured over a period of 3 minutes at a fixed shear rate ("Peak Hold") of 0.05 s"1 at 20°C.
The external structuring system may comprise a non-polymeric crystalline, hydroxyl functional structurant. Such non-polymeric crystalline, hydroxyl functional structurants generally comprise a crystallisable glyceride which can be pre-emulsified to aid dispersion into the final nonaqueous composition. Preferred crystallisable glycerides include hydrogenated castor oil or "HCO", and derivatives thereof, provided that it is capable of crystallizing in the non-aqueous composition. Other embodiments of suitable external structuring systems may comprise a naturally derived and/or synthetic polymeric structurant. Examples of suitable naturally derived polymeric structurants include: hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof. Suitable polysaccharide derivatives include: pectine, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof. Examples of suitable synthetic polymeric structurants include: polycarboxylates, polyacrylates, hydrophobically modified ethoxylated urethanes (HEUR), hydrophobically modified alkali swellable emulsions (HASE), and mixtures thereof.
Preferred polymeric structurants can be selected from the group consisting of:
hydrophobically-modified ethoxylated urethanes (HEUR); hydrophobically modified alkali swellable emulsion (HASE) polymers, and mixtures thereof.
HEUR and HASE polymeric structurants are typically used for structuring in aqueous compositions. However, such polymers have been found to be particularly effective for suspending the cationic polymer, in particulate form, in the non-aqueous composition.
HEUR polymeric structurants are water-soluble polymers, having hydrophobic end-groups, comprising blocks of ethylene glycol units, propylene glycol units, and mixtures thereof, in addition to ure thane units.
The HEUR polymeric structurants preferably has a backbone comprising one or more polyoxyalkylene segments greater than 10 oxyalkylene units in length. The HEUR polymeric structurant is preferably a hydrophobically modified polyurethane polyether comprising the reaction product of a dialkylamino alkanol with a multi-functional isocyanate, a polyether diol, and optionally a polyether triol. Preferably, the polyether diol has a weight average molecular weight between 2,000 and 12,000, preferably between 6,000 and 10,000 Preferred HEUR olymeric structurants can have the following structure:
Figure imgf000018_0001
wherein:
R is an alkyl chain, preferably a C6-C24 alkyl chain, more preferably a C12-C18 alkyl chain, n is preferably from 25 to 400, preferably from 50 to 250, more preferably from 75 to 180, X can be any suitable linking group.
Suitable HEUR polymeric structurants can have a molecular weight of from 1,000 to 1,000,000, more preferably from 15,000 to 50,000 g/mol. An example of a suitable HEUR polymeric structurant is ACUSOL™ 880, sold by DOW.
It is believed that HEUR polymeric structurants thicken via an associative mechanism, wherein the hydrophobic parts of HEUR polymers build up associations with other hydrophobes present in the composition, such as the cationic polymers in particulate form.
HASE polymers are typically synthesized by free-radical emulsion polymerization of varying mixtures of hydrophilic monomers such as acrylic acid, methacrylic acid, or maleic anhydride, lipophilic monomers such as ethyl acrylate, butyl acrylate, or methyl methacrylate, and associative monomers such as long chain alkyl (C8 to C22) acrylates or styrenic derivatives.
Preferred HASE polymeric structurants can have the following structure:
Figure imgf000018_0002
wherein:
R is preferably H or an alkyl group. When R is an alkyl group, R is preferably a C1-C6 alkyl group, more preferably a CI to C2 alkyl group. R is preferably a CI alkyl group.
Ri is preferably H or an alkyl group. When Ri is an alkyl group, R is preferably a C1-C6 alkyl group, more preferably a CI to C2 alkyl group. Ri is preferably a CI alkyl group.
R2 is any suitable hydrophobic group, such as a C4-C24 alkyl group, more preferably a C8-C20 alkyl group. R2 can also be alkoxylated. Preferably, R2 is ethoxylated, propoxylated, and combinations thereof. More preferably R2 is ethoxylated. When alkoxylated, R2 can be alkoxylated to a degree of from 1 to 60, preferably from 10 to 50. R3 is preferably H or an alkyl group. When R3 is an alkyl group, R3 is preferably a C1-C6 alkyl group, more preferably a CI to C3 alkyl group. R3 is preferably a C2 alkyl group.
The repeating units comprising R, R1; R2, and R3 can be in any suitable order, or even randomly distributed through the polymer chain.
Suitable HASE polymeric structurants can have a molecular weight of from 50,000 to 500,000 g/mol, preferably from 80,000 to 400,000 g/mol, more preferably from 100,000 to 300,000 g/mol.
The ratio of x:y can be from 1:20 to 20: 1, preferably from 1: 10 to 10: 1, more preferably from 1:5 to 5: 1. The ratio of x:w can be from 1:20 to 20: 1, preferably from 1: 10 to 10: 1, more preferably from 1:5 to 5: 1. The ratio of x:z can be from 1: 1 to 500: 1, preferably from 2: 1 to 250: 1, more preferably from 25 : 1 to 75 : 1.
An example of a suitable HASE polymeric structurants are ACUSOL™ 801S, ACUSOL™805S, ACUSOL™ 820, ACUSOL™ 823, sold by DOW.
HASE polymeric structurants are believed to structure by a combination of polyelectrolytic chain expansion and through association of the hydrophobe groups, present in the HASE polymeric structurant, with other hydrophobes present in the composition, such as the cationic polymers in particulate form.
Methods of making such HASE polymeric structurants are described in U.S. Patent No. 4,514,552, U.S. Patent No. 5,192,592, British Patent No. 870,994, and U.S. Patent No. 7,217,443.
The non-aqueous liquid composition can comprise further structurants, such as hydrogenated castor oil.
The unit dose article
Non-aqueous liquid compositions of the present invention may be comprised in unit dose articles, having at least one liquid filled compartment. A liquid-filled compartment refers to a partition of the unit dose article comprising a liquid capable of wetting a fabric e.g., clothing. Such unit dose articles comprise, in single, easy to use dosage form: a cationic polymer in particulate form, stably suspended in a non-aqueous composition which further comprises polypropylene glycol, encapsulated in a water-soluble or dispersible film.
The unit dose article can be of any form, shape and material which is suitable for holding the non-aqueous composition, i.e. without allowing the release of the non-aqueous composition, and any additional component, from the unit dose article prior to contact of the unit dose article with water. The exact execution will depend, for example, on the type and amount of the compositions in the unit dose article, the number of compartments in the unit dose article, and on the characteristics required from the unit dose article to hold, protect and deliver or release the compositions or components.
The unit dose article comprises a water-soluble or dispersible film which fully encloses at least one inner volume, comprising the non-aqueous composition. The unit dose article may optionally comprise additional compartments comprising non-aqueous liquid and/or solid components. Alternatively, any additional solid component may be suspended in a liquid-filled compartment. A multi-compartment unit dose form may be desirable for such reasons as: separating chemically incompatible ingredients; or where it is desirable for a portion of the ingredients to be released into the wash earlier or later.
It may be preferred that any compartment which comprises a liquid component also comprises an air bubble. The air bubble may have a volume of less than 50%, preferably less than 40%, more preferably less than 30%, more preferably less than 20%, most preferably less than 10% of the volume space of said compartment. Without being bound by theory, it is believed that the presence of the air bubble increases the tolerance of the unit dose article to the movement of the liquid component within the compartment, thus reducing the risk of the liquid component leaking from the compartment.
Water-soluble or dispersible film: The water-soluble or dispersible film typically has a solubility of at least 50%, preferably at least 75%, more preferably at least 95%. The method for determining water-solubility of the film is given in the Test Methods. The water-soluble or dispersible film typically has a dissolution time of less than 100 seconds, preferably less than 85 seconds, more preferably less than 75 seconds, most preferably less than 60 seconds. The method for determining the dissolution time of the film is given in the Test Methods.
Preferred films are polymeric materials, preferably polymers which are formed into a film or sheet. The film can be obtained by casting, blow -moulding, extrusion or blow extrusion of the polymer material, as known in the art. Preferably, the water-soluble or dispersible film comprises: polymers, copolymers or derivatives thereof, including polyvinyl alcohols (PVA), polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum gum and carrageenan. More preferably, the water-soluble or dispersible film comprises: polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates. Most preferably, the water-soluble or dispersible film comprises: polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC). Preferably, the level of polymer or copolymer in the film is at least 60 % by weight. The polymer or copolymer preferably has a weight average molecular weight of from 1000 to 1,000,000, more preferably from 10,000 to 300,000, even more preferably form 15,000 to 200,000, and most preferably from 20,000 to 150,000.
Copolymers and mixtures of polymers can also be used. This may in particular be beneficial to control the mechanical and/or dissolution properties of the compartments or unit dose article, depending on the application thereof and the required needs. For example, it may be preferred that a mixture of polymers is present in the film, whereby one polymer material has a higher water- solubility than another polymer material, and/or one polymer material has a higher mechanical strength than another polymer material. Using copolymers and mixtures of polymers can have other benefits, including improved long-term resiliency of the water-soluble or dispersible film to the detergent ingredients. For instance, US 6,787,512 discloses polyvinyl alcohol copolymer films comprising a hydrolyzed copolymer of vinyl acetate and a second sulfonic acid monomer, for improved resiliency against detergent ingredients. An example of such a film is sold by Monosol of Merrillville, Indiana, US, under the brand name: M8900. It may be preferred that a mixture of polymers is used, having different weight average molecular weights, for example a mixture of polyvinyl alcohol or a copolymer thereof, of a weight average molecular weight of from 10,000 to 40,000, and of another polyvinyl alcohol or copolymer, with a weight average molecular weight of from 100,000 to 300,000.
