CZ2000131A3 - Aqueous decoloring agent of keratin fibers intended for direct use and containing a mixture of water-soluble solvent and amphiphilic non-ionic or anionic polymer with at least one aliphatic chain - Google Patents

Abstract

The present invention relates to aqueous bleaching compositions keratin fibers, especially human keratin fibers, intended for direct use and containing, in the environment suitable for bleaching, at least one alkaline agent, at least one peroxidated salt and hydrogen peroxide; at least one water-soluble solvent and at least one amphiphilic non-ionic and / or anionic polymer with at least one one aliphatic chain, and one discoloration process hair using these aqueous remedies.

Description

A ready-to-use aqueous bleaching composition for keratin fibers, comprising a mixture of a water-soluble solvent and an amphiphilic nonionic or anionic polymer with at least one aliphatic chain.

Technical field

FIELD OF THE INVENTION The present invention relates to aqueous compositions for the bleaching of ready-to-use keratin fibers comprising a mixture of at least one water-soluble solvent and at least one amphiphilic nonionic and / or anionic polymer with at least one aliphatic chain. a process for decolorizing keratin fibers using such compositions and one package containing such a composition.

BACKGROUND OF THE INVENTION

Aqueous bleaching compositions formed by mixing, at the time of use, an aqueous composition comprising hydrogen peroxide with an aqueous composition containing an alkaline agent and at least one water-soluble solvent and a powder containing a peroxygenated reagent such as peroxosulfate, perborate, ammonium percarbonate or persulfates, perborates or alkali metal percarbonates.

For the bleaching of hair, the bleaching compositions are generally densely dense to be applied to a particular area of hairstyle and to prevent the composition from flowing to the face or outside the bleaching area.

The thickening or gelling effect is usually achieved by traditional thickeners such as cellulose derivatives, amidone derivatives, alginates, thickeners of silicon oxides or mixtures of reasonably selected surfactants.

However, using these traditional thickening agents, the resulting decolorizing agent significantly reduces the viscosity over time.

• ·

4.

• ··· · · · ·

Thus, there is a need for a thickening system that is capable of maintaining high viscosity throughout the decolorization process, which typically takes from 10 minutes to 1 hour.

SUMMARY OF THE INVENTION

The applicant has made a surprising discovery that it is possible to significantly improve the viscosity retention of the above-described bleaching composition by admixing the starting composition with an amphiphilic nonionic and / or anionic polymer with at least one aliphatic chain.

At the same time, it has been found that such a thickening system allows greater dilution with hydrogen peroxide-containing compositions than previously known thickening agents.

The invention therefore relates to an aqueous composition for decolorizing keratin fibers, in particular human, ready to use and comprising in a suitable decolorizing environment at least one basic agent, at least one water-soluble solvent, hydrogen peroxide, at least one peroxydated salt and at least one amphiphilic a nonionic and / or anionic polymer with at least one aliphatic chain.

In addition, the invention relates to one process for decolorizing keratin fibers using the above aqueous bleaching compositions, and one package comprising such compositions.

Other objects to which the invention relates are included in the text of the description of the invention and in the examples that follow.

Useful amphiphilic nonionic polymers containing at least one aliphatic chain include, for example

celluloses or hydroxyalkylcelluloses modified by groups containing at least one aliphatic chain of the alkyl, arylalkyl or alkylaryl type, wherein the alkyl contains 8 to 22 carbon atoms. Examples include NATROSOL PLUS GRADE 330 CS from AQUALON, BERMOCOLL EHM 100 from BEROL NOBEL or

0 0 0 0 0 • · * 0

0

9 0090 000

0009 0999 00 09 09 9>

POLYSURF 67 from HERCULES. Also included are celluloses or hydroxyalkylcelluloses modified with polyalkoxylated alkylphenol groups such as AMERCELL POLYMER HM-1500 from AMERCHOL,

- hydroxypropylguars modified with groups containing at least one aliphatic chain of 8 to 22 carbon atoms such as ESAFLOR HM 22 (22-carbon alkyl chain) from LAMBERTI, MIRACARE XC95-3 (14-carbon alkyl chain) and RE205-1 (C20 alkyl chain) from RHONE POULENC,

- polyurethanes containing at least one C8-C30-alkyl or alkenyl-type aliphatic chain as the product SER-AD FX 1100 from SERVODELBEN, or

- SMDI copolymer (Saturated Methylene Diphenyl Diisocyanate) polyethylene glycol (s) with decyl end group,

- copolymer SMDI (Saturated methylene diphenyl diisocyanate) polyethylene (s) with an alkyl (methyl / C ₈₎ as the terminal group attached to a maltodextrin matrix and diuretan HMDI (hexamethylene Methylene Di Isocyanate), oxyethylenated (66 OE) and oxypropylenovaných (14 OP) alcohols 10 to 18 carbon atoms, marketed by AKZO under the name ELFACOS T 212

copolymers of vinylpyrrolidone and hydrophobic monomers with an aliphatic chain such as ANTARON V216 or GANEX V216 (poly (vinylpyrrolidone / hexadecene)), ANTARON V220 or GANEX V220 (poly (vinylpyrrolidone / ikosen)) from I.S.P .;

copolymers of alkyl methacrylates wherein the alkyl contains 1 to 6 carbon atoms and amphiphilic monomers with at least one aliphatic chain;

- copolymers of hydrophilic methacrylates and hydrophobic monomers with at least one aliphatic chain, for example poly (polyethylene glycol methacrylate / lauryl methacrylate).

Particular preference is given to polyurethanes having at least one C10-C20 alkyl aliphatic chain and hydroxyethylcellulose modified with at least one C8-C22 alkyl group.

The amphiphilic anionic polymers with at least one aliphatic chain used according to the invention are optionally crosslinked copolymers containing hydrophilic motifs derived from one or more unsaturated monomers. having an ethylene type of unsaturation bearing one free carboxyl group and hydrophobic motifs derived from one or more unsaturated monomers having an ethylene type of unsaturation bearing one side hydrophobic chain and optionally

- mesh motifs derived from one or more unsaturated monomers.

The ethylene-type unsaturation monomer or monomers carrying one free carboxyl group may be ethacrylic acid, methacrylic acid, acrylic acid, but preferably methacrylic acid, acrylic acid and mixtures thereof.

The ethylene-type unsaturation monomer or monomers carrying one side hydrophobic chain may be (i) aliphatic alkyl esters of unsaturated carboxylic acids, or (ii) allyl aliphatic alkyl ethers.

(i) Aliphatic alkyl esters of unsaturated carboxylic acids can be, for example, alkyl ethacrylates, alkyl methacrylates and / or alkyl acrylates, wherein the alkyl contains 10 to 30 carbon atoms, preferably 12 to 22.

They include, for example, lauryl acrylates, stearyl acrylate, isodecyl acrylate, dodecyl acrylate, as well as the corresponding methacrylates, namely lauryl methacrylate, stearyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

(ii) Allyl aliphatic alkyl ethers forming hydrophobic motifs of amphiphilic anionic polymers correspond to general formula I

CH ₂ = CR'CH ₂ -OB _n -R (I) wherein R 'represents a hydrogen atom or a methyl group B represents an ethyleneoxy group n is an integer ranging from 0 to 100,

R represents a hydrocarbon group which may be

9 9 9 ·

9

9999 9999

99 9 9 9 9 9 9 9 9

9 9 9 9 9

Alkyl, aryl, alkylaryl or cycloalkyl having 8 to 30 carbon atoms, preferably 10 to 24 carbon atoms, most preferably 12 to 18 carbon atoms.

According to the invention, preferred is such a motif of the formula (I) wherein R 'denotes hydrogen, n is 10 and R is a stearyl radical (C _8).

Tzv. A crosslinking monomer is a compound having at least two double, polarizable and non-conjugated bonds. Examples which may be mentioned are diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, methylene-bis-acrylamide, polyallylsaccharose or polyallylpentaerythritol.

Amphiphilic anionic polymers corresponding to the above types are described, for example, in US-3,915,921 and US-4,509,949 (copolymers of (m) ethacrylic acid and alkyl methacrylates wherein the alkyl contains 10 to 30 carbon atoms) or in EP-0 216 479 B2 (copolymers of (m) ethacrylic acid and allyl aliphatic alkyl ethers).

Examples of preferred polymers include;

- cross-linked polymers of acrylic acid and alkyl acrylate, where the alkyl contains 10 to 30 carbon atoms, such as those marketed by GOODRICH under the names PEMULEN TRI, PEMULEN TR2 and CARBOPOL 1382,

- a cross-linked polymer of acrylic acid and alkyl methacrylates, where the alkyl contains 10 to 30 carbon atoms, such as CARBOPOL ETD 2020, marketed by GOODRICH,

- oxyethylated methacrylic acid / ethyl acrylate / stearyl methacrylate tripolymer (55/35/10),

- oxyethylated (meth) acrylic / ethyl acrylate / behenyl methacrylate (25 OE) tripolymer, and

a cross-linked methacrylic acid / ethyl acrylate / steareth-10 allyl ether tripolymer.

These amphiphilic nonionic and / or anionic polymers with at least one aliphatic chain are used in an amount of 0.01 to 10%, preferably 0.1 to 5% by weight of the aqueous composition.

· * · · · · · · ·

9

9999 ········

9 9 9

9 9 ·

9 · 9

9 9 ·

9 99

As shown above, the aqueous decolorizing composition also comprises at least one basic agent, at least one peroxydated salt, at least one water-soluble solvent, and hydrogen peroxyd.

Said alkaline agent may be ammonia or organic amines such as mono-, di- or triethanolamine, 2-amino-2-methyl-1-propanol, diaminopropane, hydroxyalkylamines and oxyethylenated and / or oxypropylened ethylenediamines.

Suitable peroxylated salts include ammonium or alkali metal persulfates, percarbonates and perborates.

Preference is given to using persulfates and, in particular, sodium and potassium persulfates.

The compositions of the present invention comprise 2 to 20%, preferably 4 to 15% by weight of the peroxylated salt.

For the purposes of the present invention, "water-soluble solvents" are those which are soluble in water at 25 ° C by more than 5% by weight.

The water-soluble solvents according to the invention are preferably aliphatic linear or branched monoalcohols having from 1 to 6 carbon atoms, aliphatic linear or branched polyols having from 3 to 20 carbon atoms, polyolethers, in particular aliphatic mono- or diethers having from 1 to 6 carbon atoms C 2 -C 9 aromatic ethers of C 6 -C 9 polylols of 2 to 9 carbon atoms.

The compositions of the present invention contain from 0.1 to 10%, preferably from 0.5 to 8% by weight of a water-soluble solvent.

They also contain 0.5 to 10%, preferably 1 to 8% by weight of hydrogen peroxide.

The bleaches according to the invention may also contain all kinds of additives commonly used in bleaches having the ability to facilitate handling and application of the composition, improve the durability or effectiveness of the composition, and improve the cosmetic properties of the treated hair.

These additives are, for example, oxygen release control agents such as magnesium carbonate or magnesium oxide, anionic, nonionic, cationic, amphoteric or zwitterionic surfactants and mixtures thereof, mineral or vegetable oils, waxes, binders, mineral fillers such as oxide

44

4 4 14

4 4

4 4

44

44

4 4 4 • 4 * 4

4

44 ·· 4 · 44 • 49 Silica and clay, substances reducing transparency such as titanium dioxide, dyes, sequestrants, fragrances and polymers.

In particular, the compositions of the invention may comprise at least one water-soluble, natural or synthetic thickening polymer and / or at least one cationic and / or amphoteric substantive polymer.

Of course, the use of one or more optional ingredients or their amounts will be decided by one skilled in the art so that the advantageous properties clearly associated with the colorant according to the invention are not, or significantly, not altered by this or these additives.

The compositions of the invention preferably comprise at least one surfactant.

Surfactants suitable for carrying out the invention are particularly the following:

(i) Anionic surfactants:

Examples of useful anionic surfactants, in admixture or alone, include salts (especially basic, especially sodium, ammonium, amino, aminoalcohol and magnesium salts) of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkyl aryl polyether sulfates, monoglyceride sulfates. , alkali sulfonates, paraffin sulfonates; alkyl _(C6-C24) sulfosuccinates, alkyl _(C6 C, ₂ 4) ethersulfosukcináty alkyl (C ₆ -C ₂₄₎ amidosulfosukcináty; alkyl (C ₂ C ₆ 4) sulfoacetates, acyl (C ₆ -C ₂₄₎ acyl sarcosinates and (C ₆ -C ₂ 4) glutamates. It is also possible to use esters of carboxyl alkyl (C ₆ -C ₂₄ ) polyglycosides such as alkyl glycoside citrates, alkyl polyglycoside tartrates and alkyl polyglycoside sulfosuccinates; alkylsulfosuccinamates; acylisethionates and N-acyltaurates. The alkyl or acyl radical of all these different compounds preferably contains 12 to 20 carbon atoms and the aryl radical preferably denotes a phenyl or benzyl group. Also useful as anionic surfactants are salts of fatty acids such as salts of oleic, ricinoleic, palmitic, stearic, coconut and hydrogenated coconut acids; acyl lactyllates wherein the acyl radical contains 8 to 20 carbon atoms. It is also possible to use alkyl-D-galaktosiduronové acids and their salts, polyoxyalkylenated alkyl (C ₆ -C ₂ 4) ether carboxylic acids, polyoxyalkylenated alkyl (C ₆ -C ₂ 4) aryletherkarboxylové acids, polyoxyalkylenated alkyl (C ₆ -C ₂ 4) amido ether carboxylic acids and their salts, especially those containing 2 to 50 alkylene oxide groups, especially ethylene oxide group and mixtures thereof.

• φ · ·· · φφ φφ • φ · φ

(ii) Nonionic surfactants: (ii) Non-ionic surfactants:

Nonionic surfactants are also well known compounds per se (see Handbook of Surfactant, MRPorter, Blackie & Son (Glasgow and London), 1991, pages 116-178), and their nature is not critical to the present invention. Thus, nonionic surfactants from the group of alcohols, α-diols, alkylphenols, polyethoxylated or polypropoxylated fatty acids having a backbone containing, for example, from 8 to 18 carbon atoms and having a number of ethylene oxide and propylene oxide groups in particular of 2 to 50 are usable. propylene oxide, condensates of ethylene oxide and propylene oxide with aliphatic alcohols, polyethoxylated aliphatic amides having preferably 2 to 30 moles of ethylene oxide, polyglycerinated aliphatic amides containing an average of 1 to 5 and preferably 1.5 to 4 glycerol groups; polyethoxylated aliphatic amines having preferably 2 to 30 moles of ethylene oxide; oxyethylated sorbitan fatty acid esters having 2 to 30 moles of ethylene oxide; fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, alkyl polyglycosides, N-alkylglucamine derivatives, amine oxides such as alkyl (C ₁₀ -C ₁₄ ) amine oxides or N-acylaminopropylmorpholine oxides. Note that alkyl polyglycosides are nonionic surfactants that fit particularly well within the scope of this invention.

(iii) Amphoteric or zwitterionic surfactants:

In particular, amphoteric or zwitterionic surfactants of a non-critical nature may be derivatives of secondary or tertiary aliphatic amines whose aliphatic chain is linear or branched and contains from 8 to 18 carbon atoms and at least one anionic group having a hydrosolubilizing effect (e.g. carboxylate, sulfonate, sulfate, phosphate or phosphonate). Further, alkyl (C ₈ -C ₂₀ ) betaines, sulfobetaines, alkyl (C ₈ -C ₂₀ ) amidoalkyl (C 1 -C ₆ ) betaines, or alkyl (C ₈ -C ₂₀ ) amidoalkyl (C 1 -C 6) sulfobetaines may be mentioned.

Amino derivatives include the products described in US Patents 2 528 378 and US-2 781 354 and incorporated in the CTFA Dictionary, 3rd Edition, 1982, under the names Amphocarboxyglycinates and Amphocarboxypropionates with the appropriate structures:

R ₁ -CONHCH ₂ CH ₂ -N (R ₂ ) (R ₃ ) (CH ₂ COO ') wherein: R 1 represents the alkyl radical of R 1 COOH present in the hydrolyzed coconut oil, heptyl, nonyl or undecyl radical, R ₂ represents β- hydroxyethyl and R ₃

99

9 · ♦ 9

* 9

9

9 9999 »999

99999999 99 99 99 99 carboxymethyl;

and

R ₁ -CONHCH ₂ CH ₂ -N (B) (C) wherein:

B represents -CH ₂ CH ₂ OX ',

C represents - (CH _{2) z} -Y ', where z = l or 2,

X 'denotes the group -CH ₂ CH ₂ -COOH or a hydrogen atom

Y 'denotes -COOH or the radical -CH ₂ -CHOH-SO 3 H

R @ 1 denotes an alkyl radical of R-COOH present in hydrolyzed coconut or linseed oil, an alkyl radical of 7,9,11 or 13 carbon atoms, an alkyl radical of 17 carbon atoms including its isoform, an alkyl unsaturated radical of 17 carbon atoms.

These compounds are included in the CTFA dictionary, 5th edition, 1993, under the names Disodium Coco-ampho-diacetate, Disodium Lauroampho-diacetate, Disodium Capryl-ampho-diacetate, Disodium Capryloampho-diacetate, Disodium Coco-amphodipropionate, Disodium Lauroampho-dipropionate, Disodium Caprylampho-dipropionate, Disodium Capryloampho-dipropionate, Lauroampho-diprapionic acid, Coco-ampho-dipropionic acid.

(iv) Cationic surfactants:

Cationic surfactants include, but are not limited to: primary, secondary or tertiary, optionally polyoxyalkylenated aliphatic amines, quaternary ammonium salts such as tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium chloride or bromide; imidazoline derivatives or amine oxides of cationic character.

The amount of surfactant in the composition according to the invention is 0.01 to 40% and preferably 0.1 to 30% of the total weight of the composition.

Substantive cationic polymers useful in accordance with the present invention may be those already known to improve the cosmetic properties of hair, particularly those described in patent applications EP-A337354 and EP-A-557203 and in French patents FR -2,270,846, 2,383,660, 2,598,611, 2,470,596 and 2,519,863.

• · · · · · · · · · · · · · · · · ·

9 6 9

4

4 ♦ 4 ·

4445 44 ·· 64

94

9 9 9 4

4

9 9 · 9 6

9 9 4 9 •

Preference is given to those cationic polymers which contain primary, secondary, tertiary and / or quaternary amino groups which may be part of the main polymer chain or may be attached directly to the main polymer chain on the side substituent.

The cationic polymers used generally have a mean molecular weight of 500 to 5 x 10 ⁶ , preferably 10 ³ to 3 10 ⁶ .

Cationic polymers include, in particular, polyamine, polyaminoamide and quaternary polyammonium polymers.

These are known products. They are mainly described in French patents. No. 2,505,348 or 2,542,997. The polymers mentioned include:

(1) Homopolymers or copolymers derived from acrylic or methacrylesters or amides and bearing at least one of the motives of the following formulas II, III, IV, V:

C = O c = o

O

I (ΠΙ)

AND

R — N ^{+ —R} 9 ^R 8 X — ch2 — c—

-CH ₂ -C c = o

ÍH

A (IV)

O = C

NH (A)

R ₇ —N ⁺ —R ₉

/ ⁿ \ _d r / Rs Φ · · φ

ΦΦ · Φ Φ φ φ φ φ φ φ φ φ φ φ φ φ φ · · · φ φ φ φ φ φ φ φ φ φ · · · · · · · kde kde kde kde kde kde kde kde different, denote a hydrogen atom or a CH ₃ radical;

A, the same or different, represents a linear or branched alkyl group having 1 to 6 carbon atoms, but preferably 2 or 3 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms;

R ₇ , R ₈ , R ₉ , the same or different, represent an alkyl group having 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group having 1 to 6 carbon atoms.

R 4 and R ₅ , the same or different, represent hydrogen or an alkyl group having 1 to 6 carbon atoms, but preferably methyl or ethyl.

X denotes an anion derived from an inorganic or organic acid such as methosulfate or a halide such as chloride or bromide.

The polymers of family (1) may additionally contain one or more comonomer-derived motifs, which may be selected from the group consisting of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on a nitrogen atom with lower C 1 -C 4 alkyl, acrylic or methacrylic acids; esters thereof, vinyl lactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.

Thus, as polymers of the family (1) we can mention:

copolymers of acrylamides and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halide, copolymers of acrylamides and methacryloyloxyethyltrimethylammonium chloride described, for example, in patent application EP-A-080976,

- copolymers of acrylamides and methacryloyloxyethyltrimethylammonium methosulphate copolymers of vinylpyrrolidone and quaternized or non-quaternized dialkylaminoalkyl acrylate or methacrylate. These polymers are described in detail in French patents 2.077.143 and 2.393.573, tripolymers of dimethylaminoethyl methacrylate, vinylcaprolactam and vinylpyrrolidone,

- copolymers of vinylpyrrolidone and methacrylamidopropyldimethylamine, • · · · φ · φ · · · · · · · · · · · • · · · · · · · ♦ · φ · φ · • · φ · φ ·

and copolymers of vinylpyrrolidone and quatized dimethylaminopropylmethacrylamide.

(2) Cellulose ether derivatives containing the quaternary ammonium groups described in French Patent 1,492,597. These polymers are also defined in the CTFA dictionary as quaternary ammonium hydroxyethylcelluloses that have reacted with an epoxy substituted with trimethylammonium.

(3) Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives with attached, water-soluble monomeric quaternary ammonium and derivatives listed specifically in U.S. Pat. No. 4,131,576 such as hydroxyalkylcelluloses and, in particular, hydroxymethyl-, hydroxyethyl- or hydroxypropylcellulose with methacryloylethyltrimethylammonium attached; methacrylamidopropyltrimethylammonium, dimethyldiallylammonium salt.

(4) Cationic polysaccharides described more prominently in U.S. Patents 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups. For example, gastric gums modified with 2,3-epoxypropyltrimethylammonium salt (e.g. chloride) are used.

(5) Polymers composed of piperazinyl motifs and bivalent straight or branched chain alkylene or hydroxyalkylene radicals interrupted by oxygen, sulfur, nitrogen or aromatic cycles or heterocycles, as well as oxidation and / or quaternization products of these polymers. Such polymers are specifically described in French patents 2.162.025 and 2.280.361.

(6) Water-soluble polyaminoamides prepared especially by polycondensation of an acid with a polyamine; these polyaminoamides may be cross-linked with epihalohydrin, diepoxide, dianhydride, unsaturated dianhydride, double unsaturated derivative, bishalohydrin, bisazetidinium, bishaloacyldiamine, alkylbishalogenide or even an oligomer formed by reaction of a difunctional compound with bishaletohydrin; The reticulating agent is used in an amount of from 0.025 to 0.35 mol per amino group.

4 4 · ·

·

4

4444 ···· • 44 4 ·· 4 «• · · ·

4 4 · 4 4

4 4 4

44 in polyaminoamide. These polyaminoamides may be alkylated or, if they carry one or more tertiary amino groups, quatized. Such polymers are specifically disclosed in French patents 2,252,840 and

2.368.508.

(7) Polyaminoamide derivatives resulting from polycondensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional reagents. By way of example, polymers of adipic acid-dialkylaminohydroxyalkyldialkylenetriamine in which the alkyl radical contains 1 to 4 carbon atoms and denotes preferably methyl, ethyl and propyl. Such polymers are described, in particular, in French patents 1,583,363.

These derivatives include, in particular, adipic acid / dimethylaminohydroxypropyl / diethylenetriamine polymers, marketed by Sandoz under the name "Cartaretine F, F4, or F8".

(8) Polymers obtained by the reaction of polyalkylene polyamines containing two primary amino groups and at least one secondary amino group with a dicarboxylic acid which may be diglycolic acid, an aliphatic saturated dicarboxylic acid having 3 to 8 carbon atoms. The molar ratio of polyalkylene polyamines to dicarboxylic acid is 0.8: 1 to 1.4: 1. The polyaminoamide thus formed is further reacted with epichlorohydrin at a molar ratio of epichlorohydrin to secondary amino group in the polyaminoamide of between 0.5: 1 and 1.8: 1. Such polymers are specifically disclosed in U.S. Patents 3,227,615 and 2,961,347.

(9) Cyclopolymers of alkyldiallylamine or dialkyldiallylammonium such as homopolymers or copolymers containing, as the main chain, motifs corresponding to formulas VI or VII

C (R ₁₂ ) -CH ₂ - (CH ₂ ) _t -CR ₁₂

C (R ₁₂ ) -CH ₂ (VII)

H, C

CH, (VI)

H, C \ _N

CH, / io

R φ · · φ φ • • kterých · · φ φ φ φ φ φ φ ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve ve R ₉ denotes a hydrogen atom or a methyl radical; R ₇ and R ₈ independently of each other denote an alkyl group having 1 to 22 carbon atoms, a hydroxy alkyl group in which alkyl preferably contains 1 to 5 carbon atoms, a lower amidoalkyl group (C 1 -C 4), or R ₇ and R ₈ may together with the nitrogen atom to which they are attached denote a heterocyclic group such as piperidinyl or morpholinyl; Y 1 is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, disulfate, disulfite, sulfate, phosphate. These polymers are specifically described in French patent 2.080.759 and its additional certificate 2.190.406.

(10) A quaternary diammonium polymer containing repeating motifs corresponding to formula VIII

R13 f’15

-N ⁺ -A 1 -N ⁺ -B ·, | X '| X '

R R (VIII)

K14 K ₁₆ where R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , identical or different, represent aliphatic, acyclic or arylaliphatic radicals having 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals or else R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ together or separately, together with the nitrogen atoms to which they are attached, denote heterocycles with an optionally second heteroatom other than nitrogen or R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent a linear or branched alkyl radical of 1 to 6 carbon atoms substituted with nitrile , ester, acyl, amide or -COO-R ₇ -D or -CO-NH-R ₇ -D, wherein R ₇ is alkylene and D a quaternary ammonium group;

A ₍ and B) represent polymethylene groups having 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain one or more aromatic cycles or one or more oxygen atoms attached to or inserted into the main chain , sulfur or sulfoxy, sulfone, disulfide, amine, alkylamine, hydroxyl, quaternary ammonium, urea, amide or ester groups; and

X 'denotes an anion derived from an inorganic or organic acid;

A 1, R ₁₃ and R 15 can form a piperazine ring with the two nitrogen atoms to which they are attached; except if A! denotes an alkylene or hydroxyalkylene, linear or branched, saturated or unsaturated radical,

9 99 9

9 99

9

9 9 9 · 9 9

9

9900 9900 99

99

9 9 9 9 • · · · ·

9

9 9 9 • 9 99 99

Bi may also denote a group

- (CH ₂ ) _n -CO-D-OC- (CH ₂ ) _n where D denotes:

(a) a glycol residue of the general formula:

-O-Z-O, wherein Z denotes a linear or branched hydrocarbon radical or group corresponding to one of the following formulas:

- (CH ₂ -CH ₂ -O) _X -CH ₂ -CH ₂ - [CH ₂ -CH (CH ₃ ) -O] _y -CH ₂ -CH (CH ₃ ) wherein x and y may be integers from 1 to 4 representing a defined and uniform degree of polymerization or any number from 1 to 4 representing a medium degree of polymerization;

b) a bis-secondary diamine residue such as a piperazine derivative;

c) a bisprimary diamine radical of the formula: -NH-Y-NH-, wherein Y denotes a hydrocarbon linear or branched radical or also a bivalent radical

-CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ -;

d) an ureylene group of the formula: -NH-CO-NH-;

X- is preferably a chloride or bromide anion.

These polymers generally have a mean molecular weight of between 1000 and 100,000.

Such polymers are specifically described in French patents 2,320,330, 2,270,846, 2,316,271, 2,336,434 and 2,413,907, and in US patents 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462. , 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020.

In particular, it is possible to use polymers which consist of repeating motifs corresponding to the general formula IX ^R 18 ^r 2o

-N ⁺ - (CH 2) n N ⁺ - (CH 2) _p - (IX) | X '| X '

^R 19 ^R 21 where R ₁₈ , R ₁₉ , R ₂₀ and R _{2b are} identical or different denote an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, e.g. Ftft ft ft values ftft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft values from 2 to 20 and X is an anion derived from inorganic or organic acids.

(11) Quaternary polyammonium polymers composed of motifs of formula (X)

R22 ^R 24

-N ⁺ - (CH ₂ ) _n -NH-CO- (CH ₂ ) q -CO-NH- (CH ₂ ) _S -N ⁺ -A 'x | x |

R ₂₃ ^R 25 (X) wherein R _22, R ₂ 3> R24 and R25, identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl, βhydroxypropylový radical or _-CH2 CH2 (OCH2CH2) _p OH, where p is 0 or an integer ranging from 1 to 6, provided that R ₂₂ , R 23, R 24 and R 25 do not simultaneously represent hydrogen, ras, identical or different, are integers ranging from 1 to 6, q is 0 or an integer between 1 and 34

X denotes a halogen atom,

A denotes a dihalide radical or preferably denotes -CH 2 -CH 2 -O-CH 2 -CH 2 -.

Such compounds are specifically disclosed in patent application EP-A-122 324.

(12) Quaternary vinylpyrrolidone and vinylimidazole polymers.

(13) Polyamines as products contained in the CTFA dictionary under the name POLYETHYLENGLYCOL (15) TALLOW POLYAMINE.

(14) Crosslinked polymers methakryloyloxyalkyl _(C-C4) trialkyl _(Ci-4) ammonium salts such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride. After homopolymerisation or

00V0

00

· · · ·

0000 0000

0 0

0 0 0 0 0 Λ

0 · 0

00

0 «0 0 0

0 0 0

0 0 0 0

0 9 0

The copolymerization is followed by crosslinking with an olefinic unsaturation compound, especially methylene bisacrylamide. In particular, a cross-linked methacryloyloxyethyltrimethylammonium acrylamide / chloride (20/80 by weight) polymer in dispersed form containing 50% by weight of the above copolymer in mineral oil may be used. This dispersion from ALLIED COLLOIDS is commercially available under the name SALCARE® SC 92. It is also possible to use a cross-linked methacryloyloxyethyl trimethylammonium chloride homopolymer containing approximately 50% by weight of homopolymer in mineral oil or liquid ester. These dispersions from ALLIED COLLOIDS are commercially available under the names SALCARE® SC 95 and SALCARE® SC 96.

Other cationic polymers useful in the present invention are polyalkylenimines, especially polyethylenimines, polymers containing vinylpiridine or vinylpiridinium motifs, polyamine-epichlorohydrin condensates, quaternary polyureylenes, and chitin derivatives.

Substantive amphoteric polymers useful in the invention may be selected from polymers containing statistically spaced K and M motifs in the polymer chain, wherein K denotes a motif derived from a monomer containing at least one basic nitrogen atom and M denotes a motif derived from an acid monomer with one or more carboxylic or sulfonic groups, or K and M may also refer to groups derived from amphionic forms of carboxybetaine or sulfobetaine monomers.

K and M may also denote a polymeric cationic chain containing primary, secondary, tertiary or quaternary amino groups in which at least one amino group carries a carboxyl or sulfone group linked via a hydrocarbon radical, or K and M form part of a polymer chain with an α, β-dicarboxylic ethylene motif wherein one of the carboxyl groups has reacted with the poles with an amine containing one or more primary or secondary carboxyl groups.

Film-forming amphoteric polymers corresponding to the above definition may be selected from the following polymers:

(1) Polymers resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxyl group such as acrylic, methacrylic, maleic, α-chloroacrylic acid and a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as dialkylaminoalkyl methacrylates, dialkylaminoalkyl acrylate, dialkylaminoalkylmethacrylamide and dialkylaminoalkyl acrylamide. Such compounds are specifically disclosed in U.S. Pat. Sodium acrylate / acrylamidopropyltrimethylammonium chloride copolymer may also be mentioned.

The vinyl compound may also be a dialkyldiallylammonium salt such as diethyldiallylammonium chloride.

(2) Polymers containing motifs derived from:

(a) from at least one monomer belonging to the group of acrylamides or methacrylamides substituted with an alkyl radical on the nitrogen atom.

(b) at least one acidic comonomer containing one or more reactive carboxyl groups; and

c) from at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amino substituents of acrylic and methacrylic acid and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl sulfate or diethyl sulfate.

Particularly preferred N-substituted acrylamides or methacrylamides according to the invention are those whose alkyl radicals contain 2 to 12 carbon atoms, in particular N-ethyl acrylamide, N-tert-butyl acrylamide, N-tert.octylacrylamide, N-octylacrylamide, N-decylacrylamide, Ndodecylacrylamide methacrylamides.

Particularly suitable acidic comonomers are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and monoesters of fumaric acid and maleic acid and their C1 -C4 alkyl anhydrides.

Preferred basic comonomers are aminoethyl methacrylate, butylaminoethyl methacrylate, Ν, Ν-dimethylaminoethyl methacrylate, N-t-butylaminoethyl methacrylate.

Particularly used are copolymers whose name in CTFA (4th edition) is Octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer.

(3) Partially or fully alkylated and cross-linked polyaminoamides derived from polyaminoamides of the general formula XI

-jýco- R ₂₆ - Co-Zj- (XI) + ···· · · · · · in which R ₂₆ represents a divalent radical derived from a saturated dicarboxylic acid, from an aliphatic mono- or dicarboxylic acid having a double bond in the chain, from the ester a lower alkanol having 1 to 6 carbon atoms with these acids or a radical derived from the addition of any of the aforementioned acid and a bisprimary or bisse Secondary amine, and Z denotes a bisprimary, mono or bisse Secondary polyalkylene polyamine and in particular denotes

a) in a ratio of 60 to 100 mol% of the radicals of the formula XII

-NH-F (CH ₂ ) _x -NH-1 - (XII)

Jp where x = 2 and p = 2 or 3, or also x = 3 and p = 2, this radical is derived from diethylenetriamine, triethylenetetraamine or dipropylenetriamine;

(b) in a ratio of 0 to 40 mole% of the above radical (XII), wherein x = 2 and p = 1, and which is derived from ethylenediamine or a radical derived from piperazine:

N—

c) in a ratio of 0 to 20 mol% of radicals

-NH- _{(CH2) 6} -NHodvozený from hexamethylenediamine. These polyaminoamines are crosslinked by the addition of a difunctional crosslinking agent belonging to the group of epihalohydrins, diepoxides, dianhydrides, double bond derivatives, in an amount of an average of 0.025 to 0.35 mol of crosslinking agent per amino group of polyaminoamide alkylated with acrylic acid, chloroacetic acid or alkanesultone.

Saturated carboxylic acids are preferably C 6 -C 10 carboxylic acids such as adipic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, terephthalic acid, ethylene double bond such as acrylic acid, mathacrylic acid, itaconic acid.

The alkanesultones used in the alkylation are preferably propanesultone or butanesultone, the alkylating agent salts are preferably sodium or potassium salts.

Polymers containing amphionic motifs of general formula XIII p18-30

N ⁺ - (CH ₂ ) _z -C—O (ΧΙΠ) wherein R ₂₇ denotes an unsaturated polymerizable group such as an acrylate, methacrylate, alkrylamide or methacrylamide group, y and z represent integers from 1 to 3, R ₂₈ and R ₂₉ represent an atom hydrogen, methyl, ethyl or propyl, R ₃₀ and R ₃₁ represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R ₃₀ and R ₃₁ does not exceed 10.

Polymers containing such units may also contain motifs derived from non-ionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate, alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.

As an example, methyl methacrylate / methyl dimethylcarboxymethyl-ammonioethyl methacrylate copolymer can be mentioned.

(5) Chitosan-derived polymers containing monomeric motifs corresponding to the following formulas XIV, XV, XVI ch ₂ oh

NHCOCH ₃ XIV

NH ₂

motif (XIV) is present in a ratio of 0 to 30%, motif (XV) in a ratio of 5 to 50% and motif (XVI) in a ratio of 30 to 90%, in this F motif R ₃₂ represents a radical of the general formula XVII

R34 ^ 35

Wherein, if q = 0, R ₃₃ , R ₃₄ , R ₃₅ , identical or different, each represents a hydrogen atom, a methyl, hydroxyl acetoxy or amine residue, R33-C- (O) qc (XVD); a monoalkylamino radical or a dialkylamino radical, optionally interrupted by one or more nitrogen atoms and / or optionally substituted by one or more amino, hydroxyl, carboxyl, thioalcohol, sulfone, thioalkyl radical in which the alkyl carries an amino group, in which case at least one of the radicals R is ₃₃ , R ₃₄ , R ₃₅ with hydrogen;

or when q = 1, R ₃₃ , R ₃₄ , R ₃₅ represent each hydrogen atom, as well as the salts formed by these compounds with bases or acids.

(6) Polymers derived by N-carboxyalkylation of chitosan such as N-carboxymethylchitosan or N-carboxybutylchitosan.

(7) Polymers as described, for example, in French Patent 1 400 366 and corresponding to the general formula (XVIII)

M6 • (CH-

(XVIU) wherein R ₃₆ represents hydrogen, CH ₃ O, CH ₃ CH ₂ O, phenyl, R ₃₇ denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R ₃₈ denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R ₃ 9 denotes a lower alkyl radical such as methyl, ethyl or a radical corresponding to the formula:

-R ₄₀ -N (R ₃₈ ) ₂ wherein R ₄₀ is -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ CH 2 -, -CH ₂ -CH (CH ₃ ) - and R ₃₈ is as previously described as well as higher homologues of these radicals containing up to 6 carbon atoms.

• 4 9 4 9 4 4 9

9 4 4 9 4

4 · · · · · · · · ·

9999 4999 9 9 · 4 6 9 4 9 (8) Amphoteric polymers -D-X-D-X- belonging to the group:

(a) polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds containing at least one motif of general formula (XIX)

-D-X-D-X- (XIX) where D denotes a radical

and X denotes the symbol E or Ε '. E or E ', identical or different, denote a divalent radical, which is a straight or branched chain alkylene radical containing up to 7 carbon atoms in the main chain, optionally substituted by hydroxyl groups, and may additionally contain oxygen, nitrogen, sulfur, up to 3 aromatic and / or heterocyclic rings. Oxygen, nitrogen, and sulfur atoms are present in the form of ethers, thioethers, sulfoxides, sulfones, sulfones, alkylamines, alkenylamines, hydroxyls, benzylamines, amine oxides, quaternary ammoniums, amides, imides, alcohols, esters and / or urethanes;

b) polymers of formula XX

-D-X-D-X- (XX) where D denotes the radical “N” and X denotes the symbol E or E 'and at least once Ε'. E is as defined above and E 'denotes a divalent radical which is a straight or branched chain alkylene radical containing up to 7 carbon atoms in the main chain, optionally substituted by one or more hydroxyl radicals, and containing one or more nitrogen atoms. The nitrogen atom is substituted by an alkyl chain, optionally interrupted by an oxygen atom, and which contains one or more carboxyl groups or one or more hydroxyl groups and is betainized by reaction with chloroacetic acid or sodium chloroacetate.

• 9 • ·· · »· ·· · · · * ··· ···· ·· ·· ·· ·· (9) Copolymers of alkyl _(Ci-C5) -vinylether / maleic anhydride partially modified semiamidifikací with Ν, Ν-dialkylaminoalkylamine such as Ν, Ν-dimethylaminopropylamine or semiesterification with N, Ndialkanoamine. These copolymers may also contain other vinyl comonomers such as vinylcaprolactam.

Among the substantive cationic or amphoteric polymers useful according to the invention, the following are particularly preferred:

dimethyldiallylammonium chloride homopolymer sold by MERCK under the name MERQUAT 100 DRY;

dimethyldiallylammonium chloride and acrylamide copolymers sold by CALGON under the name MERQUAT 2200;

- poly (quaternary ammonium) type polymers prepared and described in French patent 2,270,846, which consist of repeating motifs of the general formula XXI ch ₃ ch ₃ - [· N ⁺ - (CH ₂ ) ₃ —N ⁺ - (CH p ^ - J- (XXI) | d | cr ch ₃ ch _3, and in particular those whose mean molecular weight determined by gel permeation chromatogaphia is between 9500 and 9900,

- poly (quaternary ammonium) type polymers prepared and described in French Patent 2,270,846, which consist of repeating motifs of the general formula XXII

CH ₃ c ₂ h ₅ —E- nMch ^ j-nMch ^} | Br '| Br' (ΧΧΠ) ch ₃ c ₂ h _5, and especially those whose mean molecular weight determined by gel permeation chromatography is approximately 1200;

- the polymers of the type (quaternary ammonium) described in U.S. Patents 4,390,689, 4,702,906, 4,719,282, which consist of repeating motifs of the general formula XXIII

FEELING

CH, -N- (CH ₂ ) _p -NH-CO-D-NH- (CH ₂ ) _p -N- (CH ₂ ) ₂ -O- (CH ₂ ) ₂ 4 -

Ct

CH ₃ (ΧΧΠΙ)

Cl '

CH ₃

Φ φ · · φ Φ • • • • · · · ·

Where ρ is an integer from 1 to 6,

D represents a single bond or - (CH ₂ ) _r -CO-, wherein r is 4 or 7, and especially those whose mean molecular weight is less than 100,000, preferably less than or equal to 50,000;

- the following amphoteric copolymers:

80/20 diallyldimethylammonium chloride / acrylic acid copolymer marketed by CALGON under the name MERQUAT 280 DRY (CTFA name: Polyquaternium-22);

- dimethyldiallylammonium chloride / acrylic acid (95/5) copolymer marketed by CALGON under the name MERQUAT 295 DRY (CTFA name: Polyquaternium-22);

- a copolymer of methacrylamidopropyltrimonium chloride, acrylic acid and methyl acrylate marketed by CALGON under the name MERQUAT 2001 (CTFA name: Polyquaternium-47);

of a acrylamide / dimethyldiallylammonium chloride / acrylic acid tripolymer marketed by CALGON under the name MERQUAT PLUS 3330 DRY (CTFA name: Polyquaternium-39).

Amphoteric copolymers of Polyquaternium-22, Polyquatemium-39 and Polyquaternium-47 (CTFA names) are particularly preferred in the list of substantive polymers mentioned above.

According to the invention, the substantive cationic or amphoteric polymers represent 0.03 to 30% of the total weight of the composition.

Examples of synthetic thickening polymers include polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, polyacrylamidomethylpropanesulfonic acid or copolymers thereof. These polymers may optionally be crosslinked.

The natural thickening polymers useful in the present invention are polymers comprising a single carbohydrate motif, namely (a) guar nonionic gums;

(b) biopolysaccharide gums of microbial origin such as scleroglucan and xanthan gums;

· Ef ef · ft ef ft ft ef ef fe ft fe fe fe ft fe ft fe fe fe fe fe fe fe fe fe fe fe fe fe fe «« «« «« «« «« « (C) gums made from plant exudates such as gum arabic, ghat, karay or gum tragacanth;

(d) gums extracted from algae such as carrageenans or agar;

(e) gums made from plant extracts such as locust bean gum or pectins extracted from fruit pulp;

(f) alginates;

(g) amidones;

(h) hydroxyalkylcelluloses and carboxyalkylcelluloses;

The term "carbohydrate motif" as used herein is understood to be the monosaccharide or oligo- or polysaccharide moiety of a molecule composed of one kind of carbohydrate motifs (oligo- or poly / z / osides) or a plurality of different carbohydrate motifs (oligo- or poly / zeroside).

The carbohydrate units of all these polymers may carry one or more substituents, for example, alkyl, hydroxyalkyl, alkoxy or carboxyl groups, alkyl radicals of 1 to 4 carbon atoms.

The guar nonionic gums may optionally be modified. For example, unmodified guar gums are products sold by UNIPECTINE under the name VIDOGUM GH 175 and MAYHALL under the name JAGUAR C.

Nonionic guar gums modified with C 1 -C 4 hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups can also be used according to the invention.

These modified guar gums are well known in technology and can be prepared by reacting guar gum with the corresponding alkylene oxides. The degree of hydroxyalkylation (the ratio of the number of fixed alkylene oxide molecules relative to the original number of free hydroxyl groups) is preferably 0.4 to 1.2.

Such modified nonionic guar gums are, for example, sold by RHONE POULENC (MAYHALL) under the names JAGUAR HP8, JAGUAR HP60, JAGUAR HP 120, JAGUAR DC293 and JAGUAR HP 105 or AQUALON under the name GALACTASOL 4H4FD2.

φφ φφ • 4 9 9 4 9 9 9

9 · 9 · · Φ Φ

Biopolysaccharide gums of microbial origin such as scleroglucan and xanthan gums, gums made from plant exudates such as gum arabic, ghat, karaya or tragic gum, gums extracted from algae such as carrageenan or agar, gums made from plant extracts such as locust bean gum or pectins , alginates, amidones, hydroxyalkylcelluloses and carboxyalkylcelluloses are well known in the art and are described in particular in the "Handbook of Water Soluble Gums and Resins" by Robert L. Davidson, published by the Mc Graw Hill Book Company (1980).

Among the gums are scleroglucans represented by SANOFI BIO INDUSTRIES products named ACTIGUM CS and in particular ACTIGUM CS 11, and ALBAN MULLLER INTERNATIONAL products named AMIGEL.

Other scleroglucans may also be used, for example scleroglucan exposed to glyoxal and described in patent application FR-A-2 633 940.

Xanthan gums useful as thickeners in the compositions of the present invention include, for example, NUTRASWEET KELCO products with the names KELTROL, KELTROL T, KELTROL TF, KELTROL BT, KELTROL RD and KELTROL CG or RHODIA CHIMIE products with the names RHODICARE S and RHODICARE H.

Hydroxyalkylcelluloses are generally hydroxy (C 1 -C 4 alkyl) celluloses and especially hydroxyethylcelluloses. They are available, for example, under the names CELLOSIZE QP3L, CELLOSIZE QP4400H, CELLOSIZE QP30000H, CELLOSIZE HEC30000A or CELLOSIZE POLYMER PCG10 by AMERCHOL, under the names NATROSOL 250HHR, NATROSOL 250MR, NATROSOL 250H, NATROSOL 250M, NATROSOL 250M, NATROSOL 250M, TYLOSE H1000 at HOECHST.

Hydroxyalkylcelluloses may also be hydroxypropylcelluloses sold by AQUALON under the names KLUCEL EF, KLUCEL H, KLUCEL LHF, KLUCEL MF, KLUCEL G.

Preferred carboxyalkylcelluloses are the carboxymethylcelluloses marketed, for example, under the names BLANOSE.

9 9 9

9

9

9

9999 9999

9 9

9 9

9 9

9 9 9

99

9 9

9 9

9 9

9 ·

7M8 / SF, BLANOSE RAFFINÉE 7M, BLANOSE 7LF, BLANOSE 7MF, BLANOSE 9M31F, BLANOSE 12M31XP, BLANOSE 12M31P, BLANOSE 7M, BLANOSE 7M31, BLANOSE 7M3, from the company AONASB 7H3SXF the names CELLOGEN HP810A and CELLOGEN HP6HS9 from MONTELLO or under the name PRIMELLOSE from AVEBE.

Particularly preferred water-soluble thickening polymers useful as conventional thickening agents in the anhydrous colorless composition of the present invention are guar gums, guar gum derivatives, or hydroxyalkyl cellulose.

The water-soluble thickening polymer (s) described above is (are) generally used in an amount of 0.03 to 30% by weight, preferably in an amount of 0.3 to 15% by weight of the anhydrous composition.

It is also an object of the present invention to provide a method for bleaching keratin fibers, particularly human hair.

This procedure involves the stages of setting up

- in the preparation of the above-described ready-to-use formulation,

- in the application of said composition to the area of keratin fibers to be bleached,

- depending on the time required to obtain the desired decolorization, this period generally being from 10 minutes to 1 hour, preferably from 10 to 45 minutes, and

- removing the bleach by rinsing with water followed by shampooing and drying.

Another object of the invention is one package also called a packaging kit comprising at least two compartments, one containing the peroxygenated salt as defined above, the other containing the water-soluble solvent as described above and the third containing the aqueous composition comprising hydrogen peroxide , one or more amphiphilic nonionic and / or anionic polymers having at least one aliphatic chain have been added to one or more of these sections.

The examples which follow, which are intended to better understand the invention, are purely illustrative and not limiting.

99 • 9 ·

9

9 ·· 9 999 ♦ 9 ·· * 9 ·

9 9

9 9

9 ·

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Composition A ethoxylated decyl alcohol with 3 moles OE OE ethoxylated with 5 moles OE oleic acid oleic alcohol propylene glycol oleocetyl alcohol ethoxylated 30 moles OE

Ethylene glycol monobutyl ether aqueous ammonia solution containing 20.5% NH ₃ water

Composition B sodium persulfate potassium persulfate sodium metasilicate ammonium chloride EDTA lauryl sodium sodium cetylhydroxyethylcellulose silica g

g g 3 g 9 g

4.5 g g 9 g q.s. 100 g g 40 g 14 g g

g g 2 g

q.s. 100 g

Mix 60 g of composition A, 20 g of composition B and 100 g of an aqueous solution of 6% by weight hydrogen peroxide.

The viscosity of the composition changes very little over time and the composition has good discolouring properties.

·· 9900

19 Dec

1111 11 1 1111 1 9 111 9 9 9 9

9 1 9 9 9 9

9 11 1111

19110000 91 99

Example 2

We have prepared the following bleach (quantity in% by weight):

laureth-5 carboxylic acid 4 ethanolamine 0.6

Deceth-3

Deceth-5 1.5

PPG myristyl ether 2

Oleth-10 1.5 oil alcohol 1.5 ethanol 5 methoxyisopropanol 6.5 polyglyceryl-4 oleyl ether 2

Merquat 100 1.5

SeradFX1000 1 hydrogen peroxide 3 sequestrant 0.2 fragrance 1 water q.s. 100 ALIGN!

This composition for immediate application to the hair to be bleached was applied under the cap for 45 minutes

After rinsing and drying, a homogeneous discoloration was achieved.

• φ φ φ φ φ φ · · φ φ φ φ φ φ φ φ • • • • φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φφ φφ

Industrial applicability

A ready-to-use aqueous bleaching composition of keratin fibers comprising a mixture of a water-soluble solvent and an amphiphilic nonionic or anionic polymer with at least one aliphatic chain is useful, for example, in the manufacture of a gentle hair bleaching composition.

Claims (25)

Patent claims Aqueous bleaching composition of keratin fibers, in particular human keratin fibers, intended for direct use and comprising, in a suitable decolorizing environment, at least one basic agent, at least one peroxydated salt, hydrogen peroxide and at least one water-soluble solvent, characterized in that it comprises at least one amphiphilic nonionic and / or anionic polymer with at least one aliphatic chain. Aqueous decolorizing agent according to claim 1, characterized in that said amphiphilic nonionic polymer with at least one aliphatic chain is among the celluloses or hydroxyalkylcelluloses modified with groups containing at least one aliphatic chain of the alkyl, arylalkyl or alkylaryl type, wherein the alkyl contains 8 to 22 carbon atoms or modified with polyalkoxylated alkylphenol groups; - hydroxypropylguars modified with groups containing at least one aliphatic chain of 8 to 22 carbon atoms; - polyurethanes containing at least one aliphatic chain of the alkyl or alkenyl group type having 8 to 30 carbon atoms; - copolymers of vinylpyrrolidone and hydrophobic monomers with an aliphatic chain copolymers of alkyl methacrylates wherein the alkyl contains 1 to 6 carbon atoms and amphiphilic monomers with at least one aliphatic chain; - copolymers of hydrophilic methacrylates and hydrophobic monomers with at least one aliphatic chain. Aqueous decolorizing composition according to claims 1 and 2, characterized in that the amphiphilic nonionic polymer with at least one aliphatic chain is hydroxyethylcellulose modified with groups containing at least one C 8 -C 22 alkyl radical or polyurethane modified with at least one C 10 alkyl group. up to 20 carbon atoms. An aqueous decolorizing composition according to claim 1, wherein the amphiphilic anionic polymer with at least one aliphatic chain is a copolymer comprising - hydrophilic motifs derived from one or more monomers with 9 9 4 An ethylene type of unsaturation bearing one carboxylic acid functional group; and hydrophobic motifs derived from one or more ethylene-type unsaturation monomers carrying a single hydrophobic side chain. Aqueous bleaching composition according to claim 4, characterized in that the ethylene-type unsaturation monomer or monomers carrying one carboxylic acid functional group can be ethacrylic acid, methacrylic acid and acrylic acid, preferably methacrylic acid and acrylic acid and mixtures thereof. Aqueous decolorizing agent according to one of claims 4 and 5, characterized in that the monomer or monomers having an ethylene type of unsaturation carrying one side hydrophobic chain can be ethacrylates, methacrylates and / or alkyl acrylates, wherein the alkyl group contains 10 to 30 carbon atoms, preferably 12 to 22 carbon atoms. Aqueous decolorizing composition according to any one of claims 4 to 6, characterized in that the monomer or monomers with an ethylene type of unsaturation carrying one side hydrophobic chain may be allyl aliphatic alkyl ethers corresponding to the general formula I: CH ₂ CR'Cn ₂ -C) -B _n -I <(I) wherein R 'represents a hydrogen atom or a methyl group B is an ethyleneoxy group; n is an integer ranging from 0 to 100; R represents a hydrocarbon group which may be alkyl, arylalkyl, aryl, alkylaryl or cycloalkyl having 8 to 30 carbon atoms, preferably 10 to 24 carbon atoms. The aqueous decolorizing composition of any one of claims 4 to 7, wherein the amphiphilic anionic polymer with at least one aliphatic chain further comprises motifs derived from a crosslinking monomer comprising two double ethylene non-conjugated bonds. • • • • • • • • • • • • • • • • • • • • • • • • • ♦ · · • 9 · · · Aqueous decolorizing agent according to claim 8, characterized in that said crosslinking monomer can be diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, methylene-bis-acrylamide, polyallylsaccharose or polyallylpentaerythritol. Aqueous decolorizing composition according to any one of claims 4 to 9, characterized in that the amphiphilic anionic polymer with at least one aliphatic chain is a cross-linked copolymer of acrylic acid and an alkyl acrylate, wherein the alkyl contains 10 to 30 carbon atoms. Aqueous bleach according to any preceding claim, characterized in that the amphiphilic nonionic and / or anionic polymers with at least one aliphatic chain are present in an amount of 0.01 to 10%, preferably 0.1 to 5%, based on the total weight of the aqueous means. Aqueous decolorizing agent according to any preceding claim, characterized in that the water-soluble solvent is an aliphatic linear or branched monoalcohol having 1 to 6 carbon atoms, an aliphatic linear or branched polyol having 3 to 20 carbon atoms, polyol ethers of which in particular between aliphatic mono- or diethers of 1 to 6 carbon atoms of polylols of 2 to 9 carbon atoms and aromatic ethers of 6 to 9 carbon atoms of polylols of 2 to 9 carbon atoms. Aqueous decolorizing composition according to any preceding claim, characterized in that it contains 0.1 to 10%, preferably 0.5 to 8% of a water-soluble solvent, based on the total weight of the aqueous composition. Aqueous decolorizing agent according to any preceding claim, characterized in that the alkaline agent can be ammonia or organic amines such as mono-, di- or triethanolamine, 2-amino-2-methyl-1-propanol, diaminopropane, hydroxyalkylamines and oxyethylened and / or or oxypropylegiated ethylenediamines. Aqueous decolorizing composition according to any preceding claim, wherein said peroxylated salt is a ftft ftft ftft ft ftft ftftft fr ftft ftft Ammonium or alkali metal persulphates, percarbonates and perborates, preferably sodium or potassium persulphate. Aqueous bleaching composition according to any preceding claim, characterized in that it contains 2 to 20% by weight, preferably 4 to 15% by weight, of the peroxylated salt. Aqueous bleaching composition according to any preceding claim, characterized in that it contains 0.5 to 10% by weight, preferably 1 to 8% by weight, of hydrogen peroxide. Aqueous bleaching composition according to any preceding claim, further comprising bleaching additives such as oxygen release control agents such as magnesium carbonate or magnesium oxide, anionic, nonionic, cationic, amphoteric or zwitterionic surfactants and mixtures thereof, mineral or vegetable oils, waxes, binders, mineral fillers such as silica and clay, opacifiers such as titanium dioxide, dyes, sequestrants, fragrances and polymers. Aqueous decolorizing composition according to claim 18, characterized in that it comprises at least one water-soluble, natural and / or synthetic thickening polymer. Aqueous decolorizing composition according to claim 19, characterized in that it contains 0.03 to 30%, preferably 0.3 to 15% by weight of at least one water-soluble thickening polymer. Aqueous bleaching composition according to claim 18, characterized in that it contains at least one cationic and / or amphoteric substantive polymer. Aqueous decolorizing composition according to claim 21, characterized in that it contains 0.03 to 30% by weight of at least one cationic and / or amphoteric substantive polymer. 99 99 • 9 9 * 9 9 · 9999 9 ··· 99 9999 99 99 9 9 9 9 9 99 99 Aqueous bleaching composition according to claim 18, characterized in that it contains 0.01 to 40%, preferably 0.1 to 30% by weight of at least one surfactant. 24. A process for decolorizing keratin fibers, particularly human hair, comprising the steps of resting - in the preparation, just prior to use, of an aqueous colorant as defined in any one of claims 1 to 23 - in the application of said composition to the area of keratin fibers to be bleached, depending on the time required to achieve the desired discoloration, and - removing the bleach by rinsing with water followed by shampooing and drying. A package or kit with several compartments for decolorizing keratin fibers and in particular human keratin fibers such as hair, characterized in that it comprises at least three compartments, the first comprising a peroxydated salt as defined in claim 15, the second comprising in water a soluble solvent as defined in claim 12 and an alkaline agent as defined in claim 14 and the third comprising an aqueous composition comprising hydrogen peroxide, one or more amphiphilic nonionic and / or anionic polymers having at least one aliphatic chain have been added to one or more; more of these sections.