WO1999041347A1

WO1999041347A1 - Detergent compositions containing an amine silicone and a polymer inhibiting colour transfer

Info

Publication number: WO1999041347A1
Application number: PCT/FR1999/000269
Authority: WO
Inventors: Eric Aubay; Daniel Joubert; Christine Popoff
Original assignee: Rhodia Chimie
Priority date: 1998-02-11
Filing date: 1999-02-08
Publication date: 1999-08-19
Also published as: AU2284799A

Abstract

The invention concerns the use, in detergent compositions for clothes, as agent for protecting colours of white and coloured clothing, of an amine silicone associated with at least a organic polymer inhibiting colour transfer (preferably polyvinylpyrrolidone). The invention also concerns detergent compositions for washing clothes, comprising an amine silicone (SA) associated with at least an organic polymer inhibiting colour transfer (preferably polyvinylpyrrolidone). Finally, the invention concerns a method for protecting the colours of textile fibre articles by washing said articles in an aqueous medium containing said detergent compositions.

Description

DETERGENT COMPOSITIONS CONTAINING AN AMINE SILICONE AND AN ANTI-TRANSFER COLOR POLYMER

5 The present invention relates to the use, in detergent compositions for laundry, as a color protection agent for white or colored laundry, of an amine silicone in combination with a color transfer inhibitor polymer, it also has for subject laundry detergent compositions comprising said amine silicone associated with a color transfer inhibitor polymer, it further relates to a process for protecting the colors of textile fiber articles by washing said articles using a aqueous medium containing said detergent compositions

It is known to use in laundry detergent compositions, polyvinylpyrro dones, N-oxide polyamines and copolymers of N-vinylpyrrolidone and N-vinylimidazole to limit color transfers during washing. The study of the phenomenon color transfer during a washing machine washing operation, shows a two-step process

a first step corresponding to a desorption of the fixed dyes on the fabrics, by action of the temperature and of the other constituents of the detergent composition,

- then a second step corresponding to the redeposition of said dyes in the 0 state dissolved or dispersed in the washing bath, on other fabrics, with fixing of these dyes during drying of the laundry

It has been found that these color transfer inhibitor polymers or copolymers act only at the second stage, by limiting the redeposition of dissolved or dispersed dyes, by complex formation. On the other hand, due to the chemical absorption equilibria. - desorption of dyes, these polymers can lead to a passivation of colors, because they promote the desorption of the dye

It has now been found that the association with these polymers or copolymers, of an amino silicone allows more effective protection of colors, because it makes it possible to limit both the desorption of colors and the redeposition of dyes. two types of additives therefore provide overall protection for the laundry, whether it is white or colored

A first object of the invention consists in the use, in detergent compositions for linen, as a color protection agent for white or colored linen, of at least one amino silicone (SA) in combination with at least one polymer. 5 organic color transfer inhibitor (PAT)

For a good implementation of the invention, the amounts of amino silicone (SA) and of organic polymer color transfer inhibitor (PAT) in said compositions 2

detergents can be 0.01 to 8% (SA) and 0.05 to 5% (PAT) respectively, preferably 0.1 to 5% (especially 0.3 to 3%) (SA) and 0.2 to 3% (PAT). The weight ratio (SA) / (PAT) ratio can be from 0.1 to 20, preferably from 0.5 to 10. For a good implementation of the invention, said amino silicone (SA) can be chosen from aminopolyorganosiloxanes (APS) comprising siloxane units of general formulas

R ¹ _a Bb If O (4_ _a _ _b 2 (I) where a + b = 3, with a = 0, 1, 2 or 3 and b = 0, 1, 2 or 3

R ¹ _C Aj Si O (4_ _c _d) / 2 (II) where c + d = 2, with c = 0 or 1 and d = 1 or 2

R ¹ 2 If θ2 / 2 (III)

and possibly R ¹ e ^A f ^{If 0} (4-ef) / 2 0) ^or e + f = 0 or 1. with e = 0 or 1 and f = 0 or 1

formulas in which,

^* the symbols R ^1, identical or different, represent a linear or branched, saturated or unsaturated aliphatic radical containing from 1 to 10 carbon or phenyl atoms, optionally substituted by fluoro or cyano groups

^* the identical or different symbols A represent a primary, secondary, tertiary or quaternized amino group, linked to silicon via an SiC- bond

^* identical or different symbols B represent

. an OH function. an OR function, where R represents an alkyl group containing from 1 to 12 carbon atoms, preferably from 3 to 6 carbon atoms, very particularly 4 carbon atoms

. an OCOR 'function, where R "represents an alkyl group containing from 1 to 12 carbon atoms, preferably 1 carbon atom. the symbol A.

Preferably, said aminopolyorganosiloxanes (APS) comprise units of formula (I), (II), (III) and optionally (IV), where

^* in the units of formula (I), a = 1, 2 or 3 and b = 0 or 1 and

* in the units of formula (II), c = 1 and d = 1. Preferably, said symbol A is an amino group of formula

- R ² -N (R ³ ) (R ⁴ ) where 3

^* the symbol R ^ represents an alkylene group containing from 2 to 6 carbon atoms, optionally substituted or interrupted by one or more nitrogen or oxygen atoms,

^* the symbols R ³ and R4, identical or different, represent. H,

. an alkyl or hydroxyalkyl group containing from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms,

. an amino alkyl group, preferably primary, the alkyl group of which contains

I with 12 carbon atoms, preferably from 1 to 6 carbon atoms, optionally substituted and / or interrupted by at least one nitrogen and / or oxygen atom, said amino group being optionally quaternized, for example by an acid hydrohalide or an alkyl or aryl halide.

As example of symbol A, one can in particular mention those of formulas

- (CH ₂ ) ₃ NH ₂ - (CH ₂ ) ₃ NH ₃ ⁺ X- - (CH ₂ ) 3 N (CH ₃ ) ₂ - (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ (C-- ₈ H ₃₇ ) X ^"

- (CH ₂ ) ₃ NHCH ₂ CH ₂ NH ₂ - (CH ₂ ) ₃ N (CH ₂ CH ₂ OH) ₂

- (CH ₂ ) ₃ N (CH ₂ CH ₂ NH ₂ ) ₂

Among these, the preferred formulas are

- (CH ₂ ) ₃ NH ₂ - (CH ₂ ) ₃ NHCH ₂ CH ₂ NH ₂ and - (CH ₂ ) ₃ N (CH ₂ CH ₂ NH ₂ ) ₂ Preferably, the symbol Ri represents methyl groups , ethyl, vinyl, phenyl, trifluoropropyl, cyanopropyl. It particularly represents the methyl group (at least mainly).

Preferably, the symbol B represents an OR group where R contains from 1 to 6 carbon atoms, very particularly 4 carbon atoms, or the symbol A. In a most preferential manner, the symbol B is a methyl or butoxy group.

Preferably, said amino silicone is at least substantially linear. Most preferably, it is linear, that is to say does not contain units of formula (IV).

It can have a number-average molecular mass of the order of 2000 to 50,000, preferably of the order of 3000 to 30,000.

For a good implementation of the invention, said amino silicones (SA) or said aminopolyorganosiloxanes (APS) can present in their chain, for 100 total silicon atoms, from 0.1 to 50, preferably from 0.3 to 10, most particularly from 0.5 to 5 aminofunctionalized silicon atoms. Among the polymers or copolymers which inhibit color transfer (PAT), there may be mentioned:

. polyvinylpyrrolidones (PVP), with an average molecular weight of the order of 5,000 to 400,000, preferably of the order of 5,000 to 200,000, very particularly of 4

10 000 to 50 000 Among the commercial products can be mentioned HP 50 and HP 53 from BASF, the copolymers of N-vinylpyrro done and N-vinylimidazole, linear or branched, mass molécula ^ry average of around 5000 to 1 000 000, preferably of the order of 5000 to 200 000, especially from 10 000 to 20 000, having a ratio mola ^ry N-vmylimidazole / N-vinylpyrrohdone from 1/1 to 0.2 / 1, preferably from

0.8 / 1 to 0.3 / 1, most preferably from 0.6 / 1 to 0.4 / 1, the polyam ⁱ nes N-oxide random or block having an amine / amine N-oxide 10/1 at 1 / 1,000,000, with an average molecular weight of the order of 500 to 1,000,000, preferably of the order of 1,000 to 100,000, especially 5,000 to 100,000, such as poly (4-vιnylpyrιdιne -N-oxide) in particular, in particular poly (4-vιnylpyrιdιne-N-oxide) with an average molecular weight of approximately 50,000 and having an amine / amine N-oxide ratio of 1/4 Preferably, the colored anti-transfer organic polymer is chosen from polyvinyipyrrolidones (PVP).

According to a first particular embodiment, the combination formed by said silicone am ⁱ born (SA) and the organic polymeric color transfer inhibitors (PAT), the polyvinyipyrrolidones (PVP) in particular, further comprises a cellulase The amount of cellulase may be present, _j can range up to 5 mg, preferably 0.01 mg to 3 mg of active enzyme per gram of detergent composition

Among the cellulases, mention may be made of those described in US-A-4,435,307, GB-A-2,075,028, GB-A-2,095,275, GB-A-1,368,599, WO 92/13057, mention may in particular be made of those marketed by NOVO under the names of CELLUZYME and very particularly of CAREZYME According to a second particular embodiment, the combination formed by said amino silicone (SA) and organic color transfer inhibitor polymers (PAT), polyvinyipyrrolidones (PVP) in particular, further comprises an anti-shrinkage polymer (SRP)

The amount of anti-drying polymer (SRP) can range up to 10%, preferably from 0.1 to 5% of the weight of the detergent composition.

Among the antiperspirant polymers (SRP), non-ionic or anionic, especially terephthalic, water-soluble or water-dispersible copolyesters, preferably water-soluble or water-dispersible terephthalic copolyesters (SRP), may be polymers or oligomers whose chain comprises terephthaloyl units, oxyalkylene and / or polyoxyalkylene units in which the alkylene group is linear, cyclic or branched at C ₂ -C7, preferably linear at C ₂ or branched at C ₃ , they may optionally further comprise in their chain and or chain end (s) 5

units carrying one or more sulphonic functions SO ₃ " ⁺ , where M represents H or a cation capable of forming a salt, in particular an alkali metal salt (sodium in particular).

Units carrying sulfonic functions in the chain can be units derived from aromatic or aiiphatic diacids or diesters, such as for example isophthaloylsulfonic, terephthaloylsulfonic, succinylsulfonic units, etc. oxyalkylene or polyoxyalkylene units substituted with at least one alkylene sulfonic function, the alkylene radical is optionally interrupted by one or more oxygen atoms, oxyalkylenesulfonic whose alkylene radical is optionally interrupted by one or more oxygen atoms, arylenesulfonic, oxyarylene sulfonic, alkyleneoxyarylene sulfonic whose alkylene radical is optionally interrupted oxygen, etc. The sulphonic functions which may be present on chain end unit (s) may for example be alkylene sulphonic, benzoylsulphonic, phenylenesulphonic functions, etc.

As examples of an anti-fouling copoiyester, one can mention

- polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units, with a molar ratio (number of units) ethylèrje terephthalate and / or propylene terephthalate / (number of units) polyoxyethylene terephthalate of the order of 1 / 10 to 10/1, the polyoxyethylene terephthalate units having polyoxyethylene units having a molecular weight of the order of 300 to 10,000, with a molecular weight of the copoyester of the order of 1000 to 100,000

- polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene and / or polyoxypropyiene units, with a molar ratio (number of units) of ethylene terephthalate and / or propylene terephthalate / (number of units) of polyoxyethylene and / or polyoxypropylene on the order of 1/10 to 10/1, the polyoxyethylene and / or polyoxypropyiene units having a molecular weight of the order of 250 to 10,000, with a molecular weight of the copoyester of the order of 1000 to 100,000

(US-A-3,959,230, US-A-3,962,152, US-A-3,893,929, US-A-4,116,896, US-A-4,702,857, US-A-4,770,666, EP -A-253 567, EP-A-201 124)

- ethylene or propylene terephthalate / polyoxyethylene terephthalate copolymers comprising sulfoisophthaloye units in their chain (US-A-4,711,730; US-A-4,702,857; US-A-4,713 194)

- terephthalic copolyester oligomers with a sulfonated, sulfoaroyed polyalkyleneoxyalkyl ending and possibly containing sulfoisophthaloye units in their chain (US-A-4,721,580; US-A-5,415,807; US-A-4,877,896; US-A-5 182,043; US-A-5,599,782; US-A-4,764,289; EP-A-311,342; WO92 / 04433; WO97 / 42293) 6

- sulfonated terephthalic copolyesters with a molecular mass of less than 20,000, obtained for example from a diester of terephthaic acid, isophthalic acid, a d ⁱ ester of sulfoisophtahic acid and a diol , ethylene glycol in particular (WO95 / 32997) - the polyesters-polyurethanes obtained by reaction of a polyester of molecular mass in number 300-4000 obtained starting from a diester of terephtahque acid, possibly of a d ⁱ ester sulfoisophtahic acid and a diol, on a prepolymer with terminal isocyanate groups obtained from a polyoxyethylene glycol with a molecular weight of 600-4000 and a diisocyanate (US-A-4 201 824) - ol ⁱ Gomeres sulfonated polyesters obtained by sulfonation of a ohgomere derivative allyhque alcohol ethoxylate, dimethyl terephthalate and 1, 2 propylene diol, p _re feeling

1 to 4 sulfonated groups (US-A-4,968,451).

The detergent compositions in which said silicone amine (SA) associated with an organic color transfer inhibitor polymer (PAT), polyvinylpyrrolidone in particular (PVP), is used as a color protection agent for white or colored linen, comprise on the order of 5 to 70%, preferably at least 5 to 50% of at least one surfactant.

^Ong surfactants include anionic or nonionic surfactants conventionally used in the field of detergents for washing laundry, such as anioniαues surfactants such as alkyl ester sulphonates of formula R-CH (S0 ₃ M) -COOR ', where R represents an alkyl radical C _{_8-20,} preferably C ₁₀ -C _16, R' an alkyl radical in C-ι-C _6, preferably C 1 -C 3 and a M alkali metal (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, tπméthyl- or tetramethylammonium, dimethylpiperidinium). Der ⁱ vee of an alkanolamine (monoéthanolamme, diethanolamine, tπéthanoiamine.), alkyl sulfates of formula ROS0 ₃ M, where R represents a C ₅ -C ₂₄ , preferably C ₁₀ -C ₁₈ , alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, pr feeling on average from 0.5 to 30, preferably from 0.5 to 10 EO or PO units and;

. the alkylamide sulfates of formula RCONHROSO3M where R represents a C ₂ -C ₂₂ , preferably C ₆ -C ₂₀ , alkyl radical, R ′ a C ₂ -C ₃ alkyl radical,

M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and or propoxylenated derivatives (OP), having on average from 0.5 to 60 OE and or OP units; salts of saturated or unsaturated Cs-C ₂ 4, preferably C 14 -C ₂ n fatty acids, C ₉ -C ₂₀ alkylbenzenesulfona.es, primary or secondary alkylsulfonates in 7

^c 8 ^"c 22- ^{alkylglyceryl} sulphonates, the sulphonated polycarboxylic acids described in GB-A-1,082,179, paraffin sulphonates, N-acyl N-alkyl taurates, alkyl phosphates, isethionates, alkylsuccinamates, sulfosuccinates, monoesters or sulfosuccinate diesters, N-acyl sarcosinates, alkyl glycoside sulfates, polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derivative of an alkanolamine (monoethanoiamine, diethanolamine, triethanolamine ...); sophorolipids, such as those in acid or lactone form, derivatives of 17-hydroxyoctadecenic acid;

nonionic surfactants such as polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated, polyoxybutylene) alkylphenols in which the alkyl substituent is C ₈ -Cι ₂ and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of the TRITON X-45, X-114, X-100 or X-102 sold by Rohm & Haas Cy., the IGEPAL NP2 to NP17 from RHONE-POULENC;

. polyoxyalkylenated C ₈ -C ₂ aliphatic alcohols containing from 1 to 25 oxyalkylene units (oxyethylene, oxypropyiene); by way of example, mention may be made of TERGITOL 15-S-9, TERGITOL 24-L-6 NMW sold by Union Carbide Corp., NEODOL 45-

9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 marketed by Shell Chemical

Cy, KYRO EOB marketed by The Procter & Gamble Cy, SYNPERONIC A3 to A9 from ICI, RHODASURF IT, DB and B from RHONE-POULENC;

. products resulting from the condensation of ethylene oxide or propylene oxide with propylene glycol, ethylene glycol, with a molecular weight by weight of the order of 2000 to 10,000, such as the PLURONICs sold by BASF ;

. products resulting from the condensation of ethylene oxide or propylene oxide with ethylenediamine, such as TETRONIC sold by BASF;

. ethoxylated fatty acids and / or propoxylated C ₈ -C _{l 8} containing from 5 to 25 ethoxylated and / or propoxylated;

. amides of C ₈ -C r _j fatty acids containing from 5 to 30 ethoxylated units;

. ethoxylated amines containing from 5 to 30 ethoxylated units;

. alkoxyated amidoamines containing from 1 to 50, preferably from 1 to 25, very particularly from 2 to 20 oxyalkylene units (preferably oxyethylene;. amine oxides such as C-irj-Clδ alkyl oxides dimethylamines, alkoxy oxides C ₈ -C ₂ ethyl dihydroxy ethylamines;

. alkoxylated terpene hydrocarbons such as ethoxylated and / or propoxylated a- or b-pinenes, containing from 1 to 30 oxyethylene and or oxypropyiene units; 8

. alkylpolyglycosides obtainable by condensation (for example by acid catalysis) of glucose with primary fatty alcohols (US-A-3,598,865; US-A-4,565,647; EP-A-132,043; EP-A-132 046 ...) having a C ₄ -C ₂ alkyl group, preferably C ₈ -C- | ₈ , as well as an average number of glucose units of the order of 0.5 to 3, preferably of the order of 1.1 to 1.8, per mole of alkylpolyglycoside (APG); we can mention in particular those presenting

^* a C ₈ -C 4 alkyl group and on average 1, 4 glucose unit per mole

^* a C- alkyl group | ₂ -Ci4 and on average 1, 4 glucose unit per mole

^* a C ₈ -C -4 alkyl group and on average 1, 5 glucose unit per mole ^* a C ₈ -C alkyl group < _| <_, and on average 1, 6 glucose unit per mole sold respectively under the names GLUCOPON 600 EC®, GLUCOPON 600 CSUP®, GLUCOPON 650 EC®, GLUCOPON 225 CSUP®, by HENKEL

Said compositions can also comprise usual additives, such as mineral or organic builders, in an amount such that the total amount of detergency builder is of the order of 5 to 50% by weight of said composition, detergency builders such as

- polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines - tetraborates or borate precursors

- alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates)

- alkali metal silicates

- co-granules of hydrated alkali metal silicates and alkali metal carbonates (sodium or potassium) rich in silicon atoms in Q2 or Q3 form, described in EP-A-488 868, for powdered detergent compositions

- crystalline or amorphous aluminosiiicates of alkali metals (sodium, potassium) or ammonium, such as zeolites A, P, X, ...

- water-soluble polyphosphonates (1-hydroxy-1, 1-diphosphonate ethane, methylene diphosphonate salts, etc.) - water-soluble salts of carboxylic polymers or copolymers such as the water-soluble salts of polycarboxylic acids of molecular order from 2000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and very particularly polyacrylates of molecular mass of the order of 2,000 to 10,000 (US-A-3,308,067), the copolymers of acrylic acid and 9

of maleic anhydride with a molecular mass of the order of 5,000 to 75,000 (EP-A-66,915)

- polycarboxylate ethers (oxidisuccinic acid and its salts, monosuccinic tartrate acid and its salts, disuccinic acid tartrate and its salts - hydroxypolycarboxylate ethers

- citric acid and its salts, mellitic acid, succinic acid and their salts

- the salts of polyacetic acids (ethylenediaminetetraacetates, nitrilotriacetates, N-

(2 hydroxyethyl) -nitrilodiacetates)

- C5-C20 succinic alkyl acids and their salts (2-dodecenylsuccinates, lauryl succinates, ...)

- carboxylic polyacetal esters

- polyaspartic acid, polyglutamic acid and their salts

- polyimides derived from the polycondensation of aspartic acid and / or glutamic acid - polycarboxymethylated derivatives of glutamic acid [such as N, N- bis (carboxymethyl) glutamic acid and its salts, especially sodium ] or other amino acids

- aminophosphonates such as nitrilotris (methyiene phosphonates) other anti-fouling agents, in amounts of the order of 0.01-10%, preferably of the order of 0.1 to 5%, and very particularly of 0.2-3% by weight, agents such as

- cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose

- polyvinyl esters grafted on polyalkyiene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048)

- polyvinyl alcohols of anti-redeposition agents. in amounts of about 0.01-10% by weight for a powdered detergent composition, about 0.01-5% by weight for a liquid detergent composition, agents such as - carboxymethylcellulose

- the sulfonated polyester oligomers obtained by condensation of isophthalic acid, of dimethyl sulfosuccinate and of diethylene glycol (FR-A-2 236 926); bleaching agents, in an amount of about 0.1-20%, preferably 1-10% of the weight of said powdered detergent composition, such as 10

- perborates such as sodium perborate monohydrate or tetrahydrate

- peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, failed urea peroxyhyd, sodium peroxide, sodium persulfate - percarboxy acids and their salts (called "percarbonates") such as monoperoxyphthalate magnesium hexahydrate, magnesium metachloroperbenzoate, 4-nonylamιno-4-oxoperoxybutyrιque acid, 6-nonylamιno-6- oxoperoxycaproic acid, diperoxydodecanedioic acid, peroxysuccinic acid nonylamide, decyldiperoxysuccinic acid. preferably associated with a bleach activator generating in situ in the detergent medium, a peroxyacid carboxy as; among these activators, mention may be made of tetraacetylethylene diamme, tetraacetyl methylene diamme, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulfonate, pentaacetyl glucose, octaacetyl lactose, ... about 0.05-1.2% by weight, agents such as stilbene derivatives, pyrazohne, coumaπne, fumanic acid, cinnamic acid, azoles, methinecyanins, thiophenes, ... foam suppressants, in amounts up to 'to 5% by weight, agents such as - monocarboxylic fatty acids in C- | QC ₂ 4 or their alkali, ammonium or alkanolamine salts, triglycerides of fatty acids

- saturated or unsaturated, ahphatic, cycic, aromatic or heterocyclic hydrocarbons, such as paraffins, waxes

- N-alkyiaminotπazines - monostearylphosphates, monostearyl alcohol phosphates

- polyorganosiloxane oils or resins optionally combined with silica particles, softening agents, in amounts of about 0.5-10% by weight, agents such as clays of enzymes in amounts up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of detergent composition, enzymes such as proteases, amylases, hpases, peroxidases (US-A-3,553,139, US-A-4,101,457, US-A-4,507,219, US-A-4,261,868) and other additives such as 11

- alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerin)

- buffering agents or fillers such as sodium sulphate, carbonates or bicarbonates of alkaline earth metals. - pigments

A second subject of the invention consists of detergent compositions for washing clothes, comprising at least one amino silicone (SA) in combination with at least one organic color transfer inhibitor polymer (PAT).

The amounts of amino silicone (SA) and of organic polymer color transfer inhibitor (PAT) in said detergent compositions can be respectively from 0.01 to 8% (SA) and from 0.05 to 5% (PAT), preferably 0.1 to 5% (especially 0.3 to 3%) (SA) and 0.2 to 3% (PAT).

The weight ratio (SA) / (PAT) ratio can be from 0.1 to 20, preferably from 0.5 to 10. According to a first particular embodiment, said detergent compositions also comprise a cellulase.

The amount of cellulase which may be present can range up to 5 mg, preferably from 0.01 mg to 3 mg of active enzyme per gram of detergent composition.

According to a second particular embodiment, said detergent compositions also comprise an anti-fouling polymer (SRP). The amount of anti-fouling polymer (SRP) can range up to 10%, preferably from 0.1 to 5% of the weight of the detergent composition.

Examples of amino silicone (SA), organic polymer transfer color inhibitor (PAT), cellulase and anti-fouling polymer (SRP) have already been mentioned above. Said detergent compositions also comprise at least one surfactant.

Examples of surfactants have already been mentioned above. Said detergent compositions may also comprise usual constituents of detergent compositions for laundry, constituents which have already been mentioned above.

A final object of the invention consists in a process for protecting the colors of articles made of textile fibers (cotton in particular), colored in particular, by washing said textiles with an aqueous medium containing water and a quantity effective of said detergent compositions. Said aqueous medium can contain around 0.5 to 10 grams / liter of detergent composition. 12

It can be industrial or household washes, in a washing machine or by hand. Washing operations can be carried out at a temperature of around 25 to 90 ° C, preferably from 30 to 60 ° C

The following examples are given without limitation.

Examples

Amino silicone / PVP The amino silicone tested is the aminopolydimethylsiloxane of formula

MeO-Si (Me) ₂ -0- [Si (Me) ₂ -0] _x - [Si (Me) (A) -0] _y -Si (Me) ₂ OMe where

. x is 135 and y is 1.5

. A represents the group - (CH ₂ ) ₃ -NH- (CH ₂ ) ₂ -NH ₂ . Me represents the methyl group

The polyvinylpyrrolidone used is HP 50 from BASF.

Color protection

The color protection measures of detergent compositions comprising an amino silicone associated with a polyvinylpyrrolidone were carried out as follows: PRINCIPLE

The test simulates a simplified machine wash, using a tergotometer. It consists of washing together at 60 ° C, standard test tubes of clean red fabric and clean white fabric, with a detergent formulation

. containing an amino silicone associated with a polyvinylpyrrolidone (formulation A). containing an amino silicone (without polyvinylpyrrolidone) (formulation B)

. containing a polyvinylpyrrolidone (without amino silicone) (formulation C)

. containing neither amino silicone nor polyvinylpyrrolidone (formulation D)

The washing lasts 20 minutes and the deterioration of the color of the pieces of fabric is measured using a colorimeter; discoloration and dye transfer are evaluated by measuring the reflectances before and after washing.

APPARATUS and MATERIAL

- Tergotometer: "U.S. TESTING Co Inc" HOBOKEN N.J. Model 7243.

- Glazing machine for ironing fabric samples after washing.

- "Dr Lange LUC1 100" color measuring device. The fabrics tested are the following (standard fabrics manufactured by the CFT - Center For Test materials -):

Clean cotton R2 (red) 2 pieces per test

Clean cotton CN1 (white) 2 pieces per test 13

OPERATING MODE

The tergotometer is a device made up of 4 2-liter stainless steel pots on which agitators are fitted, which can be set to 100 cycles per minute. The pots are placed in a tank of water regulated at 60 ° C. In each pot we put 1 liter of water (French hardness 30 ° TH, obtained by diluting Contrexéville water) containing the formulation to be tested.

When the water is at temperature, the pots are introduced into the thermostatically controlled bath, simultaneously stirring and a stopwatch.

Washing takes 20 minutes; the fabrics are then rinsed three times with tap water, then wrung by hand and dried flat individually between two sheets of white absorbent paper.

The fabrics are again placed between two sheets of clean absorbent paper and ironed in a freezer at a temperature close to 110 ° C.

MEASUREMENT The color measurements are carried out with the colorimeter before and after washing, according to the "L", "a", "b" system (scale from black to white, from green to red, and from blue to yellow), to measure the variation in intensity of red color Δa = a after washing - a before washing.

Detergent formulations A, B, C and D, the composition of which (expressed in parts by weight) appears in Table 1 below, are tested as described above.

The results obtained are shown in Table 2.

These results show that:

- only formula A, according to the invention, provides effective protection for white and colored linen, since a low color transfer is obtained on white cotton (low Δa value) and slight discoloration of red cotton (low Δa value absolute)

- formula C, comprising only PVP, provides a slight color transfer on white cotton (low Δa value) but it leads to greater discoloration of red cotton than formulation A (absolute value of Δa of C> absolute value of Δa of

AT) ; - formulas B and D without PVP do not reduce the color transfer on white cotton (high Δa value). 14

Table 1

Formula A B C D Comparative Comparative Comparative

Zéo te 4A 25 25 25 25

Silicate 2 SiO ?, Na? 0 5 5 5 5

Sodium carbonate 15 15 15 15 acrylate / methacrylate copolymer 5 5 5 5 Sokalan CP5

Sodium sulfate 7.5 8.5 9.5 10.5

CMC blanose 7MXF 1 1 1 1

Perborate monohydrate 15 15 15 15

TAED granulated 5 5 5 5

Anionic surfactant 6 6 6 6 LABS Nansa

Non-ionic surfactant Symperonic A3 3 3 3 3 (ethoxylated alcohol 3 EO)

Non-ionic surfactant Symperonic A9 9 9 9 9 (ethoxylated alcohol 9 OE)

Enzymes (esperases, amylases, 0.5 0.5 0.5 0.5 cellulase, protease)

Amino silicone 2.0 2.0 0.0 0.0

PVP

1.0 0.0 0.0 0.0

Table 2

Formula A B C D Comparative Comparative Comparative

Δa 3.1 15.7 2.8 18.5 white cotton

Δa -2.5 -2.9 -3.9 -2.6 red cotton

Claims

15

1) Use, in detergent compositions for linen, as a color protection agent for white or colored linen, of an amino silicone (SA) in combination with at least one organic polymer which inhibits color transfer (PAT).

2) Use according to claim 1) characterized in that the amounts of amino silicone (SA) and of organic polymer color transfer inhibitor (PAT) in said detergent compositions are respectively from 0.01 to 8% (SA) and 0.05 to 5% (PAT), preferably 0.1 to 5% (especially 0.3 to 3%) (SA) and 0.2 to 3% (PAT).

3) Use according to claim 1) or 2) characterized in that the weight ratio (SA) / (PAT) is from 0.1 to 20, preferably from 0.5 to 10.

4) Use according to any one of claims 1) to 3), characterized in that said amino silicone (SA) is chosen from aminopolyorganosiloxanes (APS) comprising siloxane units of general formulas

R ¹ a ^{B If 0} (4-ab) / 2 (0 ^or a + b = 3, with a = 0, 1, 2 or 3 and b = 0, 1, 2 or 3

R ¹ c ^A d ^Si ° (4-cd) / 2 (") ^{or c + d =} 2, with c = 0 or 1 and d = 1 or 2

R ¹ 2 ^{If 0} 2/2 C ")

and eventually

R _e Af Si O (4_ _e _f) / ₂ (IV) where e + f = 0 or 1, with e = 0 or 1 and f = 0 or 1

formulas in which * the identical or different symbols R represent a linear or branched, saturated or unsaturated aliphatic radical containing from 1 to 10 carbon atoms or phenyl, optionally substituted by fluoro or cyano groups

* the identical or different symbols A represent a primary, secondary, tertiary or quaternized amino group, linked to silicon via a SIC- bond, * the identical or different symbols B represent. an OH function 16

. an OR function, where R represents an alkyl group containing from 1 to 12 carbon atoms, preferably from 3 to 6 carbon atoms, very particularly 4 carbon atoms

. an OCOR 'function, where R' represents an alkyl group containing from 1 to 12 carbon atoms, preferably 1 carbon atom

. the symbol A.

5) Use according to claim 4), characterized in that

^* in the units of formula (I), a = 1, 2 or 3 and b = 0 or 1, and * in the units of formula (II), c = 1 and d = 1.

6) Use according to claim 4) or 5), characterized in that said symbol A is an amino group of formula

- R ² -N (R ³ ) (R ⁴ ) where

^* the symbol R ² represents an alkylene group containing from 2 to 6 carbon atoms, optionally substituted or interrupted by one or more nitrogen or oxygen atoms,

^* the symbols R ³ and R ⁴ , identical or different, represent. H,

. an amino alkyl group, preferably primary, the alkyl group of which contains from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, optionally substituted and / or interrupted by at least one nitrogen atom and / or d oxygen, said amino group being optionally quaternized.

7) Use according to any one of claims 4) to 6), characterized in that the symbol A has the formula - (CH ₂ ) ₃ NH ₂ - (CH ₂ ) ₃ NH ₃ ⁺ X "

- (CH ₂ ) ₃ N (CH ₃ ) ₂ - (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ (C ₈ H ₃₇ ) X ^'

- (CH ₂ ) ₃ NHCH ₂ CH ₂ NH ₂ - (CH ₂ ) ₃ N (CH ₂ CH ₂ OH) ₂ - (CH ₂ ) ₃ N (CH ₂ CH ₂ NH ₂ )

8) Use according to any one of claims 4) to 7), characterized in that the symbol R1 represents a methyl, ethyl, vinyl, phenyl, trifluoropropyl, cyanopropyl group, very particularly the methyl group. 17

9) Use according to any one of claims 4) to 8), characterized in that the symbol B represents

. an OR group where R contains from 1 to 6 carbon atoms, very particularly 4 carbon atoms,. or the symbol A.

10) Use according to any one of claims 1) to 9), characterized in that said amino silicone is at least substantially linear, preferably completely linear.

11) Use according to any one of claims 1) to 10), characterized in that said amino silicone has a number average molecular weight of the order of 2000 to 50,000, preferably of the order of 3000 to 30 000.

12) Use according to any one of claims 1) to 11), characterized in that said amino silicone (SA) or said aminopolyorganosiioxane (APS) present in its chain, for 100 atoms of total silicon, from 0.1 to 50 , preferably from 0.3 to 10, very particularly from 0.5 to 5 aminofunctionalized silicon atoms.

^~ 13) Use according to any one of claims 1) to 12), characterized in that the organic polymer transfer color inhibitor (PAT), is chosen from:. polyvinyipyrrolidones (PVP), with an average molecular weight of the order of 5,000 to 400,000, preferably of the order of 5,000 to 200,000, very particularly of 10,000 to 50,000; . linear or branched N-vinylpyrrolidone and N-vinylimidazole copolymers, of average molecular weight of the order of 5,000 to 1,000,000, preferably of the order of 5,000 to 200,000, very particularly of 10,000 to 20,000, having an N-vinylimidazole / N-vinylpyrrolidone molar ratio of 1/1 to 0.2 / 1, preferably from 0.8 / 1 to 0.3 / 1, very particularly from 0.6 / 1 to 0 , 4/1; . random or block N-oxide polyamines having an amine / amine N-oxide ratio of 10/1 to 1 / 1,000,000, with an average molecular weight of the order of 500 to 1,000,000, preferably of the order of 1 000 to 100,000, particularly from 5,000 to 100,000, such as poly (4-vinylpyridine-N-oxide) in particular, in particular poly (4-vinylpyridine-N-oxide) with an average molecular weight of approximately 50,000 and having an amine / amine N-oxide ratio of 1/4. 18

14) Use according to claim 13), characterized in that the organic color transfer inhibitor polymer (PAT), is chosen from polyvinylpyrroiidones (PVP).

15) Use according to any one of claims 1) to 14), characterized in that the combination formed by said amino silicone (SA) and organic color transfer inhibitor polymers (PAT) further comprises a cellulase.

16) Use according to claim 15), characterized in that the amount of cellulase is up to 5 mg, preferably from 0.01 mg to 3 mg of active enzyme per gram of detergent composition.

17) Use according to any one of claims 1) to 16), characterized in that the combination formed by said amino silicone (SA) and organic color transfer inhibitor polymers (PAT) further comprises an anti-polymer soiling.

18) Use according to claim 17), characterized in that the amount of anti-fouling polymer is up to 10%, preferably from 0.1 to 5% relative to the detergent composition.

19) Use according to any one of claims 1) to 18) in detergent compositions for laundry comprising of the order of 1 to 70%, preferably 5 to 50% of at least one surfactant.

20) Detergent compositions for washing clothes, comprising at least one amino silicone (SA) in combination with at least one organic color transfer inhibitor polymer (PAT).

21) Detergent compositions according to claim 20) characterized in that the amounts of amino silicone (SA) and of organic polymer color transfer inhibitor (PAT) are respectively from 0.01 to 8% (SA) and from 0.05 to 5% (PAT), preferably from 0.1 to 5% (very particularly 0.3 to 3%) (SA) and from 0.2 to 3% (PAT) of the weight of said detergent compositions.

22) Detergent compositions according to claim 20) or 21), characterized in that the weight ratio (SA) / (PAT) is 0.1 to 20, preferably 0.5 to 10. 19

23) Detergent compositions according to any one of claims 20) to 22), characterized in that said amino silicone (SA) and said organic color transfer inhibitor polymer (PAT) are chosen from those defined in claims 4), 5 ), 6), 7), 8), 9), 10), 11), 12), or 13).

24) Detergent compositions according to any one of claims 20) to 23), characterized in that they further comprise a cellulase.

25) Detergent compositions according to claim 24), characterized in that the amount of cellulase is up to 5 mg, preferably from 0.01 mg to 3 mg of active enzyme per gram of detergent composition.

26) Detergent compositions according to any one of claims 20) to 25), characterized in that they comprise an anti-fouling polymer.

27) Detergent compositions according to claim 26), characterized in that the amount of anti-fouling polymer is up to 10%, preferably is of the order of 0.1 to 5% by weight of said compositions.

28) Detergent compositions according to any one of claims 20) to 27), characterized in that they comprise at least one surfactant.

29) Method for protecting the colors of articles made of textile fibers by washing said articles using an aqueous medium containing the detergent compositions forming the subject of any one of claims 20) to 28).

30) Method according to claim 29), characterized in that said aqueous medium contains of the order of 0.5 to 10 grams / liter of said detergent composition.

31) Method according to claim 29) or 30), characterized in that said washing is carried out at a temperature of the order of 25 to 90 ° C, preferably from 30 to 60 ° C