Also useful are polymer blend compositions, for example comprising hydrolytically degradable and water-soluble polymer blends such as polylactide and polyvinyl alcohol, achieved by the mixing of polylactide and polyvinyl alcohol, typically comprising 1 to 35 % by weight polylactide and from 65 % to 99 % by weight of polyvinyl alcohol. The polymer present in the film may be from 60% to 98% hydrolysed, more preferably from 80% to 90%, to improve the dissolution/dispersion of the film material.
The water-soluble or dispersible film herein may comprise additive ingredients other than the polymer or copolymer material. For example, it may be beneficial to add: plasticisers such as glycerol, ethylene glycol, diethyleneglycol, propylene glycol, sorbitol and mixtures thereof;
additional water; and/or disintegrating aids.
Other suitable examples of commercially available water-soluble films include polyvinyl alcohol and partially hydrolysed polyvinyl acetate, alginates, cellulose ethers such as
carboxymethylcellulose and methylcellulose, polyethylene oxide, polyacrylates and combinations of these. Most preferred are films with similar properties to the polyvinyl alcohol comprising film known under the trade reference M8630, sold by Monosol of Merrillville, Indiana, US.
Process of Making:
The present invention also provides for a preferred process of making a non-aqueous composition of the present invention, comprising the steps of (i) providing a cationic polymer dispersion by combining the cationic polymer with the polypropylene glycol and (ii) combining the cationic polymer dispersion with a non-aqueous liquid feed. Preferably, the cationic polymer dispersion comprises from 1 % to 35 %, more preferably from 10 % to 25 % by weight of the cationic polymer. Since the cationic polymer is in particulate form, the viscosity of the cationic polymer dispersion remains low and it can be easily incorporated into the non-aqueous liquid feed by typical mixing methods. The non-aqueous feed may comprise some or all of the remaining ingredients, including anionic and/or nonionic surfactants.
The process may include a step of forming an external structurant premix, and combining the external structurant premix with the cationic polymer dispersion, or the non-aqueous feed, or the combined cationic polymer dispersion/non-aqueous feed. Preferably, the external structurant premix comprises a structurant selected from hydrogenated castor oil, hydophobically modified ethoxylated urethanes, hydrophobically modified alkali swellable emulsions, and mixture thereof. More preferably, the external structurant premix comprises a structurant selected from hydophobically modified ethoxylated urethanes, hydrophobically modified alkali swellable emulsions, and mixture thereof.
The non-aqueous liquid composition can be comprised in a unit dose article. Such unit dose article can be prepared according to methods known in the art. For instance, the water-soluble or dispersible film is cut to an appropriate size, and then folded to form the necessary number and size of compartments. The edges are then sealed using any suitable technology, for example heat sealing, wet sealing or pressure sealing. Preferably, a sealing source is brought into contact with said film, and heat or pressure is applied to seal the film material.
The water soluble or dispersible film is typically introduced to a mould and a vacuum applied so that said film is flush with the inner surface of the mould, thus forming an indent or niche in said film material. This is referred to as vacuum-forming. Another suitable method is thermo-forming. Thermo-forming typically involves the step of forming a water-soluble or dispersible film in a mould under application of heat, which allows said film to deform and take on the shape of the mould.
Typically more than one piece of water-soluble or dispersible film material is used for making the unit dose article. For example, a first piece of film material can be vacuum pulled into the mould so that said first piece of film material is flush with the inner walls of the mould. A second piece of film material can then be positioned such that it completely overlaps with the first piece of film material. The first piece of film material and second piece of film material are sealed together. The first and second pieces of water-soluble or dispersible film can be made of the same material or can be different materials.
In a process for preparing a multi-compartment unit dose article, a piece of water-soluble or dispersible film material is folded at least twice, or at least three pieces of film material are used, or at least two pieces of film material are used wherein at least one piece of film material is folded at least once. The third piece of film material, or a folded piece of film material, creates a barrier layer that, when the film materials are sealed together, divides the internal volume of the unit dose article into two or more compartments. A multi-compartment unit dose article may also be prepared by fitting a first piece of film material into a mould. A composition, or component thereof, can then be poured into the mould. A pre-formed compartment can then be placed over the mould containing the composition, or component thereof. The pre-formed compartment also preferably contains a composition, or component thereof. The pre-formed compartment and said first piece of water-soluble or dispersible film material are sealed together to form the multi -compartment unit dose article.
