JP2019011284A - Composition for dyeing keratin fiber - Google Patents

Abstract

To provide compositions for dyeing keratin fibers with a direct dye which can provide sufficient coloring properties while being able to prevent or reduce the skin pollution by the direct dye.SOLUTION: The present invention provides a composition comprising (a) at least one kind of direct dyes, and (b) a sulfolane compound represented by the following formula (I) (where, R, R, R, R, R, R, R, and Rindependently represent a hydrogen atom, a halogen atom, and the like, but all of R, R, R, R, R, R, R, and Rdo not represent hydrogen atoms).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composition for dyeing keratin fibers, in particular a composition for dyeing keratin fibers with at least one direct dye, and a method of using the same.

  Dyeing compositions containing oxidative coloring precursors commonly referred to as oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds, and keratin fibers, particularly human hair or eyelashes Is a known practice. These oxidation bases are generally combined with couplers. These bases and these couplers are colorless or lightly colored compounds that can be combined with oxidant products to provide colored compounds via an oxidative condensation process.

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

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

  For example, WO 2015/186813 discloses a composition for dyeing hair comprising a direct dye.

  Hair coloring using direct dyes has advantages over hair coloring using oxidative dyes. That is, it has no problem of allergies, no damage to the hair, and imparts vivid color visibility.

WO 2015/186813 WO 95/15144 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 Publication No. 2 830 189

Ullmann's Encyclopedia of Industrial Chemistry, 2004, 7th edition, Fluorescent Dyes chapter Ullmann's Encyclopedia of Industrial Chemistry (2002), `` Optical Brighteners '' Kirk-Othmer Encyclopedia of Chemical Technology (1995): `` Fluorescent Whitening Agents '' `` Industrial Dyes, Chemistry, Properties, Application '', edited by Klaus Hunger, 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, pages 14-39, 2001

  However, skin contamination has been an inevitable drawback of hair coloring using direct dyes.

  Accordingly, a composition for dyeing keratin fibers comprising at least one direct dye, which can prevent or reduce skin contamination by direct dyes on the skin, for example the scalp, while effectively coloring keratin fibers Is needed.

  One object of the present invention is to provide at least one direct dye which can prevent or reduce skin contamination by direct dyes on the skin, for example the scalp, while providing a good cosmetic effect to the keratin fibers, for example good coloring properties. Is to provide a composition for dyeing keratin fibers.

The above object of the present invention is to
(a) at least one direct dye, and
(b) The following formula (I)

(Where
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently
Hydrogen atom,
A halogen atom,
Refers to a monovalent substituted or unsubstituted C _{1 to 30} aliphatic group, or a monovalent substituted or unsubstituted C _{6 to 30} aromatic radical,
(However, all of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ do not mean hydrogen atoms)
It can be achieved by a composition for dyeing keratin fibers comprising at least one sulfolane compound represented by:

  (a) The direct dye may be selected from the group consisting of an acid direct dye, a basic direct dye and a neutral direct dye, preferably an acid direct dye.

  (a) The direct dye can be selected from the group consisting of diaryl anionic azo dyes, anthraquinone dyes, quinoline based dyes, and mixtures thereof.

  The amount of (a) direct dye in the composition according to the invention is from 0.001% to 5% by weight, preferably from 0.01% to 3% by weight, more preferably from 0.05% to 2%, based on the total weight of the composition. It may be in the range of mass%.

In the above formula (I), the monovalent substituted or unsubstituted C _1-30 aliphatic group is
Saturated monovalent substituted or unsubstituted C _{1 to 30} aliphatic hydrocarbon group, preferably a substituted or unsubstituted C _{1 to 30} alkyl group linear or branched, or substituted or unsubstituted C _{3 to 30} cycloalkyl It may be an alkyl group or an unsaturated, monovalent substituted or unsubstituted C _2-30 aliphatic hydrocarbon group.

In Ueno formula (I), the substituted or unsubstituted C _{6 to 30} aromatic groups monovalent, monovalent substituted or unsubstituted C _{6 to 30} aromatic hydrocarbon group, preferably a substituted or unsubstituted _{C. 6 to It} may be a ₃₀ aryl group, or a linear or branched substituted or unsubstituted C _7-30 aralkyl group.

  (b) The sulfolane compound is 2-methyl sulfolane, 3-methyl sulfolane, 2-ethyl sulfolane, 3-ethyl sulfolane, 2,3-dimethyl sulfolane, 2,4-dimethyl sulfolane, 2,5-dimethyl sulfolane, 3, The group consisting of 4-dimethyl sulfolane, 2,3-diethyl sulfolane, 2,4-diethyl sulfolane, 2,5-diethyl sulfolane, 3,4-diethyl sulfolane, 2-phenyl sulfolane, 3-phenyl sulfolane, and mixtures thereof You can choose from.

  The amount of the (b) sulfolane compound in the composition according to the present invention is 0.5% to 30% by weight, preferably 1% to 20% by weight, more preferably 2% to 15% by weight relative to the total weight of the composition. It may be in the range of mass%.

  The composition according to the present invention may further contain water.

  The pH of the composition according to the invention may range from 2 to 7, preferably from 2 to 6, more preferably from 2 to 4.

  The composition according to the invention may further comprise (c) at least one buffer, preferably an amino acid, an amino acid derivative, or a combination of organic or inorganic acids and their salts.

  The amount of the (c) buffer in the composition according to the present invention is 0.1% to 15% by weight, preferably 0.5% to 10% by weight, more preferably 0.5 to 5% by weight, based on the total weight of the composition. It may be a range.

  The invention also relates to a method for dyeing keratin fibers comprising the step of applying a composition according to the invention to keratin fibers.

It is a graph which shows the change of the color of hair at the time of using the composition of Example 1 and Comparative Examples 1-5, and the change of the color of skin.

  In addition, from the standpoint of ease of use, compositions for dyeing hair are ready for use and therefore it is necessary to mix two or more parts of the composition when coloring hair with the composition A so-called one-component composition is preferred.

  As a result of intensive studies, the inventors have included at least one direct dye, which can prevent or reduce skin contamination by direct dye on the skin, such as the scalp, while having good cosmetic effects on keratin fibers, such as It has been found that it is possible to provide a composition for dyeing keratin fibers, preferably a one-part composition, which can provide good coloring properties.

