JP2016008190A - Composition for keratin fibers - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for dyeing keratin fibers, in particular a composition for dyeing keratin fibers, which uses a direct dye but can prevent or reduce skin staining by the direct dye on the skin such as scalp, preferably as well as the stiffness of the keratin fibers, while providing the keratin fibers with good cosmetic effects such as good coloring properties.SOLUTION: The present invention relates to a composition for dyeing keratin fibers, comprising: (a) at least one direct dye; (b) at least one aprotic polar solvent; and (c) at least one sulfur-containing reducing agent. The composition according to the present invention can prevent or reduce skin staining by the direct dye on the skin such as scalp, as well as the stiffness of the keratin fibers, while providing the keratin fibers with good cosmetic effects such as good coloring properties.

Description

  The present invention relates to compositions for keratin fibers, in particular compositions for dyeing keratin fibers with at least one direct dye and methods of use thereof.

  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, for dyeing keratin fibers, especially human hair It is known to do. These oxidation bases are generally combined with couplers. These bases and these couplers are colorless or lightly colored compounds that can be combined with oxides to give 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, JP-A-2000-186018, JP-A-2006-342159 and WO 2010/032034 (JP-T-2012-502896) disclose a composition for dyeing hair, including a direct dye. Yes.

  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.

JP-A-2000-186018 JP-A-2006-342159 WO 2010/032034 JP-T-2012-502896 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 European Patent Application Publication No. 0 354 835 European Patent Application Publication No. 0 368 763 European Patent Application Publication No. 0 432 000 European Patent Application Publication No. 0 514 282 French Patent Application Publication No. 2 679 448

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 J. Am. Chem. Soc. 1945, 67, 2218-2220 Ann. 1960, 639, pp. 146-56 J. Am. Chem. Soc. 1958, 80, 6233-6237

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

  In addition to skin contamination, hair stiffness due to acidic conditions for direct dyes is also a problem of hair coloring with direct dyes.

  One object of the present invention is to use direct dyes, but it is possible to prevent or reduce skin contamination by direct dyes on the skin, for example the scalp, preferably with keratin fiber stiffness, while providing good makeup for keratin fibers. It is to provide a composition for keratin fibers, in particular a composition for dyeing keratin fibers, which provides an effect, for example good coloring properties.

The above object of the present invention is to
(a) at least one direct dye,
(b) at least one aprotic polar solvent, and
(c) at least one sulfur-containing reducing agent,
Can be achieved by a composition for dyeing keratin fibers.

  (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.

(a) 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 represent 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 (O ⁻ ) —, X ⁺ group is contained in one of the rings A, A ′, B, B ′ or C]
And 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,
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,
-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 with aryl (preferably R ° is alkyl Group)
-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 have the same atom or group as R ₂₈ and R _29. Represent,
Formulas (III) and (III ′) contain at least one sulfonic acid group (O) ₂ S (O ⁻ ) —, X ⁺ ]
May be selected from the group consisting of

  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%.

  (b) The aprotic polar solvent is selected from the group consisting of propylene carbonate, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylsulfone, 2-propanone, dimethylsulfoxide, dimethylformamide, ethyl acetate, dimethylacetamide, and mixtures thereof. It may be selected.

  The amount of the (b) aprotic polar solvent in the composition according to the present invention is 1% by mass to 50% by mass, preferably 5% by mass to 40% by mass, more preferably 10% by mass relative to the total mass of the composition. The range may be from 30% to 30% by mass.

  (c) Sulfur-containing reducing agent is 2-mercapto-4-butanolide, glutathione, thioglycolic acid, 3-mercaptopropionic acid, thiolactic acid, L-cysteine, cysteamine, thioglycerol, L-cysteine methyl ester, L-cysteine It may be selected from the group consisting of ethyl ester, mercaptosuccinic acid, glycerol monothioglycolate, N-acetyl-L-cysteine and mixtures thereof.

  The amount of the (c) sulfur-containing reducing agent in the composition according to the present invention is from 0.1% by mass to 20% by mass, preferably from 0.5% by mass to 10% by mass, more preferably from 1 to 5%, based on the total mass of the composition. It may be in the range of mass%.

  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 80% by weight, preferably from 20% to 85% by weight, more preferably from 30 to 70% 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 3 to 7, preferably 4 to 7, more preferably 5 to 7.

  The composition according to the present invention may further comprise (d) at least one protein denaturant containing at least one nitrogen atom.

  (d) the protein denaturant containing at least one nitrogen atom is selected from the group consisting of urea, guanidine and salts thereof, thiourea, biuret, thiobiuret, ammonia, monoethanolamine, triethanolamine, and mixtures thereof May be.

  The amount of the protein denaturant comprising (d) at least one nitrogen atom in the composition according to the invention is 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably relative to the total weight of the composition. It may be in the range of 1 to 10% by weight.

  The composition according to the invention comprises (a) a first composition comprising at least one direct dye, (b) at least one aprotic polar solvent and (c) at least one sulfur-containing reducing agent. A second composition comprising preferably a first composition: a second composition is 1: 1 to 10: 1, more preferably 1: 1 to 7: 1, even more preferably 1: 1. It is preferably obtained before use by mixing at a mass ratio in the range of 5: 1.

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

  The present invention also provides a second composition comprising (a) a first composition comprising at least one direct dye, (b) at least one aprotic polar solvent and (c) at least one sulfur-containing compound. And a composition for dyeing keratin fibers such as hair.

  As a result of intensive studies, the present inventors have found that, although containing direct dyes, contamination of the skin with direct dyes on the skin, for example, the scalp, can be prevented or reduced together with the keratin fiber stiffness, while good makeup for keratin fibers. It has been found that it is possible to provide a composition for keratin fibers, in particular a composition for dyeing keratin fibers, which provides an effect, for example good coloring properties.

Therefore, the composition according to the invention is
(a) at least one direct dye,
(b) at least one aprotic polar solvent, and
(c) at least one sulfur-containing reducing agent,
including.

  The composition according to the invention is preferably a cosmetic composition for keratin fibres.

  The composition according to the invention preferably further comprises (d) at least one protein denaturant comprising at least one nitrogen atom. (d) Due to the presence of a protein denaturant containing at least one nitrogen atom, the composition according to the invention can further prevent or reduce keratin fiber wrinkles without any conventional regulators.

  In the following, the steps of constituting the composition according to the present invention will be described in detail.

[Direct dye]
The composition according to the invention comprises 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 dye or dye precursor that occurs naturally and is optionally produced by extraction (optionally purified) from a plant substrate in the presence of natural compounds such as ash or ammonia. It is understood to mean the body.

  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 apigenidins), carotenoids, tannins, orcein, santaline 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, It is preferably selected from the group consisting of apigenidine, 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.

  In terms of ionic properties, the synthetic direct dye may be selected from the group consisting of acidic (anionic) direct dyes, basic (cationic) direct dyes and neutral (nonionic) direct dyes, Includes all types of direct dyes, e.g. so-called nitro dyes, HC dyes, azo, methine, carbonyl, azine, nitro (hetero) aryl type or tri (hetero) arylmethane direct dyes, porphyrins and phthalocyanines, alone or as a mixture To do. 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.

  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

Cationic direct 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.

  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 '' means that 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 (= O ) O ^- O ^- means any direct dyes containing, G ^{- -} and one or more anionic groups G optionally may be the same or different and alkoxides O ^-, thioalkoxide S ^-, phosphonate, carboxylate and thiocarboxylate: C (Q) Q ^'- represents an anionic group selected from, Q and Q' may be the same or different and oxygen or a sulfur atom, preferably, G ^- represents a carboxylate, i.e. Q and Q 'represents 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 the dyes below.

  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 ⁺ , 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) 1 selected from optionally substituted 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 represents 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, represent 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 the group (O ⁻ ) —, X ⁺ is included in one of the rings A, A ′, B, B ′ or C, where X ⁺ is as previously defined.

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 the dye of the formula (II ′) include Acid Red 111, Acid Red 134, and Acid yellow 38.

  Anthraquinone dyes of formula (III) and (III ')

In 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,
-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 as defined above with R ₂₈ and R ₂₉ Represents the same atom or group,
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,
An example of formula (III ′) is Acid Black 48.

  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 each represents a hydrogen atom or a (O) ₂ S (O ⁻ ) —, X ⁺ group, and X ⁺ is as defined above. And
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 above,
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) contains 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 direct dye is preferably selected from acid direct dyes such as Acid Black 1, Acid Violet 43 and Acid Orange 7.

  The composition according to the invention comprises the direct dye in an amount of 0.001% to 5% by weight, preferably 0.01% to 3% by weight, more preferably 0.05% to 2% by weight, relative to the total weight of the composition. It may contain.

[Aprotic polar solvent]
The composition according to the invention comprises at least one aprotic polar solvent. Two or more aprotic polar solvents can be used in combination. Thus, a single type of aprotic polar solvent or a combination of different types of aprotic polar solvents can be used.

  The term “aprotic polar solvent” means a polar solvent that does not contain acidic hydrogen and does not act as a hydrogen bond donor.

  As aprotic polar solvents, ether-based solvents such as diethyl ether, tetrahydrofuran and dioxane, ketone-based solvents such as 2-propanone, sulfoxide-based solvents such as dimethyl sulfoxide and diethyl sulfoxide, amide-based solvents such as N, N-dimethyl Formamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, etc., ester-based solvents such as ethyl acetate, gamma An ether ester base solvent such as butyrolactone, for example, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, hexamethylphosphoric acid amide, acetonitrile, etc. can be preferably used.

  As an aprotic polar solvent, the following chemical formula (1)

An alkylene carbonate of the formula:
R ″ represents a hydrogen atom, a (C ₁ -C ₈ ) alkyl group, or a (C ₁ -C ₄ ) hydroxyalkyl group.

As alkylene carbonate, ethylene carbonate (R '' = H), propylene carbonate (R '' = CH ₃ ), glycerol carbonate (R '' = CH ₂ OH), or butylene carbonate (R '' = CH ₂ CH ₃ ) Is mentioned. Of the alkylene carbonates, propylene carbonate is preferred.

  (b) The aprotic polar solvent is selected from the group consisting of propylene carbonate, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylsulfone, 2-propanone, dimethylsulfoxide, dimethylformamide, ethyl acetate, dimethylacetamide, and mixtures thereof. It may be preferred that it be selected.

  The composition according to the invention comprises an aprotic polar solvent in an amount of 1% to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight, based on the total weight of the composition. You may contain.

[Sulfur-containing reducing agent]
The composition according to the invention comprises at least one sulfur-containing reducing agent. Two or more sulfur-containing reducing agents can be used in combination. Thus, a single type of sulfur-containing reducing agent or a combination of different types of sulfur-containing reducing agents can be used.

  The term “sulfur-containing reducing agent” means a reducing agent having at least one sulfur atom.

  It is preferred to use a thiol-based reducing agent as the sulfur-containing reducing agent.

The thiol-based reducing agent is preferably thioglycolic acid and its derivatives, in particular its esters, such as glycerol or glycol monothioglycolate, dithioglycolic acid and its derivatives, in particular its esters, such as glycerol or glycol dithioglycolate, thiolactic acid And derivatives thereof, in particular esters thereof, such as glycerol monothiolactate, 3-mercaptopropionic acid and derivatives thereof, in particular esters thereof such as glycerol 3-mercaptopropionate and ethylene glycol 3-mercaptopropionate, cysteamine and derivatives thereof, in particular C _1-4 acyl derivatives, such as N- acetyl cysteamine and N- propionyl cysteamine, thioglycerol, as monothioglycerol and its derivatives, especially esters, cysteine and Derivatives, particularly esters, such as N- acetylcysteine, N- alkanoyl cysteine and cysteine alkyl esters, glutathione reduced form, mercaptosuccinic acid, and may be selected from the group consisting of salts thereof.

  Examples of the above salts include ammonium salts, primary, secondary or tertiary amine salts, alkali metal salts, and alkaline earth metal salts. Examples of the primary, secondary or tertiary amine include monoethanolamine, diisopropanolamine and triethanolamine, respectively.

  Other suitable examples of thiol-based reducing agents that can be used in the composition according to the invention include sugar N-mercaptoalkylamides such as N- (mercapto-2-ethyl) gluconamide, β-mercaptopropionic acid, and Derivatives of thiomalic acid, pantethein, N- (mercaptoalkyl) ω-hydroxyalkylamides, such as those described in EP 0 354 835, and N-mono- or N, N-dialkylmercapto-4-butyramides For example, those described in European Patent Application Publication No. 0 368 763, aminomercaptoalkylamides such as those described in European Patent Application Publication No. 0 432 000, and alkylaminomercaptoalkylamides such as those described in European Patent Application Publication No. 0 (2/3) hydroxy-2 propyl thioglycolate and hydride described in French Patent Application No. 2 679 448 Carboxymethyl -2 but are methyl -1-ethyl thioglycolate based mixture (67/33) is not limited thereto.

  The thiol-based reducing agent has the following chemical formula (2)

Or a compound represented by the formula:
X is a structure selected from the group consisting of —O—, —S—, —NH—, and —NR ¹ —;
R ¹ is an alkyl group having 1 to 6 carbon atoms,
R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
Y is an oxygen atom or a sulfur atom,
R is a divalent organic residue optionally having a mercapto group.

X is preferably -O-, -NH-, -NCH ₃ -or -S- in view of the preparation of the permanent solution, in which case the compound exhibits a relatively high solubility in the aqueous permanent solution. .

  Y is an oxygen atom or a sulfur atom, and more preferably an oxygen atom in consideration of industrial applicability and handling characteristics.

R ² may be a hydrogen atom, a methyl group, an ethyl group or a propyl group, preferably a hydrogen atom, a methyl group or an ethyl group.

  R is a divalent organic residue optionally having a mercapto (—SH) group. R is not particularly limited as long as it is a divalent organic group, and is preferably an alkylene group. The main chain of the alkylene group preferably has 2 to 6 carbon atoms. The divalent organic residue may have a branch or a side chain. Examples of the side chain include an alkyl group and an alkenyl group.

  When R is substituted with a mercapto group, one or more mercapto groups may be present.

  Preferred examples of R include ethylene and propylene groups due to easy industrial applicability.

  Specific examples of the compound represented by the above chemical formula (2) include 2-mercapto-3-propiolactone, 2-mercapto-2-methyl-3-propiolactone, 2-mercapto-3-methyl- 3-propiolactone, 2-mercapto-3-ethyl-3-propiolactone, 2-mercapto-2,3-dimethyl-3-propiolactone, 2-mercapto-3-propiolactam, 2-mercapto- 2-Methyl-3-propiolactam, 2-mercapto-3-methyl-3-propiolactam, 2-mercapto-3-ethyl-3-propiolactam, 2-mercapto-2,3-dimethyl-3- Propiolactam, 2-mercapto-3-propiothiolactone, 2-mercapto-2-methyl-3-propiothiolactone, 2-mercapto-3-methyl-3-propiothiolactone, 2-mercapto-3 -Ethyl-3-propiothiolactone, 2-mercapto-2,3-dimethyl-3-propiothiolactone, 2-mercapto-4-butyro T (alias: 2-mercapto-4-butanolide), 2-mercapto-2-methyl-4,4-dimethyl-4-butyrolactone, 2-mercapto-3- (2-propenyl) -4-butyrolactone, 2-mercapto -4-methyl-4-butyrolactone, 2-mercapto-2-methyl-4-butyrolactone, 2-mercapto-3-methyl-4-butyrolactone, 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto-3 , 4-Dimethyl-4-butyrolactone, 2-mercapto-2-ethyl-4-butyrolactone, 2-mercapto-3-ethyl-4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4 -Butyrothiolactone, 2-mercapto-2-methyl-4-butyrothiolactone, 2-mercapto-3-methyl-4-butyrothiolactone, 2-mercapto-4-methyl-4-butyrothiolactone 2-mercapto-3,4-dimethyl-4-butyrothiolactone, 2-mercapto-2-ethyl-4-butyrothiola T, 2-mercapto-3-ethyl-4-butyrothiolactone, 2-mercapto-4-ethyl-4-butyrothiolactone, 2-mercapto-4-butyrolactam, 2-mercapto-2-methyl-4- Butyrolactam, 2-mercapto-3-methyl-4-butyrolactam, 2-mercapto-4-methyl-4-butyrolactam, 2-mercapto-3,4-dimethyl-4-butyrolactam, 2-mercapto-2-ethyl-4- Butyrolactam, 2-mercapto-3-ethyl-4-butyrolactam, 2-mercapto-4-ethyl-4-butyrolactam, 2-mercapto-5-valerolactone, 2-mercapto-2-methyl-5-valerolactone, 2- Mercapto-3-methyl-5-valerolactone, 2-mercapto-4-methyl-5-valerolactone, 2-mercapto-5-methyl-5-valerolactone, 2-mercapto-2-ethyl-5-valerolactone, 2-mercapto-3-ethyl-5-valerolactone, 2-mercapto-4-ethyl-5-valerola Kuton, 2-mercapto-5-ethyl-5-valerolactone, 2-mercapto-5-valerolactam, 2-mercapto-2-methyl-5-valerolactam, 2-mercapto-3-methyl-5-valerolactam, 2-mercapto-4-methyl-5-valerolactam, 2-mercapto-5-methyl-5-valerolactam, 2-mercapto-2-ethyl-5-valerolactam, 2-mercapto-3-ethyl-5-valero Lactam, 2-mercapto-4-ethyl-5-valerolactam, 2-mercapto-5-ethyl-5-valerolactam, 2-mercapto-5-valerothiolactone, 2-mercapto-2-methyl-5-valerothio Lactone, 2-mercapto-3-methyl-5-valerothiolactone, 2-mercapto-4-methyl-5-valerothiolactone, 2-mercapto-5-methyl-5-valerothiolactone, 2-mercapto-2- Ethyl-5-valerothiolactone, 2-mercapto-3-ethyl-5-valerothiolactone, 2-mercapto- 4-ethyl-5-valerothiolactone, 2-mercapto-5-ethyl-5-valerothiolactone, 2-mercapto-6-hexanolactone, 2-mercapto-2-methyl-6-hexanolactone, 2- Mercapto-3-methyl-6-hexanolactone, 2-mercapto-4-methyl-6-hexanolactone, 2-mercapto-5-methyl-6-hexanolactone, 2-mercapto-6-methyl-6- Hexanolactone, 2-mercapto-6-hexanolactam, 2-mercapto-2-methyl-6-hexanolactam, 2-mercapto-3-methyl-6-hexanolactam, 2-mercapto-4-methyl- 6-hexanolactam, 2-mercapto-5-methyl-6-hexanolactam, 2-mercapto-6-methyl-6-hexanolactam, 2-mercapto-6-hexanothiolactone, 2-mercapto-2- Methyl-6-hexanothiolactone, 2-mercapto-3-methyl-6-hexanothiolactone, 2-mercapto-4-methyl -6-hexanothiolactone, 2-mercapto-5-methyl-6-hexanothiolactone, 2-mercapto-6-methyl-6-hexanothiolactone, 2-mercapto-7-heptanolactone, 2-mercapto-7 -Heptanothiolactone, 2-mercapto-7-heptanolactam, 2-mercapto-8-octanolactone, 2-mercapto-8-octanothiolactone, 2-mercapto-8-octanolactam, 2-mercapto-9 -Nonalactone, 2-mercapto-9-nonathiolactone, 2-mercapto-9-nonalactam, and N-methyl or N-ethyl derivatives of these lactams.

  Among these, 2-mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methyl-2-mercapto -4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto-4-butyrolactam 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-5-valerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto -5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto- 5-Valerolactam and 2-mercapto-6-hexanolactam It preferred in view of the production. Permanent waving agents contain at least one such mercapto compound.

  These compounds may be produced by known methods. For example, such a compound can be synthesized by halogenating a lactone compound or a lactam compound and subsequently introducing a mercapto group.

  Mercaptolactone and mercaptothiolactone are obtained by halogenating a commercially available lactone or thiolactone according to the method described in J. Am. Chem. Soc. 1945, 67, pages 2218 to 2220, and Ann. 1960, pages 639, 146. It may be synthesized by a series of steps for producing a desired lactone derivative from a synthetic halide or a commercially available halide by the method described on pages ~ 56.

  Mercaptolactam was synthesized by the method described in J. Am. Chem. Soc. 1958, 80, pages 6233-6237, and Ann. 1960, 639, pages 146-56. Similarly to the production of lactone, it may be synthesized by a series of steps for synthesizing a desired lactam derivative from the obtained halide.

  (c) Sulfur-containing reducing agent is 2-mercapto-4-butanolide, glutathione, thioglycolic acid, 3-mercaptopropionic acid, thiolactic acid, L-cysteine, cysteamine, thioglycerol, L-cysteine methyl ester, L-cysteine It may be preferred to be selected from the group consisting of ethyl esters, mercaptosuccinic acid, glycerol monothioglycolate, N-acetyl-L-cysteine and mixtures thereof.

  The sulfur-containing reducing agent in the composition according to the present invention is in the range of 0.1% to 20% by mass, preferably 0.5% to 10% by mass, more preferably 1 to 5% by mass, based on the total mass of the composition. There may be.

[Protein denaturant containing at least one nitrogen atom]
The composition according to the invention preferably further comprises (d) at least one protein denaturant comprising at least one nitrogen atom. A combination of two or more protein denaturants containing at least one nitrogen atom can be used. Thus, a single type or a combination of different types can be used.

  The term “protein denaturant” refers to a substance that changes the three-dimensional protein conformation but does not cleave covalent or amide bonds or destroy protein primary structure.

  The protein denaturant containing at least one nitrogen atom is preferably not a polymer but a low molecular weight compound.

  Examples of protein denaturing agents containing at least one nitrogen atom include ammonia and organic amines.

In some embodiments, the organic amine is primary, secondary or a tertiary amine functional group, at least one linear or branched C ₁ -C ₆ alkyl having at least one hydroxyl group And may contain a group. Organic amine, in some embodiments, includes a C ₁ -C ₄ hydroxyalkyl groups or different from one which is three identical, alkanolamines such as mono-, - di - or selected from trialkanolamines May be.

  Among the compounds of this type that may be mentioned, but are not limited to, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylaminoethanolamine, 2-amino-2-methyl 1-propanol, triiso-propanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol and tris ( Hydroxymethylamino) methane.

  In some embodiments, the following chemical formula (3):

Organic amines having may also be suitable for use, wherein
W is a C ₁ -C ₆ alkylene residue which is optionally substituted with a hydroxyl group or a C ₁ -C ₆ alkyl group,
Rx, Ry, Rz and Rt, which may be the same or different and represent a hydrogen atom or a C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl or C ₁ -C ₆ aminoalkyl group.

  Examples of such amines that may be mentioned include, but are not limited to, 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

  According to some embodiments, the protein denaturant comprising at least one nitrogen atom is selected from amino acids.

  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, 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.

  In some embodiments, the amino acids may be selected from basic amino acids that include additional amine functionalities optionally included in the ring or ureido functional groups.

  Such basic amino acids, in some embodiments, have the following chemical formula (4)

May be selected from those corresponding to:
R is

,-(CH ₂ ) ₃ NH ₂ ,-(CH ₂ ) ₂ NH ₂ ,-(CH ₂ ) NHCONH ² , and

Means a group selected from

  In some embodiments, the compounds corresponding to the above formula are histidine, lysine, arginine, ornithine and citrulline.

  In some embodiments, the protein denaturant comprising at least one nitrogen atom is selected from heterocyclic organic amines. In addition to histidine already mentioned in the amino acid, it includes, but is not limited to, pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole.

  In some embodiments, the protein denaturant comprising at least one nitrogen atom is selected from amino acid dipeptides. Amino acid dipeptides include, but are not limited to, carnosine, anserine, and baleine.

  In some embodiments, the protein denaturant comprising at least one nitrogen atom is selected from compounds comprising a guanidine functional group. Exemplary protein denaturants containing at least one nitrogen atom include guanidine, arginine, creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycosylamine, metformin, agmatine, N-amidinoalanine, Examples include, but are not limited to, 3-guanidinopropionic acid, 4-guanidinobutyric acid, and 2-{[amino (imino) methyl] amino} ethane-1-sulfonic acid.

  In some embodiments, the protein denaturant containing at least one nitrogen atom is selected from alkanolamines, basic amino acids, compounds containing guanidine functional groups, and mixtures thereof.

  In some embodiments, the protein denaturant comprising at least one nitrogen atom is selected from urea and its derivatives, such as N- (2-hydroxyethyl) urea, biuret and its derivatives, and mixtures thereof. .

  (d) the protein denaturant containing at least one nitrogen atom is selected from the group consisting of urea, guanidine and salts thereof, thiourea, biuret, thiobiuret, ammonia, monoethanolamine, triethanolamine, and mixtures thereof. It may be preferable to be done.

  The amount of protein denaturant comprising at least one nitrogen atom in the composition according to the invention is 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10%, relative to the total weight of the composition. It may be in the range of mass%.

[Other ingredients]
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 80% by weight, preferably from 20% to 85% by weight, more preferably from 30 to 70% 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 3 to 7, preferably 4 to 7, more preferably 5 to 7.

  The pH of the composition according to the present invention may be adjusted to the desired value using acidifying or basifying agents commonly used in 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. Arginine, urea and monoethanolamine are preferred. It can also function as a protein denaturant.

The composition according to the invention may contain at least one organic solvent. The organic solvent is preferably water miscible. As the organic solvent, for example, C ₁ -C ₄ alkanols, such as ethanol and isopropanol, polyols and polyol ethers, for example, glycerol, 2-butoxyethanol, propylene glycol, monomethyl ether of propylene glycol, diethylene glycol monoethyl ether and monomethyl ether, And aromatic alcohols such as benzyl alcohol and phenoxyethanol, similar products, and mixtures thereof.

  The organic solvent may be present in an amount ranging from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight, more preferably from 1 to 5% by weight, based on the total weight of the composition.

  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,
At least one of them may be selected.

  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 compositions used in the present invention also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, nonionic, cationic, amphoteric or zwitterionic polymers or A mixture thereof, an antioxidant, a penetrating agent, a sequestering agent, a fragrance, a buffering agent, a dispersing agent, a conditioning agent, a film forming agent, a ceramide, a preservative and an opacifier may be contained.

  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.

[Preparation]
The composition is optional as described above, with (a) at least one direct dye, (b) at least one aprotic polar solvent, and (c) at least one sulfur-containing reducing agent as essential components. It can prepare by mixing with the component of.

  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 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. The “ready-to-use composition” may be stored in an unmodified form prior to use, or may be obtained from in-situ mixing of two or more separate compositions. In one embodiment, one of the separate compositions may comprise (a) at least one direct dye and the other of the separate compositions is (b) at least one aprotic. It may contain a polar solvent and (c) at least one sulfur-containing reducing agent.

  In this embodiment, the composition according to the invention comprises (a) a first composition comprising at least one direct dye, (b) at least one aprotic polar solvent and (c) at least one A second composition comprising a sulfur-containing reducing agent, preferably the first composition: the second composition is 1: 1 to 10: 1, more preferably 1: 1 to 7: 1, even more preferably Is preferably obtained before use by mixing at a mass ratio in the range of 1: 1 to 5: 1.

[Method]
The invention also relates to a method of using the composition according to the invention. The method according to the invention is preferably intended for dyeing keratin fibers such as hair.

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

  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., 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.

The present invention also provides
(a) a first composition comprising at least one direct dye, and
a second composition comprising (b) at least one aprotic polar solvent and (c) at least one sulfur-containing compound;
And a kit for dyeing keratin fibers such as hair.

  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.

(Examples 1-14 and Comparative Examples 1-9)
[Preparation]
First and second reagents according to Examples 1 to 14 and Comparative Examples 1 to 9 were prepared by mixing the components shown in Tables 1 to 3 at room temperature, respectively, and poured into a transparent container in the same amount. . All component amounts are based on “mass%” as the active ingredient.

[Evaluation of color difference]
After homogeneously mixing the first and second agents with a mass ratio shown in Tables 1 to 3 using a brush, the composition thus obtained was mixed with 1 g of 90% gray white human natural hair. Applied uniformly on top. 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 ^* (L ^* a ^* b ^* between the unstained original tuft color and the stained tuft color under the system) was calculated. Evaluation was performed according to the following criteria.

A large ΔE value indicates good dyeing performance.
A: ΔE value greater than 45.
B: ΔE value between 40 and 45.
C: ΔE value less than 40.

  The results are shown in Tables 1-3 (Tables 1 to 3).

[Evaluation of skin contamination]
Skin contamination with the composition was subjected to sensory evaluation by 10 experts. After the first and second agents were mixed homogeneously using a brush at the mass ratios shown in Tables 1 to 3, the composition thus obtained was used to form the surface of the forearm of 10 human experts. Applied above. The applied surface was left for 15 minutes at room temperature, and then the composition was washed thoroughly with water to dry the surface. Evaluation was performed according to the following criteria.
A: At least 80% of the 10 experts found that skin contamination was not noticeable at all.
B: At least 50% and less than 80% of the 10 experts found the skin contamination not noticeable at all.
C: At least 20% and less than 50% of the 10 experts found the skin contamination not noticeable at all.
D: Less than 20% of 10 experts found that skin contamination was not noticeable at all.

  The results are shown in Tables 1 to 3.

  (a) Uses direct dyes, but can prevent or reduce skin contamination by (a) direct dyes on the skin, e.g. scalp, while providing good cosmetic effects, e.g. good coloring properties, on keratin fibers In order to provide a composition for keratin fibers, in particular a composition for dyeing keratin fibers, (b) at least one aprotic polar solvent and (c) at least one sulfur-containing reducing agent It is recognized from the experimental results shown in Tables 1 to 3 that a combination with is required.

[Evaluation of smoothness of hair]
The smoothness of the dyed hair was subjected to a sensory evaluation by five respondents. The dyed hair tress used in [Evaluation of Color Difference] was scored according to the following criteria.
1: The hair was not smooth at all.
2: The hair was not smooth.
3: Hair was normal.
4: The hair was smooth.
5: The hair was very smooth.

  The scores were then averaged. The results are shown in Table 4.

  The composition according to the invention can also enhance the smoothness of the keratin fibers (i.e. the composition according to the invention can prevent or reduce the keratin fiber stiffness), and (d) contains at least one nitrogen atom. It can be seen from the experimental results shown in Table 4 that when containing at least one protein denaturant, the composition according to the present invention can further enhance the smoothness of keratin fibers without any conventional conditioning agents.

Claims (17)

(a) at least one direct dye,
(b) at least one aprotic polar solvent, and
(c) at least one sulfur-containing reducing agent,
A composition for dyeing keratin fibers.   The composition according to claim 1, wherein (a) the direct dye is selected from the group consisting of an acid direct dye, a basic direct dye and a neutral direct dye. (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 represent 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 (O ⁻ ) —, X ⁺ group is contained in one of the rings A, A ′, B, B ′ or C]
And 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,
-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 with aryl (preferably R ° is alkyl Group)
-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 have the same atom or group as R ₂₈ and R _29. Represent,
Formulas (III) and (III ′) contain 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.   (b) the aprotic polar solvent is selected from the group consisting of propylene carbonate, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylsulfone, 2-propanone, dimethylsulfoxide, dimethylformamide, ethyl acetate, dimethylacetamide, and mixtures thereof 5. The composition according to any one of claims 1 to 4, which is selected.   (b) The amount of the aprotic polar solvent is 1% to 50% by weight, preferably 5% to 40% by weight, more preferably 10% to 30% by weight, based on the total weight of the composition. 6. The composition according to any one of claims 1 to 5, which is a range.   (c) The sulfur-containing reducing agent is 2-mercapto-4-butanolide, glutathione, thioglycolic acid, 3-mercaptopropionic acid, thiolactic acid, L-cysteine, cysteamine, thioglycerol, L-cysteine methyl ester, L-cysteine The composition according to any one of claims 1 to 6, selected from the group consisting of ethyl ester, mercaptosuccinic acid, glycerol monothioglycolate, N-acetyl-L-cysteine and mixtures thereof.   (c) The amount of the sulfur-containing reducing agent is in the range of 0.1% to 20% by weight, preferably 0.5% to 10% by weight, more preferably 1 to 5% by weight, based on the total weight of the composition. 8. The composition according to any one of claims 1 to 7.   The composition according to any one of claims 1 to 8, further comprising water.   The amount of water is in the range of 10% to 80% by weight, preferably 20% to 85% by weight, more preferably 30 to 70% by weight, based on the total weight of the composition. Composition.   11. A composition according to claim 9 or 10, wherein the pH of the composition ranges from 3 to 7, preferably from 4 to 7, more preferably from 5 to 7.   12. The composition according to any one of claims 1 to 11, further comprising (d) at least one protein denaturant comprising at least one nitrogen atom.   (d) the protein denaturant containing at least one nitrogen atom is selected from the group consisting of urea, guanidine and salts thereof, thiourea, biuret, thiobiuret, ammonia, monoethanolamine, triethanolamine, and mixtures thereof 13. The composition of claim 12, wherein:   (d) the amount of the protein denaturant comprising at least one nitrogen atom is 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, relative to the total weight of the composition 14. A composition according to claim 12 or 13, which is a range.   (a) a first composition comprising at least one direct dye; (b) a second composition comprising at least one aprotic polar solvent and (c) at least one sulfur-containing reducing agent; Preferably the mass of the first composition: the second composition is 1: 1 to 10: 1, more preferably 1: 1 to 7: 1, and even more preferably 1: 1 to 5: 1. 15. A composition according to any one of claims 1 to 14 obtained prior to use by mixing in a ratio. Applying the composition according to any one of claims 1 to 15 to keratin fibers;
A method for dyeing keratin fibers, comprising:   (a) a first composition comprising at least one direct dye, and (b) a second composition comprising at least one aprotic polar solvent and (c) at least one sulfur-containing compound. A kit for dyeing keratin fibers such as hair.