TEST METHODS:
1) Method of measuring particle size:
The Occhio Flow Cell FC200-S (Angleur, Belgium) is used to measure the particle size distribution. The sample containing the particles to be analysed is diluted to 1 % by weight, using DPG (dipropylene glycol), to ensure single particle detection. 2 ml of the diluted sample is analysed according to the instructions provided with the device.
2) Method of measuring the solubility of water-soluble or dispersible films:
5.0 grams ± 0.1 gram of the water-soluble or dispersible film is added in a pre- weighed 400 ml beaker and 245ml ± 1ml of distilled water is added. This is stirred vigorously on a magnetic stirrer set at 600 rpm, for 30 minutes. Then, the mixture is filtered through a sintered-glass filter with a pore size of maximum 20 microns. The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining material is determined (which is the dissolved or dispersed fraction). Then, the percentage solubility or dispersibility can be calculated. 3) Method of measuring the dissolution time of water-soluble or dispersible films:
The film is cut and mounted into a folding frame slide mount for 24 mm by 36 mm diapositive film, without glass (part number 94.000.07, supplied by Else, The Netherlands, however plastic folding frames from other suppliers may be used).
A standard 600 ml glass beaker is filled with 500 ml of city water at 10°C and agitated using a magnetic stirring rod such that the bottom of the vortex is at the height of the 400 ml graduation mark on the beaker.
The slide mount is clipped to a vertical bar and suspended into the water, with the 36 mm side horizontal, along the diameter of the beaker, such that the edge of the slide mount is 5 mm from the beaker side, and the top of the slide mount is at the height of the 400 ml graduation mark. The stop watch is started immediately the slide mount is placed in the water, and stopped when the film fully dissolves. This time is recorded as the "film dissolution time".
EXAMPLES
Cationically modified hydroxyethyl cellulose (LK400, ex-DOW), having a weight average molecular weight of 400,000 g/mol and 0.5% nitrogen substitution, was dispersed in the following dispersants: PPG400, PEG200 (comparative), 1,2-propanediol (comparative), and glycerol
(comparative), to form a 4wt% dispersion of the cationically modified hydroxyethyl cellulose. The dispersions were left at room temperature for 1 week. In order to measure the difference in swelling, the height of the sediment, consisting of the swollen cationically modified hydroxyethyl cellulose, was measured.
The cationically modified hydroxyethyl cellulose dispersed in PEG200 swelled to a volume of 240% more than the volume of the cationically modified hydroxyethyl cellulose dispersed in PPG400. The cationically modified hydroxyethyl cellulose dispersed in 1,2-propanediol swelled to a volume of 420% more than the volume of the cationically modified hydroxyethyl cellulose dispersed in PPG400. The cationically modified hydroxyethyl cellulose dispersed in glycerol had fully dissolved after 1 week.
Cationically modified hydroxyethyl cellulose (LR400, ex-DOW), having a weight average molecular weight of 400,000 g/mol and 1 % nitrogen substitution, was dispersed in the following dispersants: PPG400, PEG200 (comparative), 1,2-propanediol (comparative), and glycerol (comparative), to form a 4wt% dispersion of the cationically modified hydroxyethyl cellulose. The dispersions were left at room temperature for 1 week. In order to measure the difference in swelling, the height of the sediment, consisting of the swollen cationically modified hydroxyethyl cellulose, was measured.
The cationically modified hydroxyethyl cellulose dispersed in PEG200 swelled to a volume of 266% more than the volume of the cationically modified hydroxyethyl cellulose dispersed in PPG400. The cationically modified hydroxyethyl cellulose dispersed in 1,2-propanediol, and cationically modified hydroxyethyl cellulose dispersed in glycerol had both fully dissolved after 1 week.
Examples 1 to 7 are compositions comprising a cationic polymer in particulate form, in a non-aqueous composition comprising polypropylene glycol:
Figure imgf000024_0001
Ex 4 Ex 5 Ex 6 Ex 7
Ingredient WT % WT % WT % WT %
Linear alkyl benzene sulfonic acid 17.2 17.2 17.5 17.2
CI 2- 14 Alkyl 3-ethoxylated sulphate
8.1 8.1 8.2 8.1
acid
C12-14 alkyl 7-ethoxylate 12.0 12.0 12.1 12.0
Citric acid 0.6 0.6 0.6 0.6
Palm Kernel Fatty Acid 5.6 5.6 5.7 5.6
Cleaning polymer 4.9 4.9 5.0 4.9
Chelant 1.9 1.9 2.0 1.9
Polymer LK4001 3.7 3.7 3.7 3.7
Polypropyleneglycol 4002 8.8 10.6 8.8 8.8
Polyethyleneglycol 2002 1.8 - 1.8 1.8
Acusol™ 8803 0.2 0.2 0.2 0.2
Glycerol 4.6 2.6 - 4.6
1,2 Propanediol 12.1 14.1 16.3 6.1
Dipropyleneglycol - - - 4.5
Ex 4 Ex 5 Ex 6 Ex 7
Ingredient WT % WT % WT % WT %
Acusol OP3014 0.3 0.3 - 0.3
MEA pH between 7 & 8
Water 9.1 6.0 8.7 10.5
Hydrogenated castor oil (HCO)5 0.2 0.2 0.2 0.2
Others (minors+ laundry adjuncts) up to 100%
1 Supplied by Dow Chemicals, Louisiana, United States
2 Dow Benelux, Herbert H Dowweg Terneuzen, Netherlands
3 The Dow Chemical Company, Midland, Michigan, United States
4 40 wt% dispersion of a styrene/acrylate copolymer, having an average particle size of 0.17 microns
5 Introduced via an external structurant system premix
The non-aqueous liquid compositions of examples 1 to 7 can also be encapsulated in a water- soluble film (such as M8630, supplied by Monosol), to form stable liquid-comprising unit dose articles of the present invention. The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

Claims

CLAIMS What is claimed is:
1. A non-aqueous liquid composition comprising:
a) a cationic polymer in particulate form; and
b) polypropylene glycol.
2. The non-aqueous liquid composition according any preceding claim, wherein the cationic polymer in particulate form has an volume based D90 diameter of less than 300 microns, preferably less than 200 microns, more preferably less than 150 microns.
3. The non-aqueous liquid composition according to any preceding claim, wherein the cationic polymer is a cationic polysaccharide.
4. The non-aqueous liquid composition according to claim 3, wherein the cationic polysaccharide is a cationic cellulose having the structure:
Figure imgf000027_0001
m
Structural Formula I
wherein:
m is an integer from 20 to 10,000
each R4 is H, and R1, R2, R3 are each independently selected from the group consisting of: H; Ci- C32 alkyl; Ci-C32 substituted alkyl, C5-C32 or C6-C32 aryl, C5-C32 or C6-C32 substituted aryl or C6-C32
alkylaryl, or C6-C32 substituted alkylaryl,
Figure imgf000027_0002
wherein:
n is an integer selected from 0 to 10 and
Rx is selected from the group consisting of:
Figure imgf000027_0003
A" is a suitable anion; each R5 is independently selected from the group consisting of: H; Ci-C32 alkyl; Ci-C32 substituted alkyl, C5-C32 or C6-C32 aryl, C5-C32 or C6-C32 substituted aryl, C6-C32 alkylaryl, C6-C32 substituted alkylaryl, and OH;
each R6 is independently selected from the group consisting of: H, Ci-C32 alkyl, Ci-C32 substituted alkyl, C5-C32 or C6-C32 aryl, C5-C32 or C6-C32 substituted aryl, C6-C32 alkylaryl, and C6-C32 substituted alkylaryl;
each T is independently selected from the group: H,
Figure imgf000028_0001
Rs;
Figure imgf000028_0002
each v in said polysaccharide is an integer from 1 to 10; the sum of all v indices in each Rx in said polysaccharide is an integer from 1 to 30; and in the last
OT CH2OT 0T
I I I
— CH2— CH-CH2-0— R5;— CH— CH2— O R5;— CH2— CH-CH2-R5 or
CH2OT
_ C\H _ CH2 _ Rsgroup in a chain, T is always an H.
5. The non-aqueous liquid composition according to any preceding claim, comprising from 0.01 % to 30 %, preferably from 0.05 % to 25 %, more preferably from 0.1 % to 10 % by weight of the cationic polymer in particulate form.
6. The non-aqueous liquid composition according to any preceding claim, comprising from 0.05 % to 98 %, preferably from 0.5 % to 75 %, more preferably from 3 % to 68 % by weight of polypropylene glycol.
7. The non-aqueous liquid composition according to any preceding claim, wherein the
polypropylene glycol has a molecular weight of from 208 g/mol to 4000 g/mol.
8. The non-aqueous liquid composition according to any preceding claim, wherein the
composition further comprises from 0.1 % to 30 %, preferably from 0.5 % to 15 % of spacer particles.
9. The non-aqueous liquid composition according to claim 9, wherein the spacer particles have an volume based D90 diameter of less than 5 microns, preferably from 0.1 microns to 1 micron.
10. The non-aqueous liquid composition according to any preceding claim, wherein the composition further comprises cations, preferably selected from: alkyltrimethylammonium salts, such as C12 alkyltrimethylammonium chloride, or their hydroxyalkyl substituted analogues; and/or polyvalent anions, preferably selected from: Citric Acid; Diethylene triamine pentaacetic acid (DTPA); 1-hydroxyethane 1,1-diphosphonic acid (HEDP); Maleic acid;
Polyacrylates; Polyacrylic/maleic acid copolymers; succinic acid, and mixtures thereof.
11. The non-aqueous liquid composition according to any preceding claim, wherein the
composition further comprises from 0.01% to 10%, preferably from 0.1% to 4% by weight of an external structuring system.
12. The non-aqueous liquid composition according to any preceding claim, wherein the
composition is enclosed in a water-soluble or dispersible film comprising: polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), or mixtures thereof.
13. A process for preparing the non-aqueous liquid composition of claim 1, characterized in that the process comprises the steps of:
a. providing a cationic polymer dispersion by combining the cationic polymer with the polypropylene glycol; and
b. combining the cationic polymer dispersion with a non-aqueous liquid feed.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3178913A1 (en) * 2015-12-10 2017-06-14 The Procter and Gamble Company Liquid laundry detergent composition
US10604723B2 (en) * 2014-11-11 2020-03-31 Rohm And Haas Company Cationic carbohydrate polymers for fabric care
CN113481063A (en) * 2017-12-01 2021-10-08 宝洁公司 Granular laundry softening detergent additive
US11760958B2 (en) 2017-12-01 2023-09-19 The Procter & Gamble Company Particulate laundry softening and freshening wash additive comprising perfume and softener particles
CN113481063B (en) * 2017-12-01 2024-03-22 宝洁公司 Granular laundry softening detergent additive

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Citations (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2438091A (en) 1943-09-06 1948-03-16 American Cyanamid Co Aspartic acid esters and their preparation
US2528378A (en) 1947-09-20 1950-10-31 John J Mccabe Jr Metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates and process for preparation of same
US2658072A (en) 1951-05-17 1953-11-03 Monsanto Chemicals Process of preparing amine sulfonates and products obtained thereof
GB870994A (en) 1956-11-21 1961-06-21 Rohm & Haas Aqueous emulsion copolymers and thickening procedures using them
US3915903A (en) 1972-07-03 1975-10-28 Procter & Gamble Sulfated alkyl ethoxylate-containing detergent composition
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US4234627A (en) 1977-02-04 1980-11-18 The Procter & Gamble Company Fabric conditioning compositions
US4514552A (en) 1984-08-23 1985-04-30 Desoto, Inc. Alkali soluble latex thickeners
US4514461A (en) 1981-08-10 1985-04-30 Woo Yen Kong Fragrance impregnated fabric
US4565647A (en) 1982-04-26 1986-01-21 The Procter & Gamble Company Foaming surfactant compositions
USRE32713E (en) 1980-03-17 1988-07-12 Capsule impregnated fabric
US4882220A (en) 1988-02-02 1989-11-21 Kanebo, Ltd. Fibrous structures having a durable fragrance
US5192592A (en) 1990-07-30 1993-03-09 Union Carbide Chemicals & Plastics Technology Corporation Method of coating substrates utilizing an alkali-functional associative thickner containing coating composition
US5942217A (en) 1997-06-09 1999-08-24 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US5955093A (en) 1997-06-09 1999-09-21 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US5968404A (en) 1997-06-09 1999-10-19 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor and wrinkle control
US6033679A (en) 1998-04-27 2000-03-07 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US6093769A (en) * 1997-11-19 2000-07-25 Hercules Incorporated Fluidized polymer suspensions of cationic polysaccharides in polyols and use thereof in personal care compositions
US6106738A (en) 1997-06-09 2000-08-22 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US6200949B1 (en) 1999-12-21 2001-03-13 International Flavors And Fragrances Inc. Process for forming solid phase controllably releasable fragrance-containing consumable articles
EP0686691B1 (en) 1994-06-10 2001-08-08 The Procter & Gamble Company Aqueous emulsions with brighteners
US20020193256A1 (en) * 2001-01-26 2002-12-19 Benchmark Research And Technology Suspensions of particles in non-aqueous solvents
US6579839B2 (en) 2000-02-23 2003-06-17 The Procter & Gamble Company Liquid laundry detergent compositions having enhanced clay removal benefits
US20030158344A1 (en) 2002-02-08 2003-08-21 Rodriques Klein A. Hydrophobe-amine graft copolymer
US20030165692A1 (en) 2002-01-24 2003-09-04 Friedrich Koch Coagulates containing microcapsules
US20030195133A1 (en) 2002-04-10 2003-10-16 Adi Shefer Targeted controlled delivery compositions activated by changes in pH or salt concentration
US20030203829A1 (en) 2002-04-26 2003-10-30 Adi Shefer Multi component controlled delivery system for fabric care products
US6645479B1 (en) 1997-09-18 2003-11-11 International Flavors & Fragrances Inc. Targeted delivery of active/bioactive and perfuming compositions
US20030215417A1 (en) 2002-04-18 2003-11-20 The Procter & Gamble Company Malodor-controlling compositions comprising odor control agents and microcapsules containing an active material
US20030216488A1 (en) 2002-04-18 2003-11-20 The Procter & Gamble Company Compositions comprising a dispersant and microcapsules containing an active material
EP1393706A1 (en) 2002-08-14 2004-03-03 Quest International B.V. Fragranced compositions comprising encapsulated material
US20040072720A1 (en) 2002-10-10 2004-04-15 Joseph Brain Encapsulated fragrance chemicals
US20040071742A1 (en) 2002-10-10 2004-04-15 Popplewell Lewis Michael Encapsulated fragrance chemicals
US20040071746A1 (en) 2002-10-10 2004-04-15 Popplewell Lewis Michael Encapsulated fragrance chemicals
US20040087477A1 (en) 2001-03-16 2004-05-06 Ness Jeremy Nicholas Perfume encapsulates
US20040106536A1 (en) 2000-03-20 2004-06-03 Jean Mane Solid perfumed preparation in the form of microbeads and the use thereof
US6787512B1 (en) 2003-03-19 2004-09-07 Monosol, Llc Water-soluble copolymer film packet
US7135451B2 (en) 2003-03-25 2006-11-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
US7217443B2 (en) 2000-03-06 2007-05-15 Rohm And Haas Company Binder composition
WO2007107215A1 (en) 2006-03-18 2007-09-27 Unilever Plc Fabric treatment composition and process for preparation thereof
US20090124528A1 (en) 2007-11-09 2009-05-14 James Lee Danziger Cleaning compositions comprising a multi-polymer system comprising at least one alkoxylated grease cleaning polymer
WO2009087034A1 (en) 2008-01-11 2009-07-16 Unilever Plc Shading composition
WO2009087524A1 (en) 2008-01-04 2009-07-16 The Procter & Gamble Company Enzyme and fabric hueing agent containing compositions
WO2011163371A1 (en) 2010-06-24 2011-12-29 The Procter & Gamble Company Stable non-aqueous liquid compositions comprising a cationic polymer in particulate form
WO2013095996A1 (en) * 2011-12-22 2013-06-27 Rohm And Haas Company Nonaqueous method of dispersing a water soluble polymer

Patent Citations (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2438091A (en) 1943-09-06 1948-03-16 American Cyanamid Co Aspartic acid esters and their preparation
US2528378A (en) 1947-09-20 1950-10-31 John J Mccabe Jr Metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates and process for preparation of same
US2658072A (en) 1951-05-17 1953-11-03 Monsanto Chemicals Process of preparing amine sulfonates and products obtained thereof
GB870994A (en) 1956-11-21 1961-06-21 Rohm & Haas Aqueous emulsion copolymers and thickening procedures using them
US3915903A (en) 1972-07-03 1975-10-28 Procter & Gamble Sulfated alkyl ethoxylate-containing detergent composition
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US4234627A (en) 1977-02-04 1980-11-18 The Procter & Gamble Company Fabric conditioning compositions
USRE32713E (en) 1980-03-17 1988-07-12 Capsule impregnated fabric
US4514461A (en) 1981-08-10 1985-04-30 Woo Yen Kong Fragrance impregnated fabric
US4565647A (en) 1982-04-26 1986-01-21 The Procter & Gamble Company Foaming surfactant compositions
US4565647B1 (en) 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
US4514552A (en) 1984-08-23 1985-04-30 Desoto, Inc. Alkali soluble latex thickeners
US4917920A (en) 1988-02-02 1990-04-17 Kanebo, Ltd. Fibrous structures having a durable fragrance and a process for preparing the same
US4882220A (en) 1988-02-02 1989-11-21 Kanebo, Ltd. Fibrous structures having a durable fragrance
US5192592A (en) 1990-07-30 1993-03-09 Union Carbide Chemicals & Plastics Technology Corporation Method of coating substrates utilizing an alkali-functional associative thickner containing coating composition
EP0686691B1 (en) 1994-06-10 2001-08-08 The Procter & Gamble Company Aqueous emulsions with brighteners
US5942217A (en) 1997-06-09 1999-08-24 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US5955093A (en) 1997-06-09 1999-09-21 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US5968404A (en) 1997-06-09 1999-10-19 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor and wrinkle control
US6106738A (en) 1997-06-09 2000-08-22 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US6645479B1 (en) 1997-09-18 2003-11-11 International Flavors & Fragrances Inc. Targeted delivery of active/bioactive and perfuming compositions
US6093769A (en) * 1997-11-19 2000-07-25 Hercules Incorporated Fluidized polymer suspensions of cationic polysaccharides in polyols and use thereof in personal care compositions
US6033679A (en) 1998-04-27 2000-03-07 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US6200949B1 (en) 1999-12-21 2001-03-13 International Flavors And Fragrances Inc. Process for forming solid phase controllably releasable fragrance-containing consumable articles
US6579839B2 (en) 2000-02-23 2003-06-17 The Procter & Gamble Company Liquid laundry detergent compositions having enhanced clay removal benefits
US7217443B2 (en) 2000-03-06 2007-05-15 Rohm And Haas Company Binder composition
US20040106536A1 (en) 2000-03-20 2004-06-03 Jean Mane Solid perfumed preparation in the form of microbeads and the use thereof
US20020193256A1 (en) * 2001-01-26 2002-12-19 Benchmark Research And Technology Suspensions of particles in non-aqueous solvents
US20040087477A1 (en) 2001-03-16 2004-05-06 Ness Jeremy Nicholas Perfume encapsulates
US20030165692A1 (en) 2002-01-24 2003-09-04 Friedrich Koch Coagulates containing microcapsules
US20030158344A1 (en) 2002-02-08 2003-08-21 Rodriques Klein A. Hydrophobe-amine graft copolymer
US20030195133A1 (en) 2002-04-10 2003-10-16 Adi Shefer Targeted controlled delivery compositions activated by changes in pH or salt concentration
US20030215417A1 (en) 2002-04-18 2003-11-20 The Procter & Gamble Company Malodor-controlling compositions comprising odor control agents and microcapsules containing an active material
US20030216488A1 (en) 2002-04-18 2003-11-20 The Procter & Gamble Company Compositions comprising a dispersant and microcapsules containing an active material
US20030203829A1 (en) 2002-04-26 2003-10-30 Adi Shefer Multi component controlled delivery system for fabric care products
EP1393706A1 (en) 2002-08-14 2004-03-03 Quest International B.V. Fragranced compositions comprising encapsulated material
US20040072719A1 (en) 2002-10-10 2004-04-15 Bennett Sydney William Encapsulated fragrance chemicals
US20040071746A1 (en) 2002-10-10 2004-04-15 Popplewell Lewis Michael Encapsulated fragrance chemicals
US20040071742A1 (en) 2002-10-10 2004-04-15 Popplewell Lewis Michael Encapsulated fragrance chemicals
US20040072720A1 (en) 2002-10-10 2004-04-15 Joseph Brain Encapsulated fragrance chemicals
US6787512B1 (en) 2003-03-19 2004-09-07 Monosol, Llc Water-soluble copolymer film packet
US7135451B2 (en) 2003-03-25 2006-11-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
WO2007107215A1 (en) 2006-03-18 2007-09-27 Unilever Plc Fabric treatment composition and process for preparation thereof
US20090124528A1 (en) 2007-11-09 2009-05-14 James Lee Danziger Cleaning compositions comprising a multi-polymer system comprising at least one alkoxylated grease cleaning polymer
WO2009087524A1 (en) 2008-01-04 2009-07-16 The Procter & Gamble Company Enzyme and fabric hueing agent containing compositions
WO2009087034A1 (en) 2008-01-11 2009-07-16 Unilever Plc Shading composition
WO2011163371A1 (en) 2010-06-24 2011-12-29 The Procter & Gamble Company Stable non-aqueous liquid compositions comprising a cationic polymer in particulate form
WO2013095996A1 (en) * 2011-12-22 2013-06-27 Rohm And Haas Company Nonaqueous method of dispersing a water soluble polymer

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"McCutcheon's, Emulsifiers and Detergents", 1989, M. C. PUBLISHING CO.
"Surfactant Science Series", vol. 7, MARCEL DEKKER
"Wet Strength resins and their applications", 1994, TAPPI PRESS
D. B. SOLAREK: "Modified Starches, Properties and Uses", 1986, CRC PRESS

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10604723B2 (en) * 2014-11-11 2020-03-31 Rohm And Haas Company Cationic carbohydrate polymers for fabric care
EP3178913A1 (en) * 2015-12-10 2017-06-14 The Procter and Gamble Company Liquid laundry detergent composition
WO2017100380A1 (en) * 2015-12-10 2017-06-15 The Procter & Gamble Company Liquid laundry detergent composition
CN113481063A (en) * 2017-12-01 2021-10-08 宝洁公司 Granular laundry softening detergent additive
US11760958B2 (en) 2017-12-01 2023-09-19 The Procter & Gamble Company Particulate laundry softening and freshening wash additive comprising perfume and softener particles
CN113481063B (en) * 2017-12-01 2024-03-22 宝洁公司 Granular laundry softening detergent additive

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