WO2018056235A1 - Composition for keratin fibers - Google Patents

Abstract

The present invention relates to a composition for keratin fibers, preferably hair, comprising (a) at least one cationic vinylpyrrolidone polymer; (b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and (c) at least one oxidizing agent, wherein the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more. The present invention can prevent or reduce the loss of volume of keratin fibers when the keratin fibers are colored by, for example, dyeing or bleaching, and when the colored keratin fibers are washed by, for example, shampooing.

Description

DESCRIPTION

COMPOSITION FOR KERATIN FIBERS

TECHNICAL FIELD

The present invention relates to a composition to be applied onto keratin fibers such typically for dyeing or bleaching the keratin fibers, as well as the uses thereof.

BACKGROUND ART

It is a known matter to dye keratin fibers, in particular hair, with dyeing compositions containing oxidation dyes. Oxidation dyes typically comprise oxidation dye precursors and couplers. Oxidation dye precursors, generally called oxidation bases, are colorless or weakly colored compounds which, combined with oxidizing agents, can give rise to colored and dye compounds by a process of oxidative condensation. They are in particular ortho- or para-phenylenediamines, ortho- or para-aminophenols, or heterocyclic bases. The shades obtained with these oxidation bases may be modified by combining the oxidation bases with couplers or color modifiers, the couplers being chosen in particular from aromatic

meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds. The variety of molecules used in oxidation bases and couplers allows a rich palette of colors to be obtained.

These oxidation bases and couplers are combined with oxidizing agents, typically under the presence of alkaline agents in order to enhance coloring performance. On the other hand, oxidizing agents typically in combination with alkaline agents can be used to bleach keratin fibers.

DISCLOSURE OF INVENTION

However, in some cases, the dyed or bleached keratin fibers tend to lose its volume, because the roots of the dyed or bleached keratin fibers tend to incline, and come to be difficult to lift up the keratin fibers. The loss of volume in dyed or bleached keratin fibers is not preferable, because hair styling tends to be not easy.

Also, when the roots of the dyed or bleached keratin fibers incline, the side of the roots can be more visible. Thus, the difference in color between the dyed or bleached part of the keratin fibers and newly grown undyed or unbleached part of the keratin fibers tends to be more distinct. This is not preferable either from a view point of uniform appearance of dyed or bleached keratin fibers from the root to the tip of the keratin fibers. In addition, if undyed keratin fibers are white or gray hair, for example, the loss of volume of dyed keratin fibers_, may cause old-looking.

Furthermore, the loss of volume of dyed or bleached keratin fibers tends to be worse, when the dyed or bleached keratin fibers are washed by, for example, shampooing.

Thus, it is preferable to prevent or reduce the loss of volume of keratin fibers when the keratin fibers are colored by, for example, dyeing or bleaching and/or when the colored keratin fibers are washed by, for example, shampooing. An objective of the present invention is to provide a composition for keratin fibers which can prevent or reduce the loss of volume of keratin fibers when the keratin fibers are colored and/or when the colored keratin fibers are washed. The above objective can be achieved by a composition for keratin fibers, preferably hair, comprising

(a) at least one cationic vinylpyrrolidone polymer;

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and

(c) at least one oxidizing agent

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more.

The (a) cationic vinylpyrrolidone polymer may be chosen from the group consisting of:

vinylpyrrolidone polymers comprising dimethylaminoethyl methacrylate units,

vinylpyrrolidone polymers comprising methacrylamidopropyltrimethylammonium units, and vinylpyrrolidone polymers comprising methyl vinylimidazolium units.

The cationic vinylpyrrolidone polymers comprising dimethylaminoethyl methacrylate units may be chosen from:

vinylpyrrolidone/dimethylaminoethyl methacrylate copolymers;

vinylpyrrolidone/dimethylaminoethyl methacrylate copolymers quaternized with diethyl sulphate;

vinylpyrrolidone/dimethylaminoethyl methacrylate/hydrophilic polyurethane copolymers; vinylpyrrolidone/dimethylaminoethyl methacrylate/C₈-C₁₆ olefin copolymers, quaternized or non-quaternized; and

vinylpyrrolidone/dimethylaminoethyl methacrylate/vinylcaprolactam copolymers.

The amount of the (a) cationic vinylpyrrolidone polymer may range from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and more preferably from 0.1% to 3% by weight, relative to the total weight of the composition.

The (b) cationic cyclopolymer having at least one ring-structure in the backbone of the polymer may be chosen from cationic cellulose polymers and cationic non-cellulose polymers. The cationic cellulose polymer may comprise at least one quaternary ammonium group including at least one C₈-C₃₀ hydrocarbon group.

The cationic non-cellulose polymer may be chosen from

dialkyldiallylammonium chloride homopolymers, and

dialkyldiallylammonium chloride//acrylamide copolymers.

The amount of the (b) cationic cyclopolymer having at least one ring-structure in the backbone of the polymer may range from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and more preferably from 0.1% to 3% by weight, relative to the total weight of the composition. The (c) oxidizing agent may be hydrogen peroxide.

The amount of the (c) oxidizing agent may range from 0.01% to 30%> by weight, preferably from 0.1%) to 20%> by weight, and more preferably from 1%> to 10%> by weight, relative to the total weight of the composition.

The composition according to the present invention may further comprise (d) at least one additional cationic polymer having at least one diammonium moiety in the polymer backbone which is different from the cationic polymer (a) or (b).

The amount of the (d) cationic polymer having at least one diammonium moiety may range from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and more preferably from 0.1% to 3% by weight, relative to the total weight of the composition.

The present invention also relates to a ready-to-use cosmetic composition for keratin fibers, preferably hair, comprising

a first composition comprising:

(a) at least one cationic vinylpyrrolidone polymer;

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and

(c) at least one oxidizing agent

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more, and

a second composition comprising at least one alkaline agent.

The present invention also relates to a kit for keratin fibers, preferably hair, comprising a first compartment comprising a first composition comprising:

(a) at least one cationic vinylpyrrolidone polymer;

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and

(c) at least one oxidizing agent

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more, and

a second compartment comprising a second composition comprising at least one alkaline agent.

The present invention also relates to a cosmetic process for keratin fibers, preferably hair, comprising the steps of

(1) mixing

a first composition comprising:

(a) at least one cationic vinylpyrrolidone polymer;

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and (c) at least one oxidizing agent

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more, and

a second composition comprising at least one alkaline agent to prepare a ready-to-use cosmetic composition, and

(2) applying the ready-to-use cosmetic composition to the keratin fibers.

BRIEF DESCRIPTION OF DRAWINGS

Fig. 1 shows a side view in order to show how to determine the vertical angle between a plate and the tips of a hair fiber in the evaluation of volumizing effects of the compositions according to Examples 1-5 and Comparative Examples 1-10.

BEST MODE FOR CARRYING OUT THE INVENTION After diligent research, the inventors have discovered that it is possible to provide a composition for keratin fibers which can prevent or reduce the loss of volume of keratin fibers when the keratin fibers are colored and/or when the keratin fibers are washed, by using a combination of specific two cationic polymers under specific conditions in the composition. Thus, the present invention mainly relates to a composition for keratin fibers, preferably hair, comprising

(a) at least one cationic vinylpyrrolidone polymer;

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and

(c) at least one oxidizing agent

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more.

The above composition according to the present invention can prevent or reduce the loss of volume of keratin fibers when the keratin fibers are colored by, for example, dyeing or bleaching, and/or when the colored keratin fibers are washed by, for example, shampooing.

The above composition for keratin fibers according to the present invention can be used for coloring keratin fibers due to the action of the oxidizing agent. For example, if the above composition for keratin fibers according to the present invention is used in combination with another composition including oxidation dye(s), it is possible to dye the keratin fibers due to the action of the oxidizing agent in the above composition according to the present invention. Alternatively, if the above composition for keratin fibers according to the present invention is used alone, it is possible to bleach the keratin fibers due to the action of the oxidizing agent in the above composition according to the present invention. It is preferable that the composition for keratin fibers according to the present invention is mixed with another composition including at least one alkaline agent, and the mixture thus obtained is used to color keratin fibers, in order for higher coloring performance. In addition, if the other composition includes oxidation base(s) and coupler(s), the keratin fibers can be dyed with a variety of colors.

The composition for keratin fibers according to the present invention, in particular when being combined with the above other composition including at least one alkaline agent, can prevent or reduce the loss of volume of keratin fibers when the keratin fibers are colored by, for example, dyeing or bleaching, and/or when the colored keratin fibers are washed by, for example, shampooing.

Hereafter, the present invention will be described in a detailed manner. [Composition Including Cationic Polymers]

One aspect of the present invention relates to a composition for keratin fibers, preferably hair, including a combination of the following two distinct specific cationic polymers:

(a) at least one cationic vinylpyrrolidone polymer; and

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer.

The (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other.

The weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more, preferably 2.0 or more, more preferably 3.0 or more, and even more preferably 4.0 or more. The weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) may be 30 or less, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.

(Cationic Vinylpyrrolidone Polymer)

The composition according to the present invention comprises (a) at least one cationic vinylpyrrolidone polymer. A single type of (a) cationic vinylpyrrolidone polymer may be used, or two or more different types of (a) cationic vinylpyrrolidone polymers may be used in combination.

The (a) cationic vinylpyrrolidone polymer is a homopolymer or copolymer of

vinylpyrrolidone monomers. The (a) cationic vinylpyrrolidone polymer has at least one pendent ring structure derived from the vinylpyrrolidone. On the other hand, it is preferable that the (a) cationic vinylpyrrolidone polymer comprise no ring structure in the backbone of the polymer.

The (a) cationic vinylpyrrolidone polymer may be chosen from the group consisting of:

vinylpyrrolidone polymers comprising dimethylaminoethyl methacrylate units, vinylpyrrolidone polymers comprising methacrylamidopropyltrimethylammonium units, and vinylpyrrolidone polymers comprising methylvinylimidazolium units.

The cationic vinylpyrrolidone polymers comprising dimethylaniinoethyl methacrylate units which may be chosen from:

vinylpyrrolidone/dimethylaminoethyl methacrylate copolymers; for example, vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer (20/80 by weight) sold under the trade name Copolymer 845 by the company I.S.P.,

vinylpyrrolidone/dimethylaminoethyl methacrylate copolymers quaternized with diethyl sulphate; for example, vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer quaternized with diethyl sulphate, sold under the trade names Gafquat 734, 755, 755S and 755L by the company I.S.P.,

vinylpyrrolidone/dimethylaminoethyl methacrylate/hydrophilic polyurethane copolymers; for example, vinylpyrrolidone/dimethylaminoethyl

methacrylate/hydrophilic polyurethane copolymer, sold under the trade name Pecogel GC-310 by the company U.C.I.B., or under the trade names Aquamere CI 031 and CI 511 by the company Blagden Chemicals,

vinylpyrrolidone/dimethylaminoethyl methacrylate/C -C₁₆ olefin copolymers, quaternized or non-quaternized; for example, vinylpyrrolidone/dimethylaminoethyl methacrylate/C₈-C₁₆ olefin copolymer sold under the trade names Ganex ACP1050 to 1057, 1062-1069 and 1079-1086 by the company I.S.P,

and

vinylpyrrolidone/dimethylaminoethyl methacrylate/vinylcaprolactam copolymers; for example, vinylpyrrolidone/dimethylaminoethyl methacrylate/vinylcaprolactam copolymer sold under the trade name Gaffix VC713 by the company I.S.P.

The cationic vinylpyrrolidone polymers comprising

methacrylamidopropyltrimethylammonium (MAPTAC) units which may be chosen from: vinylpyrrolidone/methacrylamidopropyltrimethylammonium copolymers; for example, vinylyrrolidone/MAPTAC copolymer sold under the trade names Gafquat ACP1011 and Gafquat HS100 by the company I.S.P,

and

vinylpyrrolidone/methacrylamidopropyltrimemylarrmionium/vinylcaprolactam terpolymers; for example, vinylpyrrolidone/MAPTAC/vinylcaprolactam terpolymer sold under the trade names Polymer ACP 1059, 1060 and 1156 by the company I.S.P.

The cationic vinylpyrrolidone polymers comprising methylvinylimidazolium units which may be chosen from

vinylpyrrolidone/methylvinylimidazolium chloride copolymers; for example, vinylpyrrolidone/methylvinylimidazolium chloride copolymer sold under the trade names Luviquat FC370, FC550, FC905 and HM552 by the company BASF, vinylpyrrolidone/methylvinylimidazolium chloride/vinylimidazole copolymers; for example, vinylpyrrolidone/methylvinylimidazolium chloride/vinylimidazole copolymer sold under the trade name Luviquat 8155 by the company BASF, and

vinylpyrrolidone/methylvinylimidazolium methosulphate copolymers; for example, vinylpyrrolidone/methylvinylimidazolium methosulphate copolymer sold under the trade name Luviquat MS370 by the company BASF.

It may be preferable that the (a) cationic vinylpyrrolidone polymer be chosen from

vinylpyrrolidone polymers comprising dimethylaminoethyl methacrylate units, more preferably chosen from vinylpyrrolidone/dimethylaminoethyl methacrylate copolymers quaternized with diethyl sulphate, and even more preferably Polyquaternium-11.

The amount of the (a) cationic vinylpyrrolidone polymer in the composition according to the present invention may range from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and more preferably from 0.1 % to 3% by weight, relative to the total weight of the composition.

(Cationic Cyclopolymer)

The composition according to the present invention comprises (b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer. A single type of the (b) cationic cyclopolymer may be used, or two or more different types of (b) the cationic cyclopolymers may be used in combination.

The (b) cationic cyclopolymer has at least one ring-structure in the backbone of the polymer. In other words, the polymer backbone includes at least one ring structure. Thus, for example, a carbon-carbon main chain of the polymer may be bonded to a ring structure, and another carbon-carbon main chain of the polymer may be bonded to the ring structure, wherein the bonding positions of the main chains are different.

The ring structure may be formed by only carbon-carbon links, and may include at least one heteroatom such as an oxygen atom and a nitrogen atom. The nitrogen atom in the ring structure may be quaternized. The ring may be a 4-8 membered ring, preferably a 4-6 membered ring, and more preferably a 5 or 6 membered ring.

It is preferable that the (b) cationic cyclopolymer comprise no ring structure which is pendent from the backbone of the polymer. The (b) cationic cyclopolymer having at least one ring-structure in the backbone of the polymer may be chosen from cationic cellulose polymers and cationic non-cellulose polymers.

The cationic cellulose polymers having at least one ring-structure in the backbone of the polymer may have at least one quaternary ammonium group.

It may be preferable that the cationic cellulose polymers be quaternized hydroxyethyl celluloses modified with at least one quaternary ammonium group comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof. The alkyl radicals borne by the quaternary ammonium group may preferably contain from 8 to 30 carbon atoms, especially from 10 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.

More preferably, the cationic cellulose polymer may comprise at least one quaternary ammonium group including at least one C₈-C₃₀ hydrocarbon group.

Examples of quaternized alkylhydroxyethylcelluloses containing C₈-C₃o fatty chains that may be mentioned include the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529- 18B (CI 2 alkyl) and Quatrisoft LM-X 529-8 (CI 8 alkyl) or Softcat Polymer SL100, Softcat SX-1300X, Softcat SX-1300H, Softcat SL-5, Softcat SL-30, Softcat SL-60 , Softcat SK-MH, Softcat SX-400X, Softcat SX-400H, SoftCat SK-L, Softcat SK-M, and Softcat SK-H, sold by the company Amerchol and the products Crodacel QM, Crodacel, QL (C12 alkyl) and Crodacel QS (CI 8 alkyl) sold by the company Croda. Among these quaternized alkylhydroxyethylcelluloses the products corresponding to INCI name Polyquaternium-67 are preferred.

From another view point, the cationic cellulose polymers could also be chosen among cationic cellulose ether(s), comprising from 4 000 to 10 000 anhydroglucose units, said

anhydroglucose units being substituted with at least:

(i) one substituent of formula

in which

R4 and R₅ represent,, independently of one another, a methyl or ethyl group,

R6 represents a linear or branched C₈-C₂₄ alkyl group or an aralkyl group in which the linear or branched alkyl part is

R₉ represents a divalent group which allows the attachment to the anhydroglucose group and which is chosen from -

q denoting 0 or 1,

B denoting a divalent group

n' being an integer ranging from 1 to 100,

X₂- represents an anion; and

(ii) one substituent of formula

in which:

R , R and R represent, independently of one another, a methyl or ethyl group,

R⁸ represents a divalent group which allows the attachment to the anhydroglucose group and which is chosen from

_p

p denoting 0 or 1 ,

A denoting a divalent group

n being an integer ranging from 1 to 100,

Xf represents an anion.

Preferably, the substituent (i) of formula

is present at an average of from 0.0003 to 0.08 mol, per mole of anhydroglucose units.

The cationic cellulose ethers that can be used in the compositions according to the present invention are preferably hydroxyethyl celluloses or hydroxypropyl celluloses. The cationic cellulose ethers that can be used in the compositions according to the present invention preferably comprise more than 4500, advantageously more than 5000, and more preferably more than 6000 anhydroglucose units.

Preferably, the cationic cellulose ethers that can be used in the compositions according to the present invention preferably comprise up to 9000, and preferably up to 8000 anhydroglucose units. These cationic cellulose ethers and the process for the preparation thereof are described in application WO 2005/000903.

According to a preferred variant, the cationic cellulose ethers that can be used in the compositions according to the present invention are formed from at least one unit (IV) and at least one of the following units (I), (II) and (III):

with the proviso that:

the total number of units (I)+(II)+(III)+(IV) is between 4000 and 10 000;

the [(III)+(IV)]/[(I)+(II)+(III)+(IV)] ratio ranges from 0.0003 to 0.8;

the [(II)+(IV)]/[(I)+(II)+(III)+(IV)] ratio ranges from 0.02 to 0.9;

the integers n and n', independently of one another, range from 0 to 5;

R₁, R₂, R₃, R4 and R₅ represent, independently of one another, a methyl or ethyl group;

represents a linear or branched C₈-C₂₄, preferably C₁₀-C₂₄, more preferably C₁₂-C₂₄ and better still C₁₂-C₁₅, alkyl group or an aralkyl group in which the linear or branched alkyl part is C₈-C₂₄;

Xf and X₂ ^" represent anions preferably chosen, independently of one another, from phosphate, nitrate, sulphate and halide (CI^", Br^", F^", Γ) ions.

According to a particular variant, the cationic cellulose ethers that can be used in the compositions according to the present invention are formed from at least one unit (IV) and at least one of the units (I), (II) or (III) above, in which Re is a linear dodecyl group.

Among the cationic cellulose ethers that can be used in the compositions of the present invention, mention may be made of the polymers of Softcat SL-5, SL-30, SL-60 and SL-100 type (INCI: Polyquaternium-67) sold by the company Amerchol. The cationic cellulose ethers that are particularly preferred are the polymers of SL-60 and SL-100 type.

On the other hand, as cationic non-cellulose polymers, mention may be made of

cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers containing, as a main constituent of the chain, units corresponding to formula (V) or (VI):

in which formulae

k and t are equal to 0 or 1 , the sum k + 1 being equal to 1 ; R₉ denotes a hydrogen atom or a methyl radical; R₇ and R₈, independently of each other, denote an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower (C1-C4) amidoalkyl group, or R₇ and Rg can denote, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidyl or morpholinyl; R₇ and R₈, independently of each other, preferably denote an alkyl group having from 1 to 4 carbon atoms; and Y^" is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. These polymers are described in particular in French patent 2 080 759 and in its Certificate of Addition 2 190 406.

Among the polymers defined above, mention may be made more particularly of the dimethyldiallylammonium chloride homopolymer sold under the name "Merquat 100" by the company Nalco (and its homologues of low weight-average molecular mass) and the copolymers of diallyldimethylammonium chloride and of acrylamide, sold under the name "Merquat 550". It may be preferable that the cationic non-cellulose polymer be chosen from

dialkyldiallylammonium chloride homopolymers such as Polyquaternium-6, and

dialkyldiallylammonium chloride//acrylamide copolymers such as Polyquaternoum-7.

The amount of the (b) cationic cyclopolymer having at least one ring-structure in the backbone of the polymer in the composition according to the present invention may range from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and more preferably from 0.1% to 3% by weight, relative to the total weight of the composition.

(Oxidizing Agent)

The composition according to the present invention comprises (c) at least one oxidizing agent. A single type of (c) oxidizing agent may be used, or two or more different types of (c) oxidizing agents may be used in combination. The (c) oxidizing agent may be chosen from hydrogen peroxide, peroxygenated salts, and compounds capable of producing hydrogen peroxide by hydrolysis. For example, the (c) oxidizing agent can be chosen from aqueous hydrogen peroxide solution, urea peroxide, alkali metal bromates and ferricyanides and persalts such as perborates and persulphates. At least one oxidase enzyme chosen, for example, from laccases, peroxidases and 2-electron oxidoreductases such as uricase may also be used as the (c) oxidizing agent, where appropriate in the presence of the respective donor or co-factor thereof.

In one embodiment, the (c) oxidizing agent is hydrogen peroxide, such as an aqueous hydrogen peroxide solution. The hydrogen peroxide concentration may range from 0.15 wt% to 12 wt% such as from 0.6 wt% to 9 wt% relative to the total weight of the (c) oxidizing agent. The concentration of compounds capable of forming hydrogen peroxide by hydrolysis may range from 0.1 wt% to 25 wt% relative to the total weight of the (c) oxidizing agent.

In one embodiment, when the (c) oxidizing agent is an aqueous hydrogen peroxide solution, the aqueous solution may comprise at least one hydrogen peroxide stabilizer, which may be chosen, for example, from alkali metal and alkaline-earth metal pyrophosphates, alkali metal and alkaline-earth metal stannates, phenacetin and salts of acids and of oxyquinoline, for example, oxyquinoline sulphate. In another embodiment, at least one stannate optionally in combination with at least one pyrophosphate is used.

It is also possible to use salicylic acid and its salts, pyridinedicarboxylic acid and its salts, paracetamol.

In the (c) oxidizing agent in the form of an aqueous hydrogen peroxide solution, the concentration of the hydrogen peroxide stabilizer may range from 0.0001 wt% to 5 wt% such as from 0.01 wt% to 2 wt% relative to the total weight of the (c) oxidizing agent.

In the (c) oxidizing agent in the form of an aqueous hydrogen peroxide solution, the concentration ratio of the hydrogen peroxide to the possible at least one stabilizer may range from 0.05: 1 to 1,000:1, such as from 0.1 : 1 to 500:1 and further such as from 1 :1 to 200: 1. The amount of the (c) oxidizing agent in the composition according to the present invention may range from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, and more preferably from 1% to 10% by weight, relative to the total weight of the composition.

(Additional Cationic Polymer)

The composition according to the present invention may comprise (d) at least one additional cationic polymer having at least one diammonium moiety in the polymer backbone which is different from the cationic polymer (a) or (b). A single type of the (d) additional cationic polymer may be used, or two or more different types of the (d) additional polymers may be used in combination.

The (d) additional cationic polymer has at least one diammonium moiety in the polymer backbone. The (d) additional cationic polymer may be represented by the following formula (VII):

in which formula (VII):

R₁₀, Rn, R₁₂ and R₁₃, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or alternatively R₁₀, R₁₁, R₁₂ and R₁₃, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second hetero atom other than nitrogen, or alternatively Ri₀, Rn, R_J2 and R₁₃ represent a linear or branched C₁-C₆ alkyl radical substituted with a nitrile, ester, acyl or amide group or a group

where Rj₄ is an alkylene and D is a quaternary ammonium group;

A_\ and Bi represent polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

X^" denotes an anion derived from an inorganic or organic acid;

Ai, R₁₀ and R₁₂ can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if Ai denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B₁ can also denote a group -

in which D denotes:

i) a glycol residue of formula:

where Z denotes a linear or branched

hydrocarbon-based radical or a group corresponding to one of the following formulae:

- -

where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; ii) a bis-secondary diamine residue such as a piperazine derivative;

iii) a bis-primary diamine residue of formula -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon-based radical, or alternatively the divalent radical

; or

iv) a ureylene group of formula

Preferably, X^" is an anion such as chloride or bromide. These polymers generally have a number-average molecular mass of between 1000 and 100 000.

Polymers of this type are described in particular in French patents 2 320 330, 2 270 846, 2 316 271, 2 336 434 and 2 413 907 and 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.

It is more particularly possible to use polymers that consist of repeating units corresponding to the following formula (VIII):

in which

R₁₀, Rn, R₁₂ and R₁₃, which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms approximately, n and p are integers ranging from 2 to 20 approximately, and X^" is an anion derived from a mineral or organic acid. One particularly preferred compound of formula (VIII) is that for which Ri₀, Rn R₁₂ and R₁₃ represent a methyl group, n=3, p=6 and X=C1, which is called Hexadimethrine chloride according to the INCI(CTFA) nomenclature.

The amount of the (d) cationic polymer having at least one diammonium moiety in the composition according to the present invention may range from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and more preferably from 0.1 % to 3% by weight, relative to the total weight of the composition.

(pH and Optional Ingredients)

The pH of the composition according to the present invention may be adjusted to the desired value using acidifying or basifying agents commonly used in the technical field of coloring keratin fibers.

The composition according to the present invention includes (c) oxidizing agent(s).

Therefore, it is preferable that the pH of the composition according to the present invention be from 1 to 6, more preferably from 2 to 5, and even more preferably from 2 to 4.

Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, ortho-phosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, and lactic acid, and sulfonic acids. Among the basifying agents, mention may be made, by way of example, of ammonium hydroxide, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines and also their derivatives, sodium or potassium hydroxide and compounds of the formula below:

wherein

W denotes an alkylene such as propylene optionally substituted by a hydroxyl or a C₁-C₄ alkyl radical, and R_a, Rb, Rc and R_d independently denote a hydrogen atom, an alkyl radical or a C₁-C₄ hydroxyalkyl radical, which may be exemplified by 1,3-propanediamine and derivatives thereof. Sodium or potassium hydroxide may also be preferable.

The acidifying or basifying agent may be used in an amount ranging from 0.001 to 15% by weight, preferably from 0.01 to 10% by weight, and more preferably from 0.1 to 5% by weight, relative to the total weight of the composition.

The composition according to the present invention may also contain various adjuvants conventionally used in compositions for coloring keratin fibers such as hair, such as oils, anionic, non-ionic, cationic, amphoteric or zwitterionic surfactants, or mixtures thereof, antioxidants, thickening agents, sequestering agents, fragrances, dispersing agents, conditioning agents, film-forming agents, ceramides, preservatives and opacifying agents. The composition according to the present invention may comprise water.

The amount of water in the composition according to the present invention may range from 50% to 99% by weight, preferably from 60% to 95% by weight, and more preferably from 70 to 90% by weight, relative to the total weight of the composition.

The form of the composition according to the present invention is not particularly limited, as long as it is water-based, and may take various forms such as an emulsion (O/W or W/O form), an aqueous gel, an aqueous solution, or the like. It is preferable that the composition according to the present invention be in the form of a water-based solution.

The composition according to the present invention can be used as a composition for coloring keratin fibers, for example by dyeing or bleaching the keratin fibers. Thus, the composition according to the present invention can be a cosmetic composition for coloring keratin fibers. The "keratin fibers" here mean fibers which include at least one keratin substance. It is preferable that at least a part of the surface of the keratin fibers be formed by keratin fibers. Examples of keratin fibers include hair, eyebrows, eyelashes, and the like. It is preferable that the composition according to the present invention be used for dyeing or bleaching hair. [Composition Including Alkaline Agent]

The composition according to the present invention including a combination of the two distinct specific cationic polymers (a) and (b) with the (c) oxidizing agent(s) under specific conditions can be used in combination with another composition including at least one alkaline agent.

Hereafter, the composition according to the present invention including a combination of the two distinct specific cationic polymers (a) and (b) with the (c) oxidizing agent(s) under specific conditions is referred to as a first composition. On the other hand, the composition including at least one alkaline agent is referred to as a second composition.

(Alkaline Agent)

The second composition comprises at least one alkaline agent. A single type of alkaline agent may be used, or two or more different types of alkaline agents may be used in combination.

As the alkaline agents, mention may be made of any inorganic or organic basic agents which are commonly used in cosmetic products such as ammonia; alkanolamines such as mono-, di- and tri-ethanolamine, isopropanolamine; sodium and potassium hydroxides; urea, guanidine and their derivatives; basic amino acids such as lysine or arginine; and diamines such as those described in the structure below:

wherein R denotes an alkylene such as propylene optionally substituted by a hydroxyl or a radical, and

R₃, R₄, R₅ and R₆ independently denote a hydrogen atom, an alkyl radical or a C₁-C₄ hydroxyalkyl radical, which may be exemplified by 1 ,3-propanediamine and derivatives thereof. Arginine and monoethanolamine are preferred.

The alkaline agent may be used in an amount ranging from 0.001 to 15% by weight, preferably from 0.01 to 10% by weight, and more preferably from 0.1 to 5% by weight, relative to the total weight of the composition. (Oxidation Dye)

The second composition may comprise at least one oxidation dye. A single type of oxidation dye may be used, or two or more different types of oxidation dyes may be used in

combination.

The oxidation dye can be selected from oxidation bases, oxidation couplers, and the acid addition salts thereof.

The oxidation base can be selected from those conventionally known in oxidation dyeing, preferably from the group consisting of ortho- and para-phenylenediamines, double bases, ortho- and para-aminophenols, heterocyclic bases and the acid addition salts thereof.

There may be mentioned in particular:

- (I) the para-phenylenediamines of the following formula (I) and their addition salts with an acid:

in which:

R₁ represents a hydrogen atom, a C₁-C₄ alkyl radical, a monohydroxy(C₁-C₄ alkyl) radical, a polyhydroxy-(C₂-C₄ alkyl) radical, a (C₁-C₄)alkoxy(C_rC₄)alkyl radical, a CrC₄ alkylradical substituted with a nitrogen-containing group, a phenyl radical or a 4'-aminophenyl radical; R₂ represents a hydrogen atom, a C₁-C₄ alkyl radical, a monohydroxy(C₁-C₄ alkyl) radical, a polyhydroxy(C₂-C₄ alkyl) radical, a (C₁-C₄)alkoxy(C₁-C₄)alkyl radical or a C₁-C₄ alkyl radical substituted with a nitrogen-containing group;

R₁ and R₂ may also form with the nitrogen atom carrying them a 5- or 6-membered nitrogen-containing heterocycle optionally substituted with one or more alkyl, hydroxyl or ureido groups;

R₃ represents a hydrogen atom, a halogen atom such as a chlorine atom, a C₁-C₄ alkyl radical, a sulpho radical, a carboxyl radical, a monohydroxy(C₁-C₄ alkyl) radical, a hydroxy(C!-C4 alkoxy) radical, an acetylamino(C₁-C₄ alkoxy) radical, a mesylamino(C₁-C₄ alkoxy) radical or a carbamoylamino(C₁-C₄ alkoxy) radical; and

R₄ represents a hydrogen or halogen atom or a C1-C4 alkyl radical. Among the nitrogen-containing groups of formula (I) above, there may be mentioned in particular the amino, mono(C)-C₄)alkylamino, (C₁-C₄)dialkylamino, (C₁-C₄)trialkylamino, monohydroxy(C₁-C₄)alkylamino, di(monohydroxy(C₁-C₄)alkyl)amino, imidazolinium and ammonium radicals.

Among the para-phenylenediamines of formula (I) above, there may be mentioned more particularly para-phenylenediamine, para-tolylenediamine, 2-chloro-paraphenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine,

2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,

Ν,Ν-dimethylpara-phenylenediamine, N,N-diethyl-para-phenylenediamine,

N,N-dipropyl-paraphenylenediamine, 4-amino-N,N-diethyl-3-methylaniline,

N,N-bis(β-hydroxyethyl)-paraphenylenediamine,

4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline,

4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-paraphenylenediamine, 2-isopropyl-para-phenylenediamine,

N-(β-hydroxypropyl)-paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3 -methylpara-phenylenediamine,

N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine,

N-(β,Υ-dihydroxypropyl)-para-phenylenediamine,

N-(4 ' -aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine,

2-β-hydroxyethyloxy-para-phenylenediamine,

2-β-acetylamino-ethyloxy-para-phenylenediamine,

N-(β-methoxyethyl)-para-phenylenediamine,

2-methyl- 1 -Ν-β-hydroxyethyl-para-phenylenediamine,

N-(4-aminophenyl)-3-hydroxy-pyrrolidine,

2-[{2-[(4-Aminophenyl)amino]ethyl}(2-hydroxyethyl)amino]-ethanol, and their addition salts with an acid.

Among the para-phenylenediamines of formula (I) above, there are most particularly preferred para-phenylenediamine, para-tolylenediamine, 2-isopropyl-paraphenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,

2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine, and their addition salts with an acid.

- (II) According to the invention, "double bases" is understood to mean compounds containing at least two aromatic rings on which amino and/or hydroxyl groups are carried.

Among the double bases which can be used as oxidation bases in the dyeing compositions in accordance with the invention, there may be mentioned in particular compounds

corresponding to the following formula (II), and their addition salts with an acid:

in which:

- Z₁ and Z₂, which are identical or different, represent a hydroxyl or -NH₂ radical which may be substituted with a C₁-C₄ alkyl radical or with a linking arm Y;

- the linking arm Y represents a linear or branched alkylene chain comprising from 1 to 14 carbon atoms, which may be interrupted by or which may end with one or more

nitrogen-containing groups and/or one or more heteroatoms such as oxygen, sulphur or -nitrogen atoms, and optionally substituted with one or more hydroxyl or C₁-C₆ alkoxy radicals;

- R₅ and represent a hydrogen or halogen atom, a C₁-C₄ alkyl radical, a

monohydroxy(C_!-C₄ alkyl) radical, a polyhydroxy(C₂-C₄ alkyl) radical, an amino(C₁-C₄ alkyl) radical or a linking arm Y;

-

and R₁₂, which are identical or different, represent a hydrogen atom, a linking arm Y or a C₁-C₄ alkyl radical; it being understood that the compounds of formula (II) contain only one linking arm Y per molecule.

Among the nitrogen-containing groups of formula (II) above, there may be mentioned in particular the amino, mono(C₁-C₄)alkylamino, (CrC₄)dialkylamino, (C₁-C₄)trialkylamino,

imidazolinium and ammonium radicals.

Among the double bases of formulae (II) above, there may be mentioned more particularly Ν,Ν' -bis(β-hydroxyethyl)-N,N' -bis(4 ' -aminophenyl)- 1 ,3 -diaminopropanol,

Ν,Ν' -bis(β-hydroxyethyl)-N,N' -bis(4 ' -aminophenyl)ethylenediamine,

N,N'-bis(4-aminophenyl)-tetramethylenediamine,

N,N'-bis(β-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine,

N,N'-bis(4-methylaminophenyl)tetramethylenediamine,

N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylene-diamine,

l,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their addition salts with an acid. Among these double bases of formula (II),

N,N'-bis(β-hydroxyethyl)-N,N'-bis(4' -aminophenyl)- 1,3 -diaminopropanol,

l,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane or one of their addition salts with an acid are particularly preferred. - (III) The para-aminophenols corresponding to the following formula (III), and their addition salts with an acid:

in which:

- R₁₃ represents a hydrogen atom, or a halogen atom such as fluorine, a CrC₄ alkyl, monohydroxy(C₁-C₄ alkyl), (C₁-C₄)alkoxy(C₁-C₄)-alkyl, amino(C₁-C₄ alkyl) or

hydroxy(C₁-C₄)alkylamino-(C₁-C₄ alkyl) radical,

- R₁₄ represents a hydrogen atom, or a halogen atom such as fluorine, a CrC₄ alkyl, monohydroxy(C₁-C₄ alkyl), polyhydroxy(C₂-C₄ alkyl), amino(C₁-C₄ alkyl), cyano(C₁-C₄ alkyl) or (C₁-C₄)alkoxy(C₁-C₄)alkyl radical.

Among the para-aminophenols of formula (III) above, there may be mentioned more particularly para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fiuorophenol,

4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,

4- amino-2-(β-hydroxyethylaminomethyl)phenol, and their addition salts with an acid.

- (IV) The ortho-aminophenols which can be used as oxidation bases in the context of the present invention are chosen in particular from 2-aminophenol,

2- amino- 1 -hydroxy-5 -methylbenzene, 2-amino- 1 -hydroxy-6-methylbenzene,

5- acetamido-2-aminophenol, and their addition salts with acid.

-(V) Among the heterocyclic bases which can be used as oxidation bases in the dyeing compositions in accordance with the invention, there may be mentioned more particularly pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their addition salts with an acid.

Among the pyridine derivatives, there may be mentioned more particularly the compounds described for example in Patents GB 1,026,978 and GB 1,153,196, such as

2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine,

2.3- diamino-6-methoxypyridine, 2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine,

3.4- diaminopyridine, and their addition salts with an acid. Among the pyrimidine derivatives, there may be mentioned more particularly the compounds described, for example, in Patents DE 2 359 399; JP 88-169571; JP 91-10659 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine,

4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine,

2.4- dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-pyrimidine, and the pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which there may be mentioned pyrazolo[l,5-a]-pyrimidine-3,7-diamine;

2.5- dimethyl-pyrazolo[l ,5-a]-pyrimidine-3,7-diamine;

pyrazolo[l,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[l,5-a]pyrimidine-3,5-diamine;

3- aminopyrazolo[l,5-a]pyrimidin-7-ol; 3-amino-pyrazolo[l,5-a]pyrimidin-5-ol;

2-(3-amino-pyrazolo-[l ,5-a]pyrimidin-7-ylamino)ethanol,

2-(7-aminopyrazolo [ 1 ,5 -a]pyrimidin-3 -ylamino)ethanol,

2- [(3 -amino-pyrazolo [ 1 ,5 -a]pyrimidin-7-yl)-(2-hydroxy-ethyl)amino] -ethanol,

2- [(7-aminopyrazolo[l,5-a]-pyrimidin-3-yl)-(2-hydroxyethyl)amino]ethanol,

5.6- dimethylpyrazolo-[l ,5-a]pyrimidine-3,7-diamine,

2,6-dimethylpyrazolo-[l ,5-a]pyrimidine-3,7-diamine,

2,5,N7,N7-tetramethyl-pyrazolo[l,5-a]pyrimidine-3,7-diamine,

3- amino-5-methyl-7-imidazolylpropyl-aminopyrazolo[l,5-a]-pyrimidine, their addition salts and their tautomeric forms, when a tautomeric equilibrium exists and their addition salts with an acid.

Among the pyrazole derivatives, there may be mentioned more particularly the compounds described in Patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 such as 4,5-diamino-l-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-l-(4'-chlorobenzyl)-pyrazole,

4,5-diamino-l,3-dimethylpyrazole, 4,5-diamino-3-methyl-l-phenylpyrazole, 4,5-diamino-l-methyl-3-phenylpyrazole, 4-amino-l,3-dimethyl-5-hydrazino-pyrazole,

1- benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-l-methylpyrazole,

4,5-diamino-l-tertbutyl-3-methylpyrazole, 4,5-diamino-l-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino- 1 -(β-hydroxyethyl)pyrazole, 4,5-diamino- 1 -ethyl-3 -methylpyrazole,

4,5-diamino- 1 -ethyl-3 -(4 ' -methoxyphenyl)pyrazole,

4,5-diamino-l-ethyl-3-hydroxy-methylpyrazole,

4,5-diamino-3-hydroxymethyl-l-methylpyrazole,

4,5-diamino-3-hydroxymethyl-l-isopropyl-pyrazole,

4,5-diamino-3-methyl-l-isopropyl-pyrazole,

4-amino-5-(2'-aminoethyl)amino-l,3-dimethylpyrazole, 3,4,5-triaminopyrazole,

1 -methyl-3 ,4,5 -triamino-pyrazole, 3 ,5-diamino- 1 -methyl-4-methylaminopyrazole,

3.5- diamino-4-(β-hydroxy-ethyl)amino-l-methylpyrazole, and their addition salts with an acid. Among the heterocyclic bases which can be used as oxidation bases, there may be mentioned more particularly diaminopyrazolopyrazolones and especially

2,3-diamino-6,7-dihydro-lH5H-[pyrazolol,2,a]pyrazol-l-one and the addition salts of these diaminopyrazolopyrazolones with an acid. The oxidation dye may be an oxidation coupler which can be selected from those

conventionally known in oxidation dyeing, preferably from the group consisting of

meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthols, heterocyclic couplers and the acid addition salts thereof. The heterocyclic couplers may be selected from the group consisting of indole derivatives, indoline derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles,

1,3-benzodioxoles, quinolines and their addition salts with an acid. These couplers are more particularly chosen from 2,4-diamino-l-(β-hydroxyethyloxy)benzene,

2- methyl-5-aminophenol, 5-N-(p-hydroxyethyl)amino-2-methylphenol, 3 -aminophenol, 2-chloro-3-amino-6-methylphenol, 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2-methylbenzene, 4-chloro-l,3-dihydroxybenzene, 2-amino-4-(p-hydroxyethylamino)-l-methoxybenzene, 1,3-diaminobenzene, 2-methyl-5-hydroxyethylaminophenol, 4-amino-2-hydroxytoluene, l,3-bis(2,4-diaminophenoxy)-propane, sesamol,

1 -amino-2-methoxy-4,5-methylene-dioxybenzene, a-naphthol, 6-hydroxyindole,

4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxy-indoline,

2.6- dihydroxy-4-methylpyridine, 1 -H-3-methylpyrazol-5-one,

l-phenyl-3-methylpyrazol-5-one, 2-amino-3-hydroxypyridine,

3,6-dimethyl-pyrazolo[3,2-c]-l,2,4-triazole, 2,6-dimethylpyrazolo[l,5-b]-l,2,4-triazole and their addition salts with an acid.

In general, the addition acid salts of the oxidation bases and couplers are chosen in particular from hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates.

The second composition may comprise an oxidation dye or dyes in an amount of 0.0001 to 20 wt%, preferably 0.0005 to 15 wt%, and more preferably 0.005 to 10 wt%, relative to the total weight of the composition. (Optional Ingredients) The second composition may also contain various adjuvants conventionally used in compositions for coloring keratin fibers such as hair, such as oils, anionic, non-ionic, cationic, amphoteric or zwitterionic surfactants, or mixtures thereof, anionic, non-ionic, cationic, amphoteric or zwitterionic polymers, or mixtures thereof, antioxidants, thickening agents, sequestering agents, fragrances, dispersing agents, conditioning agents, film-forming agents, ceramides, preservatives and opacifying agents.

The second composition may comprise water.

The amount of water in the second composition may range from 50% to 99% by weight, preferably from 60% to 95% by weight, and more preferably from 70 to 90% by weight, relative to the total weight of the composition. The form of the second composition is not particularly limited, as long as it is water-based, and may take various forms such as an emulsion (O/W or W/O form), an aqueous gel, an aqueous solution, or the like. It is preferable that the second composition be in the form of a water-based solution. The second composition can be used in combination with the first composition for coloring keratin fibers, for example by dyeing or bleaching the keratin fibers. Thus, the second composition can be a cosmetic composition for coloring keratin fibers.

[Preparation]

The first composition can be prepared by mixing the ingredients (a) to (c), as essential ingredients, and optional ingredient(s), if necessary, as explained above.

The second composition can be prepared by mixing the alkaline agent(s), as essential ingredient(s), and optional ingredient(s), if necessary, as explained above.

The method and means to mix the above essential and optional ingredients are not limited. Any conventional method and means can be used to mix the above essential and optional ingredients to prepare the first or second composition.

[Ready-To-Use Composition]

The present invention also relates to a ready-to-use cosmetic composition for keratin fibers, preferably hair, comprising

a first composition comprising:

(a) at least one cationic vinylpyrrolidone polymer;

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and

(c) at least one oxidizing agent

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more, and

a second composition comprising at least one alkaline agent. The first composition corresponds to the composition, as explained above, for keratin fibers according to the present invention including a combination of the two distinct specific cationic polymers (a) and (b) with the (c) oxidizing agent(s) under specific conditions.

The ready-to-use composition according to the present invention can be applied, as it is, to keratin fibers such as hair, for coloring the keratin fibers by, for example, dyeing or bleaching the keratin fibers. The ready-to-use composition according to the present invention can be prepared by mixing the first and second compositions.

The mixing ratio of the first and second compositions is not limited. The mixing ratio may be 1 :3 to 3:1 , preferably 1 :2 to 2: 1 , and more preferably 1 : 1 , as weight ratio.

[Kit and Process]

The present invention also relates to a kit for keratin fibers, preferably hair, comprising a first compartment comprising a first composition comprising:

(a) at least one cationic vinylpyrrolidone polymer;

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and

(c) at least one oxidizing agent

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more, and

a second compartment comprising a second composition comprising at least one alkaline agent.

It is possible to use the kit by, for example, dispensing or discharging the first composition from the first compartment, while dispensing or discharging the second composition from the second compartment, followed by treating keratin fibers such as hair with the mixture of the first and second compositions.

The present invention also relates to a cosmetic process for keratin fibers, preferably hair, comprising the steps of

(1) mixing

a first composition comprising:

(a) at least one cationic vinylpyrrolidone polymer;

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and

(c) at least one oxidizing agent

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more, and a second composition comprising at least one alkaline agent to prepare a ready-to-use cosmetic composition, and

(2) applying the ready-to-use cosmetic composition to the keratin fibers. It may be preferable that the cosmetic process according to the present invention comprise a step of washing, with or without drying, keratin fibers before and/or after the step of applying the ready-to-use cosmetic composition onto the keratin fibers.

The step of applying the ready-to-use cosmetic composition onto the keratin fibers can be performed by a conventional applicator such as a brush, or even by the hands.

The keratin fibers to which the ready-to-use cosmetic composition has been applied can be left for an appropriate time which is required to treat the keratin fibers. The time length for the treatment is not limited, but it may be from 1 minute to 1 hour, preferably 1 minute to 30 minutes, and more preferably 1 minute to 15 minutes. For example, the time for dyeing the keratin fibers may be from 1 to 20 minutes, preferably 5 to 15 minutes.

The keratin fibers may be treated at room temperature. Alternatively, the keratin fibers can be heated at 25°C to 65°C, preferably 30°C to 60°C, more preferably 35°C to 55°C, and even more preferably 40°C to 50°C, before and/or during and/or after the step of applying the ready-to-use cosmetic composition onto the keratin fibers.

The present invention may also relate to a use of a combination of:

(a) at least one cationic vinylpyrrolidone polymer; and

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer

in a composition for keratin fibers, preferably in a composition for keratin fibers comprising

(c) at least one oxidizing agent,

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more,

to prevent or reduce the loss of volume of keratin fibers when the keratin fibers are colored with the above composition for keratin fibers, with or without another composition including at least one alkaline agent, and/or when the colored keratin fibers are washed.

The above coloring is preferably for cosmetic purposes for the keratin fibers, for example, dyeing or bleaching the keratin fibers, preferably hair.

EXAMPLES

The present invention will be described in a more detailed manner by way of examples.

However, these examples should not be construed as limiting the scope of the present invention.

Examples 1-5 and Comparative Examples 1-10

[Preparation] Each of the pretreatment compositions for dyeing hair according to Examples 1-5 (Ex. 1 to Ex. 5) and Comparative Examples 1-10 (Comp. Ex. 1 to Comp. Ex. 10) was prepared by mixing the ingredients shown in Tables 1 and 2. The numerical values for the amounts of the ingredients are all based on "% by weight" as active raw materials.

The (a) and (b) in Tables 1 and 2 indicate the type of cationic polymers, based on the recitations in the claims.

Table 1

[Evaluations] (Volumizing Effects)

Each of the compositions according to Examples 1-5 and Comparative Examples 1-10 mixed with Composition A with the following formulation with a weight ratio of 1 : 1.

Composition A

4g of the mixture thus obtained as above was applied onto lg of a tress of natural Caucasian hair with a length of about 20 cm. The tress was then left for 30 minutes at room

temperature, followed by shampooing with a cationic polymer-free shampoo and rinsing with tap water. The tress was hung downwardly and dried at 25 °C under relative humidity of 40-50% over night. The dried tress was cut such that the length between the root of the tress and the cut point (tip of the tress) was 15 cm. The root of the tress was fixed on a plate. On the other hand, the tip of the tress was held and oriented upwardly, and then, the tip of the tress was released such that the tip of the tress could direct downwardly. The vertical angle between the plate and the tip of the hair fiber were measured (cf. Fig. 1). The average value was determined for the vertical angle with regard to the hair fibers in the tress.

The larger the vertical angle is, the better the volumizing effect is. The measured vertical angle was evaluated in accordance with the evaluation criteria shown below. Very Good: over 78°

Good: 75 -78°

Fair: 72-75°

Poor: less than 72° The results are shown in Tables 1 and 2.

(Lasting Effects) The tress used in the evaluation of the above "Volumizing Effects" was shampooed with a cationic polymer-free shampoo three times. The tress was hung downwardly and dried at 25 °C under relative humidity of 40-50% over night. The root of the tress was fixed on a plate. On the other hand, the tip of the tress was held and oriented upwardly, and then, the tip of the tress was released such that the tip of the tress could direct downwardly. The vertical angle between the plate and the tip of the hair fiber were measured (cf. Fig. 1). The average value was determined for the vertical angle with regard to the hair fibers in the tress. The larger the vertical angle is, the better the lasting effect is. The measured vertical angle was evaluated in accordance with the evaluation criteria shown below.

Very Good: over 78°

Good: 75 -78°

Fair: 72-75°

Poor: less than 72°

The results are shown in Tables 1 and 2.

It can be recognized from the comparisons of Examples 1-5 and Comparative Examples 1-10, shown in Tables 1 and 2, that, when a composition for keratin fibers such as hair contains a cationic vinylpyrrolidone polymer such as polyquaternium-11, and a cationic cyclopolymer having at least one ring-structure in the backbone of the polymer such as polyquaternium-67 and polyquaternium-6 wherein the weight ratio of (the amount of the cationic

vinylpyrrolidone polymer)/(the amount of the cationic cyclopolymer) is 1.5 or more, the composition can improve both volumizing and lasting effects.

In particular, it can be recognized from the comparison of Example 1 and Comparative Examples 2-4, that if the weight ratio of (the amount of the cationic vinylpyrrolidone polymer)/(the amount of the cationic cyclopolymer) is less than 1.5, the composition cannot improve both volumizing and lasting effects.

It can also be recognized from the comparison of Examples 1-4 and 5 that, when a composition for keratin fibers such as hair contains a cationic vinylpyrrolidone polymer such as polyquaternium-11, and a cationic cyclopolymer having at least one ring-structure in the backbone of the polymer such as polyquaternium-67 and polyquaternium-6 wherein the weight ratio of (the amount of the cationic vinylpyrrolidone polymer)/(the amount of the cationic cyclopolymer) is 1.5 or more, and further contains a cationic polymer having at least one diammonium moiety in the polymer backbone such as hexadimethrine chloride, both volumizing and lasting effects can be furthermore improved.

Claims

1. A composition for keratin fibers, preferably hair, comprising:

(a) at least one cationic vinylpyrrolidone polymer;

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and

(c) at least one oxidizing agent

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more.

2. The composition according to Claim 1, wherein the (a) cationic vinylpyrrolidone polymer is chosen from the group consisting of:

vinylpyrrolidone polymers comprising dimethylaminoethyl methacrylate units, vinylpyrrolidone polymers comprising methacrylamidopropyltrimethylammonium units, and

vinylpyrrolidone polymers comprising methylvinylimidazolium units.

3. The composition according to Claim 2, wherein the cationic vinylpyrrolidone

polymers comprising dimethylaminoethyl methacrylate units are chosen from:

vinylpyrrolidone/dimethylaminoethyl methacrylate copolymers;

vinylpyrrolidone/dimethylaminoethyl methacrylate copolymers quaternized with diethyl sulphate;

vinylpyrrolidone/dimethylaminoethyl methacrylate/hydrophilic polyurethane copolymers;

vinylpyrrolidone/dimethylaminoethyl methacrylate/C₈-d6 olefin copolymers, quaternized or non-quaternized; and

vinylpyrrolidone/dimethylaminoethyl methacrylate/vinylcaprolactam copolymers.

4. The composition according to any one of Claims 1 to 3, wherein the amount of the (a) cationic vinylpyrrolidone polymer ranges from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and more preferably from 0.1% to 3% by weight, relative to the total weight of the composition.

5. The composition according to any one of Claims 1 to 4, wherein the (b) cationic cyclopolymer having at least one ring-structure in the backbone of the polymer is chosen from cationic cellulose polymers and cationic non-cellulose polymers.

6. The composition according to Claim 5, wherein the cationic cellulose polymer

comprises at least one quaternary ammonium group including at least one C₈-C₃₀ hydrocarbon group.

7. The composition according to Claim 5, wherein the cationic non-cellulose polymer is chosen from

dialkyldiallylammonium chloride homopolymers, and

dialkyldiallylammonium chloride//acrylamide copolymers.

8. The composition according to any one of Claims 1 to 7, wherein the amount of the (b) cationic cyclopolymer having at least one ring-structure in the backbone of the polymer ranges from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and more preferably from 0.1% to 3% by Weight, relative to the total weight of the composition.

9. The composition according to any one of Claims 1 to 8, wherein the (c) oxidizing agent is hydrogen peroxide.

10. The composition according to any one of Claims 1 to 9, wherein the amount of the

(c) oxidizing agent ranges from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, and more preferably from 1% to 10% by weight, relative to the total weight of the composition.

11. The composition according to any one of Claims 1 to 10, wherein the composition further comprises (d) at least one additional cationic polymer having at least one diammonium moiety in the polymer backbone which is different from the cationic polymer (a) or (b).

12. The composition according to Claim 11 , wherein the amount of the (d) cationic polymer having at least one diammonium moiety ranges from 0.001%» to 10% by weight, preferably from 0.01% to 5% by weight, and more preferably from 0.1 % to 3%) by weight, relative to the total weight of the composition.

13. A ready-to-use cosmetic composition for keratin fibers, preferably hair, comprising a first composition comprising:

(a) at least one cationic vinylpyrrolidone polymer;

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and

(c) at least one oxidizing agent

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more, and

a second composition comprising at least one alkaline agent.

14. A kit for keratin fibers, preferably hair, comprising

a first compartment comprising a first composition comprising:

(a) at least one cationic vinylpyrrolidone polymer;

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and

(c) at least one oxidizing agent

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more, and

a second compartment comprising a second composition comprising at least one alkaline agent. A cosmetic process for keratin fibers, preferably hair, comprising the steps of

(1) mixing

a first composition comprising:

(a) at least one cationic vinylpyrrolidone polymer;

(b) at least one cationic cyclopolymer having at least one ring-structure in the backbone of the polymer; and

(c) at least one oxidizing agent

wherein

the (a) cationic vinylpyrrolidone polymer and the (b) cationic cyclopolymer are different from each other, and

the weight ratio of (the amount of the (a) cationic vinylpyrrolidone polymer)/(the amount of the (b) cationic cyclopolymer) is 1.5 or more, and

a second composition comprising at least one alkaline agent to prepare a ready-to-use cosmetic composition, and

(2) applying the ready-to-use cosmetic composition to the keratin fibers.