The composition according to the invention is therefore intended to dye keratin fibers,
(a) at least one direct dye, and
(b) The following formula (I)

(Where
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently
Hydrogen atom,
A halogen atom,
Refers to a monovalent substituted or unsubstituted C _{1 to 30} aliphatic group, or a monovalent substituted or unsubstituted C _{6 to 30} aromatic radical,
(However, all of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ do not mean hydrogen atoms)
At least one sulfolane compound represented by:

  The composition according to the invention is preferably a so-called one-part composition that is ready for use and therefore does not require mixing two or more parts of the composition when coloring hair with the composition. .

  Hereinafter, the composition according to the present invention will be described in detail.

[Direct dye]
The composition according to the invention comprises (a) 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 dyes can be used.

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

  The direct dye may be a natural direct dye or a synthetic direct dye.

  The expression “natural direct dye” refers to any naturally occurring and optionally produced by extraction (optionally purified) from animals such as plant substrates or insects in the presence of natural compounds such as ash or ammonia. Is understood to mean a dye or a dye precursor.

  Natural direct dyes include quinone dyes (e.g., Lawson and juglone), alizarin, purpurin, lacaic acid, carminic acid, kermesic acid, purprogaline, protocatechualdehyde, indigoids such as indigo, sorghum, isatin, betanin, curcuminoids (e.g. curcumin), Spinulosin, various types of chlorophyll and chlorophyllin, hematoxylin, hematein, brazilein, brazirine, safflower dyes (e.g., cartamine), flavonoids (e.g., rutin, quercetin, catechin, epicatechin, morin, apigenidin, and sandalwood), anthocyan (e.g., apigeninidine) And apigenin), carotenoids, tannins, orcein, Santarin and cochineal carmine.

  Extracts or exudates containing natural direct dyes, especially henna-based extracts, curcuma longa extracts, sorghum leaf sheath extracts, haematoxylon campechianum extracts, green tea extracts, pine bark extracts, cocoa extracts It is also possible to use logwood extracts.

  Natural direct dyes include curcuminoid, santaline, chlorophyllin, hematoxylin, hematein, brazilein, brazirine, sorghum, lacqueric acid, lawson, juglone, alizarin, purpurin, carminic acid, kermesic acid, pulprogaline, protocatechaldehyde, indigoid, isatin, spinulosin, Preferably selected from the group consisting of apigenin, orcein, betanin, flavonoids, anthocyan, and extracts or leachates containing these compounds.

  Alternatively, the natural direct dye may preferably be selected from, for example, hydroxylated quinones, indigoids, hydroxyflavones, santalines A and B, isatin and its derivatives, and brazirin and its hydroxylated derivatives.

  The hydroxylated quinone is preferably benzoquinone, naphthoquinone, and mono- or polyhydroxylated anthraquinone, which are optionally substituted with groups such as alkyl, alkoxy, alkenyl, chloro, phenyl, hydroxyalkyl and carboxyl. Yes.

  Naphthoquinone is preferably Lawson, juglone, flaviolin, naphthazarin, naphthopurine, rapacol, plumbagin, chloroplumbagin, droselone, 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 spinulosin, atromentin, aurentioglyocladin, 2,5-dihydroxy-6-methylbenzoquinone, 2-hydroxy-3-methyl-6-methoxybenzoquinone, 2,5-dihydroxy-3 1,6-diphenylbenzoquinone, 2,3-dimethyl-5-hydroxy-6-methoxybenzoquinone and 2,5-dihydroxy-6-isopropylbenzoquinone.

  Anthraquinone is preferably alizarin, quinizarin, purpurin, carminic acid, chrysophanol, kermesic acid, rhein, aloe emodin, pseudopurpurin, quinizarin carboxylic acid, frangulaemodin, 2-methylquinizarin, 1- Hydroxyanthraquinone and 2-hydroxyanthraquinone.

  Indigoids are preferably indigo, indirubin, isoindigo and Tyrian 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.

  The direct dye may be selected from the group consisting of acidic (anionic) direct dyes, basic (cationic) direct dyes and neutral (nonionic) direct dyes.

  Non-limiting examples of synthetic dyes include (nonionic) neutral, anionic (acidic), and cationic (basic) dyes such as azo, methine, carbonyl, azine, nitro (hetero) aryl types Or tri (hetero) arylmethane direct dyes, porphyrins and phthalocyanines are included alone or as a mixture.

  More specifically, the azo dye contains a —N═N-functional group, and the two nitrogen atoms of this functional group do not participate simultaneously in the ring. However, it is not excluded that one of the two nitrogen atoms of the -N = N-sequence is involved in the ring.

  More specifically, methine family dyes are compounds comprising at least one sequence selected from> C = C <and -N = C <, wherein two atoms of these sequences are simultaneously in the ring. Is not involved. However, it is specified that one of these sequences of nitrogen or carbon atoms can participate in the ring. More specifically, this family of dyes is derived from the following types of compounds: Pure methine (comprising one or more of the above-mentioned -C = C- sequences); azomethine (comprising at least one or more of the sequences -C = N-), e.g. azacarbocyanine and their isomerism , Diazacarbocyanines and their isomers, tetraazacarbocyanines; mono- and diarylmethanes, indoamines (or diphenylamines), indophenols, indoanilines.

  Concerning carbonyl family dyes, for example, acridone, benzoquinone, anthraquinone, naphthoquinone, benzoanthrone, anthrone, pyrantron, pyrazole anthrone, pyrimidinoanthrone, flavantron, indanthrone, flavone, (iso) violanthrone, isoindolinone And synthetic dyes selected from benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole or coumarin dyes.

  With respect to the dyes of the cyclic azine family, mention may be made in particular of azine, xanthene, thioxanthene, fluoridine, acridine, (di) oxazine, (di) thiazine or pyronin dyes.

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

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

  Examples of particularly suitable synthetic direct dyes include nitrobenzene dyes, azo, azomethine or methine direct dyes, azacarbocyanines such as tetraazacarbocyanine (tetraazapentamethine), quinones, especially anthraquinone, naphthoquinone or benzoquinone direct dyes, or azine , Xanthene, triarylmethane, indoamine, phthalocyanine and porphyrin direct dyes may be mentioned alone or as a mixture. Even more preferably, these synthetic direct dyes are selected from nitrobenzene dyes, azo, azomethine or methine direct dyes and tetraazacarbocyanine (tetraazapentamethine), alone or as a mixture.

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

  Therefore, the following formula

In particular, the direct cationic dyes corresponding to
D represents a nitrogen atom or a -CH group,
R ₁ and R ₂ are the same or different and can be substituted with a hydrogen atom; a —CN, —OH, or —NH ₂ group, or optionally contain oxygen or nitrogen, and include one or more C ₁ -C a heterocycle may be substituted with _alkyl groups may form together with the carbon atoms of the benzene ring, C ₁ -C ₄ alkyl group; represents or 4'-aminophenyl group,
R ₃ and R ′ ₃ are the same or different and are a halogen atom selected from a hydrogen atom, chlorine, bromine, iodine and fluorine, a cyano group, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ Represents an alkoxy group or an acetyloxy group,
X ⁻ represents an anion preferably selected from chloride, methyl sulfate and acetate,
A is the following structure

A group selected from
Wherein R ₄ represents a C ₁ -C ₄ alkyl group that can be substituted with a hydroxyl group;

Where
R ₅ represents a hydrogen atom, a C ₁ -C ₄ alkoxy group or a halogen atom, for example, bromine, chlorine, iodine or fluorine,
R ₆ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, or optionally contains oxygen and / or is optionally substituted with one or more C ₁ -C ₄ alkyl groups Together with the carbon atom of the benzene ring,
R ₇ 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, methyl sulfate and acetate;
E is the following structure

Represents a group selected from
Wherein R ′ represents a C ₁ -C ₄ alkyl group,
When m = 0 and D ₁ represents a nitrogen atom, E is also of the structure

Or a group having
In the formula, R ′ represents a C ₁ -C ₄ alkyl group.

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

  The use of some fluorescent dyes may make it possible to obtain more visible colors on dark hair than with conventional hydrophilic or hydrophobic direct dyes. In addition, these fluorescent dyes also allow hair thinning without damage when applied to dark hair.

  As used herein, the term “fluorescent dye” is understood to mean a fluorescent compound and an optical brightener. In at least one embodiment, the fluorescent dye is soluble in the medium of the composition.

  Fluorescent dyes are fluorescent compounds that absorb visible light, for example wavelengths in the range of 400 to 800 nm, and can re-emit light in the higher wavelength visible region.

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

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

  The optical brighteners of the present disclosure are also “brighteners”, or “fluorescent brighteners”, or “fluorescent brightening agents” or “FWA”, or “fluorescent brighteners”. The compounds are known as “whitening agents”, or “whitening agents” or “fluorescent whiteners”. Because they do not absorb visible light, they only absorb ultraviolet light (wavelengths in the range of 200 to 400 nanometers) and absorb the absorbed energy in the visible part of the spectrum, generally blue and / or green, i.e. 400 to 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, 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 compositions of the present disclosure include compounds known from the art, such as those described in FR 2 830 189.

  In particular, the soluble fluorescent compounds mentioned include those belonging to the following families: That is, naphthalimide, coumarin, xanthene, particularly xanthenodiquinolidine and azaxanthene, naphthactam, azlactone, oxazine, thiazine, dioxazine, azo compound, azomethine, methine, pyrazine, stilbene, ketopyrrole, and pyrene.

  When present, fluorescent dyes are preferred, and more specifically those that re-emit orange fluorescence.

  In terms of ionic properties, (a) the direct dye may be selected from the group consisting of acid direct dyes, basic direct dyes and neutral direct dyes, which are all types of direct dyes, for example so-called nitro dyes and Includes 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 (a) the direct dye is selected from acidic direct dyes.

  Anionic direct dyes are generally known as “acid direct dyes” because of their affinity with alkaline substances (for example, “Industrial Dyes, Chemistry, Properties, Application”, edited by Klaus Hunger, Wiley-VCH Verlag (See 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, pages 14-39, (See 2001).

The term "anionic direct dye", at least one sulfonic acid group SO ₃ and / or at least one carboxylic acid group C (O) O and / or at least one phosphonic acid group P in its structure (= O) O ^- O and optionally one or in more anionic groups G ^- means any direct dyes including, G, which may be the same or different and alkoxides O, thioalkoxide S, phosphonates , Carboxylate and thiocarboxylate: represents an anionic group selected from C (Q) Q ′, Q and Q ′ may be the same or different and each represents an oxygen or sulfur atom, preferably G represents a carboxylate salt, that is, Q and Q ′ represent an oxygen atom.

Preferred anionic dyes of the formulations of the present invention include 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 Selected from dyes, each of these dyes containing at least one sulfonic, phosphonic or carboxylic acid group with a cationic counter ion 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 the 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 a hydrogen atom or
-Alkyl,
-Alkoxy, alkylthio,
-Hydroxyl, mercapto,
-Nitro,
-R ° -C (X) -X'-, R ° -X'-C (X)-, R ° -X'-C (X) -X ''-(R ° is a hydrogen atom or alkyl or Represents an aryl group, X, X ′ and X ″ may be the same or different and each represents an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group),
-(O) ₂ S (O ^- )-, X ⁺ , as defined above
- previously defined ^{(O) CO - -, X} +,
-(O) P (O ₂ ^- )-, 2X ⁺ , defined above,
-R ''-S (O) _2- (R '' represents a hydrogen atom or an alkyl, aryl, (di) (alkyl) amino or aryl (alkyl) amino group, preferably phenylamino or a phenyl group),
-R '''-S (O) _2- X'- (R''' represents an alkyl or optionally substituted aryl group, X 'is as defined above),
-(Di) (alkyl) amino,
optionally substituted with one or more groups selected from i) nitro, ii) nitroso, iii) (O) ₂ S (O ⁻ ) —, X ⁺ , and iv) alkoxy with X ⁺ Aryl (alkyl) amino,
An optionally substituted heteroaryl, preferably a benzothiazolyl group,
-Cycloalkyl, especially cyclohexyl,
-Ar-N = N- (Ar is an optionally substituted aryl group, preferably one or more alkyl, (O) ₂ S (O ^- )-, X ⁺ or phenylamino groups Represents phenyl which is optionally substituted),
Or alternatively two consecutive groups R ₇ and R ₈ , or R ₈ and R ₉ , or R ₉ and R ₁₀ together form a condensed benzo group A ′, R ′ ₇ and R ′ ₈ , or R ′ ₈ and R ′ ₉ or R ′ ₉ and R ′ ₁₀ together form a condensed benzo group B ′, and A ′ and B ′ are i) nitro, ii) nitroso, iii) (O) ₂ S (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 selected from aryl (alkyl) amino Optionally substituted with one or more groups, X ⁺ , R °, X, X ′, X ″ and Ar are as previously defined;
Represents a group selected from
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 )- R _a and R _{b, which} may be the same or different, each represents a hydrogen atom or an aryl group, or R _a and R _b together with the carbon atom having them form a spirocycloalkyl. Preferably W represents a sulfur atom or R _a and R _b together form cyclohexyl;
Formulas (II) and (II ′) are those wherein at least one sulfonic acid (O) ₂ S (O ⁻ ) —, X ⁺ or phosphonic acid (O) P (O ₂ ⁻ ) 2X ⁺ or carboxylic acid (O) C It is understood that (O ⁻ ) —, X ⁺ group is included in one of the rings A, A ′, B, B ′ or C, where X ⁺ is as defined above
Examples of dyes of formula (II) include 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 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, and Pigment Red 57 are listed.
Examples of dyes of formula (II ′) include Acid Red 111, Acid Red 134, Acid yellow 38];
b) Anthraquinone dyes of the 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 a hydrogen atom or a halogen atom or
-Alkyl,
-Hydroxyl, mercapto,
-Alkoxy, alkylthio,
-Optionally substituted, preferably aryloxy or arylthio (X + is substituted with one or more groups selected from alkyl and (O) ₂ S (O-)-, X + Defined as above),
Aryl (alkyl) amino (X ⁺ is as defined above) optionally substituted with one or more groups selected from alkyl and (O) ₂ S (O ⁻ ) —, X ⁺ is there),
-(Di) (alkyl) amino,
-(Di) (hydroxyalkyl) amino,
-(O) ₂ S (O ^- )-, X ⁺ (where X ⁺ is as defined above),
Represents a group selected from
Z ′ represents a hydrogen atom or an NR ₂₈ R ₂₉ group, and R ₂₈ and R ₂₉ may be the same or different, a hydrogen atom or
-Alkyl,
-Polyhydroxyalkyl, for example hydroxyethyl,
-One or more groups, in particular i) alkyl, for example methyl, n-dodecyl, n-butyl, ii) (O) ₂ S (O ⁻ ) —, X ⁺ (X ⁺ is as defined above) Iii) R ° -C (X) -X'-, R ° -X'-C (X)-, R ° -X'-C (X) -X ''- Substituted aryl (R °, X, X ′ and X ″ are as defined above, preferably R ° represents an alkyl group),
-Cycloalkyl, especially cyclohexyl,
Represents a group selected from
Z represents a group selected from hydroxyl and NR ′ ₂₈ R ′ ₂₉ , R ′ ₂₈ and R ′ ₂₉ may be the same or different, and R ₂₈ and R _{29 as} defined above Represents the same atom or group as
It is understood that formulas (III) and (III ′) contain at least one sulfonic acid group (O) ₂ S (O ⁻ ) —, X ⁺ , where X ⁺ is as previously defined,
Examples of dyes of formula (III) include 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,
Examples of formula (III ′) include Acid Black 48]; and
g) Quinoline-based dyes of formula (IV)

[In the 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 a (O) ₂ S (O ⁻ ) —, X ⁺ group, where X ⁺ is as defined above And
Or alternatively, 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. , X ⁺ is as defined previously,
G represents an oxygen or sulfur atom or an NR _e group, R _e represents a hydrogen atom or an alkyl group, in particular G represents an oxygen atom,
It is understood that formula (IV) comprises at least one sulfonic acid group (O) ₂ S (O ⁻ ) −, X ⁺ , where X ⁺ is as previously defined,
Examples of formula (IV) include Acid Yellow 2, Acid Yellow 3, and Acid Yellow 5.

  The acid direct dye is preferably selected from the group consisting of Yellow 5, Orange 4, EXT. Violet 2, Acid Black 1 and Acid Violet 43 (CI 60730).

  The composition according to the present invention may contain (a) a direct dye in an amount of 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the composition. .

  The composition according to the present invention may contain (a) a direct dye in an amount of 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, based on the total mass of the composition. .

  The composition according to the present invention comprises (a) a direct dye, 0.001% to 5% by weight, preferably 0.01% to 3% by weight, more preferably 0.05% to 2% by weight, based on the total weight of the composition. It may be contained in an amount of%.

[Sulfolane compound]
The composition according to the invention comprises (b) at least one specific sulfolane compound. Two or more specific sulfolane compounds can be used in combination. Thus, a single type of specific sulfolane compound or a combination of different types of sulfolane compounds can be used.

  The (b) sulfolane compound used in the present invention has the following formula (I)

(Where
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently
Hydrogen atom,
A halogen atom,
Refers to a monovalent substituted or unsubstituted C _{1 to 30} aliphatic group, or a monovalent substituted or unsubstituted C _{6 to 30} aromatic radical,
(However, all of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ do not mean hydrogen atoms)
Can be represented by

  In the above formula (I), the halogen atom may be a fluorine, chlorine, bromine or iodine atom.

In Ueno formula (I), the monovalent substituted or unsubstituted C _{1 to 30,} preferably C _{1 to 20,} more preferably C _{1 to 10} aliphatic group,
Substituted or unsubstituted C _{1 to 30} monovalent saturated, preferably C _{1 to 20,} more preferably C _{1 to 10} aliphatic hydrocarbon radical, preferably a linear or branched substituted or unsubstituted C _1-30, preferably C _{1 to 20,} more preferably C _{1 to 10} alkyl group, or a substituted or unsubstituted C _{3 to 30,} preferably C _{4 to 20,} more preferably C _{5 to 10} cycloalkyl group, or It may be an unsaturated, monovalent substituted or unsubstituted _C2-30 , preferably _C2-20 , more preferably a _C2-10 aliphatic hydrocarbon group.

Examples of linear or branched C _1-30 , preferably C _1-20 , more preferably C _1-10 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl. , Isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

_{Examples of} C _3-30 , preferably C _4-20 , more preferably C _5-10 cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Can be mentioned.

As examples of unsaturated monovalent C _2-30 , preferably C _2-20 , more preferably C _2-10 aliphatic hydrocarbon groups, linear or branched C _2-30 , preferably C _2-20 , more preferably C _{2 to 10} alkenyl group include a vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl, 2-butenyl, pentenyl, hexenyl and the like, C _{2 to 30} , Preferably C _2-20 , more preferably C _2-10 cycloalkenyl groups such as cyclopentenyl group, cyclohexenyl group and the like.

In the above formula (I), the monovalent substituted or unsubstituted _C6-30 , preferably _C6-20 , more preferably _C6-10 aromatic groups are monovalent substituted or unsubstituted _C6-30. It may be a C _6-20 , more preferably a C _6-10 aromatic hydrocarbon group. The term “aromatic group” as used herein means a group comprising at least one aromatic moiety. Thus, monovalent substituted or unsubstituted C _6-30 , preferably C _6-20 , more preferably C _6-10 aromatic groups are substituted or unsubstituted C _6-30 , preferably C _6-20 , more Preferably it may be a _C6-10 aryl group, or a linear or branched substituted or unsubstituted _C7-30 , preferably _C7-20 , more preferably a _C7-10 aralkyl group.

Examples of C _6-30 , preferably C _6-20 , more preferably C _6-10 aryl groups include phenyl, tolyl, xylyl, mesityl and the like.

Examples of linear or branched C _7-30 , preferably C _7-20 , more preferably C _7-10 aralkyl groups include benzyl and phenethyl groups.

Monovalent _C1-30 , preferably _C1-20 , more preferably _C1-10 aliphatic groups or monovalent _C6-30 , preferably _C6-20 , more preferably _C6-10 aromatic examples of existing optionally be substituent on group, monovalent functional groups such as halogen atom (fluorine, chlorine, bromine or iodine atom), a hydroxyl group, C ₁ -C ₆ alkoxy group, an amino group, C ₁ -C ₆ alkylamino group, C ₁ -C ₆ dialkylamino group, nitro group, carbonyl group, acyl group, carboxyl group, cyano group and the like can be mentioned.

Substituted or unsubstituted C _{1 to 30} monovalent, preferably C _{1 to 20,} more preferably a substituted or unsubstituted C _{6 to 30} of C1~10 aliphatic group or a monovalent, preferably C _{having 6 to 20,} more preferably The C _6-10 aromatic group optionally contains at least one heteroatom selected from the group consisting of oxygen, nitrogen and sulfur atoms in the above substituent or the hydrocarbon main chain of the group. It may be.

  Specific examples of the (b) sulfolane compound used in the present invention include 2-methyl sulfolane, 3-methyl sulfolane, 2-ethyl sulfolane, 3-ethyl sulfolane, 2,3-dimethyl sulfolane, 2,4-dimethyl. Sulfolane, 2,5-dimethylsulfolane, 3,4-dimethylsulfolane, 2,3-diethylsulfolane, 2,4-diethylsulfolane, 2,5-diethylsulfolane, 3,4-diethylsulfolane, 2-phenylsulfolane, 3 -Phenyl sulfolane, 2,3-diphenyl sulfolane, 2,4-diphenyl sulfolane, 2,5-diphenyl sulfolane, 3,4-diphenyl sulfolane, 2-fluorosulfolane, 3-fluorosulfolane, 2,3-difluorosulfolane, 2 , 4-difluorosulfolane, 2,5-difluorosulfolane, 3,4-difluorosulfolane, 2-vinylsulfolane, 3-vinylsulfolane, 2,3-divinylsulfolane (2,3-d ivinylsulflane), 2,4-divinyl sulfolane, 2,5-divinyl sulfolane, 3,4-divinyl sulfolane, 2-allyl sulfolane, 3-allyl sulfolane, 2,3-diallyl sulfolane, 2,4-diallyl sulfolane, 2, 5-diallyl sulfolane, 3,4-diallyl sulfolane, 2-methoxy sulfolane, 3-methoxy sulfolane, 2,3-dimethoxy sulfolane, 2,4-dimethoxy sulfolane, 2,5-dimethoxy sulfolane, 3,4-dimethoxy sulfolane, Examples include 2-ethoxysulfolane, 3-ethoxysulfolane, 2,3-diethoxysulfolane, 2,4-diethoxysulfolane, 2,5-diethoxysulfolane, and 3,4-diethoxysulfolane.

  (b) The sulfolane compound is 2-methyl sulfolane, 3-methyl sulfolane, 2-ethyl sulfolane, 3-ethyl sulfolane, 2,3-dimethyl sulfolane, 2,4-dimethyl sulfolane, 2,5-dimethyl sulfolane, 3, The group consisting of 4-dimethyl sulfolane, 2,3-diethyl sulfolane, 2,4-diethyl sulfolane, 2,5-diethyl sulfolane, 3,4-diethyl sulfolane, 2-phenyl sulfolane, 3-phenyl sulfolane, and mixtures thereof Is preferably selected from.

  (b) The sulfolane compound is more preferably selected from the group consisting of 2-methylsulfolane, 3-methylsulfolane, 2-ethylsulfolane, 3-ethylsulfolane, and mixtures thereof.

  More preferably, the (b) sulfolane compound is selected from the group consisting of 2-methylsulfolane, 3-methylsulfolane, and mixtures thereof.

It should be noted that the (b) sulfolane compound described in formula (I) cannot be sulfolane. This is because not all of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ in formula (I) represent a hydrogen atom [in other words, the formula ( In I), at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is not a hydrogen atom.

  (b) The sulfolane compound is preferably in liquid form at a temperature in the range of 0 to 70 ° C., preferably 10 to 50 ° C., more preferably 20 to 40 ° C., even more preferably at room temperature (25 ° C.). .

  Since the composition according to the present invention contains (b) a sulfolane compound, (a) skin contamination by direct dye on the skin such as the scalp can be prevented or reduced, while keratin fibers can be effectively colored.

  The amount of the (b) sulfolane compound in the composition according to the present invention may be 0.5% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more based on the total mass of the composition.

  The amount of the (b) sulfolane compound in the composition according to the present invention may be 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, with respect to the total mass of the composition.

  The amount of the (b) sulfolane compound in the composition according to the present invention is in the range of 0.5 to 30% by weight, preferably 1 to 20% by weight, more preferably 2 to 15% by weight, based on the total weight of the composition. May be.

[water]
The composition according to the present invention may further contain water.

  The amount of water in the composition according to the invention is in the range from 10% to 90% by weight, preferably from 20% to 85% by weight, more preferably from 30 to 80% by weight, based on the total weight of the composition. May be. The pH of the composition according to the invention in this case may be in the range 2 to 7, preferably 2 to 6, more preferably 2 to 4.

[Buffer]
The composition according to the invention preferably further comprises (c) at least one buffer. Two or more buffering agents can be used in combination. Thus, a single type of buffer or a combination of different types of buffers can be used.

  The buffer can stabilize the pH of the composition according to the invention.

  The buffer is preferably an amino acid, an amino acid derivative, or a combination of an organic acid or inorganic acid and a salt thereof, more preferably an amino acid and an amino acid derivative, and even more preferably an amino acid.

  The amino acids that can be used are of natural or synthetic origin in L, D or racemic form and contain at least one acid functional group selected from carboxylic acid, sulfonic acid, phosphonic acid and phosphoric acid functional groups. Amino acids may be in their neutral or ionic form.

  Amino acids include, but are not limited to, glycine, aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, lysine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine , Proline, serine, taurine, threonine, tryptophan, tyrosine and valine. Glycine is more preferred. This is because glycine can also function to reduce skin contamination.

  Examples of organic acids include lactic acid, citric acid and malic acid.

  Examples of salts include alkali metal salts such as sodium salts, potassium salts, alkaline earth metal salts such as calcium salts, and ammonium salts.

  The amount of (c) buffer in the composition according to the invention is in the range of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 0.5 to 5% by weight, relative to the total weight of the composition. May be.

[Other ingredients]
The pH of the composition according to the invention may be adjusted to the desired value using acidifying or basifying agents commonly used in dyeing keratin fibers, or using conventional buffer systems. .

  Among the acidifying agents, examples include 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, examples include ammonium hydroxide, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamine and their derivatives, sodium hydroxide and potassium hydroxide and the following formulae

In the formula:
R is an alkylene, for example represents a propylene hydroxyl or C ₁ -C ₄ alkyl group are optionally substituted, R _1, R _2, R ₃ and R ₄ are independently hydrogen atom, an alkyl group or a C It represents ₁ -C ₄ hydroxyalkyl groups, which may be exemplified by 1,3-propane diamine and derivatives thereof. Sodium hydroxide or potassium hydroxide is preferred. This is also because it can function in situ to form the buffer (c).

  The acidifying agent or basifying agent is present in an amount ranging from 0.0001 to 15% by weight, preferably from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight, based on the total weight of the composition. Also good.

  The composition according to the invention may comprise at least one thickener.

The thickener may be selected from organic and inorganic thickeners. Organic thickener
(i) associative thickener,
(ii) cross-linked acrylic acid homopolymer,
(iii) (meth) acrylic acid and acrylic acid (C ₁ -C ₆₎ crosslinked copolymers of alkyl,
(iv) nonionic homopolymers and copolymers comprising at least one of an ethylenically unsaturated ester monomer and an ethylenically unsaturated amide monomer;
(v) ammonium acrylate homopolymer and copolymer of ammonium acrylate and acrylamide,
(vi) polysaccharides such as cellulose and its derivatives, and
(vii) C ₁₂ ~C ₃₀ fatty alcohols,
May be selected from at least one of them.

  The thickener is preferably selected from polysaccharides such as starch, xanthan gum, and hydroxyethylcellulose.

As used herein, the expression “associative thickener” includes both hydrophilic and hydrophobic units, for example, at least one C ₈ -C ₃₀ fatty chain and at least one hydrophilic unit. Including amphiphilic thickener.

The viscosity of the composition according to the present invention is not particularly limited. Viscosity can be measured at 25 ° C. with a viscometer or rheometer, preferably with a conical plate geometry. Preferably, the viscosity of the composition according to the invention may range from 1 to 2000 Pa.s, preferably from 1 to 1000 Pa.s, for example at 25 ° C. and 1 s ⁻¹ .

  The thickener may be present in an amount ranging from 0.001 to 10% by weight, preferably from 0.01 to 10% by weight, for example from 0.1 to 5% by weight, based on the total weight of the composition.

  The composition according to the invention also comprises various adjuvants conventionally used in compositions for dyeing hair, such as anionic, nonionic, cationic, amphoteric or zwitterionic polymers or their It may contain a mixture, an antioxidant, a penetrating agent, a sequestering agent, a fragrance, a dispersant, a regulator, a film-forming agent, a ceramide, a preservative and an opacifier.

  The form of the composition according to the present invention is not particularly limited as long as it is water-based, and may take various forms such as an emulsion, an aqueous gel, and an aqueous solution.

  The composition according to the present invention is a composition for dyeing keratin fibers, preferably a cosmetic composition for dyeing keratin fibers. “Keratin fiber” as used herein means a fiber comprising at least one keratin material. It is preferable that at least a part of the surface of the keratin fiber is formed of keratin fibers. Examples of keratin fibers include hair, eyebrows, eyelashes and the like. The composition according to the invention is preferably used for dyeing hair.

[Preparation]
The composition according to the invention comprises (a) at least one direct dye and (b) at least one sulfolane compound according to formula (I) above as essential components mixed with the optional components described above. Can be prepared.

  The methods and means for mixing the above essential and optional ingredients are not limited. Any conventional methods and means can be used for mixing the above essential and optional ingredients to prepare the composition according to the invention.

  The composition according to the invention is preferably a so-called one-part composition or a ready-to-use composition. For the purposes of the present invention, the expression “ready-to-use composition” is defined herein as a composition that is readily applied to keratin fibers such as hair.

  Compared to so-called two-part compositions, so-called one-part compositions do not require mixing the components in the composition before use. Therefore, it is easy for consumers to use the composition according to the invention for dyeing keratin fibers. Furthermore, the stable coloring of keratin fibers is possible for the composition according to the invention because the mixing of the components at the exact mixing ratio required for a two-part composition for dyeing keratin fibers fails. It is impossible.

[Method]
The invention also relates to a method for dyeing keratin fibers comprising the step of applying a composition according to the invention to keratin fibers.

  The step of applying the composition according to the invention to the keratin fibers can be carried out with a conventional application device, for example with a brush or also by hand.

  The keratin fibers to which the composition according to the invention has been applied can be left for the appropriate time needed to treat the keratin fibers. The length of time for treatment is not limited, but may 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 may be 1 to 20 minutes, preferably 5 to 15 minutes.

  Keratin fibers may be treated at room temperature. Alternatively, the keratin fibers may be used at 25 to 65 ° C., preferably 30 during the step of applying the composition according to the invention to the keratin fibers and / or leaving the keratin fibers to which the composition according to the invention is applied. C. to 60.degree. C., more preferably 35.degree. C. to 55.degree. C., even more preferably 40.degree.

  The keratin fibers may be rinsed after the step of applying the composition according to the present invention to keratin fibers and / or after leaving the keratin fibers to which the composition according to the present invention is applied.

  The invention may also relate to the use of the composition according to the invention for dyeing keratin fibers such as hair.

[use]
The invention relates to (a) at least one sulfolane compound of (b) at least one sulfolane compound according to formula (I) in a composition for dyeing keratin fibers, comprising at least one direct dye, on the skin, for example on the scalp. While this composition can be used to prevent or reduce skin contamination by direct dyes, this composition can provide good cosmetic effects, such as good coloring properties, to keratin fibers.

  The invention is explained in more detail by means of examples. However, these examples should not be construed as limiting the scope of the invention.

(Example 1 and Comparative Examples 1 to 5)
[Preparation]
A cosmetic composition for dyeing hair according to Example 1 and Comparative Examples 1 to 5 was prepared by mixing the components shown in Table 1 at room temperature and poured into a transparent container in the same amount. All component amounts are based on “mass%” as the active ingredient.

[Evaluation of hair color difference]
Each composition according to Example 1 and Comparative Examples 1-5 was uniformly applied onto a 1 g lock of 100% gray natural human hair. The tress was then left for 15 minutes at 40 ° C., followed by washing the tress with water, shampooing, rinsing once and drying. The tress color difference before and after the above staining process was evaluated by using Minolta CM-580. ΔE ^* (between unstained original and stained tuft color, based on CIE1976) was determined. The results are shown in Table 1 and FIG.

The greater ΔE ^* , the better the staining.

[Evaluation of skin color difference]
Each composition according to Example 1 and Comparative Examples 1-5 was applied uniformly on the human forearm. The composition was then left for 15 minutes at room temperature, followed by extensive washing with water and drying. The tress color difference before and after the above staining process was evaluated using Minolta CM-580. ΔE ^* (between unstained original and stained tuft color, based on CIE1976) was determined. The results are shown in Table 1 and FIG.

The smaller ΔE ^{*, the} better the skin contamination.

  When the cosmetic composition for dyeing hair containing a direct dye further contains the sulfolane compound described in formula (I) described above, the cosmetic composition is a direct dye on the skin such as the scalp. It can be seen from Example 1 that skin contamination due to can be prevented or reduced while providing a good cosmetic effect to the hair, for example good coloring properties. On the other hand, Comparative Examples 1 to 5 do not contain the sulfolane compound described in Formula (I) as compared to Example 1, and thus provide a good cosmetic effect for keratin fibers, for example, good coloring properties, It is not possible to prevent or reduce skin contamination by direct dyes on the skin such as the scalp.

Claims (13)

(a) at least one direct dye, and
(b) The following formula (I)
(Where
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently
Hydrogen atom,
A halogen atom,
Refers to a monovalent substituted or unsubstituted C _{1 to 30} aliphatic group, or a monovalent substituted or unsubstituted C _{6 to 30} aromatic radical,
(However, all of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ do not mean hydrogen atoms)
A composition for dyeing keratin fibers, comprising at least one sulfolane compound represented by:   The composition according to claim 1, wherein (a) the direct dye is selected from the group consisting of acid direct dyes, basic direct dyes and neutral direct dyes, preferably acid direct dyes. (a) The direct dye is
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 a hydrogen atom or
-Alkyl,
-Alkoxy, alkylthio,
-Hydroxyl, mercapto,
-Nitro,
-R ° -C (X) -X'-, R ° -X'-C (X)-, R ° -X'-C (X) -X ''-(R ° is a hydrogen atom or alkyl or Represents an aryl group, X, X ′ and X ″ may be the same or different and each represents an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group),
-(O) ₂ S (O ^- )-, X ⁺ (X ⁺ represents an organic or inorganic cationic counterion),
^{- (O) CO - -,} X +,
-(O) P (O ₂ ^- )-, 2X ⁺ ,
-R ''-S (O) _2- (R '' represents a hydrogen atom or an alkyl, aryl, (di) (alkyl) amino or aryl (alkyl) amino group, preferably phenylamino or a phenyl group),
-R '''-S (O) _2- X'- (R''' represents an alkyl or optionally substituted aryl group),
-(Di) (alkyl) amino,
optionally substituted with one or more groups selected from i) nitro, ii) nitroso, iii) (O) ₂ S (O ⁻ ) —, X ⁺ , and iv) alkoxy with X ⁺ Aryl (alkyl) amino,
An optionally substituted heteroaryl, preferably a benzothiazolyl group,
-Cycloalkyl, especially cyclohexyl,
-Ar-N = N- (Ar is an optionally substituted aryl group, preferably one or more alkyl, (O) ₂ S (O ^- )-, X ⁺ or phenylamino groups Represents phenyl which is optionally substituted),
Or alternatively two consecutive groups R ₇ and R ₈ , or R ₈ and R ₉ , or R ₉ and R ₁₀ together form a condensed benzo group A ′, R ′ ₇ and R ′ ₈ , or R ′ ₈ and R ′ ₉ or R ′ ₉ and R ′ ₁₀ together form a condensed benzo group B ′, and A ′ and B ′ are i) nitro, ii) nitroso, iii) (O) ₂ S (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 selected from aryl (alkyl) amino Optionally substituted with one or more groups,
Represents a group selected from
W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent group i) -NR- or ii) methylene-C (R _a ) (R _b )-, and R _a and R _b are the same May be present or different and represents a hydrogen atom or an aryl group, or R _a and R _b together with the carbon atom having them form a spirocycloalkyl, preferably W represents a sulfur atom Or R _a and R _b together form cyclohexyl,
Formulas (II) and (II ′) are those wherein at least one sulfonic acid (O) ₂ S (O ⁻ ) —, X ⁺ or phosphonic acid (O) P (O ₂ ⁻ ) 2X ⁺ or carboxylic acid (O) C A (O ⁻ ) —, X ⁺ group is contained in one of the rings A, A ′, B, B ′ or C];
Anthraquinone dyes of formula (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 a hydrogen atom or a halogen atom or
-Alkyl,
-Hydroxyl, mercapto,
-Alkoxy, alkylthio,
An aryloxy or arylthio (X ⁺ is optionally substituted, preferably substituted with one or more groups selected from alkyl and (O) ₂ S (O ⁻ ) —, X ⁺ Represents an organic or inorganic cationic counterion),
Aryl (alkyl) amino optionally substituted with one or more groups selected from alkyl and (O) ₂ S (O ⁻ ) —, X ⁺
-(Di) (alkyl) amino,
-(Di) (hydroxyalkyl) amino,
-(O) ₂ S (O ^- )-, X ⁺ ,
Represents a group selected from
Z ′ represents a hydrogen atom or an NR ₂₈ R ₂₉ group, and R ₂₈ and R ₂₉ may be the same or different, a hydrogen atom or
-Alkyl,
-Polyhydroxyalkyl, for example hydroxyethyl,
One or more groups, in particular i) alkyl, for example methyl, n-dodecyl, n-butyl, ii) (O) ₂ S (O ⁻ ) —, X ⁺ , iii) R ° -C (X ) -X'-, R ° -X'-C (X)-, R ° -X'-C (X) -X ''-optionally substituted aryl (preferably R ° is an alkyl group) Represents
-Cycloalkyl, especially cyclohexyl,
Represents a group selected from
Z represents a group selected from hydroxyl and NR ′ ₂₈ R ′ ₂₉ , and R ′ ₂₈ and R ′ ₂₉ may be the same or different and are the same atom or group as R ₂₈ and R ₂₉ Represents
Formulas (III) and (III ′) contain at least one sulfonic acid group (O) ₂ S (O ⁻ ) —, X ⁺ ];
And a quinoline-based dye of formula (IV)
[In the 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 each represents a hydrogen atom or a (O) ₂ S (O ⁻ ) —, X ⁺ group, and X ⁺ is an organic or inorganic cation. Represents the sex counter ion,
Or alternatively, 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. ,
G represents an oxygen or sulfur atom or an NR _e group, R _e represents a hydrogen atom or an alkyl group, in particular G represents an oxygen atom,
Formula (IV) contains at least one sulfonic acid group (O) ₂ S (O ⁻ ) −, X ⁺ ]
2. The composition of claim 1, wherein the composition is selected from the group consisting of:   (a) The amount of the direct dye is in the range of 0.001% to 5% by weight, preferably 0.01% to 3% by weight, more preferably 0.05% to 2% by weight, based on the total weight of the composition. The composition according to any one of claims 1 to 3. A monovalent substituted or unsubstituted C _1-30 aliphatic group
Saturated monovalent substituted or unsubstituted C _{1 to 30} aliphatic hydrocarbon group, preferably a substituted or unsubstituted C _{1 to 30} alkyl group linear or branched, or substituted or unsubstituted C _{3 to 30} cycloalkyl _5. The composition according to any one of claims 1 to 4, which is an alkyl group or an unsaturated, monovalent substituted or unsubstituted _C2-30 aliphatic hydrocarbon group. The monovalent substituted or unsubstituted C _6-30 aromatic group is a monovalent substituted or unsubstituted C _6-30 aromatic hydrocarbon group, preferably a substituted or unsubstituted C _6-30 aryl group, or linear Or a composition according to any one of claims 1 to 4 which is a branched substituted or unsubstituted _C7-30 aralkyl group.   (b) the sulfolane compound is 2-methyl sulfolane, 3-methyl sulfolane, 2-ethyl sulfolane, 3-ethyl sulfolane, 2,3-dimethyl sulfolane, 2,4-dimethyl sulfolane, 2,5-dimethyl sulfolane, 3, The group consisting of 4-dimethyl sulfolane, 2,3-diethyl sulfolane, 2,4-diethyl sulfolane, 2,5-diethyl sulfolane, 3,4-diethyl sulfolane, 2-phenyl sulfolane, 3-phenyl sulfolane, and mixtures thereof The composition according to any one of claims 1 to 6, which is selected from:   (b) The amount of the sulfolane compound ranges from 0.5 to 30% by weight, preferably from 1 to 20% by weight, more preferably from 2 to 15% by weight, based on the total weight of the composition. The composition as described in any one of these.   The composition according to any one of claims 1 to 8, further comprising water.   10. A composition according to any one of claims 1 to 9, wherein the pH of the composition ranges from 2 to 7, preferably from 2 to 6, more preferably from 2 to 4.   11. The composition according to any one of claims 1 to 10, further comprising (c) at least one buffer, preferably an amino acid, an amino acid derivative or a combination of an organic or inorganic acid and a salt thereof.   (c) The amount of buffering agent ranges from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, more preferably from 0.5 to 5% by weight, based on the total weight of the composition. Composition. Applying the composition according to any one of claims 1 to 12 to keratin fibers,
A method for dyeing keratin fibers, comprising: