CN103415279A

CN103415279A - Composition

Info

Publication number: CN103415279A
Application number: CN2012800124516A
Authority: CN
Inventors: S·N·巴彻勒
Original assignee: Unilever NV
Current assignee: Unilever NV
Priority date: 2011-03-10
Filing date: 2012-01-26
Publication date: 2013-11-27
Also published as: WO2012119810A2; BR112013022596A2; WO2012119810A3; EP2683353A2

Abstract

Hair dye composition comprising a polymer dye, the polymer dye comprising a positively charged polymer covalently bound to a negatively charged reactive dye in which the reactive dye is a bis-azo dye of the structure (I) in which the A ring is substituted by at least one heterocyclic reactive group and/or a sulphonate group.

Description

Compositions

The present invention relates to comprise Haircare composition and a kind of hair colouring methods of polymeric dye.

Background of invention

US4182612(Gillette) the covalently bound cationic polymer of polymine for chromotrichial dyestuff is disclosed.Dyestuff used does not carry the electronegative substituent group that can produce low key tone.

FR2456764(L ' Or é al) disclose and connected the quaternary polyamines for chromotrichial dyestuff.Dyestuff used does not carry the electronegative substituent group that can produce low key tone.

WO2008/009579(Ciba) and WO2009/090121 to WO2009/090125(BASF) the covalently bound dye of positive ion to polymer is disclosed for chromotrichia.

Common unsettled Unilever application WO2011/113680 discloses a kind of composition for hair dying, and it comprises the positively charged polymer covalently bonded to electronegative reactive dye.Yet, unexposed concrete reactive dye of the present invention.

Consider prior art, still need to provide the improved composition for hair dying of dark blue tone to human hair.Skipper is called in hair dyeing as the basis of black dull and brown tune.

Invention is described

The present invention relates to a kind of composition for hair dying that comprises polymeric dye, described polymeric dye comprises the positively charged polymer covalently bonded to electronegative reactive dye, wherein said reactive dye be following structure two-azo dye:

Wherein said A ring is replaced by least one heterocyclic active group and/or sulfonate groups.

In aspect second, the invention provides the hair colouring methods that is applied to hair by the compositions by first aspect of the present invention.

In aspect the 3rd, the present invention relates to the purposes of above-mentioned polymer for pigmented hair.

Detailed Description Of The Invention

Dye polymer

Compositions of the present invention comprises as the dye polymer defined in claim 1.

The hydrolysis reactive dye be wherein active group with hydroxide radical anion HO ^-, rather than with the dyestuff of polymer reaction.Preferably, in compositions, contain with respect to the reactive dye of the existing dyestuff of every 10000ppm lower than the 100ppm hydrolysis, more preferably less than 5ppm.Most preferably, in compositions, there are not the reactive dye of hydrolysis.This dyestuff can be removed by dialysis.

The reactive dye of hydrolysis are not covalently bonded to polymer.Reactive dye with two active groups, formed covalent bond with polymer reaction at one, and another with HO ^-In the situation of reaction, do not classify as the dyestuff of the hydrolysis in category of the present invention.

Reactive dye

In the present invention, the reactive dye of polymer used are the blueness of following form two-azo dye:

Wherein A ring is by the heterocyclic active group with optionally by sulfonate groups, replaced, and B encircles the group that optionally is selected from heterocyclic active group, sulfo group oxygen ethylsulfonyl active group and sulfonate groups and replaces.

Preferably, the B ring is replaced by the heterocyclic active group.

The heterocyclic active group preferably is bonded to halogen or quaternary ammonium group, the nitrogenous aromatic ring of Cl and F most preferably, the NH of itself and polymer ₂Or the NH radical reaction forms covalent bond.Preferred heterocyclic active group is dichlorotriazine base, difluoro chloropyrimide, single Cyanuric trifluoride base, single fluorine chlorotriazine base, dichloro-quinoxaline, two Cyanuric trifluorides, monochloro triazine radical and trichloropyrimidine.

Especially preferred heterocyclic active group is:

R wherein ₁Be selected from H or alkyl, preferably H.

X is selected from F or Cl.

When X=Cl, Z ₁Be selected from-Cl ,-NR ₂R ₃,-OR ₂,-SO ₃Na.

When X=F, Z ₁Be selected from-NR ₂R ₃.

R ₂And R ₃Be independently selected from H, alkyl and aryl.Aryl is phenyl preferably, and preferably by-SO ₃Na or-SO ₂CH ₂CH ₂OSO ₃Na replaces.Alkyl group is methyl or ethyl preferably.

Preferably, heterocyclic active group position bonding between on A and B ring.

Phenyl can further be replaced by suitable uncharged organic group, and the molecular weight of preferred described organic group is lower than 200.Preferred group comprises-CH ₃,-C ₂H ₅With-OCH ₃.

Alkyl can further be replaced by suitable uncharged organic group, and the molecular weight of preferred described organic group is lower than 200.Preferred group comprises-CH ₃,-C ₂H ₅,-OH ,-OCH ₃,-OC ₂H ₄OH.

Most preferred heterocyclic active group is selected from:

With

N=1 or 2 wherein, preferably 1.

Preferably, reactive dye contain and surpass the active group of, preferably two or three.

Polymer

Polymer comprise for dyestuff, react free-SH ,-OH ,-NH or-NH ₂Group.More preferably, polymer contain at least one-NH or-NH ₂Group, most preferably at least five-NH or-NH ₂Group.

When mentioning polyamine by the covalent bonding reactive dye, it will be understood by those skilled in the art that active group no longer is present in this dye polymer.Below will illustrate this situation for three active groups:

Preferably, polymer is with cationic charge generally at pH5.0.Preferably, polymer comprises quaternary amine base or tertiary amine.

The example of this polymer is polymine, PPI, polyvinylamine, polyvinyl imines, amino silicones (aminosilcone).

Preferably, with before dyestuff reacts, the weight average molecular weight of polymer is 500 to 1000000, preferably 800 to 60000, most preferably 800 to 2500.

Use Zetasizer Nano(Malvern) by dynamic light scattering, carry out determining molecular weight.

Preferably, polymer is polyamine.Preferably, polyamine is selected from polymine, polypropylene-imines, polyvinylamine and polyvinyl imines.

Polyamine is poly-alkylamine, and straight or branched normally.Polyamine comprises primary, secondary or tertiary amine, or its mixture.Preferably, polyamine comprises the ethylidene alkyl, and forms polymer by the ring-opening polymerisation of aziridine, so that polymine (PEI) to be provided.PEI is most preferred.

Perhaps, by the polyamine alkoxylate, so that oxyalkylated PEI to be provided, for example, the polymine of ethoxylation (EPEI).In this, single or multiple amine functional groups react with one or more alkylen groups, to form the polyalkylene oxide side chain.Alkylene oxide can be homopolymer (for example, oxirane) or random or block copolymer.

The PEI that is suitable for using in the present composition can have general formula: (NHCH2CH2-) _x[N (CH2CH2NH2) CH2CH2-] _y, wherein x is approximately 1 to about 120000 integer, preferably approximately 10 to approximately 20000, more preferably from about 20 to approximately 10000, and y is approximately 1 to about 60000 integer, preferably approximately 10 to approximately 30000, more preferably from about 20 to approximately 12000.The instantiation of polymine is PEI-300, PEI-500, PEI-600, PEI-700, PEI-800, PEI-1000, PEI-1500, PEI-1800, PEI-2000, PEI-2500, PEI-5000, PEI-10000, PEI-25000, PEI50000 and PEI-70000, wherein the number-average molecular weight of integer representation polymer.So the PEI of name can obtain by Aldrich.

In the PEI alkoxylate, most preferably during ethoxylation, PEI is oxyalkylated by part, makes at least one NH ₂Or NH---preferred at least one NH ₂---can be used for reacting with reactive dye.Preferred degree of alkoxylation is that 0.2 to 50% primary amine and secondary amine are alkoxylated.

An example of PEI structure is:

Compositions

Unless specifically note in addition, all wt % value of hereinafter quoting is based on the percentage by weight of Hiar treatment compositions gross weight.

Preferably, compositions comprises 0.2 to 10 % by weight, the most preferably dye polymer of 0.5 to 3 % by weight.

Preferably, the pH of compositions is 4 to 11, more preferably 8 to 10, most preferably 8.5 to 9.5.

Can commonly use buffer and/or alkali (as NaOH, NH by use ₄OH) and/or acid (as, HCl) control pH.

Product form

Compositions of the present invention is mixed with to hair coloring compositions, and it can adopt various forms, comprise, for example, mousse, gel, water preparation (lotion), cream, spraying and nourishing agent (tonic).These product forms are well known in the art.

Preferred product is water preparation, cream, spraying, aerosol mouse or gel.

In order to improve the hair sense of touch, compositions preferably contains the hair care composition of opsonic activity thing, and described opsonic activity material is cationic surfactant or polysiloxanes, fatty alcohol, fatty acid, fatty ester, fatty acid amide or its mixture for example.

Cationic surfactant

If exist, suitable conditioning surfactant comprises those that are selected from cationic surfactant, and it is used alone or as a mixture.Preferably, cationic surfactant has general formula N ⁺R ¹R ²R ³R ⁴, R wherein ¹, R ², R ³And R ⁴(C independently ₁To C ₃₀) alkyl or benzyl.Preferably, R ¹, R ², R ³And R ⁴In one, two or three are (C independently ₄To C ₃₀) alkyl, and other R ¹, R ², R ³And R ⁴(C ₁-C ₆) alkyl or benzyl.More preferably, R ¹, R ², R ³And R ⁴In one or two be (C independently ₆To C ₃₀) alkyl, and other R ¹, R ², R ³And R ⁴Group is (C ₁-C ₆) alkyl or benzyl.Optionally, alkyl can in alkyl chain, comprise one or more esters (OCO-or-COO-) and/or ether (O-) key.Alkyl can be chosen wantonly by one or more hydroxyl and replace.Alkyl can be straight or branched, and, for the alkyl with 3 or more carbon atoms, can be ring-type.Alkyl can be the saturated one or more carbon-to-carbon double bonds (for example, oleyl) that maybe can contain.Alkyl optionally on alkyl chain by the ethoxylation of one or more inferior ethoxyl group.

For according to the suitable cation surfactant of hair conditioner composition of the present invention, comprising CTAB, mountain Yu base trimethyl ammonium chloride, the cetyl pyridinium chloride, tetramethyl ammonium chloride, tetraethylammonium chloride, the octyl group trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, the octyldimethyl benzyl ammonium chloride, the decyl dimethyl benzyl ammonium chloride, the stearoyl dimethyl benzyl ammonium chloride, two dodecyl dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, Adeps Bovis seu Bubali base trimethyl ammonium chloride, dihydro Adeps Bovis seu Bubali base alkyl dimethyl ammonium chloride (for example, Arquad2HT/75 from Akzo Nobel), the cocoyl trimethyl ammonium chloride, PEG-2-oleoyl ammonium chloride and corresponding hydroxide thereof.How suitable cationic surfactant comprises having CTFA name quaternary ammonium salt-5(Quaternium-5), quaternary ammonium salt-31(Quaternium-31) and quaternary ammonium salt-18(Quaternium-18) those materials.Any mixture of above-mentioned material is also suitable.For according to the useful especially cationic surfactant of conditioner of the present invention, being CTAB, for example, as GENAMIN CTAC, buy from Hoechst Celanese.For according to another useful especially cationic surfactant of conditioner of the present invention, being mountain Yu base trimethyl ammonium chloride, for example, as GENAMIN KDMP, buy from Clariant.

For another example of the present invention's a cationoid surfactant, be following (i) and compositions (ii), independent or use together with one or more other cationic surfactants:

(I) corresponding to the amido amine of general formula (I):

R1CONH(CH2)mN(R2)R3

R wherein ¹The hydrocarbyl chain with 10 or more carbon atoms, R ²And R ³Be independently selected from the hydrocarbyl chain of 1 to 10 carbon atom, and m is 1 to about 10 integer; With

(ii) acid.

As used in this article, the term hydrocarbyl chain refers to the alkyl or alkenyl chain.

Preferred amido amine compound is corresponding to those of formula (I), wherein R ¹To have approximately 11 to the about hydrocarbyl residue of 24 carbon atoms, R ²And R ³To have 1 to the about hydrocarbyl residue of 4 carbon atoms independently of one another, preferred alkyl, and m is 1 to about 4 integer.

Preferably, R ²And R ³Methyl or ethyl.

Preferably, m is 2 or 3, that is, and and ethylidene or propylidene.

Useful preferred amide base amine comprises the stearamide propyl dimethylamine herein, the stearamide propyl diethylamine, stearmide ethyl diethylamine, stearmide ethyl dimethylamine, the palmitamide diemethylamine, palmitamide propyl group diethylamine, palmitamide ethyl diethylamine, palmitamide ethyl dimethylamine, mountain Yu amido propyl dimethylamine, mountain Yu amido propyl diethylamine, mountain Yu amide ethyl diethylamine, mountain Yu amide ethyl dimethylamine, Semen arachidis hypogaeae amido propyl dimethylamine, Semen arachidis hypogaeae amido propyl diethylamine, Semen arachidis hypogaeae-amide ethyl diethylamine, Semen arachidis hypogaeae amide ethyl dimethylamine, and composition thereof.

Useful particularly preferred amido amine is stearamide propyl dimethylamine, stearmide ethyl diethylamine herein, and composition thereof.

Useful commercially available amido amine comprises herein: with trade name LEXAMINE S-13 from Inolex(Philadelphia, Pennsylvania, USA) that buy and with trade name AMIDOAMINE MSP from Nikko(Tokyo, the stearamide propyl dimethylamine of Japan) buying, the stearmide ethyl diethylamine of buying from Nikko with trade name AMIDOAMINE S, with trade name INCROMINE BB from Croda(north Humberside, the mountain Yu amido propyl dimethylamine of England) buying, and with trade name SCHERCODINE series from the Scher(Clifton, New Jersey, the various amido amine of USA) buying.

Can there is protonated acid.Acid can be the protonated any organic or inorganic acid of amido amine that can make in conditioner composition.Useful appropriate acid comprises hydrochloric acid, acetic acid, tartaric acid, fumaric acid, lactic acid, malic acid, succinic acid herein, and composition thereof.Preferably, acid is selected from acetic acid, tartaric acid, hydrochloric acid, fumaric acid, lactic acid, and composition thereof.

The Main Function of acid is to make the amido amine in Hiar treatment compositions protonated, at the Hiar treatment compositions situ, forms tertiary ammonium salt (TAS) thus.TAS is in fact a kind of quaternary ammonium salt or vacation-quaternary ammonium cation surfactant of perishability.

Suitably, comprise that enough acid makes the existing amido amine that surpasses 95 % by mole (293K) protonated.

In compositions of the present invention, the level of cationic surfactant is generally 0.01 % by weight to 10 % by weight of compositions, more preferably 0.05 % by weight to 7.5 % by weight, most preferably 0.1 % by weight to 5 % by weight.

Siloxanes

Compositions of the present invention can contain the emulsifying droplet of silicone conditioning agent, be used to strengthening conditioning performance.

Suitable siloxanes comprises polydiorganosiloxanepolyurea, particularly has the polydimethylsiloxane of CTFA name dimethicone (dimethicone).What also be applicable to the present composition (particularly shampoo and conditioner) is the polydimethylsiloxane with hydroxyl end groups, and it has CTFA name dimethyl polysiloxane alcohol (dimethiconol).What also be applicable to the present composition is to have lightly crosslinked siloxane glue, for example disclosed in WO96/31188.

The viscosity of the siloxanes of emulsifying self (not being the viscosity of Emulsion or final hair care composition) is generally and is at least 10,000cst under 25 ℃, the viscosity of siloxanes self is preferably at least 60,000cst, most preferably at least 500,000cst, be at least ideally 1,000,000cst.Preferably, viscosity is no more than 10 ⁹Cst is so that preparation.

The siloxanes that is used for the emulsifying of shampoo Compositions of the present invention usually will have and be less than 30 in compositions, preferably be less than 20, be more preferably less than 10 microns, ideally the average siloxanes droplet size of 0.01 to 1 micron.The siloxane emulsion that usually will have the average siloxanes droplet size of 0.15 micron of ￡ is called microemulsion.

The siloxanes that is used for the emulsifying of conditioner composition of the present invention usually will have and be less than 30 in compositions, preferably be less than 20, be more preferably less than 15 size.Preferably, average siloxanes droplet is greater than 0.5 micron, more preferably greater than 1 micron, is desirably 2 to 8 microns.

Can measure the siloxane particles size by laser scattering technology, for example, use the 2600D Particle Size Analyzer from Malvern Instruments.

The example of suitable preformed Emulsion comprises Xiameter MEM1785 and the microemulsion DC2-1865 that can buy from Dow Corning.These are Emulsion/microemulsions of dimethyl polysiloxane alcohol.Crosslinked siloxanes natural gum also can be buied with the form of emulsifying in advance, and it is conducive to convenient preparation.

The siloxanes classification also preferably comprised at shampoo of the present invention and conditioner is the siloxanes of amino-functional." siloxanes of amino-functional " refers to and contains at least one primary amine, secondary amine or tertiary amine groups, or the siloxanes of quaternary ammonium group.The example of the siloxanes of suitable amino-functional comprises: the polysiloxanes with CTFA name " amino dimethicone ".

The instantiation that is applicable to the siloxanes of amino-functional of the present invention is that amino silicone oil DC2-8220, DC2-8166 and DC2-8566(are all from Dow Corning).

Suitable season siloxane polymer is described in EP-A-0530974.Preferred season, siloxane polymer was K3474, from Goldschmidt.

Also suitable is the silicone oil of amino-functional and the Emulsion of nonionic and/or cationic surfactant.

The siloxane emulsion of preformed amino-functional can also be from the supplier of silicone oil, and for example Dow Corning and General Electric buy.Concrete example comprises that DC939 cation Emulsion and nonionic Emulsion DC2-7224, DC2-8467, DC2-8177 and DC2-8154(are all from Dow Corning).

Non-silicone oil

The suitable level of siloxanes total amount is preferably 0.01 % by weight to 10 % by weight of total composition, more preferably 0.1 % by weight to 5 % by weight, most preferably 0.5 % by weight to 3 % by weight.

According to compositions of the present invention, can also comprise dispersion, nonvolatile, water-insoluble oiliness conditioner.Preferably such non-silicone conditioning oiliness conditioner is present in conditioner composition.

" insoluble " refers to that material is under 25 ℃, with 0.1%(w/w) concentration water insoluble (distilled water or equivalent) in.

Suitable oiliness or fat material are selected from hydrocarbon ils, fatty ester, and composition thereof.The straight chain hydrocarbon ils will preferably contain has an appointment 12 to about 30 carbon atoms.Also suitable is alkenyl monomer, for example C ₂-C ₆The polymeric hydrocarbon of alkenyl monomer.

The instantiation of suitable hydrocarbon ils comprises paraffin oil, mineral oil, saturated and undersaturated dodecane, saturated and undersaturated tridecane, the saturated and undersaturated tetradecane, saturated and undersaturated pentadecane, saturated and undersaturated hexadecane, and composition thereof.Also can use the branched chain isomer of these compounds, and the hydrocarbon of higher chain length.

Suitable fatty ester is characterised in that to have at least 10 carbon atoms, and comprises the ester with the hydrocarbyl chain that is derived from fatty acid or alcohol.The monocarboxylate comprises alcohol and/or the sour ester of formula R ' COOR, and wherein R ' and R mean the alkyl or alkenyl residue independently, and the carbon atom summation in R ' and R is at least 10, preferably at least 20.Also can use two of carboxylic acid-and trialkyl and alkenyl esters.

Particularly preferred fatty ester is monoglyceride, diglyceride and triglyceride, more specifically glycerol and long-chain carboxylic acid (for example, C ₁-C ₂₂Carboxylic acid) monoesters, diester and three esters.Preferred material comprises cocoa butter, palm stearin, Oleum Helianthi, soybean oil and Oleum Cocois.

Oiliness or fat material exist with the level of 0.05 % by weight to 10 % by weight suitably, preferably 0.2 % by weight to 5 % by weight, more preferably from about 0.5 % by weight to 3 % by weight.

It is acceptable and be applicable to be locally applied to the conditioning surfactant of hair that such compositions will comprise one or more used for cosmetic usually.

Compositions of the present invention also will be mixed fatty alcohol usually.It is believed that in care composition, to be combined with fatty alcohol and cationic surfactant is especially favourable, because this has caused cationic surfactant to be scattered in the formation of lamellar phase wherein.

Representational fatty alcohol comprises 8 to 22 carbon atoms, more preferably 16 to 22.Fatty alcohol normally contains the compound of straight chained alkyl.The example of suitable fatty alcohol comprises spermol, stearyl alcohol, and composition thereof.The use of these materials is also favourable, because they help the integral body conditioning characteristic of the present composition.

The level of the fatty alcohol in conditioner of the present invention usually will be in the scope of 0.01 to 10 % by weight of compositions, preferably 0.1 % by weight to 8 % by weight, more preferably 0.2 % by weight to 7 % by weight, most preferably 0.3 % by weight to 6 % by weight.The weight rate of cationic surfactant and fatty alcohol is 1:1 to 1:10 suitably, and preferably 1:1.5 to 1:8, be 1:2 to 1:5 best.

Cationic polymer

Cationic polymer may reside in preparation.

The homopolymer that suitable cationic polymer can be replaced by cation or can be formed by the monomer of two or more types.Weight average molecular weight (the M of polymer _W) be generally 100000 to 2 megadaltons.Polymer will have the cation nitrogen-containing group, as quaternary ammonium or protonated amino, or its mixture.

If the molecular weight of polymer is too low, opsonic action is poor so.If too high, while so existence being toppled over, cause the problem of the high extensional viscosity of compositions wire drawing.

The cation nitrogen-containing group will exist as the substituent group on the part of the total monomer units of cationic polymer usually.Therefore, when polymer is not homopolymer, can contain interval body non-cationic monomeric unit.Such polymer is described in CTFA Cosmetic Ingredient Directory(CTFA cosmetic ingredients catalogue), the 3rd edition.Select the ratio of cation and non-cationic monomeric unit, with generation, have the polymer of the cationic charge density of required scope, described cationic charge density is generally 0.2 to 3.0meq/gm.Kjeldahl method described in the test chemical of the nitrogen determination by the US pharmacopeia is measured the cationic charge density of polymer suitably.

Suitable cationic polymer comprises, for example, have the vinyl monomer of cationic amine or quaternary ammonium functional group and the copolymer of water solublity interval body monomer, described interval body monomer is (methyl) acrylamide, alkyl and dialkyl group (methyl) acrylamide, alkyl (methyl) acrylate, vinyl caprolactone and ethenyl pyrrolidone for example.The monomer that alkyl and dialkyl group replace preferably has the C1-C7 alkyl, more preferably the C1-3 alkyl.Other suitable interval bodies comprise vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol.

According to particular types and the pH of compositions, cationic amine can be primary amine, secondary amine or tertiary amine.Usually, preferred secondary amine and tertiary amine, especially tertiary amine.

Vinyl monomer and amine that amine replaces can be with the polymerizations of amine form, then by the quaternized ammonium that changes into.

Cationic polymer can comprise and is derived from amine-and/or the mixture of the monomeric unit of the monomer of quaternary ammonium-replacement and/or compatible interval body monomer.

Suitable cationic polymer comprises, for example:

-cation diallyl quaternary ammonium polymer, comprise, for example, the copolymer of dimethyl diallyl ammonium chloride homopolymer and acrylamide and dimethyl diallyl ammonium chloride, be called polyquaternary ammonium salt (Polyquaternium) 6 and polyquaternary ammonium salt 7 in industry (CTFA);

-have an inorganic acid salt (as U.S. patent 4,009, described in 256) of the amino-Arrcostab of the homopolymer of unsaturated carboxylic acid of 3 to 5 carbon atoms and copolymer;

-PAMC (described in WO95/22311).

Operable other cationic polymers comprise the cationic polysaccharide polymer, as cationic cellulose derivative, and cationic starch derivative and cationic guar derivative.

The cationic polysaccharide polymer be applicable in the present composition comprises the monomer with following formula:

A-O-[R-N ⁺(R ¹)(R ²)(R ³)X ^-]，

Wherein: A is the dewatered grape saccharide residue, as starch or cellulose dewatered grape saccharide residue.R is alkylene, oxygen alkylene, polyoxy alkylene or hydroxyl alkylene base, or its combination.R ¹, R ²And R ³Mean independently alkyl, aryl, alkaryl, aralkyl, alkoxyalkyl or alkoxy aryl, each group contains at most approximately 18 carbon atoms.The sum of the carbon atom of each cationic moiety (that is, R ¹, R ²And R ³The summation of middle carbon atom) preferably approximately 20 or still less, and X is counter anion.

The cationic cellulose of another kind of type comprises the polymeric quaternary ammonium salts of the epoxide reactive hydroxyethyl-cellulose replaced with the lauryl dimethyl ammonium, is called polyquaternary ammonium salt 24 in industry (CTFA).These materials can be buied from Amerchol Corporation, for example, and with trade name Polymer LM-200.

Other suitable cationic polysaccharide polymer comprise the cellulose ether that contains quaternary nitrogen (for example, as U.S. patent 3,962, described in 418), and the copolymer of the cellulose of etherificate and starch (for example, as U.S. patent 3,958, described in 581).

Operable specially suitable cationic polysaccharide polymer type is cationic guar derivative, as guar gum hydroxypropyl-trimethyl ammonium chloride (can from Rhodia, be purchased with its JAGUAR trade mark series).The example of such material is JAGUAR C13S, JAGUAR C14, JAGUAR C15, JAGUAR C17 and JAGUAR C16Jaguar CHT and JAGUAR C162.

Can use the mixture of above arbitrarily cationic polymer.

In the gross weight of cationic polymer gross weight based on compositions, cationic polymer is usually with 0.01 to 5%, and preferably 0.05 to 1%, more preferably 0.08% to 0.5% level is present in compositions of the present invention.

Other optional members

Compositions of the present invention can contain other compositions of 0.01 to 2 % by weight of total composition, be used to strengthening the property and/or consumer's acceptability.Such composition comprises spice, dyestuff and pigment, pH adjusting agent, pearling agent or opacifier, viscosity modifier, antiseptic and natural hair nutrient, as botanical, fruit extract, sugar derivatives and aminoacid.

Preferably, compositions is the washing-off type Hiar treatment compositions.Rinse-off compositions is applicable to hair, and preferably wet, and, before by rinsing, removing, rest on hair and reach 1 hour, preferably rest on hair and be thirty minutes long.

For more color is provided, preferably dye polymer is mixed with the similar dye polymer made with reactive red or Yellow reactive dyes.Preferably, reactive red or Yellow reactive dyes are list-azo or two-azo-compound.Perhaps, reactive red can be connected on the main polymer chain identical with two-azo active dyestuff with yellow dye.

For fear of ambiguity, " one (a) " in literary composition refers to one or more.

To further illustrate the present invention by following non-limiting example now.

Experiment

The preparation of dye polymer

Will as shown in the formula two-the azo active blue dyestuff reacts (wherein Mw is weight average molecular weight) with branched polyethylenimine (Mw=2000) and branched polyethylenimine (Mw=750000):

。The dyestuff of hydrolysis by thin layer chromatography, do not detected.

Prepared following polymer

Table 1

For dyestuff, use 50000L mol ^-1Cm ^-1Extinction coefficient, by the UV-VIS of dye-polymer, absorb to calculate the dyestuff % by weight based on polymer.

Pigmented hair

The golden hair bundle of 1.4g people's bleaching is placed in to the aqueous solution of 1.4g dye polymer, and stirred for 60 seconds.Aqueous solution contains 1.4 % by weight dye polymers.Take out topknot, rinsing is 60 seconds in demineralized water, and drying is also used the reflectometry color, and be expressed as CIE L*a*b* value.

The L* value is as follows.

Table 2

?	L*
		Contrast (processing without dyestuff)	63
DP1	32
		DP2	24
DP3	38

Dye polymer makes hair-dyeing effectively, causes L* to have substantial degradation.Dye polymer with low Mw provides more painted.

Table 3

The dye polymer of 0.1 % by weight and 0.5 % by weight is joined in preparation.Dye polymer used is the PEI that Lupasol G35(has Mw=2000 that is bonded to of 100 % by weight, from BASF) reactive blue 171.

Claims

1. composition for hair dying, it comprises polymeric dye, described polymeric dye comprises the positively charged polymer covalently bonded to electronegative reactive dye, wherein said reactive dye be following structure two-azo dye:

Wherein the A ring is replaced by least one heterocyclic active group and/or sulfonate groups.

2. according to the composition for hair dying of claim 1, the B of wherein said azo dye ring is replaced by least one heterocyclic active group and/or sulfo group oxygen ethylsulfonyl active group and/or sulfonate groups.

3. according to the composition for hair dying of claim 1 or 2, wherein said B ring is replaced by the heterocyclic active group.

4. according to the composition for hair dying of aforementioned any one claim, wherein said heterocyclic active group is selected from dichlorotriazine base, difluoro chloropyrimide, single Cyanuric trifluoride base, single fluorine chlorotriazine base, dichloro-quinoxaline, two Cyanuric trifluorides, monochloro triazine radical and trichloropyrimidine.

5. according to the composition for hair dying of aforementioned any one claim, wherein said heterocyclic active group is selected from following structure:

R wherein ₁Be selected from H or C1-C6 alkyl, preferably H; X is selected from F or Cl, makes when X=Cl Z ₁Be selected from-Cl ,-NR ₂R ₃,-OR ₂,-SO ₃Na, and when X=F, Z ₁Be selected from-NR ₂R ₃R ₂And R ₃Be independently selected from H, alkyl and aryl.

6. according to the composition for hair dying of claim 5, Z wherein ₁Aryl by-SO ₃Na or-SO ₂CH ₂CH ₂OSO ₃The phenyl that Na replaces.

7. according to the composition for hair dying of claim 6, Z wherein ₁Substituted aryl further be selected from-CH ₃,-C ₂H ₅With-OCH ₃Group replace.

8. according to the composition for hair dying of claim 5, wherein said alkyl is to be selected from-CH ₃,-C ₂H ₅,-OH ,-OCH ₃,-OC ₂H ₄The substituent group of OH.

9. according to the composition for hair dying of claim 1 to 5 any one, wherein said heterocyclic active group is selected from:

With

N=1 wherein.

10. according to the composition for hair dying of aforementioned any one claim, wherein said reactive dye contain two or three active groups.

11. according to the composition for hair dying of aforementioned any one claim, wherein said compositions contains lower than 50ppm hydrolysed reactive dye/10000ppm dye polymer.

12. according to the composition for hair dying of aforementioned any one claim, wherein said positively charged polymer is polyamine.

13. according to the composition for hair dying of claim 12, wherein said polyamine is polymine (PEI).

14. according to the composition for hair dying of claim 13, wherein said polyamine is the polymine (EPEI) of ethoxylation.

15. according to the composition for hair dying of aforementioned any one claim, it comprises 0.5 to 3% dye polymer of total composition weight.

16. according to the composition for hair dying of aforementioned any one claim, wherein pH is 8 to 10.

17. be applied to by the compositions that will comprise polymeric dye the method that hair carrys out pigmented hair, described polymeric dye comprises the positively charged polymer covalently bonded to electronegative reactive dye, wherein said reactive dye be following structure two-azo dye:

18. polymeric dye is for the purposes of pigmented hair, described polymeric dye comprises the positively charged polymer covalently bonded to electronegative reactive dye, wherein said reactive dye be following structure two-azo dye: