JP7237469B2 - Method and kit for dyeing keratin fibers - Google Patents

Description

The present invention relates to methods and kits for dyeing keratinous fibers, preferably hair, with at least one direct dye.

Dyeing keratinous fibers, especially human hair, with dyeing compositions containing oxidative coloring precursors, commonly referred to as oxidative bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. known to do. These oxidation bases are commonly combined with couplers. These bases and these couplers are colorless or lightly colored compounds that can be combined with oxidant products to yield colored compounds via an oxidative condensation process.

This type of coloring by oxidation makes it possible to obtain colors with very high visibility, coverage on gray hair, and a wide variety of shades, but the use of oxidizing agents and alkaline agents (especially repeated applications or other (in combination with hair treatment) causes damage to keratin fibers.

On the other hand, it is also known to dye keratin fibers, especially human hair, with dyeing compositions containing direct dyes. Conventional direct dyes are in particular of the benzene nitrate, anthraquinone, nitropyridine, azo, xanthine, acridine, azine and triarylmethane type or natural colorants.

For example, JP 2002-241245 and WO2009/047916 disclose compositions for dyeing hair containing direct dyes.

Hair coloring using direct dyes has advantages over hair coloring using oxidation dyes. It has few allergy problems, is non-damaging to hair, and provides vivid color visibility.

However, skin staining or scalp staining is recognized as an inevitable drawback of hair coloring using direct dyes. Accordingly, there is a need for methods and kits for dyeing keratin fibers that can reduce or minimize contamination to the skin or scalp without compromising good coloring properties.

Japanese Patent Application Laid-Open No. 2002-241245 WO2009/047916 Patent application WO 95/15144 Patent application WO 95/01772 EP 714 954 FR 2 189 006 FR 2 285 851 FR-2 140 205 EP 1 378 544 EP 1 674 073 French Patent Application No. 2 830 189 US 4,131,576 EP 503 853 FR 2 416 723 US 2,798,053 US 2,923,692 EP-A-0 173 109 US 3,915,921 US 4,509,949 WO 00/31154 EP-A-0 750 899 Patent US 5,089,578 EP-A750 899 US-5,089,578 WO-00/68282 WO 98/44012

Ullmann's Encyclopedia of Industrial Chemistry, 2004, 7th Edition, Chapter "Fluorescent Dyes" Ullmann's Encyclopedia of Industrial Chemistry (2002), "Optical Brighteners" Kirk-Othmer Encyclopedia of Chemical Technology (1995): "Fluorescent Whitening Agents." “Industrial Dyes, Chemistry, Properties, Application”, Klaus Hunger, ed. Wiley-VCH Verlag GmbH & Co KGaA, Weinheim 2003 "Ullman's Encyclopedia of Industrial Chemistry", Azo Dyes, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a03 245, point 3.2 "Ullman's Encyclopedia of Industrial Chemistry", Textile Auxiliaries, 2002 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a26 227 "Ashford's Dictionary of Industrial Chemicals", 2nd edition, pp. 14-39, 2001 Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol. 18, No. 40 (2 non-patent document years), pp. 323-336; Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering, Macromolecules, Vol. ; Solution properties of micelle networks formed by nonionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior - Langmuir, 2 Non-Patent Literature Year, vol.16, no.12, pp.5324-5332; Stimuli-responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers, Polym. Preprint, Div. Polym. Chem, 40(2), (1999), pp. 220-221. G. Fonnum, J. Bakke, and Fk. Hansen - Colloid Polym. Sci 271, 380.389 (1993) Walter Noll, "Chemistry and Technology of Silicones" (1968) Academic Press Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics

It is an object of the present invention to provide methods and kits and compositions intended for dyeing keratin fibers that use direct dyes but reduce or minimize staining of the skin or scalp with direct dyes. It is an object of the present invention to provide a method, a kit, and a composition for imparting good coloring properties to keratin fibers.

The above object is a method for dyeing keratin fibers, preferably hair, comprising:
treating keratin fibers with a mixture of a first composition and a second composition;
the first composition comprises (a) at least one direct dye and (b) water;
the second composition comprises (c) at least one oil;
Requirement (1) that at least one of the first composition and the second composition:
Y/X ratio >20, preferably >50, more preferably >100(1)
(here,
Y indicates the yield stress (Pa) of the composition,
X indicates strain (%) at yield stress)
and
(d) can be achieved by a method comprising the step wherein air bubbles are present in the composition meeting essential requirement (1).

(d) the bubbles are stable such that more than 85 vol%, preferably more than 90 vol%, more preferably more than 95 vol% of the bubbles, relative to the total volume of the bubbles, are maintained at 25°C for 2 months; is preferred.

It may be preferred that the second composition meets essential requirement (1) above.

(d) Bubbles may contain air.

(d) the average size of the cells may be less than 20 μm;

(d) The amount of air bubbles is 1% to 30% by volume, preferably 5% to 25% by volume, more preferably 10% to 20% by volume, relative to the total volume of the composition containing air bubbles. may

The amount of the first composition in the mixture of the first and second compositions is 40% to 90%, preferably 45% to 85%, more preferably 40% to 90% by weight, relative to the total weight of the mixture. It may be 50% by mass to 80% by mass.

The amount of the second composition in the mixture of the first and second compositions is 10% to 50%, preferably 15% to 45%, more preferably 10% to 50% by weight, relative to the total weight of the mixture. It may be 20% by mass to 40% by mass.

The amount of (b) water in the first composition is 40% to 95% by weight, preferably 50% to 90% by weight, more preferably 60% by weight, relative to the total weight of the first composition. It may be up to 85% by mass.

The pH of the first composition may range from 2-7, preferably 2-6, more preferably 2-4.

The amount of (c) oil in the second composition is 50% to 98%, preferably 60% to 95%, more preferably 70% by weight relative to the total weight of the second composition. It may be up to 90% by mass.

At least one of the first composition and the second composition may comprise (e) at least one thickening agent.

The above object is also a kit for dyeing keratin fibers, preferably hair, comprising:
(1) a first compartment comprising a first composition; and
(2) comprising a second compartment comprising a second composition;
the first composition comprises (a) at least one direct dye and (b) water;
the second composition comprises (c) at least one oil;
At least one of the first composition and the second composition has the following condition (1):
Y/X ratio >20, preferably >50, more preferably >100(1)
(here,
Y indicates the yield stress (Pa) of the composition,
X indicates strain (%) at yield stress)
and
(d) can be achieved by kits in which air bubbles are present in the composition satisfying condition (1).

The above object is also a method for preparing a composition for dyeing keratinous fibers, preferably hair, comprising:
(d) introducing air bubbles into at least one of the first composition and the second composition;
the first composition comprises (a) at least one direct dye and (b) water;
the second composition comprises (c) at least one oil;
The composition into which (d) air bubbles have been introduced is subjected to the following conditions (1):
Y/X ratio >20, preferably >50, more preferably >100(1)
(here,
Y indicates the yield stress (Pa) of the composition,
X indicates strain (%) at yield stress)
and mixing the first composition and the second composition to prepare a composition for dyeing keratin fibers.

The present invention is also the use of (d) air bubbles in a composition for dyeing keratinous fibers, preferably hair, to prevent or reduce contamination of the skin or scalp during dyeing of keratinous fibers with the composition. and the composition is
(a) at least one direct dye, and (b) at least one aqueous phase comprising water, and
(c) at least one oil phase comprising at least one oil;
At least one of the aqueous phase and the oil phase has the following conditions (1):
Y/X ratio >20, preferably >50, more preferably >100(1)
(here,
Y indicates the yield stress of the phase (Pa),
X indicates strain (%) at yield stress)
and
(d) bubbles are present in the phase satisfying condition (1);
Regarding use.

The present invention also relates to a method for dyeing keratin fibers, preferably hair, comprising:
treating keratin fibers with a mixture of a first composition and a second composition;
the first composition comprises (a) at least one direct dye and (b) water;
the second composition comprises (c) at least one oil;
(d) air bubbles are present in at least one of the first composition and the second composition;
The amount of bubbles is 1% by volume or more, preferably 5% by volume or more, more preferably 10% by volume or more, and 90% by volume or less, preferably 80% by volume or less, relative to the total volume of the composition containing bubbles, More preferably, it relates to a method including a step of 70% by volume or less.

FIG. 5 is a graph showing a conceptual diagram of one of the possible options for determining the yield stress and the strain corresponding to the yield stress.

After extensive research, the present inventors have discovered a method and kit, as well as a composition, intended for dyeing keratinous fibers, which uses direct dyes but reduces or minimizes staining of the skin or scalp by the direct dyes. It has now been found that it is possible to provide methods and kits and compositions that can limit the amount of time required and at the same time impart good coloring properties to keratinous fibers.

Accordingly, one of the aspects of the present invention is a method for dyeing keratinous fibers, preferably hair, comprising:
treating keratin fibers with a mixture of a first composition and a second composition;
the first composition comprises (a) at least one direct dye and (b) water;
the second composition comprises (c) at least one oil;
At least one of the first composition and the second composition has the following condition (1):
Y/X ratio >20, preferably >50, more preferably >100(1)
(here,
Y indicates the yield stress (Pa) of the composition,
X indicates strain (%) at yield stress)
and
(d) air bubbles are present in the composition satisfying condition (1);
It relates to a method, including steps.

Preferably, the mixture used for dyeing keratin fibers according to the invention has a low viscosity and/or a soft texture.

Another aspect of the invention is a kit for dyeing keratinous fibers, preferably hair, comprising:
(1) a first compartment comprising a first composition; and
(2) comprising a second compartment comprising a second composition;
the first composition comprises (a) at least one direct dye and (b) water;
the second composition comprises (c) at least one oil;
At least one of the first composition and the second composition has the following condition (1):
Y/X ratio >20, preferably >50, more preferably >100(1)
(here,
Y indicates the yield stress (Pa) of the composition,
X indicates strain (%) at yield stress)
and
(d) relates to kits in which air bubbles are present in the composition satisfying condition (1).

Another aspect of the present invention is a method of preparing a composition for dyeing keratinous fibers, preferably hair, comprising:
(d) introducing air bubbles into at least one of the first composition and the second composition;
the first composition comprises (a) at least one direct dye and (b) water;
the second composition comprises (c) at least one oil;
The composition into which (d) air bubbles have been introduced is subjected to the following conditions (1):
Y/X ratio >20, preferably >50, more preferably >100(1)
(here,
Y indicates the yield stress (Pa) of the composition,
X indicates strain (%) at yield stress)
and mixing the first composition and the second composition to prepare a composition for dyeing keratin fibers.

Preferably, the composition prepared by the method according to the invention and used for dyeing keratin fibers has a low viscosity and/or a soft texture.

The methods and kits according to the present invention, as well as the compositions prepared by the methods according to the present invention, are capable of imparting good coloration to keratin fibers such as hair while reducing/minimizing staining to the skin or scalp. .

The methods and kits according to the invention, as well as the compositions prepared by the methods according to the invention, can reduce or minimize skin/scalp staining due to the presence of air bubbles. Without wishing to be bound by any theory, it is believed that the air bubbles may provide a barrier effect and protect the skin/scalp from the direct dyes used by the present invention.

Surprisingly, the presence of air bubbles does not impair the coloring properties of the present invention. Without wishing to be bound by any theory, the mixture obtained by mixing the first and second compositions, as well as the composition prepared according to the method according to the invention, is very thin. A layer is formed on the keratin fibres, allowing air bubbles to easily escape from the thin layer or to move to the air, so that direct uptake of the dye in said mixture or composition by the keratin fibres, is not negatively affected. It is conceivable that

Surprisingly, the air bubbles also show that the mixture obtained by mixing the first and second compositions, and the composition prepared by the method according to the invention, has a low viscosity and/or a soft texture. can provide. Therefore, the mixture or composition can provide a good feel for use.

The invention is described in detail below.

[Method for dyeing keratin fibers]
A method for dyeing keratin fibers, preferably hair, according to the invention is:
treating keratin fibers with a mixture of a first composition and a second composition;
the first composition comprises (a) at least one direct dye and (b) water;
the second composition comprises (c) at least one oil;
At least one of the first composition and the second composition has the following condition (1):
Y/X ratio >20, preferably >50, more preferably >100(1)
(here,
Y indicates the yield stress (Pa) of the composition,
X indicates strain (%) at yield stress)
and
(d) Air bubbles are present in the composition satisfying condition (1).

The first composition and the second composition respectively form the aqueous phase and the oil phase of the mixture of the first and second compositions. Accordingly, the first composition and the second composition may be referred to as the aqueous phase composition and the oil phase composition, respectively.

{first composition}
The first composition comprises at least one direct dye and water.

(direct dye)
The first composition contains at least one direct dye. Two or more direct dyes can be used in combination. Thus, a single type of direct dye or a combination of different types of direct dye can be used.

A direct dye means a colored substance that does not require the use of an oxidizing agent to develop its color.

Direct dyes may be natural direct dyes or synthetic direct dyes.

The expression "natural direct dyes" means any dye that occurs naturally and is manufactured by extraction (optionally purified) from plant substrates or animals such as insects, optionally in the presence of natural compounds, e.g. ash or ammonia. are understood to mean dyes or dye precursors of

Natural direct dyes include quinone dyes (e.g. lawsone and juglone), alizarin, purpurin, laccaic acid, carminic acid, chermesic acid, purpurogallin, protocatechualdehyde, indigoids such as indigo, sorghum, isatin, betanin, curcuminoids (e.g. curcumin). , spinulosin, various types of chlorophyll and chlorophyllins, hematoxylin, hematein, brazilein, brazilin, safflower dyes (e.g. carthamine), flavonoids (e.g. rutin, quercetin, catechin, epicatechin, morin, apigenidin and sandalwood), anthocyans (e.g. apigenidin and apigenin), carotenoids, tannins, orcein, santaline and cochinyl carmine.

Extracts or decoctions containing natural direct dyes, especially henna base extract, curcuma longa extract, sorghum leaf sheath extract, haematoxylon campecianum extract, green tea extract, pine bark extract, cocoa extract , and logwood extract can also be used.

Natural direct dyes include curcuminoids, santalin, chlorophyllin, hematoxylin, hematein, brazilein, brazilin, sorghum, laccaic acid, lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechualdehyde, indigoid, isatin, spinulosine , apigenin, orcein, betanin, flavonoids, anthocyans, and extracts or decoctions containing these compounds.

Alternatively, natural direct dyes may preferably be selected from, for example, hydroxylated quinones, indigoids, hydroxyflavones, santalin A and B, isatin and its derivatives, and brazilin and its hydroxylated derivatives.

Hydroxylated quinones are preferably benzoquinones, naphthoquinones, and mono- or polyhydroxylated anthraquinones, optionally substituted with groups such as alkyl, alkoxy, alkenyl, chloro, phenyl, hydroxyalkyl and carboxyl. there is

Naphthoquinone is preferably lawsone, juglone, flaviolin, naphthazaline, naphthopurpurin, lapacol, plumvadin, chloroplumvadin, droseron, shikonin, 2-hydroxy-3-methyl-1,4-naphthoquinone, 3,5-dihydroxy- 1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2-methoxy-5-hydroxy-1,4-naphthoquinone and 3-methoxy-5-hydroxy-1,4-naphthoquinone.

Benzoquinone is preferably spinulosine, atromentine, aurentioglyocladin, 2,5-dihydroxy-6-methylbenzoquinone, 2-hydroxy-3-methyl-6-methoxybenzoquinone, 2,5-dihydroxy-3 ,6-diphenylbenzoquinone, 2,3-dimethyl-5-hydroxy-6-methoxybenzoquinone and 2,5-dihydroxy-6-isopropylbenzoquinone.

Anthraquinones are preferably alizarin, quinizarin, purpurin, carminic acid, chrysophanol, chermesic acid, rhein, aloe-emodin, pseudopurpurin, quinizarincarboxylic acid, furanglaemodin, 2-methylquinizarin, 1- hydroxyanthraquinone and 2-hydroxyanthraquinone.

Indigoids are preferably indigo, indirubin, isoindigo and tilian purple.

Hydroxyflavones are preferably quercetin and morin.

The expression "synthetic direct dye" is understood to mean any dye or dye precursor produced by chemical synthesis.

Direct dyes may be selected from the group consisting of acidic (anionic) direct dyes, basic (cationic) direct dyes, and neutral (non-ionic) direct dyes.

Non-limiting examples of synthetic dyes include (nonionic) neutral, anionic (acidic) and cationic (basic) dyes, e.g. azo, methine, carbonyl, azine, There are nitro(hetero)aryl-type or tri(hetero)arylmethane direct dyes, porphyrins and phthalocyanines.

More specifically, azo dyes contain a -N=N- functional group, the two nitrogen atoms of which are not included in the ring simultaneously. However, it is not excluded that one of the two nitrogen atoms in the -N=N- sequence participates in the ring.

The methine family of dyes are more particularly compounds containing at least one sequence selected from >C=C< and -N=C<, two atoms of these sequences being in a ring not included at the same time. However, it is specified that one of the nitrogen or carbon atoms of these sequences may be included in the ring. More specifically, this family of dyes arises from the following types of compounds: pure methines (containing one or more of the -C=C- sequences described above); azomethines (with at least one or more -C =N-sequences), e.g., azacarbocyanines and their isomers, diazacarbocyanines and their isomers, tetraazacarbocyanines; mono- and diarylmethanes; indoamines (or diphenylamines); indophenols; Indian aniline.

For dyes of the carbonyl family, for example acridones, benzoquinones, anthraquinones, naphthoquinones, benzoanthrones, anthranthrones, pyranthrones, pyrazoleanthrones, pyrimidinoanthrones, flavanthrones, indanthrones, flavones, (iso)violanthrones, isoindolinones. , benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole or coumarin dyes.

As regards the dyes of the cyclic azine family, mention may be made in particular of the azine, xanthene, thioxanthene, fluorindine, acridine, (di)oxazine, (di)thiazine and pyronine dyes.

Nitro(hetero)aromatic dyes are more particularly nitrobenzene or nitropyridine direct dyes.

For porphyrin or phthalocyanine type dyes, cationic or non-cationic compounds optionally containing one or more metals or metal ions such as alkali metals and alkaline earth metals, zinc and silicon are used. You can

Examples of particularly suitable synthetic direct dyes include, alone or in mixtures, nitrobenzene dyes, azo, azomethine or methine direct dyes, azacarbocyanines such as tetraazacarbocyanines (tetraazapentamethine), quinones, especially anthraquinones, Mention may be made of naphthoquinone or benzoquinone direct dyes or direct dyes of azines, xanthenes, triarylmethanes, indoamines, phthalocyanines and porphyrins. Even more preferably, these synthetic direct dyes, alone or as mixtures, are selected from nitrobenzene dyes, azo, azomethine or methine direct dyes and tetraazacarbocyanines (tetraazapentamethine).

Among the azo, azomethine, methine or tetraazapentamethine direct dyes that can be used according to the invention are patent applications WO 95/15144, patent applications WO 95/01772 and EP 714 954, FR 2 189 006, FR 2 285 851, FR -2 140 205, EP 1 378 544 and the cationic dyes described in EP 1 674 073.

Cationic direct dyes corresponding to the following formulas may therefore very particularly be mentioned:

[In the formula,
D represents a nitrogen atom or -CH group,
R ₁ and R ₂ are the same or different and can be substituted with hydrogen atoms; -CN, -OH or _-NH2 groups, or together with the carbon atoms of the benzene ring, one or more C ₁ represents a C 1 -C ₄ alkyl group optionally forming an oxygen-containing or nitrogen-containing heterocycle which can be substituted _with a -C ₄ alkyl group; or a 4′-aminophenyl group;
R ₃ and R' ₃ are the same or different, hydrogen atom, halogen atom selected from chlorine, bromine, iodine and fluorine, cyano group, C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy; represents a group or an acetyloxy group,
X ⁻ represents an anion preferably selected from chloride, methylsulphate and methylacetate,
A has the following structure:

(wherein R ₄ represents a C ₁ -C ₄ alkyl group that can be substituted with a hydroxyl group)
represents a group selected from],

[In the formula,
R ₅ represents a hydrogen atom, a C ₁ -C ₄ alkoxy group or a halogen atom such as bromine, chlorine, iodine or fluorine,
R ₆ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, together with the carbon atoms of the benzene ring, optionally containing oxygen and/or optionally one or more C ₁ -C ₄ alkyl groups. forming a substituted heterocyclic ring,
_R7 represents a hydrogen atom or a halogen atom such as bromine, chlorine, iodine or fluorine,
D ₁ and D ₂ are the same or different and represent a nitrogen atom or a -CH group;
m=0 or 1,
X ⁻ represents a cosmetically acceptable anion, preferably selected from chloride, methylsulphate and methylacetate,
E is the following structure:

(Wherein, R' represents a _C1 - _C4 alkyl group)
represents a group selected from;
When m=0 and D ₁ represents a nitrogen atom, E can also have the structure:

(Wherein, R' represents a _C1 - _C4 alkyl group)
can also be shown].

Synthetic direct dyes may be selected from fluorescent dyes. Two or more types of fluorescent dyes can be used in combination.

The use of some fluorescent dyes makes it possible to obtain a more visible color on dark hair than with conventional hydrophilic or hydrophobic direct dyes. Furthermore, these fluorescent dyes may also allow lightening of hair without damaging it when applied to dark hair.

As used herein, the term "fluorescent dye" is understood to mean fluorescent compounds and optical brighteners. In at least one embodiment, the fluorescent dye is soluble in the medium of the first composition.

Fluorescent dyes are fluorescent compounds capable of absorbing visible light, eg wavelengths in the range of 400 to 800 nm, and re-emitting light in the visible region of higher wavelengths.

According to one embodiment, fluorescent dyes useful in the present invention re-emit orange fluorescence. They exhibit maximum re-emission wavelengths in the range, for example, from 500 to 700 nm.

Non-limiting examples of fluorescent dyes include compounds known in the art, such as those described in Ullmann's Encyclopedia of Industrial Chemistry, 2004 publication, 7th edition, chapter "Fluorescent Dyes".

Optical brighteners of the present disclosure are also referred to as "brighteners" or "fluorescent brighteners" or "fluorescent brightening agents" or "FWA" or "fluorescent white They are colorless and transparent compounds known under the name of fluorescent whitening agents, or whitening agents, or fluorescent whiteners. Because they do not absorb visible light, only ultraviolet light (wavelengths in the range of 200-400 nanometers), they transfer the absorbed energy to the visible part of the spectrum, generally blue and/or green, i.e. 400-550 This is because it converts to higher wavelength fluorescence emitted at wavelengths in the nanometer range.

Optical brighteners are known in the art, for example they are described in Ullmann's Encyclopedia of Industrial Chemistry (2002), "Optical Brighteners" and Kirk-Othmer Encyclopedia of Chemical Technology (1995): "Fluorescent Whitening Agents "It is described in.

Fluorescent dyes that can be used in the first composition of the present disclosure include compounds known from the art, for example those described in FR-A-2 830 189.

Soluble fluorescent compounds that may be mentioned in particular belong to the following families: naphthalimides, coumarins, xanthenes, in particular xanthenodiquinolizine and azaxanthene; naphtholactam; azlactone; oxazine; thiazine; dioxazine; methine; pyrazine; stilbene; ketopyrrole; and pyrene.

If present, the fluorescent dye is more particularly preferred to re-emit orange fluorescence.

From the point of view of their ionic nature, the direct dyes may be selected from the group consisting of acid direct dyes, basic direct dyes and neutral direct dyes, which includes all possible types of direct dyes, e.g. so-called nitro dyes. and HC dyes. Acid direct dyes have an anionic moiety in their chemical structure. Basic direct dyes have a cationic moiety in their chemical structure. Neutral direct dyes are nonionic.

According to one embodiment, it is preferred that the direct dyes are selected from acid direct dyes.

Anionic direct dyes are commonly known as "acidic direct dyes" due to their affinity with alkaline substances (e.g. "Industrial Dyes, Chemistry, Properties, Application", Klaus Hunger ed. Wiley-VCH Verlag GmbH & Co KGaA, Weinheim 2003). Anionic or acid dyes are known in the literature (e.g. "Ullman's Encyclopedia of Industrial Chemistry", Azo Dyes, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a03 245, point 3.2 "Ullman's Encyclopedia of Industrial Chemistry", Textile Auxiliaries, 2002 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a26 227 and "Ashford's Dictionary of Industrial Chemicals", 2nd edition, pp. 14-39, 2001).

The term "anionic direct dye" has in its structure at least one sulfonic acid group SO ₃ ^- and/or at least one carboxylic acid group C(O)O ^- and/or at least one phosphate group P( ═O)O ⁻ O ⁻ and optionally one or more anionic groups G ⁻ (wherein G ⁻ can be the same or different, alkoxide O ⁻ , thioalkoxide S ⁻ , Phosphonate ions, carboxylate ions and thiocarboxylate ions: from C(Q)Q′ ⁻ (wherein Q and Q′ may be the same or different and represent an oxygen atom or a sulfur atom) represents an anionic group of choice, preferably G ^- represents a carboxylate ion, ie Q and Q' represent an oxygen atom).

Preferred anionic dyes of the formulations of the present invention are acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, anionic styryl dyes, and indigoids and acidic natural dyes. dyes, each of these dyes containing at least one sulfonic acid, phosphonic acid or carboxylic acid group with a cationic counterion X ⁺ , X ⁺ preferably selected from alkali and alkaline earth metals represents an organic or inorganic cationic counterion such as Na ⁺ and K ⁺ .

Preferred acid dyes may be selected from:
a) diaryl anionic azo dyes of formula (II) or (II'):

(In the formulas (II) and (II'),
· R ₇ , R ₈ , R ₉ , R ₁₀ , R' ₇ , R' ₈ , R' ₉ and R' ₁₀ may be the same or different, and may be hydrogen atoms or
- Alkyl;
- alkoxy, alkylthio;
- hydroxyl, mercapto;
- Nitro;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (where R° is a hydrogen atom or represents an alkyl group or an aryl group; represents) represents);
- (O) ₂ S(O ^- )-, X ⁺ defined above;
- (O)CO ^- -, X ⁺ as defined above;
- (O)P( _O2 ^- )-, 2X ⁺ as defined above;
- R''-S(O) _2- (R'' represents a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group, preferably a phenylamino or phenyl group);
-R'''-S(O) ₂ -X'- (R''' represents an alkyl or optionally substituted aryl group and X' is as defined above);
- (di)(alkyl)amino;
- optionally substituted with one or more groups selected from i) nitro, ii) nitroso, iii) (O) _2S (O ^- )-, X ⁺ , and iv) alkoxy with X ⁺ aryl(alkyl)amino;
- optionally substituted heteroaryl, preferably benzothiazolyl groups;
- cycloalkyl, especially cyclohexyl,
- Ar-N=N- (Ar is an optionally substituted aryl group, preferably one or more alkyl, (O) _2S (O ^- )-, X ⁺ or a phenylamino group represents a phenyl substituted with the choice)
represents a group selected from;
Alternatively, two adjacent groups _R7 and _R8 , or _R8 and _R9 , or _R9 and _R10 together form a fused benzo group A', _R'7 and R' ₈ , or R' ₈ and R' ₉ , or R' ₉ and R' ₁₀ together form a fused benzo group B', A' and B' being i) nitro, ii) nitroso, iii) (O) _2S (O ^- )-, X ⁺ , iv) hydroxyl, v) mercapto, vi) (di)(alkyl)amino, vii) R°-C(X)-X'-, viii) R°-X'-C(X)-, ix) R°-X'-C(X)-X''-, x) Ar-N=N- and xi) optionally substituted aryl ( optionally substituted with one or more groups selected from alkyl)amino, wherein X ⁺ , R°, X, X′, X″ and Ar are as defined above;
- W is a sigma bond σ, an oxygen or sulfur atom, or a divalent group i) -NR- (R is as defined above) or ii) methylene -C(R _a )(R _b )- and R _a and R _b may be the same or different and represent a hydrogen atom or an aryl group, or R _a and R _b together with the carbon atoms bearing them are spiro forming cycloalkyl, preferably W represents a sulfur atom or Ra and Rb together form cyclohexyl;
Formulas (II) and (II') have at least one sulfonate (O) ₂ S(O ^- )-, X ⁺ or phosphonate (O)P(O ₂ ^- ) 2X ⁺ or carboxylate (O)C( O ⁻ )-, X ⁺ groups in one of the rings A, A′, B, B′ or C, with X ⁺ as defined above).

Examples of dyes of formula (II) are Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37 , Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Food Red 17, Acid Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113 , Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Pigment Red 57;
Acid Red 111, Acid Red 134, Acid yellow 38 may be mentioned as examples of dyes of formula (II').
b) anthraquinone dyes of formulas (III) and (III'):

(In the formulas (III) and (III'),
- R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ may be the same or different and may be hydrogen atoms, halogen atoms or
- Alkyl;
- hydroxyl, mercapto;
- alkoxy, alkylthio;
- optionally substituted with one or more groups preferably selected from alkyl and (O) _2S (O ^- )-, X ⁺ , where X ⁺ is as defined above optionally substituted aryloxy or arylthio;
- ^{alkyl and aryl} ( _alkyl )amino;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- (O) ₂ S(O ^- )-, X ⁺ (X ⁺ is as defined above)
represents a group selected from;
- Z' represents _a hydrogen atom or an _NR28R29 group, wherein _R28 and _R29 may be the same or different, a hydrogen atom or:
- Alkyl;
- polyhydroxyalkyls such as hydroxyethyl;
- one or more groups, in particular i) alkyl, such as methyl, n-dodecyl, n-butyl, ii), (O) _2S (O ^- )-, X ⁺ (X ⁺ is as previously defined ), iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''-(R°, X , X′ and X″ are as defined above, preferably R° represents an alkyl group);
- represents a group selected from cycloalkyl, especially cyclohexyl;
- Z represents a group selected from hydroxyl and NR' ₂₈ R' ₂₉ , wherein R' ₂₈ and R' ₂₉ may be the same or different and are the same as R ₂₈ and R ₂₉ defined above; representing the same atom or group;
It is understood that formulas (III) and (III') contain at least one sulfonate group (O) ₂ S(O ^- )-, X ⁺ where X ⁺ is as defined above)

Examples of dyes of formula (III) are Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41 , Acid Violet 42, Acid Violet 43, Mordant Red 3, EXT Violet 2,
And Acid Black 48 can be mentioned as an example of the dye of formula (III').
and
g) Quinoline-based dyes of formula (IV):

(In formula (IV),
- R ₆₁ represents a hydrogen or halogen atom or an alkyl group;
- R ₆₂ , R ₆₃ and R ₆₄ may be the same or different and represent a hydrogen atom or (O) ₂ S(O ^- )-, X ⁺ group, where X ⁺ is the above-defined is the street,
or R ₆₁ and R ₆₂ or R ₆₁ and R ₆₄ together form a benzo group optionally substituted with one or more (O) ₂ S(O ^- )-, X ⁺ groups; , where X ⁺ is as previously defined;
- G represents an oxygen or sulfur atom or an NR _e group, R _e represents a hydrogen atom or an alkyl group, especially G represents an oxygen atom;
It is understood that formula (IV) contains at least one sulfonate group (O) _2S (O ^- )-, X ⁺ , where X ⁺ is as defined above)

Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5 may be mentioned as examples of dyes of formula (IV).

Acid direct dyes may preferably be selected from the group consisting of Yellow 5, Orange 4, EXT. Violet 2, Acid Black 1 and mixtures thereof.

The first composition may contain a direct dye in an amount of 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, relative to the total mass of the first composition. good.

The first composition may contain a direct dye in an amount of 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, relative to the total mass of the first composition. good.

The first composition contains a direct dye in an amount of 0.001% to 5% by weight, preferably 0.01% to 3% by weight, more preferably 0.1% to 1% by weight, based on the total weight of the first composition. may be contained in any amount.

(water)
The first composition contains water.

The amount of water in the first composition may be 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, relative to the total mass of the first composition.

The amount of water in the first composition may be 95% by weight or less, preferably 90% by weight or less, more preferably 85% by weight or less, relative to the total weight of the first composition.

The amount of water in the first composition is 40% to 95% by weight, preferably 50% to 90% by weight, more preferably 60% to 85% by weight, relative to the total weight of the first composition. %.

(thickener)
The first composition may contain at least one thickening agent.

Preferably, the first composition may contain at least one hydrophilic thickening agent. When two or more hydrophilic thickeners are used, they may be the same or different.

Hydrophilic thickeners can increase the viscosity of the aqueous phase of the first composition and the mixture of the first and second compositions.

According to the present invention, the "hydrophilic thickener" is capable of increasing the viscosity of the first composition, at room temperature (25°C), atmospheric pressure and a shear rate of 1 s ^-1 (viscosity is Cone/ At least 20 cps, preferably at least 50 cps, is introduced into the first composition.

Hydrophilic thickeners are preferentially selected from non-associative thickening polymers with sugar units, non-associative thickening polymers without sugar units, associative thickening polymers and mixtures of these compounds. be done.

In the present invention, the term "sugar unit" means an oxygen-containing hydrocarbonaceous compound containing some alcohol functionality, with or without aldehyde or ketone functionality, and containing at least 4 carbon atoms.

A sugar unit may optionally be modified by substitution and/or by oxidation and/or by dehydration.

The sugar units that may be included in the composition of the hydrophilic thickening polymer of the invention are preferably derived from the following sugars: glucose, galactose, arabinose, rhamnose, mannose, xylose, fucose, anhydrogalactose, galacturon. Acid, glucuronic acid, mannuronic acid, galactose sulfate, anhydrous galactose sulfate and fructose.

Non-associative thickening polymers with sugar units that may be mentioned in particular include natural gums such as:
a) tree or shrub exudates, including:
- gum arabic (branched polymers of galactose, arabinose, rhamnose and glucuronic acid);
- Gutti gum (polymers derived from arabinose, galactose, mannose, xylose and glucuronic acid);
- karaya gum (polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid);
- gum tragacanth (or tragacanth) (a polymer of galacturonic acid, galactose, fucose, xylose and arabinose);
b) gums obtained from algae, including:
- agar (polymers derived from galactose and anhydrous galactose);
- alginates (polymers of mannuronic and glucuronic acids);
- carrageenan and furcereran (polymers of galactose sulfate and anhydrous galactose sulfate);
c) Gums derived from seeds or tubers, including:
- guar gum (polymer of mannose and galactose);
- locust bean gum (polymer of mannose and galactose);
- fenugreek seed gum (polymer of mannose and galactose);
- tamarind gum (polymer of galactose, xylose and glucose);
- Konjac gum (polymer of glucose and mannose);
d) microbial gums, including:
- xanthan gum (polymers of glucose, mannose acetate, mannose/pyruvate and glucuronic acid);
- gellan gum (polymer of partially acylated glucose, rhamnose and glucuronic acid);
- scleroglucan gum (glucose polymer);
d) plant extracts containing:
- cellulose (glucose polymer);
- Starch (glucose polymer) and
- Inulin.

These polymers can be modified physically or chemically. As a physical treatment, mention may be made in particular of temperature.

Chemical treatments that may be mentioned include esterification, etherification, amidation and oxidation reactions. These treatments can result in polymers that can be nonionic, anionic or amphoteric, among others.

Preferably, these chemical or physical treatments are applied to guar gum, locust bean gum, starch and cellulose.

The nonionic guar gums that can be used according to the invention can be modified with C ₁ -C ₆ (poly)hydroxyalkyl groups.

Among the C ₁ -C ₆ (poly)hydroxyalkyl groups, mention may be made, for example, of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

These guar gums are well known in the prior art and may be prepared, for example, by reacting the corresponding alkene oxide, such as propylene oxide, with guar gum to give a guar gum modified with hydroxypropyl groups.

The degree of hydroxyalkylation preferably ranges from 0.4 to 1.2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present in the guar gum.

Such nonionic guar gums, optionally modified with hydroxyalkyl groups, are marketed, for example, by the company Rhodia Chimie under the tradenames Jaguar HP8, Jaguar HP60 and Jaguar HP120.

Plant-derived starch molecules that may be used in the present invention may be grains or tubers. The starch is thus selected from, for example, maize starch, rice starch, cassava starch, barley starch, potato starch, wheat starch, sorghum starch and pea starch.

Starches can be chemically or physically modified, inter alia, by one or more of the following reactions: pregelatinization, oxidation, cross-linking, esterification, etherification, amidation, heat treatment.

Distarch phosphate or compounds rich in distarch phosphate, e.g. Prejel VA-70-T AGGL (gelatinized cassava distarch phosphate), Prejel TK1 (gelatinized cassava distarch phosphate) by Avebe acid) and Prejel 200 (gelatinized acetylcassava distarch phosphate) or the product provided by National Starch under the reference Structure Zea (gelatinized corn distarch phosphate) is preferentially used. It will be.

Amphoteric starches can also be used according to the invention, these amphoteric starches comprising one or more anionic groups and one or more cationic groups. The anionic group and the cationic group may be attached to the same reactive site or to different reactive sites on the starch molecule; they are preferably attached to the same reactive site. The anionic groups may be of carboxyl, phosphate or sulfate type, preferably carboxyl. Cationic groups can be of the primary, secondary, tertiary or quaternary amine type.

Starch molecules may be derived from any plant starch source such as corn, potato, oat, rice, tapioca, sorghum, barley or wheat, among others. It is also possible to use the starch hydrolysates mentioned above. The starch is preferably derived from potatoes.

The non-associative thickening polymers of the present invention can be cellulosic polymers that do not contain C ₁₀ -C ₃₀ fatty chains in their structure.

According to the present invention, the term "cellulosic polymer" means any polysaccharide compound which has in its structure an array of glucose residues linked together via β-1,4 bonds. Contemplated, in addition to unsubstituted cellulose, cellulose derivatives may be anionic, cationic, amphoteric or nonionic.

Accordingly, the cellulose polymers that may be used in accordance with the present invention may be selected from unsubstituted cellulose, including those in microcrystalline form, and cellulose ethers.

Among these cellulosic polymers, cellulose ethers, cellulose esters and cellulose ester ethers are well known.

One of the cellulose esters is inorganic cellulose esters (cellulose nitrate, sulfate, phosphate, etc.), organic cellulose esters (cellulose monoacetate, triacetate, amidopropionate, acetate butyrate, acetate propionate, and acetate triacetate). Melitate, etc.), and mixed organic/inorganic esters of cellulose, such as cellulose acetate butyrate sulfate and cellulose acetate propionate sulfate. Among the cellulose ester ethers, mention may be made of hydroxypropylmethylcellulose phthalate and ethylcellulose sulfate.

Among the nonionic cellulose ethers which are free of _C10 - _C30 fatty chains, ie "non-associative", are ( _C1 - _C4 )alkylcelluloses such as methylcellulose and ethylcellulose (e.g. Ethocel standard from Dow Chemical). 100 Premium); (poly)hydroxy(C ₁ -C ₄ )alkylcelluloses such as hydroxymethylcellulose, hydroxyethylcellulose (eg Natrosol 250 HHR from Aqualon) and hydroxypropylcellulose (eg Klucel EF from Aqualon); ) hydroxy(C ₁ -C ₄ )alkyl(C ₁ -C ₄ )alkyl mixed celluloses such as hydroxypropylmethylcellulose (eg Methocel E4M from Dow Chemical); hydroxyethylmethylcellulose, hydroxyethylethylcellulose (eg from Akzo Nobel); Bermocoll E 481 FQ) and hydroxybutylmethylcellulose may be mentioned.

Among the anionic cellulose ethers without fatty chains, mention may be made of (poly)carboxy(C ₁ -C ₄ )alkylcelluloses and their salts. Examples include carboxymethylcellulose, carboxymethylmethylcellulose (eg Blanose 7M from Aqualon) and carboxymethylhydroxyethylcellulose, and sodium salts thereof.

Among cationic celluloses without fatty chains, cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with water-soluble quaternary ammonium monomers, especially as described in patent US 4,131,576, such as especially methacryloylethyltrimethylammonium. (Poly)hydroxy(C ₁ -C ₄ )alkylcelluloses, such as hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses, grafted with , methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salts. Commercial products corresponding to this definition are more particularly those sold under the names Celquat L 200® and Celquat H 100® by the company National Starch.

Among the non-associative thickening polymers without sugar units that may be used according to the invention are crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked thereof. Acrylamide copolymers, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and acrylamide, either alone or in mixtures thereof, may be mentioned.

A first family of non-associative thickening polymers suitable for use is represented by crosslinked acrylic acid homopolymers.

Among homopolymers of this type, those crosslinked with sugar-based allyl alcohol ethers, such as the products sold under the names Carbopol 980, 981, 954, 2984 and 5984 by the company Noveon, or Synthalen by the company 3 VSA. Mention may be made of the products sold under the names M and Synthalen K. These polymers have the INCI name of Carbomer.

The non-associative anionic thickening polymer can also be a crosslinked (meth)acrylic acid copolymer, such as the polymer sold under the name Aqua SF1 by Noveon.

Non-associative thickening polymers may be selected from crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and their crosslinked acrylamide copolymers.

Among the partially or completely neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide, mention may be made in particular of the products described in Example 1 of document EP 503 853, which It is possible to refer to said document on polymers of

The composition may also contain ammonium acrylate homopolymers or copolymers of ammonium acrylate and acrylamide as non-associative thickening polymers.

One of the ammonium acrylate homopolymers that may be mentioned is the product sold under the name Microsap PAS 5193 by the company Hoechst. One of the copolymers of ammonium acrylate and acrylamide that may be mentioned is the product or product PAS 5193 sold under the name Bozepol C Nouveau by the company Hoechst. For the description and preparation of such compounds, reference may be made in particular to FR 2 416 723, US 2,798,053 and US 2,923,692.

Acrylic type cationic thickening polymers may also be used.

Among the hydrophilic thickening polymers, mention may be made of, in particular, associative polymers of nonionic, anionic, cationic or amphoteric nature, which are well known to those skilled in the art.

It is noted that associative polymers are polymers that can reversibly associate with each other or with other molecules in an aqueous medium.

Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region.

The term "hydrophobic group" means at least 10 carbon atoms, preferably 10-30 carbon atoms, particularly 12-30 carbon atoms, more It means a group or polymer having a hydrocarbon-based chain, saturated or unsaturated, straight or branched, containing atoms.

Preferably, the hydrocarbon-based group is derived from a monofunctional compound. By way of example, hydrophobic groups can be derived from fatty alcohols such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also refer to hydrocarbon-based polymers such as polybutadiene.

One of the anionic types of associative polymers that may be mentioned is the following:
- (a) comprising at least one hydrophilic unit and at least one fatty-chain allyl ether unit, more particularly the hydrophilic unit being an ethylenically unsaturated anionic monomer, more particularly vinyl carboxylic acid, most In particular those composed of acrylic acid or methacrylic acid or mixtures thereof.

Among these anionic associative polymers, particularly preferred according to the invention are 20% to 60% by weight acrylic and/or methacrylic acid, 5% to 60% by weight lower alkyl (meth)acrylates, fatty chain allyl A polymer formed from 2% to 50% by weight of an ether and 0% to 1% by weight of a cross-linking agent, which is a well-known copolymerizable unsaturated polyethylenic monomer such as diallyl phthalate, allyl ( meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.

Among the latter polymers, particularly most preferred are the crosslinked terpolymers of methacrylic acid, ethyl acrylate and polyethylene glycol (10OE) stearyl alcohol ether (steareth-10), especially the names Salcare SC80® and Salcare SC90 by CIBA. ®, which are aqueous 30% emulsions of crosslinked terpolymers of methacrylic acid, ethyl acrylate and steareth-10 allyl ether (40/50/10).
- (b) containing i) at least one hydrophilic unit of unsaturated olefinic carboxylic acid type and ii) at least one hydrophobic unit of (C ₁₀ -C ₃₀ )alkyl ester of unsaturated carboxylic acid type.

(C ₁₀ -C ₃₀ )alkyl esters of unsaturated carboxylic acids that are useful in the present invention are, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and their corresponding methacrylates, Includes lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Anionic polymers of this type are described and prepared, for example, according to patents US 3,915,921 and US 4,509,949.

One of this type of anionic associative polymer that will be used in more detail is 95% to 60% by weight acrylic acid (hydrophilic units), 4% to 40% by weight _C10 ~ C ₃₀ alkyl acrylates (hydrophobic units) and 0-6% by weight of cross-linkable monomers, or 98%-96% by weight of acrylic acid (hydrophilic units), 1% by weight~ 4% by weight of C ₁₀ -C ₃₀ alkyl acrylates (hydrophobic units) and 0.1% to 0.6% by weight of crosslinkable monomers such as those described above.

Among said polymers mentioned above, those which are particularly most preferred according to the invention are Pemulen TR1®, Pemulen TR2®, Carbopol 1382® and even more preferentially Pemulen TR1® by Goodrich. Trademark) and the product sold under the name Coatex SX® by the company SEPPIC.

Mention may also be made of the acrylic acid/lauryl methacrylate/vinylpyrrolidone terpolymers sold under the name Acrylidone LM by the company ISP.
- (c) maleic anhydride/ _C30 - _C38 alpha-olefin/alkyl maleate terpolymer, for example the product sold under the name Performa V1608® by NewPhase Technologies (maleic anhydride/ _C30 ˜C ₃₈ α-olefin/isopropyl maleate copolymer).
- (d) acrylic terpolymers, including:
i) about 20% to 70% by weight of α,β-monoethylenically unsaturated carboxylic acid [A],
ii) about 20% to 80% by weight of α,β-monoethylenically unsaturated non-surfactant monomers other than [A];
iii) about 0.5% to 60% by weight of a nonionic monourethane which is the product of the reaction of a monohydrogen surfactant with a monoethylenically unsaturated monoisocyanate;
Terpolymers such as those described in patent application EP-A-0 173 109, more particularly in Example 3, i.e. methacrylic acid/methyl acrylate/behenyl alcohol dimethyl-meta-isopropenyl as aqueous 25% dispersion benzyl isocyanate ethoxylated (40OE) terpolymer;
- (e) copolymers comprising among these monomers α,β-monoethylenically unsaturated carboxylic acids and esters of α,β-monoethylenically unsaturated carboxylic acids and oxyalkylenated fatty alcohols.

Preferentially, these compounds also contain α,β-monoethylenically unsaturated carboxylic acid esters and esters of C ₁ -C ₄ alcohols as monomers.

An example of this type of compound that may be mentioned is Aculyn 22® sold by Rohm & Haas, which is a methacrylic acid/ethyl acrylate/oxyalkylated stearyl methacrylate terpolymer; Aculyn 88 sold by Rohm & Haas.
- (f) an amphiphilic polymer comprising at least one ethylenically unsaturated monomer and comprising at least one hydrophobic moiety having sulfo groups in free or partially or fully neutralized form . These polymers may or may not be crosslinked. They are preferably crosslinked.

Ethylenically unsaturated monomers having _a sulfo group are, _in particular, N-(C ₁ -C ₂₂ )alkyl(meth)acrylamido(C ₁ -C ₂₂ )alkylsulfonic acids, also partially or fully neutralized forms thereof, and mixtures thereof.

(Meth)acrylamido(C ₁ -C ₂₂ )alkylsulfonic acids such as acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropane sulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidodecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid Acids and their partially or completely neutralized forms will more preferentially be used.

2-Acrylamido-2-methylpropanesulfonic acid (AMPS), also partially or fully neutralized forms thereof, will more particularly be used.

Polymers of this family include random amphiphilic AMPS polymers modified by reaction with _C6 - _C22 n-monoalkylamines or di-n-alkylamines, and from those described in WO 00/31154. may be specifically selected. These polymers are, for example, (meth)acrylic acids, their β-substituted alkyl derivatives or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride , itaconic acid, or maleic acid, or mixtures of these compounds.

Preferred polymers of this family are selected from amphiphilic copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

These same copolymers are also (meth)acrylic acids, their β-substituted alkyl derivatives or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride. It may also contain one or more ethylenically unsaturated monomers that do not contain fatty chains, such as acid, itaconic acid or maleic acid, or mixtures of these compounds.

These copolymers are described, inter alia, in patent application EP-A-0 750 899, patent US 5,089,578 and the following publication by Yotaro Morishima:
- Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol. 18, No. 40 (2000), pp. 323-336;
- Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering, Macromolecules, 2000, 33, 10, 3694-3704;
- Solution properties of micelle networks formed by nonionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior - Langmuir, 2000, 16, 12, 5324-5332;
- Stimuli-responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers, Polym. Preprint, Div. Polym. Chem, 40(2), (1999), 220-221.

Among these polymers, the following may be mentioned:
- 15% to 60% by weight of AMPS units and 40% to 85% by weight of ( _C8 - _C16 )alkyl (meth)acrylamide or ( _C8 - _C16 )alkyl (meth)acrylate units relative to the polymer crosslinked or non-crosslinked, neutralized or non-neutralized copolymers, such as those described in patent application EP-A750 899;
- terpolymers comprising 10 mol% to 90 mol% acrylamide units, 0.1 mol% to 10 mol% AMPS units and 5 mol% to 80 mol% n-( _C6 - _C18 )alkylacrylamide units, e.g. in patent US-5,089,578 what is described.

Fully neutralized copolymers of AMPS and dodecyl methacrylate may also be mentioned, as well as crosslinked and uncrosslinked copolymers of AMPS and n-dodecyl methacrylamide, such as those described in the Morishima article referenced above. .

Among the cationic associative polymers, the following may be mentioned:
(a) a cationic associative polyurethane;
(b) The compound sold under the name Aqua CC by Noveon, which corresponds to the INCI name for polyacrylate-1 crosspolymer.

Polyacrylate-1 crosspolymer is the polymerization product of a mixture of monomers including:
- di( _C1 - _C4 alkyl)amino( _C1 - _C6 alkyl) methacrylate,
- one or more C1 _{- C30} alkyl esters of (meth)acrylic acid,
- polyethoxylated _C10 - _C30 alkyl methacrylates (20-25 mol ethylene oxide units),
- 30/5 polyethylene glycol/polypropylene glycol allyl ether,
- hydroxy methacrylate ( _C2 - _C6 alkyl), and
- Ethylene glycol dimethacrylate.
(c) Quaternized (poly)hydroxyethyl cellulose modified with at least one fatty chain containing group such as an alkyl, arylalkyl or alkylaryl group containing at least 8 carbon atoms, or mixtures thereof. The alkyl groups carried by the quaternized cellulose or hydroxyethyl cellulose mentioned above preferably contain from 8 to 30 carbon atoms. An aryl group preferably denotes a phenyl, benzyl, naphthyl or anthryl group. Examples of quaternized alkyl hydroxyethyl celluloses containing _C8 - _C30 fatty chains that may be mentioned are the products Quatrisoft LM 200®, Quatrisoft LM-X 529-18- A®, Quatrisoft LM-X 529-18B® (C ₁₂ alkyl) and Quatrisoft LM-X 529-8® (C ₁₈ alkyl), products Crodacel QM sold by Croda ®, Crodacel QL ® (C ₁₂ alkyl) and Crodacel QS ® (C ₁₈ alkyl) and the product Softcat SL 100 ® marketed by Aqualon.
(d) a cationic polyvinyl lactam polymer;

Such polymers are described, for example, in patent application WO-00/68282.

Examples of cationic poly(vinyl lactam) polymers according to the present invention include vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethacryl-amidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacrylamidepropylammonium tosylate. Late terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamidepropylammonium tosylate or chloride terpolymers are particularly used.

Amphoteric associative polymers are preferably selected from those containing at least one acyclic cationic unit. Even more particularly those prepared from or comprising 1 to 20 mol %, preferably 1.5 to 15 mol %, even more particularly 1.5 to 6 mol % of fatty chain monomers relative to the total number of moles of monomers preferable.

Amphoteric associative polymers according to the invention are described and prepared, for example, in patent application WO 98/44012.

Preferred among the amphoteric associative polymers according to the invention are acrylic acid/(meth)acrylamidopropyltrimethylammonium chloride/stearyl methacrylate terpolymers.

Associative polymers of nonionic type that can be used according to the invention are preferably selected from:
(a) Copolymers of vinylpyrrolidone and fatty chain hydrophobic monomers, examples of which may be mentioned are:
- the products Antaron V216® or Ganex V216® (vinylpyrrolidone/hexadecene copolymer) sold by the company ISP,
- the products Antaron V220® or Ganex V220® (vinylpyrrolidone/eicosene copolymer) sold by the company ISP,
(b) Copolymers of C ₁ -C ₆ alkyl methacrylates or acrylates and amphiphilic monomers containing at least one fatty chain, for example the oxyethylenated acrylic sold under the name Antil 208® by the company Goldschmidt. methyl acid/stearyl acrylate copolymer;
(c) copolymers of hydrophilic methacrylates or acrylates and hydrophobic monomers containing at least one fatty chain, such as polyethylene glycol methacrylate/lauryl methacrylate copolymers;
(d) Polyurethane polyethers containing in their chains both hydrophilic blocks, usually polyoxyethylene, and hydrophobic blocks, which may be single aliphatic and/or cycloaliphatic and/or aromatic sequences. ;
(e) polymers having an aminoplast ether backbone containing at least one fatty chain, such as the Pure Thix® compounds sold by Sud-Chemie;
(f) cellulose or derivatives thereof modified with groups containing at least one fatty chain such as alkyl, arylalkyl or alkylaryl groups or mixtures thereof, wherein the alkyl groups are of _C8 or Derivatives of these, in particular:
* non-ionic alkyl hydroxyethyl cellulose, such as the products Natrosol Plus Grade 330 CS and Polysurf 67 (C ₁₆ alkyl) sold by Aqualon;
* Nonionic nonoxynyl hydroxyethyl cellulose, such as the product Amercell HM-1500 sold by Amerchol;
* non-ionic alkylcelluloses, such as the product Bermocoll EHM 100 sold by the company Berol Nobel;
(g) associative guar derivatives, e.g. hydroxypropyl guar modified with fatty chains, e.g. the product Esaflor HM 22 (modified with _C22 alkyl chains) marketed by Lamberti; marketed by Rhodia Chimie; products Miracare XC 95-3 (modified with _C14 alkyl chains) and product RE 205-146 (modified with _C20 alkyl chains).

Preferably, the polyurethane polyether comprises at least two hydrocarbon-based lipophilic chains containing 6 to 30 carbon atoms separated by hydrophilic blocks, the hydrocarbon-based chains being side chains or hydrophilic It may also be the terminal chain of the sex block. In particular, it is possible to envisage one or more side chains. Additionally, the polymer may contain hydrocarbon-based chains at one or both ends of the hydrophilic block.

Polyurethane polyethers can be in the form of multiblock, especially triblock. A hydrophobic block can be at each end of the chain (eg, a triblock copolymer with a hydrophilic central block) or can be distributed on both ends and throughout the chain (eg, a multiblock copolymer). These same polymers can also be graft polymers or star polymers.

Nonionic fatty chain polyurethane polyethers can be triblock copolymers, the hydrophilic blocks of which are polyoxyethylene chains containing 50 to 1000 oxyethylene groups. Nonionic polyurethane polyethers contain urethane linkages between hydrophilic blocks, hence the origin of the name.

By extension, also included among non-ionic fatty chain polyurethane polyethers are those in which hydrophilic blocks are linked to lipophilic blocks via other chemical bonds.

Examples of nonionic fatty chain polyurethane polyethers that may be used in the present invention are Rheolate 205® with urea functionality sold by Rheox, or Rheolate® 208, 204 or 212, Acrysol RM 184® may also be used.

Mention may also be made of the product Elfacos T210® with C ₁₂ -C ₁₄ alkyl chains and the product Elfacos T212® with C ₁₈ alkyl chains from Akzo.

The product DW 1206B® from Rohm & Haas with _C20 alkyl chains and urethane linkages sold at 20% solids content in water may also be used.

Solutions or dispersions of these polymers, particularly in water or aqueous/alcoholic media, may also be used. Examples of such polymers that may be mentioned are Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company Rheox. The products DW 1206F and DW 1206J sold by Rohm & Haas may also be used.

Polyurethane polyethers which can be used according to the invention are in particular those described in the document G. Fonnum, J. Bakke, and Fk. Hansen - Colloid Polym. Sci 271, pp. 380-389 (1993).

Polyurethane polyethers obtainable by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol containing 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate. It is even more particularly preferred to use

Such polyurethane polyethers are sold inter alia by the company Rohm & Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is maltodextrin (4%) and a polycondensate of polyethylene glycol, stearyl alcohol and methylene bis(4-cyclohexyl isocyanate) (SMDI) containing 15% by weight of 150 or 180 mol of ethylene oxide in a matrix of water (81%) Aculyn 44® is a mixture of polyethylene glycol, decyl alcohol and methylenebis ( 4-cyclohexyl isocyanate) (SMDI)].

Preferably, hydrophilic thickeners are selected from polymers that do not contain any sugar units.

More preferentially, the hydrophilic thickener comprises associative or non-associative thickening polymers with acrylic or methacrylic units and 2-acrylamido-2-methylpropanesulfonic acid units and/or salified forms thereof. selected from polymers;

In a preferred variant of the invention, the hydrophilic thickener is an acrylic acid homopolymer or copolymer, in particular 2-acrylamido-2-methylpropanesulfonic acid and/or acrylic acid homopolymers, homopolymers or copolymers in their chloride form. , in particular 2-acrylamido-2-methylpropanesulfonic acid and/or copolymers of their chloride forms, more particularly 2-acrylamido-2-methylpropanesulfonic acid and/or their chloride forms and copolymers of acrylamide, or 2 -acrylamido-2-methylpropanesulfonic acid and/or copolymers of their chloride forms and hydroxyethyl acrylate, said polymers optionally being crosslinked or non-crosslinked.

Examples of hydrophilic thickeners that may be mentioned are carboxyvinyl polymers, such as the Carbopol products (carbomer) and Pemulen products (acrylates/C10-C30-alkyl acrylate copolymers); polyacrylamides, such as the name Sepigel 305 by the company SEPPIC. (CTFA name: Polyacrylamide/C13-C14 Isoparaffin/Laureth 7); sodium copolymer/polysorbate 60), Simulgel 800 (CTFA name: sodium polyacryloyldimethyltaurate/polysorbate 80/sorbitan oleate) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyltaurate copolymer/isohexadecane/polysorbate 80); optional Polymers and copolymers of 2-acrylamido-2-methylpropanesulfonic acid, such as poly(2-acrylamido-2-methylpropanesulfonic acid) (CTFA) sold under the tradename Hostacerin AMPS by Clariant, neutralized with Name: Polyacryloyldimethyltaurate ammonium) copolymers of 2-acrylamido-2-methylpropanesulfonic acid and hydroxyethyl acrylate, e.g. Simulgel NS and Sepinov EMT 10 sold by SEPPIC; cellulose derivatives, e.g. there is a mixture. Acryloyl dimethyl taurate copolymers such as Simulgel FL, Simulgel 800 and Simulgel 600 may be preferred.

The amount of the hydrophilic thickener in the first composition may be 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the first composition. good.

The amount of the hydrophilic thickener in the first composition is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, relative to the total mass of the first composition. good.

The first composition contains 0.01% to 15% by weight, preferably 0.1% to 10% by weight, and more preferably 1 to 5% by weight of a hydrophilic thickener, relative to the total weight of the first composition. %.

(other optional ingredients)
The first composition may contain at least one optional ingredient other than the aqueous phase thickener.

The first composition may comprise one or several cosmetically acceptable organic solvents, which are alcohols, especially monohydric alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol. diols such as ethylene glycol, propylene glycol, and butylene glycol; other polyols such as glycerol, sugars and sugar alcohols; and ethers such as ethylene glycol monomethyl, monoethyl and monobutyl ether, propylene glycol monomethyl, monoethyl and monobutyl ether, and butylene. Glycol monomethyl, monoethyl and monobutyl ethers are also possible.

In that case, the organic solvent is used at a concentration of 0.01% to 20% by weight, preferably 0.1% to 15% by weight, more preferably 1% to 10% by weight, relative to the total weight of the first composition. May be present.

The pH of the first composition may be adjusted to the desired value using acidifying or basifying agents commonly used in dyeing keratin fibers, or using conventional buffer systems.

The first composition is preferably acidic. Therefore, it is preferred that the pH of the composition is between 2 and 7, more preferably between 2 and 6, even more preferably between 2 and 4.

Among the acidifying agents, mention may be made, by way of example, of inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.

Among the basifying agents, for example, ammonium hydroxide, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines, also their derivatives, sodium hydroxide and potassium hydroxide, and the formula:

(In the formula,
W represents alkylene, such as propylene optionally substituted with hydroxyl or C ₁ -C ₄ alkyl groups, and R _a , R _b , R _c and R _d are independently hydrogen atoms, alkyl groups or indicates a _C1 - _C4 hydroxyalkyl group)
which can be exemplified by 1,3-propanediamine and derivatives thereof. Sodium hydroxide or potassium hydroxide are preferred. because it can also function in situ to form a (c) buffer.

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

The first composition may also include in the composition for dyeing hair an anionic, cationic, nonionic, or amphoteric polymer; an anionic, cationic, nonionic, or amphoteric surfactant; or inorganic UV-screening agents; peptides and their derivatives; protein hydrolysates; swelling agents and penetrating agents; hair loss agents; anti-dandruff agents; sunscreens; vitamins or provitamins; fragrances; preservatives, co-preservatives, stabilizers; and mixtures thereof.

The amount of these adjuvants is not limited, but is 0.01% to 30% by weight, preferably 0.1% to 20% by weight, more preferably 1% to 10% by weight, relative to the total weight of the first composition. may be

(preparation)
The first composition can be prepared by mixing the essential ingredients, as well as optional ingredients, as described above.

The methods and means for mixing the above essential and optional ingredients are not limited. Any conventional method and means, such as a mixer or agitator, can be used to mix the essential and optional ingredients to prepare the first composition.

{second composition}
The second composition contains at least one oil.

(oil)
The second composition contains at least one oil. When two or more oils are used they may be the same or different.

As used herein, “oil” means a fatty compound or fatty substance that is in liquid or pasty (non-solid) form at room temperature (25° C.) and atmospheric pressure (760 mmHg). As oils, those commonly used in cosmetics can be used alone or in combination. These oils may be volatile or non-volatile.

The oils may be hydrocarbon oils, non-polar oils such as silicone oils, polar oils such as vegetable or animal oils and ester or ether oils, or mixtures thereof.

The oil may be selected from the group consisting of oils of vegetable or animal origin, synthetic oils, silicone oils, hydrocarbon oils, and fatty alcohols.

Examples of vegetable oils include, for example, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, Mention may be made of soybean oil, peanut oil, and mixtures thereof.

Examples of animal oils include, for example, squalene and squalane.

Examples of synthetic oils may include alkane oils such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.

Ester oils are preferably liquid esters of saturated or unsaturated, linear or branched C ₁ -C ₂₆ aliphatic mono- or polyacids and saturated or unsaturated, linear or branched with C ₁ -C ₂₆ aliphatic monohydric alcohols or polyhydric alcohols, and the total number of carbon atoms in these esters is 10 or more.

Preferably, in the case of esters of monoalcohols, at least one of the alcohols and acids from which the esters of the invention are derived is branched.

Among monoesters of monoacids and monoalcohols, ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononane Mention may be made of isononyl acid, isodecyl neopentanoate and isostearyl neopentanoate.

Esters of C ₄ -C ₂₂ dicarboxylic or tricarboxylic acids and C ₁ -C ₂₂ alcohols, and monocarboxylic, dicarboxylic or tricarboxylic acids and non-sugar C ₄ -C ₂₆ dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols. Esters may also be used.

Diethyl Sebacate, Isopropyl Lauroyl Sarcosinate, Diisopropyl Sebacate, Bis(2-ethylhexyl) Sebacate, Diisopropyl Adipate, Di-n-Propyl Adipate, Dioctyl Adipate, Bis(2-Ethylhexyl) Adipate, Diadipate Isostearyl, bis(2-ethylhexyl) maleate, triisopropyl citrate, triisocetyl citrate, triisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, trioctyldodecyl citrate, trioleyl citrate, neopentyl diheptanoate Particular mention may be made of glycols, diethylene glycol diisononanoate.

As ester oils sugar esters and diesters of C ₆ -C ₃₀ , preferably C ₁₂ -C ₂₂ fatty acids can be used. It is recalled that the term "sugar" means an oxygen-containing hydrocarbon-based compound containing some alcohol functionality, with or without aldehyde or ketone functionality, and containing at least 4 carbon atoms. be done. These sugars may be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars that may be mentioned are sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose and derivatives thereof, especially alkyl derivatives such as the methyl derivative. , for example methyl glucose.

Sugar esters of fatty acids are in particular from the group comprising esters or ester mixtures of the aforementioned sugars with linear or branched, saturated or unsaturated C ₆ -C ₃₀ , preferably C ₁₂ -C ₂₂ fatty acids. You may choose. When they are unsaturated, these compounds may have 1-3 conjugated or non-conjugated carbon-carbon double bonds.

Esters according to this variant may also be selected from monoesters, diesters, triesters, tetraesters, and polyesters, and mixtures thereof.

These esters are, for example, oleates, laurates, palmitates, myristates, behenates, coconut fatty acid esters, stearates, linoleates, linolenates, caprates, and arachidonic acid esters. Esters, or mixtures thereof, such as mixed esters of oleopalmitic acid, oleostearic acid, and palmitostearic acid, among others, and pentaerythrityl tetraethylhexanoate.

More particularly, mono- and diesters, especially monooleate or dioleate esters of sucrose, glucose or methylglucose, stearates, behenates, oleopalmitates, linoleates, linolenates, and An oleostearate is used.

An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is methylglucose dioleate.

Examples of preferred ester oils include diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexanoate. -ethylhexyl, 2-ethylhexyl octanoate, 2-ethylhexyl (caprylate/caprate), methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, lauric acid isohexyl, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrityl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, Mention may be made of diethyl sebacate, and mixtures thereof.

Examples of artificial triglycerides include, for example, caprylic caprylyl glyceride, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, tri(capric/caprylic) glyceryl and Mention may be made of tri(capric/caprylic/linolenic)glyceryl.

Examples of silicone oils include linear organopolysiloxanes, such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane; cyclic organopolysiloxanes, such as cyclohexasiloxane, octamethylcyclotetrasiloxane; , decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; and mixtures thereof.

Preferably, the silicone oil is selected from liquid polydialkylsiloxanes, in particular liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes containing at least one aryl group.

These silicone oils may also be organically modified. Organomodified silicones that can be used according to the invention are silicone oils as defined above, which in their structure have one or more organic functional groups bonded via a hydrocarbon-based group. is a silicone oil containing

Organopolysiloxanes are defined in more detail in Walter Noll, Chemistry and Technology of Silicones (1968) Academic Press. They may be volatile or non-volatile.

If they are volatile, the silicones are more particularly selected from those having a boiling point between 60° C. and 260° C., and more particularly selected from:
(i) cyclic polydialkylsiloxanes containing 3 to 7, preferably 4 to 5, silicon atoms; These are, for example, inter alia the octamethylcyclotetrasiloxane sold by the company Union Carbide under the name Volatile Silicone® 7207 or by the company Rhodia under the name Silbione® 70045 V2, by the company Union Carbide Decamethylcyclopentasiloxane, sold under the name Silbione® 70045 V5 by Rhodia under the name Volatile Silicone® 7158, and dodeca sold under the name Silsoft 1217 by Momentive Performance Materials methylcyclopentasiloxane, and mixtures thereof. Mention may also be made of cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Silicone Volatile® FZ 3109 sold by Union Carbide Company.

Mixtures of cyclic polydialkylsiloxanes and organosilicon compounds, such as mixtures of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and octamethylcyclotetrasiloxane and oxy-1,1'-bis(2, Mixtures with 2,2',2',3,3'-hexatrimethylsilyloxy)neopentane may also be mentioned.
(ii) a linear volatile polydialkylsiloxane containing from 2 to 9 silicon atoms and having a viscosity at 25° C. of 5×10 ⁻⁶ m ² /s or less; An example is the decamethyltetrasiloxane sold especially under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in an article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of silicones is measured according to ASTM Standard 445 Appendix C at 25°C.

Nonvolatile polydialkylsiloxanes can also be used. These non-volatile silicones are more particularly selected from polydialkylsiloxanes, among which polydimethylsiloxanes containing trimethylsilyl end groups can be mentioned primarily.

Among these polydialkylsiloxanes, mention may be made, without limitation, of the following commercial products:
- the 47 and 70 047 series of Silbione® oils sold by the company Rhodia or Mirasil® oils, such as the 70 047 V 500 000 oil;
- Mirasil® series oils marketed by Rhodia;
- Dow Corning 200 series oils, e.g. DC200 with a viscosity of 60 000 ^mm2 /s;
- Viscasil® oils from General Electric and certain oils from the SF series from General Electric (SF 96, SF 18).

Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the 48 series oils from Rhodia.

Among the silicones containing aryl groups, mention may be made of polydiarylsiloxanes, especially polydiphenylsiloxanes and polyalkylarylsiloxanes such as phenylsilicone oils.

Phenylsilicone oils may be selected from phenylsilicones of the formula:

(In the formula,
R ₁ to R ₁₀ are, independently of each other, saturated or unsaturated, linear, cyclic or branched C ₁ to C ₃₀ hydrocarbon-based groups, preferably C ₁ to C ₁₂ hydrocarbon-based groups, and more preferably a C ₁ -C ₆ hydrocarbon group, especially a methyl, ethyl, propyl or butyl group, and
m, n, p and q are each independently an integer between 0 and 900 inclusive, preferably between 0 and 500 inclusive, more preferably between 0 and 100 inclusive and
However, the sum of n+m+q is non-zero).

Examples that may be mentioned are products marketed under the following names:
- 70 641 series of Silbione® oils from Rhodia;
- Rhodia Rhodorsil® 70 633 and 763 series oils;
- Oil of Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;
- Silicones from the Bayer PK series, e.g. the PK20 product;
- Certain oils from the General Electric SF series, such as SF 1023, SF 1154, SF 1250 and SF 1265.

Phenyl trimethicone (R ₁ to R ₁₀ in the above formula are methyl; p, q, and n=0; m=1) is preferred as the phenyl silicone oil.

The organically modified liquid silicone may contain, inter alia, polyethyleneoxy groups and/or polypropyleneoxy groups. Mention may therefore be made of the silicone KF-6017 proposed by Shin-Etsu Chemical Co., Ltd., and the Silwet® L722 and L77 oils from Union Carbide.

Hydrocarbon oils can be selected from:
- _C6 - _C16 lower alkanes, linear or branched, optionally cyclic. Examples that may be mentioned are hexane, undecane, dodecane, tridecane and isoparaffins, such as isohexadecane, isododecane and isodecane;
- Linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffin, liquid petrolatum, polydecene and hydrogenated polyisobutene, such as Parleam®, and squalane.

Preferred examples of hydrocarbon oils include, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oils (e.g. liquid paraffin), paraffin, naphthalene, etc.; hydrogenated polyisobutene, isoeicosane and decene/ butene copolymers; as well as mixtures thereof.

The term "aliphatic" in fatty alcohols means containing a relatively large number of carbon atoms. Thus, alcohols having 4 or more, preferably 6 or more, more preferably 12 or more carbon atoms are included within the scope of fatty alcohols. Fatty alcohols may be saturated or unsaturated. Fatty alcohols may be linear or branched.

Aliphatic alcohols have the structure R-OH, where R is saturated and unsaturated containing 4 to 40 carbon atoms, preferably 6 to 30 carbon atoms, more preferably 12 to 20 carbon atoms. (selected from saturated, linear and branched groups). In at least one embodiment, R may be selected from C ₁₂ -C ₂₀ alkyl and C ₁₂ -C ₂₀ alkenyl groups. R may or may not be substituted with at least one hydroxyl group.

Examples of fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol. , erucyl alcohol, and mixtures thereof.

Preferably, the fatty alcohol is a saturated fatty alcohol.

Fatty alcohols are therefore linear or branched, saturated or unsaturated C ₆ -C ₃₀ alcohols, preferably linear or branched, saturated C ₆ -C ₃₀ alcohols, more preferably linear chain. It can be selected from saturated C ₁₂ -C ₂₀ alcohols, branched or branched.

As used herein, the term "saturated fatty alcohol" means an alcohol having a long fatty saturated carbon chain. The saturated fatty alcohol is preferably selected from any linear or branched saturated _C6 - _C30 fatty alcohol. Among linear or branched saturated C ₆ -C ₃₀ fatty alcohols, linear or branched saturated C ₁₂ -C ₂₀ fatty alcohols can preferably be used. Any linear or branched saturated C ₁₆ -C ₂₀ fatty alcohol can more preferably be used. Branched C ₁₆ -C ₂₀ fatty alcohols can even more preferably be used.

Examples of saturated fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or mixtures thereof (eg, cetearyl alcohol) and behenyl alcohol can be used as saturated fatty alcohols.

According to at least one embodiment, the fatty alcohol used in the second composition according to the invention is preferably selected from octyldodecanol, hexyldecanol and mixtures thereof.

The amount of oil in the second composition according to the invention may be 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, relative to the total weight of the second composition. .

The amount of oil in the second composition according to the invention may be 98% by weight or less, preferably 95% by weight or less, more preferably 90% by weight or less, relative to the total weight of the second composition. .

The amount of oil in the second composition according to the invention is 50% to 98%, preferably 60% to 95%, more preferably 70% by weight relative to the total weight of the second composition. It may be up to 90% by mass.

(thickener)
The second composition may contain at least one thickening agent.

Preferably the second composition may comprise at least one lipophilic thickener. If more than one lipophilic thickener is used, these may be the same or different.

According to the present invention, the “lipophilic thickener” is capable of increasing the viscosity of the second composition at room temperature (25° C.), atmospheric pressure and a shear rate of 1 s ⁻¹ (viscosity is cone/plate viscosity meter, Haake R600 rheometer, etc.) is introduced into the second composition to at least 20 cps, preferably at least 50 cps.

The lipophilic thickeners used in the composition according to the invention may be selected from inorganic lipophilic thickeners and organic lipophilic thickeners and mixtures of these compounds.

The inorganic lipophilic thickeners that may be used in the compositions according to the invention are preferably inorganic particles substantially composed of inorganic oxides and/or hydroxides.

These particles are preferably insoluble in water at room temperature (25° C.). The term "insoluble" means a solubility of less than 0.5% by weight.

Preferably, the number average primary size of these inorganic particles is in the range 0.01 to 500 μm, preferably in the range 0.1 to 200 μm and even more preferentially in the range 1 to 100 μm.

In the present invention, the term "primary particle size" means the largest dimension that can be measured between two diametrically opposed points on an individual particle.

The size of the inorganic particles may be determined by transmission electron microscopy, by specific surface area measurements by the BET method, or by laser particle size analysis.

The inorganic particles that may be used in accordance with the present invention may be of various morphologies, such as spherical, acicular, flaky or platelet morphology.

In a preferred variant of the invention, the inorganic lipophilic thickeners are platelet-shaped particles.

Inorganic lipophilic thickeners that may be used in cosmetic compositions according to the invention may preferably be selected from silicas and silicates.

The silicates of the present invention may be natural or chemically modified (or synthetic).

Silicates are comparable to optionally hydrated silicas in which some of the silicon atoms are Al ³⁺ , B ³⁺ , Fe ³⁺ , Ga ³⁺ , Be ²⁺ , Zn ^{2 +} , Mg ²⁺ , Co ³⁺ , Ni ³⁺ , Na ⁺ , Li ⁺ , Ca ²⁺ , Cu ²⁺ and other metal cations.

More particularly, the silicates that may be used in the context of the present invention are selected from the smectite family, such as montmorillonite, hectorite, bentonite, beidellite and saponite, and clays of the vermiculite, stevensite and chlorite families.

These clays may be of natural or synthetic origin. Keratin materials and cosmetically compatible and acceptable clays are preferably used.

The silicates may be selected from montmorillonite, bentonite, hectorite, attapulgite and sepiolite, and mixtures thereof.

Thus, mention may be made of the compounds sold under the names Laponite XLG and Laponite XLS by the company Laporte.

The silicate is preferably selected from bentonite and hectorite.

The silicates may be modified with compounds selected from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylarylsulfonates and amine oxides, and mixtures thereof.

Suitable silicates for use include quaternium-18 bentonites such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by Rheox, Tixogel VP by United Catalyst and Claytone 34, Claytone 40 and Claytone XL by Southern Clay. stearalkonium bentonite, such as those sold under the names Bentone 27 by Rheox, Tixogel LG by United Catalyst, and Claytone AF and Claytone APA by Southern Clay; Quantanium-18/benzalkonium Bentonites, such as those sold by Southern Clay under the names Claytone HT and Claytone PS, quaternium-18 hectorite, such as Bentone Gel DOA, Bentone Gel ECO5, Bentone Gel EUG, Bentone Gel IPP, Bentone Gel ISD by Rheox. , Bentone Gel SS71, Bentone Gel VS8 and Bentone Gel VS38, and those sold under the names Simagel M and Simagel SI 345 by the company Biophil.

The silicates that may be used in the composition according to the invention are in particular selected from modified hectorites, such as hectorites modified with C ₁₀ -C ₁₂ fatty acid ammonium chlorides, especially distearyldimethylammonium chloride and stearylbenzyldimethylammonium chloride. may be

As already explained, the inorganic lipophilic thickener that may be used in the composition according to the invention may be silica.

The silica that may be used in the composition according to the invention is preferably fumed silica.

Fumed silica may be obtained by hydrolyzing volatile silicon compounds in an oxyhydrogen flame at elevated temperature to produce finely divided silica. This method makes it possible in particular to obtain hydrophilic silicas which have a large number of silanol groups on their surface. Such hydrophilic silicas are known, for example, under the names Aerosil 130®, Aerosil 200®, Aerosil 255®, Aerosil 300® and Aerosil 380® by the company Degussa. , and Cab-O-Sil HS-5®, Cab-O-Sil EH-5®, Cab-O-Sil LM-130®, Cab-O-Sil MS by Cabot Corporation. -55® and Cab-O-Sil M-5®.

It is possible to chemically modify the surface of the silica through chemical reactions leading to a reduction in the number of silanol groups. In particular it is possible to replace the silanol groups with hydrophobic groups, resulting in hydrophobic silicas.

This hydrophobic group may be:
(a) Trimethylsiloxy groups, especially obtained by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as silica silylate according to the CTFA (6th edition, 1995). They are marketed, for example, under the references Aerosil R812® by the company Degussa and Cab-O-Sil TS-530® by the company Cabot.
(b) Dimethylsilyloxy groups or polydimethylsiloxane groups, especially obtained by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane.

Silicas thus treated are known as silica dimethyl silylate according to the CTFA (6th edition, 1995). They are, for example, Aerosil R972® and Aerosil R974® by Degussa, and Cab-O-Sil TS-610® and Cab-O-Sil TS-720® by Cabot. ) under the reference name.

Preferably, the fumed silica that may be used in the composition according to the invention is hydrophilic, for example the product sold under the name Aerosil 200®.

Preferably, the inorganic lipophilic thickener is selected from organophilic clays and hydrophilic fumed silicas, and mixtures thereof.

More preferentially, inorganic lipophilic thickeners are Hectorite modified with C ₁₀ -C ₁₂ fatty acid ammonium chlorides, especially distearyldimethylammonium chloride and stearylbenzyldimethylammonium chloride, and Aerosil 200®. It is selected from hydrophilic fumed silicas such as hydrophilic silicas sold under the name.

Even more preferentially, the inorganic lipophilic thickener is distearyldimethyl, such as hectorite modified with a _C10 - _C12 fatty acid ammonium chloride, in particular the product sold under the name Bentone 38VCG by the company Elementis. It is selected from hectorite modified with ammonium chloride and hectorite modified with stearylbenzyldimethylammonium chloride, such as the product sold under the name Bentone 27V by the company Elementis.

As already explained, the lipophilic thickeners that may be used in the compositions according to the invention may also be selected from organic lipophilic thickeners.

Preferably, the organic lipophilic thickeners are semicrystalline polymers, non-silicone polyamides, silicone polyamides, saccharide or polysaccharide monoalkyl or polyalkyl esters, N-acyl amino acid amide derivatives, polystearyl acrylates and/or alkylene and/or It is selected from polymers containing styrene blocks, elastomeric organopolysiloxanes, solid fatty esters, especially C ₈ -C ₃₀ , preferably C ₁₈ -C ₂₄ fatty acid esters, and mixtures of these compounds. These copolymers may be diblock, triblock or multiblock polymers, radial block polymers, also known as star copolymers, or comb polymers.

Among the _C8 - _C30 , preferably _C18 - _C24 fatty acid esters, _C8 - _C30 , preferably _C18 - _C24 fatty acids and polyol mono-, di- or triesters, more particularly C Mention may be made of mono-, di- or triesters of ₈ - _C30 , preferably _C18 - _C24 fatty acids and glycerol. In particular, mixtures of compounds such as mixtures of mono-, di- and triesters of behenic acid and glycerol may be used.

Most particularly, the organic lipophilic thickeners are semi-crystalline polymers, non-silicone polyamides, silicone polyamides, polymers containing alkylene and/or styrene blocks such as polystearyl acrylate, solid fatty esters, especially _C8 - _C30 . , preferably C ₁₈ -C ₂₄ fatty acid esters, and mixtures of these compounds.

Even more preferentially, the organic lipophilic thickeners are C ₈ -C ₃₀ , preferably C ₁₈ -C ₂₄ fatty acid esters and mixtures thereof, even better C ₈ -C ₃₀ , preferably C _{18 .} selected from esters of _-C24 fatty acids and polyols, more particularly _C8 - _C30 , preferably _C18 - _C24 fatty acids and glycerol mono-, di- or triesters.

Preferably, the lipophilic thickener is selected from organic thickeners. Glyceryl behenate may be more preferred as a lipophilic thickener.

In another embodiment of the invention, the lipophilic thickener may be a linear C ₁₈ -C ₂₄ hydroxylated fatty acid, preferably saturated. More preferably, the linear C ₁₈ -C ₂₄ hydroxylated fatty acid may be 12-hydroxystearic acid. This compound is marketed inter alia by the company Thai Kawaken under the reference name 12-Hydroxystearic Acid Premium Grade 12H-P.

The amount of lipophilic thickener in the second composition may be 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, relative to the total mass of the second composition. good.

The amount of lipophilic thickener in the second composition may be 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, relative to the total mass of the second composition. good.

The second composition contains a lipophilic thickener of 0.01% to 25% by weight, preferably 0.1% to 20% by weight, more preferably 1% by weight, relative to the total weight of the second composition. It may be contained in an amount of up to 15% by mass.

(other optional ingredients)
The second composition may contain at least one optional ingredient other than the oil phase composition thickener.

(preparation)
The second composition can be prepared by mixing the essential ingredients, as well as optional ingredients, as described above. Any other optional ingredients may be added to the second composition.

The method and means of mixing the above essential and optional ingredients are not limited. Any conventional method and means, such as a mixer or agitator, can be used to mix the essential and optional ingredients to prepare the second composition.

{bubble}
The first composition and/or the second composition contain at least one type of foam. In other words, either the first composition or the second composition, or both the first and second compositions may contain at least one air bubble.

The bubble type is not restricted. Therefore, a single type of gas may be used for the bubbles. For example, oxygen, nitrogen or carbon dioxide may be used. Alternatively, gas mixtures may be used for the bubbles. Thus, mixtures of oxygen, nitrogen and carbon dioxide may be used.

It may be preferred to use air as the gas. Therefore, it may be preferred that the bubbles comprise or consist of air.

The bubble diameter or size is not limited. It may be preferred that the bubbles are fine bubbles. The cells may have an average diameter or average size of less than 100 μm, preferably less than 50 μm, more preferably less than 20 μm, even more preferably less than 10 μm.

Air bubbles are preferably present in the first composition and/or the second composition, which composition is subject to the following conditions (1):
Y/X ratio >20, preferably >50, more preferably >100(1)
(here,
Y indicates the yield stress (Pa) of the composition,
X indicates strain (%) at yield stress)
can satisfy

"Pa" means Pascal.

The yield stress of the composition, and the strain corresponding to the yield stress, may be determined by any conventional rheometer. For example, a formulation corresponding to the composition may be subjected to rheological tests to determine a stress-strain diagram for the formulation. The stress at the tangent point between the two linear regions in the stress-strain diagram can be determined as the yield stress (Y in condition (1) above), and the strain giving the yield stress is the strain corresponding to the yield stress (Y) (X in condition (1) above) can be determined.

If the straight line region does not correspond to an exact straight line, a straight line approximation may be performed to determine the approximate straight line, or the approximate straight line may be used instead of the straight line region.

When shear stress is used in the stress-strain diagram, and the stress-strain diagram includes a first linear region, a non-linear region, and a second linear region, these indicate that the formulation is solid-like. Corresponding to the regions where the formulation behaves, where the formulation is in a solid-to-liquid transition state, and where the formulation behaves like a liquid. In such cases, two straight lines may be extended from the first and second straight regions and the intersection of the two straight lines determined as shown in FIG. The shear stress at the intersection corresponds to the yield stress (Y) in condition (1) above, and the strain at the intersection corresponds to strain (X) in condition (1) above.

A straight line approximation may be performed to determine the approximate straight line, if the first and/or second straight line regions correspond/do not correspond to exact straight lines, and the first and/or second straight lines Approximate straight lines may be used instead of regions.

It may be preferable for the second composition to satisfy condition (1) above. Therefore, it may be preferred that the second composition contains air bubbles.

The amount of air bubbles in the first composition and/or the second composition is not limited.

The amount of air bubbles may be 1% by volume or more, preferably 5% by volume or more, more preferably 10% by volume or more, relative to the total volume of the composition containing air bubbles.

The amount of air bubbles may be 90% by volume or less, preferably 80% by volume or less, more preferably 70% by volume or less, relative to the total volume of the composition containing air bubbles.

Therefore, the amount of air bubbles is 1% to 90% by volume, preferably 5% to 80% by volume, more preferably 10% to 70% by volume, relative to the total volume of the composition containing air bubbles. good too.

In certain embodiments, the amount of air bubbles is 1% to 30%, preferably 5% to 25%, more preferably 10% to 20% by volume, relative to the total volume of the composition containing air bubbles. %.

Preferably, the foam is stable such that more than 85 vol%, preferably more than 90 vol%, more preferably more than 95 vol% of the foam relative to the total volume of the foam is maintained at 25°C for 2 months. .

(aeration)
Bubbles in the first composition and/or the second composition can be prepared by mixing gas into the composition.

The method and means for mixing the gas into the first composition and/or the second composition are not limited. Any conventional method and means, such as mixers or agitators, can be used to mix the gas into the composition.

The oil used in the second composition, or the second composition itself used to form the oil phase of the mixture of the first and second compositions, is preferably aged. Aging may be performed by allowing the oil or second composition to stand for a specified period of time, such as several days.

{Processing of keratin fibers}
According to the method of the invention, the first and second compositions are mixed.

The mixing ratio of the first composition and the second composition is not limited. For example, the mixing ratio (mass basis) of the first composition and the second composition is 10:90-90:10, 20:80-80:20, 30:70-70:30, 40:60- It may be 60:40 or 50:50.

According to the method of the invention, the keratin fibers are then treated with a mixture of the first and second compositions for dyeing the keratin fibers.

A mixture of the first and second compositions may therefore be regarded as a cosmetic composition for dyeing keratin fibres. By "keratin fiber" is meant here a fiber containing at least one keratin substance. At least part of the surface of the keratin fibers is preferably made of keratin fibers. Examples of keratin fibers include hair, eyebrows, eyelashes, and the like. Preferably, the method according to the invention is used for dyeing hair.

Treatment of keratinous fibers can be performed by applying a mixture of the first and second compositions to the keratinous fibers.

The step of applying the mixture of the first and second compositions to the keratin fibers can be done with a conventional applicator such as a brush or even by hand.

The keratin fibers to which the mixture of the first and second compositions has been applied can be left for the appropriate amount of time required to treat the keratin fibers. The length of time for treatment is not limited, but it can be from 1 minute to 1 hour, preferably from 1 minute to 30 minutes, more preferably from 1 minute to 15 minutes. For example, the time for dyeing keratin fibers can be 1-20 minutes, preferably 5-15 minutes.

Keratin fibers may be treated at room temperature. Alternatively, the keratin fibers are heated to 25° C. to 65° C., preferably between 25° C. and 65° C., during the step of applying the mixture of the first and second compositions to the keratin fibers and/or allowing the keratin fibers to which the mixture has been applied. It can be heated at 30°C to 60°C, more preferably 35°C to 55°C, even more preferably 40°C to 50°C.

After applying the mixture of the first and second compositions to the keratin fibers and/or after leaving the keratin fibers to which the mixture has been applied, the keratin fibers may be rinsed.

[kit]
The kit according to the invention for dyeing keratin fibres, preferably hair:
(1) a first compartment comprising a first composition; and
(2) comprising a second compartment comprising a second composition;
the first composition comprises (a) at least one direct dye and (b) water;
the second composition comprises (c) at least one oil;
At least one of the first composition and the second composition is:
Y/X ratio >20, preferably >50, more preferably >100(1)
(here,
Y indicates the yield stress (Pa) of the composition,
X indicates strain (%) at yield stress)
satisfies the condition (1) of and
(d) air bubbles are present in the composition satisfying condition (1);

The above explanations regarding the first and second compositions and the components therein for the method according to the invention are also applicable to the explanations for the kits according to the invention.

Kits according to the present invention can be prepared by those skilled in the art based on conventional packaging techniques. A kit according to the invention comprises at least first and second compartments, each of which individually contains the first and second compositions, respectively. The first and second compartments may be provided with distribution or evacuation means, such as pumps. The first and second compartments may be separately contained in two separate containers. Alternatively, the first and second compartments may be in a single container.

For example the following steps:
(i) dispensing or expelling the first composition from the first compartment;
(ii) dispensing or expelling the second composition from the second compartment;
(iii) mixing the first and second compositions; and
(iv) The kit can be used by applying the mixture to the keratin fibers to dye the keratin fibers.

(iii) the mixing step can be performed manually by blending the first and second compositions by hand or automatically by using a static mixer which may be equipped with a kit for example; is.

If necessary, a step of rinsing and/or drying may be performed after step (iv).

[Method for preparing the composition]
A method for preparing a composition for dyeing keratinous fibers, preferably hair, according to the invention is:
(d) introducing air bubbles into at least one of the first composition and the second composition;
the first composition comprises (a) at least one direct dye and (b) water;
the second composition comprises (c) at least one oil;
The composition in which (d) air bubbles are introduced is as follows:
Y/X ratio >20, preferably >50, more preferably >100(1)
(here,
Y indicates the yield stress (Pa) of the composition,
X indicates strain (%) at yield stress)
and mixing the first composition and the second composition to prepare a composition for dyeing keratin fibers.

The above description of the first and second compositions and the components therein for the method of dyeing keratinous fibers according to the invention also applies to the method of preparing the composition for dyeing keratinous fibers according to the invention. description can be applied.

The step of introducing air bubbles into at least one of the first composition and the second composition can be performed as described in the (Aeration) section above.

The method and means of mixing the first and second compositions are not limited. Any conventional method and means, such as a mixer or agitator, can be used to mix the first and second compositions.

A gas is mixed with a second composition adjusted to satisfy condition (1) above, bubbles are formed in the second composition, and then the second composition containing bubbles is mixed with the first composition. to form a composition comprising an oil phase and an aqueous phase for dyeing keratin fibers.

The oil used in the second composition, or the second composition itself used to form the oil phase of the composition for dyeing keratin fibers, is preferably aged. Aging may be performed by allowing the oil of the second composition to stand for a specified period of time, such as several days.

(form)
The mixture used in the method for dyeing keratin fibers according to the invention or the composition prepared by the method according to the invention is preferably in liquid form at 25° C. and atmospheric pressure (760 mmHg).

The mixture used in the method for dyeing keratin fibers or the composition prepared by the method according to the invention may be of any type such as W/O, O/W, W/O/W and O/W/O types. may be in the form of If the mixture used in the process for dyeing keratin fibers or the composition prepared by the process according to the invention is an emulsion, the emulsion may be W/O, O/W, W/O/W and O It may be in the form of a /W/O emulsion, preferably an O/W emulsion.

The mixture used in the method for dyeing keratin fibers or the composition prepared by the method according to the invention is of the O/W type, more preferably an O/W emulsion, even more preferably an O/W gel. It may be preferred to be in the form of an emulsion.

[use]
The composition prepared by the method according to the invention can be used as a cosmetic composition, preferably a hair cosmetic composition, more preferably a cosmetic composition for dyeing hair.

In particular, the composition prepared by the method according to the invention can be used for the direct dyeing of keratin fibers such as hair. The composition prepared by the method according to the invention cannot be used for oxidation dyeing of keratin fibres. Therefore, the compositions prepared by the method according to the invention cannot contain oxidation bases and/or couplers.

The present invention is also the use of (d) air bubbles in a composition for dyeing keratinous fibers, preferably hair, to prevent or reduce contamination of the skin or scalp during dyeing of keratinous fibers with the composition. hand,
The composition
(a) at least one direct dye, and (b) at least one aqueous phase comprising water, and
(c) at least one oil phase comprising at least one oil;
At least one of the aqueous phase and the oil phase has the following conditions (1):
Y/X ratio >20, preferably >50, more preferably >100(1)
(here,
Y indicates the yield stress of the phase (Pa),
X indicates strain (%) at yield stress)
and
(d) bubbles are present in the phase satisfying condition (1);
Regarding use.

The statements relating to (a) direct dye, (b) water, (c) oil, and (d) air bubbles for the method or kit according to the invention are applicable to the statements for use according to the invention.

The use according to the invention can also provide compositions with low viscosity and/or soft texture for dyeing keratin fibers. Therefore, the composition can also provide a good feel for use.

The invention will be explained in more detail by means of examples. However, these examples should not be construed as limiting the scope of the invention. The following examples are presented as non-limiting illustrations of the technical field of the invention.

(Example 1)
An aqueous formulation containing the ingredients shown in Table 1 for the aqueous phase of the composition according to Example 1 was prepared by mixing the ingredients shown in Table 1. All figures relating to the amounts of ingredients given in Table 1 are based on the "% by weight" of the active material given in the table.

An oleaginous formulation containing the ingredients shown in Table 2 for the oil phase of the composition according to Example 1 was prepared by mixing the ingredients shown in Table 2. All figures relating to the amounts of ingredients given in Table 2 are based on the "% by weight" of the active material given in the table.

The above oily formulation was aged for 2 days. 50 g of the oily formulation was then removed and placed in the Magenta blender and mixed with air for 3 minutes to aerate the oily formulation. After mixing, the aerated oily formulation was observed using an optical microscope and found to contain fine air bubbles less than 20 μm in diameter. Based on the density measurements of the oily formulation before and after aeration, the bubble volume was determined to be 15% by volume according to the following formula:

Air bubbles vol%=
[(Density of oily compound before aeration - Density of oily compound after aeration)/(Density of oily compound before aeration - Density of air*)] x 100
* Air Density: 0.0128g/ml

3 g of the aerated oily formulation and 7 g of the aqueous formulation were taken out and gradually mixed for 60 seconds using a spatula to prepare 10 g of the composition according to Example 1.

[Comparative example 1]
3 g of the unaerated unaerated oil-based formulation (see Table 2) and 7 g of the aqueous formulation were taken and slowly mixed for 60 seconds using a spatula to prepare 10 g of the composition according to Comparative Example 1.

(in vitro evaluation)
(color capture)
4 g each of the compositions according to Example 1 and Comparative Example 1 were applied to a 100% Chinese natural white hair mesh using a hair color brush at a temperature of 27°C. After application, the hair mesh was wrapped using polyethylene wrap and then the wrapped hair mesh was kept at 40° C. for 15 minutes. The wrap was then removed and the hair mesh was washed with water. The cleaned hair mesh was then washed with shampoo and again with water. The hair mesh was then wiped with a paper towel and left at 40°C for 30 minutes to dry. The color of the hair mesh before and after the above coloring method was measured using a colorimeter (Konica Minolta Spectrophotometer CM-3600d), and the difference (ΔE) in color (wavelength 360-740 nm) for Example 1 and Comparative Example 1 was calculated. Judged.

Table 3 shows the results.

(skin contamination)
0.05 ml each of the compositions according to Example 1 and Comparative Example 1 were placed in a 1 ml syringe, then the composition was applied as a 5 mm diameter circle onto Japanese forearm skin. After 30 minutes, the forearm was washed with running water, followed by shampooing and washing with water again. The forearm was dried using paper towels. Residual staining on the forearm was visually assessed according to a score of 1-5. Here 1 means very weak contamination and 5 means very high contamination.

Table 3 shows the results.

As shown in Table 3, skin staining was reduced by the presence of air bubbles in the oil phase in the composition according to Example 1. On the other hand, the presence of air bubbles did not affect the hair coloring.

(stickiness and texture)
A Texture Analyzer (TA.XT plus Texture Analyzer) was used under the following conditions to evaluate the texture of the compositions according to Example 1 and Comparative Example 1.

Probe: 5mmφ stainless steel Speed before test: 1mm/sec Speed after test: 1mm/sec Speed after test: 10mm/sec Test mode: Compression Target mode: Distance distance 5mm
Trigger force: 0.1g

A small droplet of each composition was placed on the surface of the analyzer and the probe was then immersed and then withdrawn from the composition under the test conditions described above. A graph was obtained between the force (mg) applied to the composition by the probe and the distance (mm) the probe moved into the composition. The graph was then analyzed to calculate the tensile force (mg) (which relates to viscosity) and compressive force (mg) (which relates to soft texture).

Table 4 shows the results.

As shown in Table 4, the introduction of air bubbles can impart a reduced viscosity and an increased soft texture to the composition according to Example 1 compared to the composition according to Comparative Example 1, thus the composition according to the invention. enhance the cosmetic properties of the product.

[In vivo evaluation]
(color capture)
40 g each of the compositions according to Example 1 and Comparative Example 1 were applied to half of the hair of a Japanese model using a hair color brush at a temperature of 27°C. After application, the applied hair was wrapped using polyethylene wrap and then the hair was kept at room temperature for 30 minutes. The wrap was then removed and the hair was washed with water. The washed hair was then washed with shampoo and washed again with water. The hair was then dried using a hair dryer. The color of the dyed hair was evaluated by visual check by comparing the dyed hair to the undyed hair.

Table 5 shows the results.

(scalp contamination)
0.05 ml each of the compositions according to Example 1 and Comparative Example 1 were placed in a 1 ml syringe, then the composition was applied as a 5 mm diameter circle onto the scalp of the Japanese model. After 30 minutes, the scalp was washed with running water, followed by shampooing and washing with water again. The scalp was dried using a hair dryer. Stain remaining on the scalp was visually assessed according to a score of 1-5. Here 1 means very weak contamination and 5 means very high contamination.

Table 5 shows the results.

As shown in Table 5, scalp staining was reduced by the presence of air bubbles in the oil phase in the composition according to Example 1. On the other hand, the presence of air bubbles did not significantly affect the hair coloring.

[Aeration tendency test]
An oleaginous formulation containing the ingredients shown in Table 6 for the oil phase of the composition according to the invention was prepared by mixing the ingredients shown in Table 6. All figures relating to the amounts of ingredients given in Table 6 are based on the "mass %" of the active material given in the table.

The above oily formulation was aged for 2 days. 50 g of the oily formulation was then removed and placed in the Magenta blender and mixed with air for 3 minutes to aerate the oily formulation. Rheological measurements were performed on the oily formulation thus obtained by using a rheometer, ARES RFS, TA instruments, under the following conditions.

Method: Strain sweep Strain %: 0.01 to 1000%
frequency 1Hz
Shape dimension: 40mm cone plate temperature: 25℃
Setting interval: 30 μm

The rheological measurements described above yielded initial curves for G′ (storage modulus) and G″ (loss modulus) versus strain (%). From these curves, the relationship between strain (%) versus shear stress (τ) A graph was obtained, showing the linear region (where the formulation behaves like a solid), the non-linear region (solid-to-liquid transition), and again the linear region (where the formulation behaves like a liquid). ).Two linear lines were extended from the two linear regions and intersected, and the intersection of these lines gave the yield stress (Pa) at a particular strain (%). The ratio of the two parameters (yield stress/strain %) was determined.

Immediately after mixing with the air, the oily formulation was visually observed using an optical microscope to see if it contained fine air bubbles. "Aeration" was rated as yes if fine air bubbles with an average size of 20 μm or less were observed and maintained at room temperature for 2 months. On the other hand, if it was not maintained at room temperature for 2 months, it was rated as "no aeration".

Table 7 shows the results.

The above tests were then also performed on the aqueous formulations shown in Table 1.

50 g of the aqueous formulation shown in Table 1 was taken and placed in the Magenta blender and mixed with air for 3 minutes to aerate the aqueous formulation, serving as Control 2. After mixing, the yield stress, strain and (yield stress/strain) ratio were determined as described above, and visual observations for the formation of dense, fine bubbles were also evaluated as described above.

Table 8 shows the results.

Formulations with a yield stress (Pa)/strain (%) ratio>100 showed a very high propensity to aerate. That is, they were aerated with bubbles having an average size of 20 μm or less (the amount of bubbles was determined to be between 15% and 20% by volume), and the bubbles were very stable (2 months at room temperature). while).

For formulations with a ratio greater than 50 (eg Example 4), cells with an average size <20 μm (having an amount between 15% and 20% by volume) were formed. If this ratio was less than 20, it was difficult to aerate the formulation.

From the above results, formulations with a high yield stress/strain ratio may have a higher tendency to withstand shear (solid-like behavior) and thus several types of shear (mixing, pumping, extrusion, frothing, It is understood that it is easy to create a bubble by applying battering, etc.) and then maintain it for a long period of time. On the other hand, formulations with a low yield stress/strain ratio may rupture (liquid-like behavior) even with very weak shear, thus such formulations can be used without the addition of any additional blowing agent. It is difficult to create air bubbles inside.

In the above studies, the yield stress/strain for the oil phase was primarily evaluated. However, it is clear that if the aqueous phase is adjusted to have a yield stress/strain greater than 20, preferably greater than 50, more preferably greater than 100, the aqueous phase can also be aerated and have stable, fine-bubbles. is.

Claims (12)

A method for dyeing keratin fibers comprising:
treating keratin fibers with a mixture of a first composition and a second composition;
said first composition comprises (a) at least one direct dye and (b) water;
said second composition comprises (c) 66% to 90% by weight, relative to the total weight of the second composition, of at least one hydrocarbon oil;
The second composition comprises (e) mono-, di- and triesters of behenic acid and glycerol, 12-hydroxystearin, from 5% to 15% by weight relative to the total weight of the second composition. at least one thickening agent selected from acids and mixtures thereof ;
wherein the second composition meets the following condition (1):
Y/X ratio >20 (1)
(here,
Y represents the yield stress (Pa) of the second composition,
X indicates strain (%) at yield stress)
and
(d) air bubbles are present in the second composition satisfying condition (1);
A method comprising steps. 2. The method of claim 1, wherein (d) the foam is stable such that greater than 85% by volume of the foam, relative to the total volume of the foam, is maintained at 25°C for 2 months. 3. The method of claim 1 or 2 , wherein (d) the bubbles comprise air. 4. A method according to any one of claims 1 to 3 , wherein (d) the cells have an average size of less than 20 [mu]m. 5. The method according to any one of claims 1 to 4 , wherein (d) the amount of air bubbles is from 1% to 30% by volume relative to the total volume of the second composition containing air bubbles. 6. The composition of claims 1 to 5 , wherein the amount of said first composition in said mixture of said first composition and said second composition is 40% to 90% by weight relative to the total weight of the mixture. A method according to any one of paragraphs. 7. The composition of claims 1 to 6 , wherein the amount of said second composition in said mixture of said first composition and said second composition is 10% to 50% by weight relative to the total weight of the mixture. A method according to any one of paragraphs. 8. Any one of claims 1 to 7 , wherein the amount of (b) water in the first composition is from 40% to 95% by weight relative to the total weight of the first composition. the method of. 9. The method of any one of claims 1-8 , wherein the first composition has a pH of 2-7. A kit for dyeing keratin fibers, comprising:
(1) a first compartment comprising a first composition; and
(2) comprising a second compartment comprising a second composition;
said first composition comprising (a) at least one direct dye and (b) water;
said second composition comprises (c) 66% to 90% by weight, relative to the total weight of the second composition, of at least one hydrocarbon oil;
The second composition comprises (e) mono-, di- and triesters of behenic acid and glycerol, 12-hydroxystearin, from 5% to 15% by weight relative to the total weight of the second composition. at least one thickening agent selected from acids and mixtures thereof ;
wherein the second composition meets the following condition (1):
Y/X ratio >20 (1)
(here,
Y represents the yield stress (Pa) of the second composition,
X indicates strain (%) at yield stress)
and
(d) air bubbles are present in the second composition satisfying condition (1);
kit. A method of preparing a composition for dyeing keratin fibers comprising:
(d) introducing air bubbles into the second composition ;
said second composition comprises (c) 66% to 90% by weight, relative to the total weight of the second composition, of at least one hydrocarbon oil;
The second composition comprises (e) mono-, di- and triesters of behenic acid and glycerol, 12-hydroxystearin, from 5% to 15% by weight relative to the total weight of the second composition. at least one thickening agent selected from acids and mixtures thereof ;
wherein the second composition meets the following condition (1):
Y/X ratio >20 (1)
(here,
Y represents the yield stress (Pa) of the second composition,
X indicates strain (%) at yield stress)
and a process satisfying
A method comprising mixing a first composition comprising (a) at least one direct dye and (b) water and said second composition to prepare a composition for dyeing keratin fibers. (d) the use of air bubbles in a composition for dyeing keratin fibers to prevent or reduce contamination of the skin or scalp during dyeing the keratin fibers with the composition, comprising:
the composition comprising:
(a) at least one direct dye; and (b) at least one aqueous phase comprising water;
and,
(c) 66% to 90% by weight, relative to the total weight of the oil phase, of at least one hydrocarbon oil , and
(e) 5% to 15% by weight, relative to the total weight of the oil phase, of at least one selected from mono-, di- and triesters of behenic acid and glycerol, 12-hydroxystearic acid, and mixtures thereof. at least one oil phase comprising one thickening agent , said oil phase comprising
The following mandatory requirements (1):
Y/X ratio >20 (1)
(here,
Y indicates the yield stress (Pa) of the oil phase,
X indicates strain (%) at yield stress)
and
(d) bubbles are present in the oil phase satisfying condition (1);
use.

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