TW201138892A - Method of treating hair - Google Patents

Abstract

A method for colouring hair, comprising the step of applying to the hair a composition comprising a dye polymer in which the dye polymer is obtainable the reaction of a NH2 group directly and covalently bound to an aromatic ring dye (i) with a reactive group of a polymeric compound (ii) in which the reactive group is selected from the group consisting of isocyanate; oxazolone; epoxide ester, and anhydride.

Description

201138892 VI. Description of the Invention: [Technical Field] The present invention relates to a method of dyeing hair. [Prior Art] A variety of cationic polymer dyes have been disclosed as colorants for human hair', for example, 1^4,228,259,118 4,182,612 or? 11 2 456 764, WO 2008/009579, and WO 2009/090121 to WO 2009/090125.

Zollinger revealed in Color Chemistry (Wiley-VCH 2003) that several million different color compounds have been synthesized. A large number of dyes contain NH2 groups covalently bonded to the aromatic ring in the dye. However, there is still a need in the art for a dye containing an NH2 group covalently bonded to an aromatic ring in the dye to attach to the polymer. The present invention relates to a method of dyeing hair comprising the step of applying a composition comprising a dye polymer to the hair, wherein the dye polymer is used, preferably by Obtaining i) by reacting a Nh2 group directly covalently bonded to an aromatic ring in the dye with ii) a reactive group in the polymeric compound; wherein the reactive group is selected from the group consisting of isocyanates, oxazolone, epoxides, a group of esters and anhydrides. [Embodiment] The reaction indicates that by the reaction step of the reaction polymer with the nh2 group of the dye, a dye polymer is formed together with the method of the invention of 154381.doc 201138892, and the nh2 group is directly covalently bonded to The dye of the Fang Fanyu m Fang Duo ring. The reactive polymer has a group reactive with nh2 selected from the group consisting of „isocyanate S, acetophenone, epoxide, vinegar and

Sf car is best for epoxide or Xuan, the best for rape. In the self-acting category, it is preferred to activate vinegar. Suitable post-polymerization modifications for the reactive polymers useful in the present invention are detailed in

Gauthier, M.A., Gibson, μ·Ι. and Klok Ή-Α., Angew. Chem.

Int. 2009, 48, 48058, preferably, the reaction is selected from the group consisting of: reaction (a): ester and anhydride oxime, Η II dye-Ν-C-Ζ 〇 dye-nh2 RO-c-z __ where R is Examples of hydrazine, alkyl, aryl or a suitable R group selected to form a c〇〇r group to form an anhydride include

Z-based polymer. The best 'reaction' has the following form: Dye - nh2 +

Polymer n~polymer dye.

•NH

HOOC: 0 polymer - 〇 - c - polymer Η 非 Non-limiting examples of polymers formed by such reactions are: 154381.doc 201138892 Dyes - νη ο. η2 η • C~T CH3o

[Η2Η3ί"Η C-C

\^0 Dyes ΝΗ2 η2 η -C—〒 ch3〇 Ο

Η•C—C~b* I Η COOH J Η^°? I Dye ΝΗ 2 C—CH-* Η h3c Η2 I ·*——C-C-

a * HOOC Η 2 I -C-C-Η ΝΗ dye Dye ΝΗ 〇 CH3

Dye-νη2 -^ Dye-_H3C' Η2 I 1 -~c-c

N(CH3)3 〇

Η•C—C—I η COOH b Dye ΝΗ HOOC Η2 I —C—C—Η 0 h2 —c—c H The catalyst can be used to accelerate the reaction. The shai·# reaction is discussed in Macromolecules 1994, 27, 7121-7126. Reaction (b): epoxide

Non-limiting examples are: polymers formed by such reactions 154381.doc 201138892 h3c H2 I -c-c-i> Ό H3C n h2 M C-C"〇^>

r H"OC •c—π h3c ί h2 I-c—c-

Dye-nh2 H3C H2 I -c-c-

w a

HOOC, H2 I-c-c- H

Dye-NH dye-nh2 h3c h2 I-c-c-

OH .h3c ί h2 Ic-c- NH I (CH2)3

Dye-NH

OH

b NH (CH2)3 side (ch3) MCH3)3

Reaction (c): Oxazolone and Isocyanate The following examples illustrate the reaction with oxazolone and isocyanate 154381.doc 201138892 z z oy

N H2N - dye

NH H dye-N-

OZ—N=C=0 〇H2N—Dye 〇Z—N—C—N—Dye Dyes Examples of dyes are described in Industrial Dyes (edited by K. Hunger, Wiley VCH 2003) and colour index (Society) In the Dyers and Colourists and the American Associate of Textile Chemists and Colorists. The dye should contain a covalent bond with the aromatic & ment in the dye! ^^ group where § haifangxiang is better, NH2 is covalently bonded to the aromatic ring of the dye and the color of the dye The group is conjugated. ' < section

Preferably, the dye is preferably in the aromatic ring structure of the dye to include a good dye.

Disperse yellow 11 ch3o · 154381.doc 201138892

Acid Violet 50 〇 Preferably, the dye does not contain a reactive group or a polymerizable double bond. The dye containing the reactive group is composed of a chromophore attached to a reactive group which undergoes an addition or substitution reaction with the -OH, -SH and -ΝΗ2 groups to form a covalent bond. Reactive dyes are described in Industrial Dyes (edited by K. Hunger, Wiley VCH 2003). Dye Index (Society of Dyers and Colourists and American Association of Textile Chemists and

Many reactive dyes are listed in Colorists. Reactive groups are, for example, di-tris-trimethyl, difluoro-a pyrimidine, monofluorotriazinyl, di-haloquinoxaline, vinyl stone, monofluorobifluorene, monochlorotriazinyl, bromopropylamine And three gas beta bites. The dye system has an absorption coefficient greater than 4000 mol.i L cm-i at any wavelength between 400 nm and 700 nmi, preferably greater than 1 〇〇〇〇m〇rl l(10)·, with /fry Py — 2 _ machine molecule. Preferably, the molar absorption coefficient is measured in an organic solvent (preferably, the cm cell is preferably selected from the group consisting of organic dyes selected from the group consisting of: aminoketones, anthracenes, azos, oxazines, Pyridazine, triphenyldioxazine, triphenylmethane, naphthoquinone imine, xanthene and: good: dimethyl ketone chromophore type, best azo: car father dye system 蒽 S Kun. dye Can be cationic, anionic or brother + charged. Uncharged dye: 154381.doc 201138892 See examples of disperse dyes for examples. See examples of acid and direct dyes for examples of dyes with anionic charge. Examples of cationically charged dyes Dyeing class. The dye is preferably uncharged or has an anionic charge. Optimally, the dye is an anionically charged dye. A preferred dye system containing a 2 group covalently bonded to an aromatic ring in the dye: Acid Violet 1; Acid Violet 3; Acid Violet 6; Acidic Purpura; Acid Violet 13; Acid Violet 14; Acid Violet 19; Acid Violet 2〇; Acid Violet%; Acid Violet 36:1'·Acid Violet 41; Acid Violet 42; Acid Violet 43; Acid Violet Acid Violet 51; Acid Violet 63; Acid Violet 48; Acid Sex Blue 25; Acid Blue 4〇; Acid Blue 40:1; Acid Blue 41; Acid Blue 45; Acid Blue 47; Acid Blue 49; Acid Blue 51; Acid Blue 53; Acid Blue 56; Acid Blue 61; Acid Blue Acid Blue 62; Acid Blue 69; Acid Blue 78; Acid Blue 81:1; Acid Blue 92; Acid Blue 96; Acid Blue 1〇8; Acid Blue m; Acid Blue 215; Acid Blue 230; Acid Blue 277; Acid blue 344; Acid blue 丨17; Acid blue 124; Acid blue 129; Acid blue 129:1; Acid blue 138; Acid blue 145; Direct violet 99; Direct violet 5; Direct violet 72; Direct violet 16; Direct purple 77; direct purple 83; food black 2; direct blue 33; direct blue 41, direct blue 22; direct blue 71; direct blue 72; direct blue 74; direct blue 75; direct blue 82; direct blue 96; Blue 11〇; direct blue m; direct blue 120 'direct blue 120:1; direct blue 121; direct blue 122; direct blue 123; direct blue 124; direct blue 126; direct blue 127; direct blue 128; direct blue 129; Direct blue 13〇; direct blue 132; direct blue 133; direct blue 135 'direct blue 138; direct blue 140; direct blue 145; direct blue 148; direct blue 149; direct blue 159; direct blue 162; direct blue 163; Black 154 381.doc 201138892 2, eating tm black 1, sputum acid amine group replaced by NH2; test violet 2; test i 5 'alkaline steep 糸 12, alkaline purple 14; alkaline purple 8; alkaline blue Alkaline blue 16; test blue 17; test # it j 7 . superior t. μ Fu f blue 47, alkaline blue 99; disperse blue]; disperse blue 5; disperse blue 6; disperse shoes q. Also # , , , ^ Knife double monitor 9, disperse blue u; disperse blue 19; disperse blue 2〇; disperse blue 28; disperse blue 40; disperse blue 56; disperse blue 60; disperse blue 81 knife loose blue 83, knife Blue 87; Disperse blue 1〇4, • Disperse blue (1); Disperse violet 1; Disperse violet 4, Disperse violet 8, Disperse violet 17' disperse violet 26; Disperse violet 28; Solvent violet 26; Solvent blue 12; Solvent blue 13; Solvent Blue 18; Solvent Blue 68; Solvent Blue 76'·Disperse Red 4; Disperse Red 11; Disperse Red 15; Disperse Red 31; Disperse Red 53; Disperse Red 55; Disperse Red 6〇; Disperse Red 63; Disperse Red 86, Knife scattered,, work 91, knife red 92; test red 2; test red 3; test red 4; alkaline red 5; alkaline red 6; alkaline red 9; alkaline red 30; ; for yellowing 11, alkaline yellow 5; alkaline yellow 6; alkaline yellow 7; alkaline yellow 9; alkaline brown 1; alkaline brown 2; alkaline brown 4; alkaline brown 5; alkaline brown 17 ;Minute Disperse orange 3; disperse orange 3:1; disperse orange 6; disperse orange u; disperse green 2; acid red 33, acid red 30; acid red 34; acid yellow 7; acid yellow 9; acid yellow 66, acid green 20; Acid Green 33; Acid Brown 4; Acid Brown 9; Disperse Black 9; Disperse Black 3; Disperse Black 4; Disperse Black 7 and Acid Black! . More preferred dyes are selected from the group consisting of mono-azo dyes containing a phenyl group attached directly to an azo group, wherein the phenyl group has an nh2 group covalently bonded thereto. Description of the Reactive Polymer The reaction polymer, preferably a single system olefin, can be synthesized by polymerizing a monomer. Preferably 2 mol% to 80 mol%, more preferably 5 m〇l% to 55 mol% of the monomer is selected from containing or forming an isocyanate, oxazolone, epoxidized 154381.doc •10-201138892, ester or A monomer of an anhydride group. Preferred suitable monomers include maleic anhydride, glycidyl acrylate, 2-glycidyl methacrylate, 2-vinyl-4,4-dimercapto-5-oxazolone, vinyl isocyanate, 2-Isocyanate ethyl methacrylate, Ν-methacryloxy amber quinone imine. The reactive polymer may comprise a comonomer. Preferred co-monomers may be selected from the group consisting of olefins, acrylates and styrene. Suitable co-monomers include diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, mercapto vinyl ether, mercaptoacrylic acid, 2-propenylaminomethyl-l _propane sulfonic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, methyl methacrylate, methyl acrylate, hydroxy methacrylate Ethyl ester, ethyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, butyl methacrylate, butyl acrylate, acrylamide, butyl methacrylate, acrylic acid third Butyl ester, sodium 4-ethoxysulfonate, styrene, benzyl methacrylate, acrylic acid, ethyl acetate, vinyl ratio, sodium acrylate, diethylaminoethyl methacrylate Esters (preferred), 4-vinylphenol, methacrylic acid, acrylonitrile, 4_vinyl-9Η-carbazole, sodium methacrylate, 4,4-dimethyl-2-vinyloxazole·5 (4Η)-ketone, 4,4-dimercapto-2-(prop-1-en-2-yl)oxazole-5(4Η)-one, vinyl η-pyrrolidone, 4-pentenoic acid 2-cyanopropyl Ethyl acrylate, stearyl acrylate, methoxyethyl methacrylate, methyl ether methacrylate, poly(ethylene glycol) ethyl ether methacrylate, poly(ethylene glycol) Methyl ether decyl acrylate, isopropyl methacrylate, 2-hydroxypropyl methacrylate, 2-isocyanatoethyl methacrylate, 2-(methylthio) methacrylate Ethyl ester, 2-aminoethyl methacrylate hydrochloride (preferred), A I54381.doc 201138892 based furfuryl acrylate, cyclohexyl methacrylate, 2,2,2-methacrylic acid Trifluoroethyl ester, tetrahydrofuranyl methacrylate, hexyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, N-isopropyl acrylamide, N,N-didecyl Acrylamide, 2-ethylhexyl methacrylate, 2-(didecylamino)ethylmercaptopropenylamine, 3-sulfopropyl methacrylate, 5·methyl-4-side oxygen Potassium 5-en-1-sulfonate, 2-butoxyethyl methacrylate, 2-(t-butylamino)ethyl methacrylate, 2-propenylamine-2 -methyl-1-propanesulfonic acid, 4- Alkenylbenzoic acid, N-(6-aminopyridin-2-yl)propenylamine, N-(3-aminophenyl)propenylamine, 2-propenylaminopyridine, 4-vinylphenyl Boric acid, itaconic acid, 2-aminoethyl methacrylate and mercapto vinyl ether. The monomers in the polymer can be arranged in any suitable manner. For example, the alternating copolymer has regularly alternating monomeric residues; the periodic copolymer has a monomeric residue type arranged in a repeating sequence; the random copolymer has a random sequence of monomeric residue types; the statistical copolymer has Monomer residues arranged according to known statistical rules; block copolymers have two or more homopolymer subunits linked by covalent bonds. Most preferably, the polymer is a random copolymer. The molecular weight of the polymer is preferably 2,000 or more. The preferred range is from 2,000 to 1 〇〇〇 〇〇〇 ‘the better range is from 5,000 to 100 〇〇〇. In this context, the molecular weight is the number average molecular weight. This is the general arithmetic mean of the molecular weights of individual macromolecules. It is determined by measuring the molecular weight of the polymer molecules, summing the molecular weights, and dividing them by the molecular weight determined by gel permeation chromatography. In yet another embodiment, the polymerization is carried out. The compound may comprise an isocyanate. Evil 154381.doc -12- 201138892 A nonoxyl polymer of the side of an oxazolone, epoxide, ester or anhydride. Dye Polymer Description Preferably, the polymeric compound within the dye polymer is covalently bonded to (1) (9) dye molecules. More preferably 140 dye molecules. The best (1) anthraquinone dye molecule. In addition to the charge on the dye, the polymer may contain a cationically charged group with an anionic charge. For polymers having a cationic group on the comonomer, the dye is preferably uncharged or anionically charged. Preferably, the polymer is free of primary amines. The dye is preferably uncharged or has an anionic charge. Most preferably, the dye has an anion charge. Anionic dyes are preferred when the polymer has a (iv) subgroup on the comonomer. Dye polymers having a poly(mercapto vinyl ether-alternating maleic anhydride) polymer which reacts with an anion dye are particularly preferred. A combination of polymeric dyes can be used to obtain a multi-palette. For dyeing hair, S, two or more polymer dyes are preferred in color, and the three polymer dyes are particularly preferred. Most effective is the use of a dye polymer mixture containing a red dye polymer, a yellow dye polymer, and a blue dye polymer. Variations in the fractions of blue, yellow and red in the mixture result in a number of colors 'e.g. black and brown. The poly(methyl vinyl ether-alternating maleic anhydride) polymer which reacts with the anionic dye is optimal. Preferably, the anionic dye contains hydrazine or two, preferably i sulfonate groups. The content of the polymer dye in the composition is preferably 总1 154381.doc •13·201138892 wt% to 1 Wt°/. Optimum 〇·〇4 wt% to 0.4 wt% to 5 wt%, more preferably 〇1 wt%. The method of the present invention comprises a rinsing step. Preferably, the method of the invention comprises applying the dye composition directly to dry or wet hair. Preferably, the application temperature is 18t to 38. (: Preferably, the composition is a shampoo, conditioner or hair dye composition. If ''and the system shampoo' then preferably comprises from 5 wt% to 5 wt% of the total composition. Preferably, the cleansing surfactant comprises an anionic and an amphoteric surfactant. If the composition is a conditioning composition, it preferably comprises a conditioning active such as a fatty alcohol 'fatty acid, Fatty amides and samarium oxides, cationic surfactants, etc. Preferably, the composition contains a perfume. Preferably, the 'perfume is present in a total composition of 〇〇1 Wt% to 5 wt%. Preferably, the pH of the composition of the invention is from 3 to 9, preferably from 4 to 8. Preferably, the composition contains more than 4% by weight of water based on the total composition. Preferably, the composition is liquid and The viscosity of the liquid is greater than 4%/white at 293 K. Viscosity is measured using the ball viscosity, and the viscosity of the liquid is calculated using Stoke's law (St〇ke, s Law). The invention is illustrated by the following non-limiting examples: Example 1 Reaction Scheme DAQ. 154381.doc 201138892

1 g of polymer (PMVEMA 'CAS: 9011-16-9, Mn = 80000, Mw = 210000, available from Aldrich) and 069.069 g acid blue 62 and 〇〇3〇g 1,4-monoamine hydrazine The brewed (DAQ) dye was mixed in 5 〇mi tetrahydrobite and heated at 65 ° C for 8 hours. The obtained polymer was further washed three times with CHCl3 to remove unreacted dye, followed by vacuum drying overnight at r.t. Finally, the resulting polymer containing unreacted maleic anhydride is subjected to a hydrolysis treatment to produce a moderately acidic carboxylic acid group. The polymer is coded as ρι. Example 2 The reaction of Example i was repeated using an anionically charged dye Acid Blue 62 (AB62).

1 g of the polymer was mixed with 〇·1 g of the dye in 50 mi of tetrahydrofuran and heated at 154381.doc -15-201138892 6 5 C for 8 hours. The resulting ancestors were taken and the polymer was precipitated in petroleum ether and dried in vacuo. Two reactions were carried out using a polymer having an initial molecular weight (Mw) of 2 〇 0,000 and 2,000, and the resulting dye polymer was coded as P2 and P3. The polymer you are white τςργ八w Λ ’, (the knife is GantrezTM AN 119 and

Anl69) obtained. Producing a similar polymer with DAQ and encoding p4 and p5 respectively correspond to

GantrezTM AN 119 and Anl69. Example 3: Hair dyeing properties 0_04 wt was prepared in demineralized water. /. Dye polymer solution. Human gold hair samples (weight - 1.4 g) were placed in 7 ml of dye polymer solution and mixed for 6 sec seconds' removed and dried. The hair color was assessed by measuring the reflectance of the sample using a reflectometer and expressing the color as the CIE L*a*b* value and the ΔΕ value relative to the unstained control. The sample was then rinsed in water for 60 seconds under the tap water, dried and re-measured. The sample was then washed in 〇 5 g/L sodium lauryl ether sulfate (3 ethoxy) surfactant solution for 6 sec seconds, rinsed in demineralized water, dried and re-measured. The results are summarized as follows: Human hair △E P1 P2 P3 P4 P5 Initial 12.4 8.6 12.2 14.5 9S Washed with water 8.6 6.5 7.7 83 6A Washing 7.5 7.8 7.3 ΗΛ is —' The above example confirms that the hair has been dyed. 154381.doc -16 -

Claims (1)

201138892 VII. Patent application scope: 1 . A hair dyeing method comprising the step of applying a composition comprising a dye polymer to hair, wherein the dye polymer can be directly covalently bonded by an aromatic ring in the dye oxime) The NH2 group of the knot is obtained by reacting with a reactive group in the polymer compound (1), wherein the reactive group is selected from the group consisting of isocyanate acetonide, epoxide, ester and anhydride. 2. The method of claim 1, comprising the step of applying a composition comprising a dye polymer to the hair, wherein the dye polymer is by NH2 group covalently bonded directly to the aromatic ring in the dye oxime. The group is obtained by reacting with a reactive group in the polymer compound (1), wherein the reactive group is selected from the group consisting of isocyanates, oxazolone, epoxides, esters and anhydrides. 3. The method of claim 1 or claim 2, wherein the reactive group in the polymeric compound (1) is an epoxide or anhydride group. 4. The method according to any one of the preceding claims, wherein the reactive group in the polymerized compound (1) is an anhydride group. 5. The method of any of the preceding claims, wherein the dye oxime has an anionic charge. The method of any one of the preceding claims, wherein the dye polymer is a poly(methyl sethoxy ether-alternating sulphate liver) polymer which reacts with an anionic dye. The method of any of the preceding claims, wherein the dye polymer is preferably present in the composition in an amount of from 5% by weight to 5% by weight of the total composition. 8. The method of claim 7, wherein the dye polymer is present in the aqueous solution in an amount from 0.04 wt% to 0.4 wt% of the total combination 154381.doc 201138892. The method of any of the preceding claims, wherein the composition comprises a mixture of three or more polymeric dyes. I 〇· 刖 刖 刖 求 求 求 求 求 求 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该The method of claim 10, wherein the dye i) is selected from the group consisting of chromophores. The method of any one of the preceding claims, wherein the compound ii) in the dye polymer is covalently bonded to from 1 to 10 dye molecules i). The method of any of the preceding claims, wherein the method further comprises rinsing the hair after applying the composition comprising the dye. 154381.doc 201138892 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 154381.doc