CN1835730B

CN1835730B - Lightening dye composition comprising at least one cationic direct dye containing mixed chromophores

Info

Publication number: CN1835730B
Application number: CN2004800235158A
Authority: CN
Inventors: H·萨马恩; L·赫考伊特
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2003-06-16
Filing date: 2004-06-16
Publication date: 2011-03-16
Anticipated expiration: 2024-06-16
Also published as: KR20060021898A; JP2006527744A; CN1835730A; WO2004112738A1; MXPA05013749A; BRPI0411495A; FR2855967B1; JP4728230B2; EP1648402A1; FR2855967A1

Abstract

The invention relates to a tinctorial brightener composition containing, in an appropriate dyeing medium, an oxidizing agent, an alkaline agent provided in a quantity so that the pH of the composition is greater than 7, and a cationic mixed colorant containing a number of chromophores that are bound to one another by a binding arm, whereby at least two of the chromophores are different, and the chromophores exhibit an absorbency ranging from 400 to 800 nm. The invention makes it possible to obtain particularly resistant colorations.

Description

Comprise at least a painted lightening composition with the direct dye of positive ion that mixes chromophore

The present invention relates to comprise the dye composite of the direct dye of positive ion that contains different chromophores, in particular for the painted compositions of keratin fiber blast (lightening).The invention still further relates to the colouring method that uses said composition, and relate to the purposes that said composition is used for the keratin fiber blast.

With the especially human hair of the dye composite dyeing keratin fibres that contains oxidation dye precursors, be known practice, described oxidation dye precursors is commonly referred to oxidation base, for example neighbour or p-phenylenediamine (PPD), neighbour or para-aminophenol and heterocyclic compound.These oxidation bases are colourless or the chemical compound of light colour, when combining with oxygenated products, can produce colored compound by the oxidative condensation process.

It is also known to these oxidation bases are combined with colour coupler or dyeing regulator, the tone that is obtained by these oxidation bases may change, and colour coupler or dyeing regulator particularly are selected from for example benzazolyl compounds of two amines between aromatic series, m-aminophenyl phenols, a diphenols and some heterocyclic compound.

Can obtain shades of colour as the various molecules of oxidation base and colour coupler are feasible.

This oxidation dyeing method is to apply to keratin fiber the mixture of developing alkali or developing alkali and colour coupler, and uses aqueous hydrogen peroxide solution as oxidant, makes the mixture rinsing fiber then of having an effect on fiber.The dyeing that is obtained by said method is permanent, dense and anti-external factor, particularly fast light, vile weather, washing, sweat and friction.Usually this method of carrying out at alkaline pH makes dyeing and blast fiber to carry out simultaneously, and this is come out by the final staining reaction that can obtain than primitive color brighter (lighter) in practice.In addition, the fiber blast has in the higher advantageous effects of probability that produces the advantageous effects of consistent color under the situation of gray hair and Show Color just makes Show Color under the situation of natural colour hair.

Coming dyeing keratin fibres by direct staining also is known practice.The method that is generally used for direct staining is to apply direct dyes to keratin fiber, and described direct dyes is the colored dyeing molecule that fiber is had affinity, makes the described dyestuff rinsing fiber then of having an effect on fiber.

For example using, direct dyes or azo, xanthene, acridine, azine or the triarylmethane class dyestuff of nitrobenzene, anthraquinone dye, nitropyridine class are known practices.

These direct dyess can be made up of one or more chromophores, and these chromophores can be identical or different.The dyestuff of being made up of several chromophores for example is described among document FR1540423, EP1133975, EP1133976, US5708151 and the WO 02/078596.

The dyeing of using direct dyes to obtain is temporary transient or semipermanent dyeing, because direct dyes is attached to interactional essence on the keratin fiber and direct dyes from fiber surface and/or fibre core desorbing, be the reason of direct staining power difference and fastness to washing and color fastness to perspiration difference.

Some direct dyes can be combined with oxidant, thereby can realize the blast of fiber painted the time.For example, patent application EP 810851 has described the dye composite that contains direct dyes, and described direct dyes contains the quaternized nitrogen-atoms of at least one azo or azomethine type, and described dye composite can mix with oxidising composition immediately at alkaline pH.

But the gained color is not always satisfactory aspect the fastness of color.They disappear under the effect of shampoo, may be seen indistinctly on the keratin fiber of blast.In addition, when dye composite comprises the direct dyes mixture, color in time passing and change, this change is every kind of dyestuff for the different affinitys of keratin fiber and resists outside agent (as shampoo) and cause.

Target of the present invention provide do not have a direct dyes shortcoming can be used for the painted direct dyes of blast.Especially, one of target of the present invention provides direct dyes, and described direct dyes is still enough stable in the presence of oxidant and/or basifier, can obtain the blast and the dyeing of described fiber simultaneously.Another target of the present invention provides direct dyes, described direct dyes can change required tone, do not pass the problem that color changes in time and do not exist, and described direct dyes can make and treats that painted keratin fiber is dyed with the same dense with oxidation dye, it is to light, the same with described oxidation dye stable to the patience of vile weather, washing and sweat, and lasting.

The present invention has realized above-mentioned target, a theme of the present invention is the blast dye composite that comprises oxidant, basifier and cation mixed dye in suitable dyeing medium, the consumption of wherein said basifier is to make said composition pH greater than 7 amount, described cation mixed dye comprises the several chromophores that link together by connector (linker), at least two in these chromophores is different, and described chromophore shows at least one absorption maximum between 400-800nm.

Theme of the present invention also relates to the colouring method that uses said composition.

Another theme of the present invention relates to the present composition and is used for dyeing keratin fibres, and especially the purposes of human keratin fiber (as hair) relates in particular to the fastness (fastness) that obtains good anti-shampoo.

Especially, the present composition can obtain the blast and the dyeing of keratin fiber, and wherein this blast and dyeing are firm with respect to various outside agent, are firm for shampoo particularly.In addition, said composition can also avoid passing in time the problem that color changes.

Describedly be used for cation of the present invention to mix direct dyes be stable at lightening composition especially, this lightening composition comprises basifier (as ammonia) and/or oxidising agent (as hydrogen peroxide).Especially, when this mixed dye is used for non-lightening composition when (promptly not comprising basifier or any blast combination of agents thing), with when this mixed dye when comprising basifier (as ammonia) or oxidant (as aqueous hydrogen peroxide solution), or the compositions that comprises basifier and oxidant is simultaneously sent out the painted of tuft and is not changed basically when using together.

Among the present invention, be used for cation mixed dye of the present invention and be the dyestuff that its cationic charge can form the major part of the major part of chromophore and/or connector, or its cationic charge by substituent group at chromophore and/or the dyestuff that on connector, exists.

According to the present invention, term " chromophore " is meant the group derived from dyestuff, promptly derived from the group that the molecule of at least one absorption maximum is arranged in visible radiation scope (400-800nm), this absorb the Oxidation that requires not have formerly or with the combination of other any chemical substance.

For purpose of the present invention, when the chemical constitution of chromophore not simultaneously, will think that described chromophore is different.These chromophores can be derived from variety classes or derived from the chromophore of identical type, as long as they have different chemical constitutions.For example, chromophore can be selected from the azo dye kind, but the group chemical constitution of forming them is different.

A kind of particular embodiment according to the present invention, this mixed dye comprise at least a cation chromophore and preferred at least two kinds of cation chromophores, and this connector may be cation or non-cationic.

As useful in the present invention chromophore, can mention group: acridine derived from following dyestuff, the acridine ketone, anthranthrones, the anthrapyrimidine class, the anthraquinone class, azines, the azo class, the azomethine class, benzanthrones, benzimidazole, the benzimidazole ketone, benzindole class (benzindoles) Benzooxazole kind, benzo pyran, benzothiazoles, the benzoquinone class, two-azines (bis-azines), two-isoindoline class (bis-isoindolines), anilino-formyl class (carboxanilides), Coumarins, cyanine glycoside (azepine carbonyl anthocyanin, diaza carbonyl anthocyanin, dinitrogen diaze hemicyanine glycosides (diazahemicyanin), half anthocyanin (hemicyanin) and four azepine carbonyl anthocyanins), diazines, diketopyrrolopyrroles dioxazines, diphenylamine, diphenylmethanes, the dithiazine class, flavonoid is flavanthrones and flavonoid for example, fluorindines, first Class, the hydrazone class is aryl hydrazone class particularly, the hydroxyl ketone, indamines, the indanthrone class, indigoid (indigoids) and false indigoid, indophenols, the indoaniline class, the isoindoline class, the isoindoline class, the isoindoline ketone, isoviolanthrone class (isoviolanthrones), lactone, methine class (methines), the naphthalimide class, the naphthanilide class, naphtholactams, the naphthoquinone class, nitro dye is nitro (mixing) aromatic series dyestuff oxadiazole class oxazine class particularly, perilones, perinones perylene class, the azophenlyene class, phenothiazines, phthalocyanines, polyenoid class/carotenoids, the porphyrin class, pyranthrone, pyrazolanthrones (pyrazolanthrones), the pyrazoline ketone, pyrimidinoanthrones, the pyronine class, the quinacridine ketone, quinolines, quinophthalone class (quinophthalones), squaranes, the stilbene class, the tetrazolium class, thiazide, the thioindigo class, the thiopyronine class, the triarylmethane class, the xanthene class.

As useful in the present invention chromophore, can mention group more especially: acridine derived from following dyestuff, the acridine ketone, anthranthrones, the anthraquinone class, azines, the azo class, the azomethine class, benzanthrones, the benzoquinone class, two-azines, cyanine glycoside (azepine carbonyl anthocyanin, diaza carbonyl anthocyanin, dinitrogen diaze hemicyanine glycosides (diazahemicyanin), half anthocyanin (hemicyanin) and four azepine carbonyl anthocyanins), diazines, diketopyrrolopyrroles dioxazines, diphenylmethanes, the dithiazine class, flavonoid is flavanthrones and flavonoid for example, first

Class, the hydrazone class is aryl hydrazone class particularly, indamines, the indanthrone class, indigoid and false indigoid, indophenols, the indoaniline class, different a surname and blue ketone, the methine class, the naphthalimide class, naphtholactams, the naphthoquinone class, nitro dye is nitro (mixing) aromatic series dyestuff particularly, the azophenlyene class, phenothiazines, phthalocyanines, polyenoid class/carotenoids, the porphyrin class, pyranthrone, the quinacridine ketone, quinophthalone class (quinophthalones), the tetrazolium class, thiazide, the thioindigo class, the thiopyronine class, the triarylmethane class, the xanthene class.

Among operable nitro chromophore, can mention group derived from following chemical compound with non-limiting way according to the present invention:

-1,4-diaminourea-2-Nitrobenzol

-1-amino-2-nitro-4-(beta-hydroxy ethylamino) benzene

-1-amino-2-nitro-4-two (beta-hydroxy ethyl) aminobenzene

-1,4-two (beta-hydroxy ethylamino)-2-Nitrobenzol

-1-beta-hydroxy ethylamino-2-nitro-4-two-(beta-hydroxy ethyl-amino) benzene

-1-beta-hydroxy ethylamino-2-nitro-4-aminobenzene

-1-beta-hydroxy ethylamino-2-nitro-4-(ethyl) (beta-hydroxy ethyl) aminobenzene

-1-amino-3-methyl-4-beta-hydroxy ethylamino-6-Nitrobenzol

-1-amino-2-nitro-4-beta-hydroxy ethylamino-5-chlorobenzene

-1,2-diaminourea-4-Nitrobenzol

-1-amino-2-beta-hydroxy ethylamino-5-Nitrobenzol

-1,2-two (beta-hydroxy ethylamino)-4-Nitrobenzol

-1-amino-2-[three (hydroxymethyl) methylamino]-the 5-Nitrobenzol

-1-hydroxyl-2-amino-5-Nitrobenzol

-1-hydroxyl-2-amino-4-Nitrobenzol

-1-hydroxyl-3-nitro-4-aminobenzene

-1-hydroxyl-2-amino-4, the 6-dinitro benzene

-1-beta-hydroxy ethyoxyl-2-beta-hydroxy ethylamino-5-Nitrobenzol

-1-methoxyl group-2-beta-hydroxy ethylamino-5-Nitrobenzol

-1-beta-hydroxy ethyoxyl-3-methylamino-4-Nitrobenzol

-1-beta, gamma-dihydroxy propoxyl group-3-methylamino-4-Nitrobenzol

-1-beta-hydroxy ethylamino-4-beta, gamma-dihydroxy propoxyl group-2-Nitrobenzol

-1-beta, gamma-dihydroxypropyl amino-4-trifluoromethyl-2-Nitrobenzol

-1-beta-hydroxy ethylamino-4-trifluoromethyl-2-Nitrobenzol

-1-beta-hydroxy ethylamino-3-methyl-2-Nitrobenzol

-1-beta-aminoethyl amino-5-methoxyl group-2-Nitrobenzol

-1-hydroxyl-2-chloro-6-ethylamino-4-Nitrobenzol

-1-hydroxyl-2-chloro-6-amino-4-Nitrobenzol

-1-hydroxyl-6-two (beta-hydroxy ethyl) amino-3-Nitrobenzol

-1-beta-hydroxy ethylamino-2-Nitrobenzol

-1-hydroxyl-4-beta-hydroxy ethylamino-3-Nitrobenzol.

Among operable azo chromophore, can mention derived from the group that is described in the cationic azo dyestuff among patent application WO 95/15144, WO 95/01772 and the EP-714954 according to the present invention.

What can also mention in derived from the group of following azo dye is the following material that is described in the ColorIndex International third edition:

-Red-1 200 7

-Indian yellow 9

-acid black 1

-alkalescence red 22

-alkalescence red 76

-basic yellow 57

-bismarck brown 16

-quinoline yellow 6

-acid orange 7

-Xylene Red 33

-acid red 35

-bismarck brown 17

-acid yellow 23

-acid orange 24

-disperse black 9.

Can also mention 1-(4 '-ADP base azo)-2-methyl-4-[two (beta-hydroxy ethyl) amino] benzene and 4-hydroxyl-3-(2-methoxyphenyl azo)-1-naphthalene sulfonic aicd.

What can mention in the quinone chromophore is group derived from following dyestuff:

-Red-1 200 5

-solvent violet 13

-acid violet 43

-disperse violet 1

-disperse violet 4

-disperse blue 1

-disperse violet 8

-disperse blue 3

-dispersion red 11

-acid blue 62

-disperse blue 7

-alkali blue 22

-disperse violet 15

-alkali blue 99

With following chemical compound:

-1-N-methyl morpholine propyl group amino-4-hydroxy anthraquinone

-1-amino propyl amino-4-methylamino anthraquinone

-1-amino propyl amino anthraquinone

-5-beta-hydroxy ethyl-1, the 4-diamino-anthraquinone

-2-aminoethylamino anthraquinone

-1,4-two (beta, gamma-dihydroxypropyl amino) anthraquinone.

What can mention in azine (azine) chromophore is group derived from following compounds:

-alkali blue 17

-alkalescence red 2.

Among the operable indoamine chromophore according to the present invention, what can mention is group derived from following compounds:

-2-beta-hydroxy ethylamino-5-[two (β-4 '-hydroxyethyl) amino]-anilino--1, the 4-benzoquinone;

-2-beta-hydroxy ethylamino-5-(2 '-methoxyl group-4 '-amino) anilino--1, the 4-benzoquinone;

-3-N (2 '-chloro-4 '-hydroxyl) phenyl acetylaminohydroxyphenylarsonic acid 6-methoxyl group-1, the 4-benzoquinone imine;

-3-N (3 '-chloro-4 '-methylamino) phenyl urea groups-6-methyl isophthalic acid, the 4-benzoquinone imine;

-3-[4 '-N-(ethylamino formyl methyl) amino] phenyl urea groups-6-methyl isophthalic acid, the 4-benzoquinone imine.

Can also mention being described in document US 5888252, EP 1133975, WO03/029359, and EP 860636, and WO 95/01772, the chromophore among WO 95/15144 and the EP 714954.Can also mention and be described in encyclopedia " The chemistry of syntheticdye ", K.Venkataraman, 1952, Academic Press, the 1-7 volume, encyclopedia " Kirk-Othmer " " Chemical Technology ", " Dyes and Dye Intermediate " chapter, 1993, Wiley﹠amp; Sons, and encyclopedia " Ullmann ' s Encyclopedia ofIndustrial Chemistry " the 7th edition, Wiley﹠amp; Chromophore in each chapter of Sons.

Preferably, chromophore is selected from particularly aryl hydrazone, phenothiazine, acridine, anthocyanin four azepine carbonyl anthocyanins, anthraquinone, methine, azomethine, diketopyrrolopyrrolecocrystals, indigo and nitro nitro (mixing) aromatic series chromophore particularly for example of azo, xanthene, hydrazone.

According to one even more a plurality of particular, chromophore is selected from particularly aryl hydrazone, anthocyanin four azepine carbonyl anthocyanins, anthraquinone, methine, azomethine and nitro nitro (mixing) aromatic series chromophore particularly for example of azo, hydrazone.

This mixed-cation dyestuff preferably comprises the different chromophores of 2-4 kind, with preferred two or three different chromophore.

According to a particular, mixed dye is a dication at least, and cation implant (cationic filler) carries by chromophore and/or by connector.According to the version of this embodiment, at least two chromophores are cation chromophores, and connector can be a cationization.

Preferably, mixed dye of the present invention is corresponding to following structural formula

Dyestuff 1-L-dyestuff 2

Wherein L is cation or non-cationic connector, and dyestuff 1 is different chromophores with dyestuff 2.

The cation chromophore normally contains the chromophore of quaternary nitrogen (quaternized nitrogen) atom.

These cation chromophores are, for example directly or comprise the chromophore of following group as substituent group: alkylammonium, imidazoles, pyridine, quinoline, acridine, benzimidazole, the two triazoles (benzobistriazolium) of benzo, benzopyrazoles (benzopyrazolium) (or indazole), benzopyridazinium, benzoquinolium, benzothiazole, benzotriazole benzoxazole, bipyridyl, two tetrazoliums, thiazoline, imidazopyridine, indole, isoquinolin, naphtho-imidazoles Nai Bing oxazole, naphtho-pyrazoles oxadiazole oxazole oxazole and pyridine, azophenlyene Fen oxazole, pyrazine, pyrazoles, the pyrazolyl triazole, pyridine-imidazole, quinoline (quinolium), tetrazolium, thiadiazoles, thiazole, thiazole and pyridine (thiazolopyridinium), the thiazolyl imidazoles, thiopyrylium, triazole or xanthene group.

Preferably, these chromophores directly or as substituent group comprise alkylammonium, imidazoles, pyridine, acridine, benzimidazole, benzopyrazoles (benzopyrazolium) (or indazole), benzopyridazinium, bipyridyl, two tetrazolium, imidazopyridine, indole, naphtho-imidazoles, naphtho-pyrazoles, azophenlyene, pyrazine, pyrazoles, pyridine-imidazole, tetrazolium or xanthene group.

The example of useful in the present invention cation chromophore is described in front.

In patent application WO 95/01772, WO 95/15144, EP714954, EP 318294 and WO03/029359, provided other example.

According to a kind of version, mixed dye comprises the cationic azo chromophore.These chromophores for example are described in

EP?0?850?636，

FR?2?788?433，EP?920?856，WO?99/48465，FR?2?757?385，

EP-850?637，EP?918?053，WO?97/44004，FR?2?570?946，

FR?2?285?851，DE?2?538?363，FR?2?189?006，FR?1?560?664，

FR?1?540?423，FR?1?567?219，FR?1?516?943，FR?1?221?122，

DE?4?220?388，DE?4?137?005，WO?01/66646，US 5?708?151，

WO?95/01772，WO?95/15144，GB?1?195?386，US?3?524?842，

US?5?879?413，EP?1?062?940，EP?1?133?976，GB?738?585，

DE?2?527?638，FR?2?275?462，GB?1974-27645，ActaHistochem.(1978)，61(1)，48-52，Tsitologiya(1968)，10(3)，403-5，Zh.Obshch.Khim.(1970)，40(1)，195-202，Ann.Chim.(Rome)(1975)，65(5-6)，305-14，Journal?ofthe?Chinese?Chemical?Society(Taipei)(1998)，45(1)，209-211，Rev.Roum.Chim.(1988)，33(4)，377-83，Text.

Res.J.(1984)，54(2)，105-7，Chim.Ind.(Milan)(1974)，56(9)，600-3，Khim.Tekhnol.(1979)，22(5)，548-53，Ger.Monatsh.Chem.(1975)，106(3)，643-8，MRLBull.Res.Dev.(1992)，6(2)，21-7，Lihua?Jianyan，Huaxue?Fence(1993)，29(4)，233-4，Ann.Chim.(Rome)(1975)，65(5-6)，305-14，Dyes?Pigm.(1992)，19(1)，69-79，Dyes?Pigm.(1989)，11(3)，163-72

In the present invention, the term connector is meant atom or one group of atom that chromophore is separated from mixed dye.The atom of connector must satisfy following condition: the position of absorption maximum on wave-length coverage of forming the chromophore of mixed dye, absorption maximum when promptly not linking together by connector with respect to each chromophore independent measurement, change and be no more than 30 nanometers, be no more than 15 nanometers more especially, preferably be no more than 10 nanometers.Connector can be cationization or non-cationic.Preferably, these connector right and wrong are cationic.

According to a kind of version, thereby connector is to separate atom or one group of atom that each chromophore stops the electron delocalization of each chromophore.

Connector is C for example ₁-C ₂₀, preferred C ₁-C ₁₄With in addition C more particularly ₁-C ₆The chain based on hydrocarbon of straight chain, side chain or cyclic optional replacement, one or more carbon atoms of described chain based on hydrocarbon can by at least one hetero atom for example sulfur, nitrogen or oxo for and/or by at least one contain heteroatomic group for example carbonyl replace, described chain based on hydrocarbon can be undersaturated or contain at least one optional alkylidene that replaces; The optional arlydene that replaces; The optional bivalence terephthalate amido that replaces; The optional divalent heterocycle that replaces is the bivalence triazine radical for example, or-the NH-CO-group.

Described chain based on hydrocarbon, and (Asia) alkyl, can replace, for example by particularly C1-C6 alkoxyl, C1-C6 (many) hydroxy alkoxy base, amino, the alkyl amino replacement of at least one hydroxyl, alkoxyl, described alkyl amino comprises one or more optional identical or different C1-C6 alkyl that have at least one hydroxyl, at least one halogen etc.

The example of the connector that can mention comprises alkylidene (C _nH _2n), more particularly contain 1-14 carbon atom and preferred 1-6 carbon atom, for example methylene, ethylidene, propylidene etc. optionally are substituted as mentioned above, optional by at least one hetero atom for example sulfur, nitrogen or oxygen be interrupted and/or contained heteroatomic group for example carbonyl be interrupted; Optional (mix) arlydene that replaces, for example phenylene or naphthylene, phenanthrylene, triazine radical, pyrimidine radicals, pyridine radicals, pyridazinyl or quinoxalinyl, it is optional replacement; Alkyl-aryl-alkyl group or alkyl-heteroaryl-alkyl group, the moieties of these groups more particularly comprise 1-6 carbon atom.

Above-mentioned (mixing) arlydene can be replaced by one or more following groups: the C1-C6 alkyl; The C1-C6 alkoxyl; C2-C6 (many) hydroxy alkoxy base; Amino; Amino with one or more identical or different C1-C6 alkyl and/or the replacement of C6 aryl, optional at least one hydroxyl that has of described alkyl, described C6 aryl is optional by one or more C1-C6 alkyl, C1-C6 alkoxyl, C2-C6 (many) hydroxy alkoxy base or amino the replacement, perhaps the amino that is replaced by one or more optional identical or different C1-C6 alkyl that have at least one hydroxyl; Trifluoromethyl; Cyano group; The alkyl amido of alkyl amido, particularly C1-C6; R represents the RCOO-of C1-C6 alkyl.

The special more example that can mention comprises:

Wherein R can be H, CF ₃, CO ₂Me, CO ₂Et, CN or CONH ₂, R ' represents hydrogen atom, and is optional by one or more hydroxyls, C ₁-C ₂Alkoxyl, C ₂-C ₄(many) hydroxy alkoxies base, amino, C ₁-C ₂(2) C of alkylamine replacement ₁-C ₈Alkyl or the optional aryl that replaces, R " the expression hydrogen atom, optional by one or more hydroxyls, C ₁-C ₂Alkoxyl, C ₂-C ₄(many) hydroxy alkoxies base, amino, C ₁-C ₂(2) C of alkyl amino replacement ₁-C ₄Alkyl or the optional aryl that replaces, n are greater than 0, more especially between the 1-10 and preferably between 1-5; Guarantee the electric neutrality of chemical compound by the receivable anion An of one or more cosmetics.

The connector that can mention comprises the triazines that is described among the WO 03/029359, the alkylidene of mentioning in US5708151 and alkyl-aryl-alkyl of mentioning in US 5708151.

It should be noted that to purpose of the present invention and all be considered connector at any alkylidene that main chain connects dyestuff 1/ dyestuff 2.

An is the organic or inorganic anion, is selected from for example halide anion such as chlorine, bromine, fluorine or iodine anion; Hydroxyl, sulfate radical; Bisulfate ion; (C ₁-C ₆) alkyl sulfate for example methylsulfate or ethyl sulphate; Phosphate radical; Carbonate; Bicarbonate radical; The perchlorate; Acetate; Tartrate anion; Citrate; Oxalate; (C ₁-C ₆) alkyl azochlorosulfonate methanesulfonate for example; The optional C that uses ₁-C ₄The aryl sulfonic acid root that alkyl replaces, for example 4-tosylate.

With way of example, mixed dye can be represented by following formula:

Wherein L is aforesaid connector, and R1 and R1 ' are independently selected from alkyl, and preferred C1-C6 alkyl is optional by one or more hydroxyls, C ₁-C ₂Alkoxyl, C ₂-C ₄(many) hydroxy alkoxies base, amino, C ₁-C ₂(2) alkyl amino or the optional aryl replacement that replaces and R2 and R2 ' are independently selected from the C1-C6 alkyl, and be optional by one or more hydroxyls, C ₁-C ₂Alkoxyl, C ₂-C ₄(many) hydroxy alkoxies base, amino or C ₁-C ₂(2) alkyl amino replaces; The optional phenyl that replaces; An represents one or more identical or different, unit prices or multivalent anions, as top definition.

The example corresponding to the cation direct dye of following formula that can mention comprises:

Compositions of the present invention contains the mixed dye of 0.001-20% usually with respect to composition total weight.Preferably, with respect to composition total weight, mixed dye quantity is at 0.005-10%, even more preferably at 0.01-5%.

Dyestuff of the present invention can begin according to known chemical reactions preparation own from the functionalized chromophore that can react with selected connector.For example, when connector was triazine group, chromophore should contain reactive amino, OH or SH base so, synthetic can carrying out according to following scheme.

According to first step, with first chromophore and form maybe can form connector chemical compound for example cyanuric chloride mix.After this reaction is finished, in reaction medium, add second chromophore.This order can repeat and form the same number of number of times of reactive group on the chemical compound that maybe can form connector.

For preparation mixed dye dyestuff 1-L-dyestuff 2, connector to the molar ratio of dyestuff 1 usually 10: 1-0.5: between 1, and preferably equal 1: 1.This ratio can change when using more than a connector or several chromophore.

Reaction temperature is usually at-10 ℃-+130 ℃, preferred-5 ℃-+100 ℃.Response time is depended on the reactivity and the reaction temperature of the reactant of existence.Usually, the response time is 10 minutes-8 hours, preferred 30 minutes-4 hours.

The pH of reaction is generally 3-10, preferred 4-8.

Reaction can carried out separately or in as the water of mixture and/or organic solvent.Several publications have been described chemically combined reaction between two identical chromophores.The example that can mention comprises document ISBN 0901956759, and WO 02/78596, and DE 19845640, WO 03/029359 and US 5708151.

In addition, above-mentioned reaction or connector with can be that dyestuff also can not be the reaction of two kinds of different chemical compounds of dyestuff, at document WO 03/029359 for example, DE 3335956, WO03/30909, WO 03/18021, Journal of Medicinal Chemistry 43 (9), 2000,1892-97; Chemiker Zeitung 117 (7-8), 1987, be described among the 241-5.

The present composition comprises basifier, and this basifier can be any basifier that is generally used for cosmetics.These basifiers that can mention for example are ammonia, alkaline carbonic acid salt, alkanolamine, as single-, two-and three-ethanolamine and derivant thereof, sodium hydroxide, potassium hydroxide and following formula (II) chemical compound:

Wherein W is unsubstituted or by hydroxyl or C ₁-C ₄The propylidene that alkyl replaces; Ra that can be identical or different, Rb, Rc and Rd represent hydrogen atom, C ₁-C ₄Alkyl or C ₁-C ₄Hydroxy alkyl.

The pH of dye composite of the present invention is preferably at 8-11.

The present composition comprises oxidant.This oxidant is the oxidant that is generally used for keratin fibre oxidation dyeing, they are for example hydrogen peroxide, urea peroxide, alkali metal bromate, persalt such as perborate and persulfate, peracid and oxidation alcohol, in oxidase, can mention peroxidase, 2-electronics oxidoreductase such as uricase (uricases) and 4-electronics oxygenase such as laccase.Preferred especially hydrogen peroxide.

Dye composite of the present invention also can comprise the direct dyes that one or more are generally used for the dyeing keratinous fibres field.In this respect, can mention nitrobenzene dye, azo direct dye and methine direct dyes especially.These direct dyess can be nonionic, anionic property or cationic.Preferably, these extra direct dyess are cationic.

Dye composite of the present invention can contain one or more oxidation bases and/or one or more colour couplers that is generally used for dyeing keratinous fibres.

What can mention in the oxidation base is p-phenylenediamine (PPD) class, diphenyl Alkylenediamine class, p-aminophenyl phenols, two p-aminophenyl phenols (bis-para-aminophenols), o-aminophenol class and heterocycle bases, and addition salts.

May be particularly mentioned m-diaminobenzene. class, m-aminophenyl phenols, a diphenols (meta-diphenols), naphthyl colour coupler and heterocyclic coupler agent in the colour coupler, and addition salts.

In compositions of the present invention, with respect to the gross weight of dye composite, the amount that colour coupler exists separately is generally about 0.001-10%, preferably about 0.005-6%.

Be present in the oxidation base in the present composition, with respect to the gross weight of dye composite, the amount of Cun Zaiing is generally about 0.001-10% separately, preferably about 0.005-6%.

Usually, the addition salts that can be used for oxidation base among the present invention and colour coupler is selected from the addition salts with acid especially, for example methyl or sulfovinate, citrate, succinate, tartrate, lactate, toluene fulfonate, benzene sulfonate, phosphate and acetate of hydrochloride, hydrobromide, sulfate, alkyl sulfate for example, with with the addition salts of alkali, for example sodium hydroxide, potassium hydroxide, ammonia, amine or alkanolamine.

Being suitable for painted medium, being also referred to as dye carrier, is the cosmetic medium, is made up of the mixture of water or water and at least a organic solvent usually, and described organic solvent is used for being dissolved in the insufficient chemical compound of water dissolubility.Can mention for example C as organic solvent ₁-C ₄Low-level chain triacontanol is ethanol and isopropyl alcohol for example; Polyhydric alcohol and polyol ethers be butoxy ethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether for example, and aromatic alcohols for example benzylalcohol or phenyl phenol, or its mixture.

With respect to the dye composite gross weight, the ratio that solvent preferably exists is about 1-40%, even 5-30% more preferably from about.

Dye composite of the present invention also can comprise the multiple auxiliary agent that is generally used in the hair dyeing composition, anion for example, cation, nonionic, both sexes or zwitterionic surfactant or its mixture, anion, cation, nonionic, both sexes or amphoteric ion polymer or its mixture, inorganic or organic thickening agent, anion particularly, cation, nonionic and both sexes associtation polymer thickening agent, antioxidant, penetrating agent, chelating agen, aromatic, buffer agent, dispersant, filler for example can be the volatilization or the silicone of nonvolatile or modification, film former, ceramide, antiseptic and opacifier.

With respect to the weight of compositions, above-mentioned auxiliary agent exists with the amount of 0.01-20 weight % separately usually.

Needless to say, the added compound that selection is this or these kinds are optional that those skilled in the art will be careful makes the inherent favourable character of oxidation dyeing composition of the present invention not be subjected to or not be subjected to substantially the adverse effect of these added compound addings.

Colouring compositions according to the present invention can be various ways, for example is liquid, Emulsion or gel form, or for being fit to any other form of dyeing keratin fibres, particularly people's hair.

Method of the present invention is that compositions as defined above wherein of the present invention is applied to the method on the fiber.This oxidant can add in the said composition in use, perhaps can be from containing its oxidising composition, simultaneously or in succession its adding is comprised in the compositions of this mixed dye.In this case, described oxidant is comprised in the compositions except comprising this mixed dye a kind of.

According to a particular, the present composition that comprises mixed dye preferably mixes with the compositions that comprises at least a oxidant in being suitable for painted medium when in use, and the amount of described oxidant is the amount that is enough to the blast that obtains expecting.Then the mixture that obtains is applied on the keratin fiber.After about 3-50 minute action time, preferably about 5-30 minute, rinsing keratin fiber, shampoo were washed, rinsing is dry then once more.

Oxidising composition can also contain and is generally used in the hair colouring compositions and various auxiliary agents as defined above.

The pH of oxidising composition that comprises oxidant is for after dye composite mixes, and the pH that is applied to the resulting composition on the keratin fiber is preferably at about 7-12, more preferably at 8-11.Can be by being generally used in the dyeing keratinous fibres and as defined above acidulant or basifier is adjusted to expected value.

Finally being applied to and promptly can be various ways with compositions on the keratin fiber, for example is the form of liquid, Emulsion or gel, perhaps for being applicable to particularly other any forms of people's hair of dyeing keratin fibres.

Another theme of the present invention is many compartments dyeing apparatus or test kit, and wherein first compartment blast dye composite and second compartment that comprises this mixed-cation dyestuff as defined above that comprise the invention described above comprises oxidant.Described device can be equipped with and be used to apply the device of expectation mixture to the hair, for example device of describing among the applicant's the patent FR-2586913.

The following examples are used to illustrate the present invention rather than limit the scope of the invention.

Embodiment

Synthetic embodiment

Step 1:

Under agitation will add in the 500ml there-necked flask in room temperature at the 2.4g cyanuric chloride in the 50ml acetone.Reaction medium is transparent.Additional proportion is respectively the water of 50ml and 100ml and the mixture of ice, and reaction medium is positioned in the ice territory at 0 ℃.

After stirring several seconds, obtain the white suspension body.PH value is 2.8.Use Dropping funnel adding 3.2g (i) is dissolved in the solution in the 100ml water, by saturated K ₂CO ₃Solution carefully keeps the pH of reaction medium at 4-6, and keeps reaction medium in the temperature that is lower than 5 ℃.

Behind this reinforced end, by the saturated K of even adding ₂CO ₃Solution-stabilized pH to 4.8.Then mixture is returned to room temperature.94%) and contrast formation product that mass spectrum (m/z:363-365-367) shows exclusiveness basically (ii) HPLC (relative purity:.

Comprise then and be dissolved in 50ml H in advance ₂3.42g solution (iii) in the O/EtOH mixture (1/1) is added in the above-mentioned reaction medium, carefully keeps pH at 4-6.Add finish after, keep pH between 4.9-5 15 minutes.Then in 44 ℃ of reacting by heating media 2.5 hours.Reaction medium is cooled to room temperature, pours into then in the conical flask that contains 1 liter of isopropyl alcohol and acetone soln.Precipitation appears.Filtering-depositing is dry and analyze in exsiccator.Obtaining 6.08g (productive rate=86%) purity equals 98% (purity relatively, (product (iv) for brown ceramic powder HPLC).

Step 2:

9g is dissolved in (iv) being positioned in the 300ml water to be equipped with condenser, pH probe and to contain in the there-necked flask of charging hopper of 1N sodium hydroxide solution.Then reaction medium is heated to 85 ℃ (oil bath temperatures: 96 ℃) and uses sodium hydroxide solution that pH is transferred to 7.7-8.Add the amine (3ml) that is diluted in the 20ml water then very lentamente, carefully monitor pH (pH＜8).In case reinforced finishing just is heated to reaction medium 92 ℃ (oil bath temperatures: 118 ℃) and stirs up to pH and be stabilized in 7.7-8.

After reaction 1 hour, the cooling reaction medium is poured in the conical flask that contains 1 liter of acetone then.Product is precipitated out.Filter dry and analysis in exsiccator then.(chemical compound is (productive rate=82%, HPLC purity: 92%) v) to obtain the 7.1g brown ceramic powder.

Mass spectrum (ESI+): m/z=352

NMR ( ¹H, 400MHz, MeOD): 3.86-3.87ppm (wide s, 4H), and 4.05ppm (s, 6H), 4.12ppm (s, 6H), 4.88ppm (wide s, 4H), and 7.10-7.12ppm (d, 2H), 7.28-7.26ppm (d, 2H), and 7.55 ppm (s, 2H), 7.69ppm (s, 2H), and 7.77-7.79ppm (d, 2H), 7.97-7.95ppm (d, 2H), and 8.09-8.04ppm (m, 4H)

Reagent implementation step 2 shown in below using has been synthesized following chemical compound.

Dyeing embodiment

By dyestuff C1-C5 (consumption: 4.7 * 10 ^-4Mol) and following dye composite prepare dye composite described in the table 1:

Compositions A

As (50/50C8/C10) alkyl polyglucoside of 60% aqueous buffer solution, sell with title Oramix by SEPPIC company	10g
		Benzylalcohol	10g
The PEG400 that contains 8 ethylene oxide units	12g
		Mixed dye C1-C5	4.7×10 ^-4mol
20.5% ammonia	13g
		Demineralized water	Add to 100g

Compositions B

As (50/50C8/C10) alkyl polyglucoside of 60% aqueous buffer solution, sell with title Oramix by SEPPIC company	10g
		Benzylalcohol	10g
The PEG400 that contains 8 ethylene oxide units	12g
		Mixed dye C1-C5	4.7×10 ^-4mol
The amino methyl propanol	In right amount to pH10.5
		Demineralized water	Add to 100g

When in use, (weight is to weight, pH=3.5) aqueous hydrogen peroxide solution or mix with acidifying water (pH=3.5) with above-mentioned composition and 40V.

This dye composite is 9.5-10 at mixed pH.

Mixture is applied on natural Lycoperdon polymorphum Vitt (NG) that contains 90% poliosis or the hair strands of the perming (permanent-waved) Lycoperdon polymorphum Vitt (PG).The time of staying on hair strands is room temperature 20 minutes.Shampoo is washed described hair strands then.

After the drying, by vision with by measuring L ^*a ^*b ^*(CM 2002 colorimeters, light source D65-10CSI) evaluate color absorbing state.

The result puts in order in following table 1.

Table 1

The hair type	Compositions	L ^＊	a ^＊	b ^＊	Blast/non-blast dye composite
						NG	C1+A+H ₂O ₂	36.7	3.0	2.5
	The C1+A+ acidifying water	37.7	3.0	3.0
							C1+B+H ₂O ₂	36.5	3.1	1.0
	The C1+B+ acidifying water	37.2	3.4	1.4	1.3
						PG	C1+A+H ₂O ₂	34.5	2.0	2.5
	The C1+A+ acidifying water	35.6	2.5	2.2
							C1+B+H ₂O ₂	35.2	2.4	2.0
	The C1+B+ acidifying water	35.5	2.7	1.4	1.6
						NG	C2+A+H ₂O ₂	36.2	3.5	1.2
	The C2+A+ acidifying water	36.4	3.3	2.5
							C2+B+H ₂O ₂	36.3	4.0	0.2

The C2+B+ acidifying water	37.6	4.0	0.0	1.9
					PG	C2+A+H ₂O ₂	33.9	3.0	0.7
The C2+A+ acidifying water	36.2	3.5	0.9

	C2+B+H ₂O ₂	36.1	4.2	-0.4
					The C2+B+ acidifying water	36.6	3.8	0.6	2.8
NG	C3+A+H ₂O ₂	35.6	3.3	0.9
					The C3+A+ acidifying water	36.5	3.1	1.5
	C3+B+H ₂O ₂	36.9	4.1	0.0
					The C3+B+ acidifying water	36.3	3.1	1.5	0.9
PG	C3+A+H ₂O ₂	34.2	2.4	1.5
					The C3+A+ acidifying water	35.1	2.5	1.3
	C3+B+H ₂O ₂	33.5	2.4	1.1
					The C3+B+ acidifying water	34.6	2.7	1.1	0.6
NG	C4+A+H ₂O ₂	36.0	3.7	1.0
					The C4+A+ acidifying water	37.7	3.8	1.0
	C4+B+H ₂O ₂	36.4	3.5	1.3
					The C4+B+ acidifying water	37.4	4.0	0.9	1.4
PG	C4+A+H ₂O ₂	34.1	2.0	2∶3

The C4+A+ acidifying water	34.7	2.5	1.5
						C4+B+H ₂O ₂	34.8	2.9	1.5
The C4+B+ acidifying water	35.5	3.1	0.9	2.3
					NG	C5+A+H ₂O ₂	36.2	3.2	-0.2
The C5+A+ acidifying water	38.4	3.3	0.0

	C5+B+H ₂O ₂	37.0	3.5	0.2
					The C5+B+ acidifying water	36.7	3.2	0.5	0.6
PG	C5+A+H ₂O ₂	33.5	2.8	0.7
					The C5+A+ acidifying water	35.4	2.9	0.2
	C5+B+H ₂O ₂	34.4	3.0	0.9
					The C5+B+ acidifying water	36.5	3.5	-0.1	3.2

Calculate the comparison between blast and the non-blast condition in the following manner:

ΔE = \sqrt{{(L_{1} * - L_{nl} *)}^{2} + {(a_{l} * - a_{nl} *)}^{2} + {(b_{l} * - b_{nl} *)}^{2}}

Wherein, L ^* ₁, a ^* ₁, b ^* ₁The chromatic value of representative under the blast condition, and L ^* _N1, a ^* _N1, b ^* _N1The chromatic value of representative under non-blast condition.

These structures show that resulting intensive painted composition for dye media is insensitive.Especially, (medium A+H under the blast condition ₂O ₂) and under non-blast condition (medium B+ acidifying water), obtain close painted.

The shampoo fastness

Following dye composite is from dyestuff C1-C5 (4.7 * 10 ^-4Mol) and dye carrier A prepare.

In when dyeing, (weight is to weight, pH=3.5) aqueous hydrogen peroxide solution mixing with above-mentioned composition and 40V.This dye composite is 9.5-10 at mixed pH.

Then painted hair strands shampoo is washed 6 times dyeing between twice shampoo washing.The initial color of color after 6 shampoo washings and colored hair thread is compared by vision with by colour measurement.This shampoo fastness (shampoo fastness) measures according to following formula Δ E in painted natural hair and painted hair-waving, L before it has used shampoo to wash 6 times ₀ ^*a ₀ ^*b ₀ ^*L after numerical value and shampoo are washed 6 times ₁ ^*a ₁ ^*b ₁ ^*L on every type the tuft of numerical value ^*a ^*b ^*Numerical value is measured:

ΔE = \sqrt{{(L_{1} * - L_{0} *)}^{2} + {(a_{1} * - a_{0})}^{2} + {(b_{1} * - b_{0} *)}^{2}}

This colour measurement is the result be summarised in the following table 2.

Table 2

These results show that lightening composition of the present invention demonstrates the selectivity between extraordinary shampoo fastness and very little natural hair and the hair-waving.

Claims

1. blast dye composite, it is included in oxidant, basifier and cation mixed dye in the suitable dyeing medium, and wherein the consumption of basifier is to make said composition pH greater than 7 amount, and this cation mixed dye is corresponding to following structure:

Anion An wherein is the organic or inorganic anion, is selected from halide anion; Hydroxyl, sulfate radical; Bisulfate ion; C ₁-C ₆Alkyl sulfate; Phosphate radical; Carbonate; Bicarbonate radical; The perchlorate; Acetate; Tartrate anion; Citrate; Oxalate; C ₁-C ₆Alkyl azochlorosulfonate; The optional C that uses ₁-C ₄The aryl sulfonic acid root that alkyl replaces.

2. compositions as claimed in claim 1, wherein with respect to the gross weight of compositions, the amount of mixed dye is 0.005%-10%.

3. as the compositions of claim 1 or 2, also comprise the mixed dye direct dyes in addition of one or more claim 1 or 2 definition.

4. as the compositions of claim 1 or 2, comprise the oxidation base that is selected from p-phenylenediamine (PPD) class, diphenyl Alkylenediamine class, p-aminophenyl phenols, o-aminophenol class and heterocycle bases and addition salts thereof.

5. as the compositions of claim 1 or 2, comprise the colour coupler that is selected from m-diaminobenzene. class, m-aminophenyl phenols, a diphenols, naphthyl colour coupler and heterocyclic coupler agent and addition salts thereof.

6. as the compositions of claim 1 or 2, wherein pH is 8-11.

7. as the compositions of claim 1 or 2, wherein said basifier be selected from ammonia, alkaline carbonic acid salt, list-, two-and three-ethanolamine, sodium hydroxide, potassium hydroxide and following formula (II) chemical compound:

Wherein W is unsubstituted or by hydroxyl or C ₁-C ₄The propylidene that alkyl replaces; Identical or different Ra, Rb, Rc and Rd represent hydrogen atom, C ₁-C ₄Alkyl or C ₁-C ₄Hydroxy alkyl.

8. as the compositions of claim 1 or 2, wherein said oxidant is a hydrogen peroxide.

9. the method for oxidising dyeing keratin fiber is characterised in that to apply each defined dye composite of claim 1-6 to fiber, and stops blast and the painted time that is enough to produce expectation.

10. method as claimed in claim 9, it comprises oxidant, wherein said oxidant is comprised in the compositions that is different from claim 1 or the 2 defined compositionss that comprise mixed dye.

11. multi-compartment device, wherein first compartment dye composite and second compartment that comprise claim 1 comprises oxidant, and wherein dye composite comprises basifier and mixed dye.

12. the blast dye composite of claim 1 is used for the purposes of blast dyeing keratin fibres.

13. the purposes of claim 12 obtains good shampoo fastness.

14. the purposes of claim 12 obtains the fastness of good dyeing with respect to the time.

15. the purposes of claim 12, being passed in time is stable dye composite.