GB2446257A - Cationic dyes comprising a 2-oxo-tetrahydrothiophen-3-ylamino substituent for dyeing keratin-containing fibres - Google Patents

Cationic dyes comprising a 2-oxo-tetrahydrothiophen-3-ylamino substituent for dyeing keratin-containing fibres Download PDF

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Publication number
GB2446257A
GB2446257A GB0800663A GB0800663A GB2446257A GB 2446257 A GB2446257 A GB 2446257A GB 0800663 A GB0800663 A GB 0800663A GB 0800663 A GB0800663 A GB 0800663A GB 2446257 A GB2446257 A GB 2446257A
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Prior art keywords
dye
hydrogen
dyes
formula
acid
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GB0800663D0 (en
Inventor
Victor Eliu
Beate Froehling
Dominique Kauffmann
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
Ciba Holding AG
Ciba SC Holding AG
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4986—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with sulfur as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B26/00—Hydrazone dyes; Triazene dyes
    • C09B26/02—Hydrazone dyes
    • C09B26/04—Hydrazone dyes cationic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
    • C09B44/16—1,3-Diazoles or hydrogenated 1,3-diazoles ; (Benz)imidazolium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
    • C09B44/20—Thiazoles or hydrogenated thiazoles

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Cosmetics (AREA)

Abstract

Dyes of formula (1): <EMI ID=1.1 HE=28 WI=48 LX=837 LY=674 TI=CF> <PC>```wherein D is a cationic radical consisting or comprising an anthraquinone, acridine, azo, azomethine, hydrazomethine, benzodifuranone, coumarine, diketopyrrolopyrrole, dioxazine, diphenylmethane, formazan, indigoid, indophenol, naphthalimide, naphthaquinone, nitroaryl, merocyanine, methine, oxazine, perinone, perylene, pyrenequinone, phthalocyanine, phenazine, quinoneimine, quinacridone, quinophthalone, stilbene, styryl, triphenylmethane, xanthene, thiazine, thioxanthene or direct dye; may be used for dyeing keratin-containing fibres.

Description

Cationic Dyes The present invention relates to cationic dyes,
compositions thereof, and to their use for the dyeing of organic materials, such as keratin fibers, wool, leather, silk, cellulose or poly-amides, especially keratin-containing fibers, cotton or nylon, and preferably hair, more preferably human hair.
It is known, for example, from WO 95/01772 that cationic dyes can be used for the dyeing of organic material, for example keratin, silk, cellulose or cellulose derivatives, and also syn- thetic fibers, for example polyamides. Cationic dyes exhibit very brilliant shades. A disad-vantage is their unsatisfactory fastness to washing.
The technical problem is to provide dyes that are distinguished by deep dying having good fastness properties with respect to washing, light, shampooing and rubbing.
Accordingly, the present invention relates to cationic hair dyes of formula D is the radical of anthraquinone, acndine, azo, azomethine, hydrazomethine, benzodifuranone, coumanne, diketopyrrolopyrrol, dioxaxine, diphenylmethane, formazane, indigoid, indophenol, naphtalimide, naphthaquinone, nitroaryl, merocyani ne, methine, oxazine, pennone, perylene, pyrenequinone, phtalocyanine, phenazi ne, quinoneimine, quinacndone, quinophtalone, stilbene, styryl, triphenylmethane, xanthene, thiazine dye and thioxanthene dye; Q is C1-C30alkylene, -C2-C1 alkenylene, -C5-C1 0arylene-, -C5-C1 0cycloalkylene-or -C1 -C10alkylene(C5-C10arylene)-which may be interrupted and/or terminated at one or both ends by one or more than one -0-, -S-, -N=, -N(R1)-, SO2, -(CH2CH2-0)15-, -(CH2CH2CH2-O)15-, -C(O)-, -C(O)-C1-C12alkenylene, -C(O)O-, -OCO-, -Nt--R1 -CON(R1)-, -C(NR1R2)2-, -(R1)NC(O)-, -CSR1-or an optionally substituted, saturated or unsaturated, fused or non-fused aromatic or nonaromatic (hetero)cyclic) bivalent radical optionally comprising at least one heteroatom; -0-; -S-; -N(R1)-; SO2; -(CH2CH2-O)15-; -C(0)-; -C(O)-C1-C12alkenylene; -C(0)0-, -OCO-; -Nt-; -CON(R1)-; -C(NR1R2)2-; R1 -(R1)NC(O)-; CSR1; saturated or unsaturated, fused or non-fused aromatic or nonaro-matic bivalent radical optionally comprising at least one heteroatom; which is optionally substituted by C1-C39alkyl, C1-C30alkoxy, -C2-C12alkenyl, C5-C10aryl, C5-C10cycloalkyl, Ci-C1oalkyl(C5-C10arylene), hydroxy or D; R1 and R2 independently from each other are hydrogen; or unsubstituted or substituted, straight-chain or branched, monocyclic or polycyclic, interrupted or uninterrupted Ci-C14alkyl; C1-C14 hydroxyalkyl; C1-C14 aminoalkyl; C2-C14alkenyl; C6-C10aryl; C6-C10aryl-C1-C10alkyl; or C5-C10alkyl(C5-C10aryl).
Preferably in formula (1) D is the radical of anthraquinone, acridine, azo, azomethine, hydrazomethine, benzodifu-ranone, coumarine, diketopyrrolopyrrol, dioxaxine, diphenylmethane, formazane, indigoid, indophenol, naphtalimide, naphthaquinone, nitroaryl, merocyanine, methine, oxazine, perinone, perylene, pyrenequinone, phtalocyanine, phenazine, quinoneimine, quinacndone, quinophtalone, stilbene, styryl, tnphenylmethane, xanthene, thiazine dye and thioxanthene dye; Q is -C2-C1 2alkenylene, -C5-C10arylene-, -C5-C10cycloalkylene-or -C1-C1 0alkylene(C5-C1oarylene)-which may be interrupted by one or more than one -0-, -S-, -NR3-or SO2; -(CH2CH2-O)15-; -C(O)-; -C(O)-C1-C12alkenylene; -C(O)O-; -OCO-; -N(R1)-; -Nt--R1 -CON(R1)-; -C(NR1R2)2; -(Ri)NC(O)-; -CSR1-; -0-; -S-; -CS-; -S(O)-; or-S(O)2-; and R1, R2 and R3 independently from each other are hydrogen; unsubstituted or substituted, straightchain or branched, monocyclic or polycyclic, interrupted or uninterrupted C1-C14alkyl; C2-C14alkenyl; C-C10aryl; C6-C10aryl-C1-C10alkyl; or C5-Cioalkyl(C5-C10aryl).
C1-C14alkyl is for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2'-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1,1,3,3'-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl, .undecyl, dodecyl or tetradecyl.
C2-C12alkylene is for example methylene, ethylene, propylene, isopropylene, n-butylene, sec- butylene, tert-butylene, n-pentylene, 2-pentylene, 3-pentylene or 2,2'-dimethylpropylene, n-hexylene, n-octylene, 1,1,3,3'-tetramethylbutylene, 2-ethylhexylene, nonylene, decylene, undecylene or dodecylene.
Alkylene may be straight-chain, branched, or, from C5alkyl upwards, monocyclic or poly- cyclic, and may be interrupted by hetero atoms, such as such as 0, S, -Ca-, N, NH, NRa, -OCO, C0(ORa), CONRa, -(Rb)NC(O)-; for example C1-C10alkylene may be a resisue such as: -CH2CH2-O-CH2CH2-O-CH2CH2--CH2CH2-O-CH2CH2--CH2CH7-O-CH2-, -CH2-O-CH2-, -CH2CH2-CH2CH2-O-CH2-CH2-, -CH2CH2-CH(N(CH3)2)-CH2-CH2-, CH2-NH2-CH2-CH2-, -CH2CH2-NH-CH2CH2-, -CH2CH2-NCH3-CH2CH2-, -CO-CH2-, -CH2CO-, -CH2CH2-NHCO-CH2CH2-, -CH2CH2-CONH-CH3-CH2CH2-, -CH2CH2-NCH3CO-CH2CH2-, -CH2CH2-CONCH3-CH3-CH2CH2-, -CH2-NHCO-CH2CH2-, -CH2CH2-NHCO-CH2-, -CH2CH2-CONH-CH2-or -CH2-CONH-CH2CH2-.
R3 and Rb independently from each other are hydrogen; C1-C12alkyl, which may be substituted by one or more C1-C5alkyl, C1-C5-alkoxy or hydroxyl; -(CO)-H; -(CO)-C1-C5alkyI; phenyl or phenyl-C1-C4alkyI, wherein the phenyl moiety may be substituted by one or more C1-C5alkyl, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5alkylamino, -NO2, carboxy or hydroxyl.
C5-C10cycloalkylene is for example cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene or cyclodecylene.
C5-C10arylene is for example phenylene or naphthylene.
Aryl-alkylene is for example C5-C1 0aryl-C1 -C1 0alkylene.
Alkyl-arylene is for example C1-C10aIkyl-C5-C1 0arylene.
"Anion" denotes, for example, an organic or inorganic anion, such as halide, preferably chloride and fluoride, sulfate, hydrogen sulfate, phosphate, boron tetrafluonde, carbonate, bicarbonate, oxalate or C1-C8alkyl sulfate, especially methyl sulfate or ethyl sulfate; anion also denotes lactate, formate, acetate, propionate or a complex anion, such as the zinc chloride double salt.
The anion is especially a halide, preferably chloride, bromide or fluoride, sulfate, hydrogen sulfate, benzenesulfonate, tosylate, methyl sulfate, ethyl sulfate, phosphate, formate, acetate or lactate.
The anion is more especially fluoride, chloride, bromide, methyl sulfate, ethyl sulfate, formate or acetate.
Preferred are dyes of formula (1), wherein D is selected from a nitroaryl, an anthraquinone, a naphthoquinone, a pyrenequinone, a phathylocyanine, a formazane, a methin, an azomethine, a dioxaxine, a phenazine, an azo, an indophenol, a stilbene, a tnphenylmethane, a xanthene, a thioxanthene and a direct dye; and more preferably wherein D is a cationic direct dye.
Even more preferred are dyes of formula (1), wherein R * c +1 D is a radical of formula (Ia) *Ni1 An (1b) An - X1-T1-R5 R5-T1-X1 G2 -R4 \ or(lc) ; R;or(ld) *TX An 4G, N An-
-T -R
X1 is a bivalent radical selected from -N=N-; -CRN-; -NCR8-; -NR8-NCR9-; and -R8CN-NR9-; T1 is a bivalent radical of a substituted or unsubstituted aromatic or heteroaromatic compound; G1 is N; or a radical CR10; G2 is -0-; or -S-; R4 and R5 independently from each other are hydrogen; halogen; C1-C16alkyl, which may be interrupted with heteroatoms; phenyl; a carboxylic acid radical; a sulfonic acid radical; hydroxy; nitrile; C1-C16alkoxy; (poly)-hydroxy-C2-C4-alkoxy; halogen; SO2NR6R7; SR6; NR6R7; OR6; SO2; COOR6; NR6COR7; or CONR6; R6 and R7 independently from each other are hydrogen; C1-C12alkyI, which may be substituted by one or more C1-C5alkyl, C1-C5-alkoxy or hydroxyl; -(00)-H; -(C0)-C1-C5alkyI; phenyl or phenyl-C1-C4aIkyI, wherein the phenyl moiety may be substituted by one or more C1-C5alkyl, 01-C5alkoxy, halogen, -NH2, mono-C1-C5aIkyI-amino, di-C1-C5alkylamino, -NO2, carboxy or hydroxy; R8 and R9 independently from each other are hydrogen; C1-C14aIkyl; C2-C14alkenyl; C5 C10aryl; C1-C10alkyI-C5-C10aryI; or C5-C10aryl-C1-C10aIkyl; R10 is hydrogen; C1-C14alkyl; C2-C14alkenyl; C6-C10aryl; C5-C10aryI-(C1-C10aIkyl); or -Ci-C1oalkyl(C5-C1oaryl); and An is an anion.
Most preferred are dyes of formula (1), wherein D is aradical of (Ia1) An X1-T--R5 (Ia2) An -
A-
(1b1) R__Ti_XT'] An or (Ic1) ; *_NG__X_T_R, wherein X1, T1 R4, R5and An are defined as above.
Preferred are dyes of formula (1), wherein Q is a bivalent radical of formula (I a) -(T)(Z)-, T is a radical selected from saturated or unsaturated, linear or branched -C1-C12alkylene; -C(O)-; -(CH2CH2-O)15-; -(CH2CH2CH2-O)15-; -0(0)0-; -OC(O)-; -N(R1)-; -CON(R1)-; -(R1)NC(O)-; -0-; -S-; -S(O)-; -S(O)2-; -S(0)2-N(R1)-; and -N(R1)(R2)-; * N * Z is-(CH2)2-S02-; -CH2-CHR-CO-NR'-; or a biradical of formula (1 b) (Ic) Da; D R and R' independently from each other are hydrogen; or C1-C6 alkyl; D is Ra; Dia+; or a and b independently from each other are 1, 2 or 3; Ra is chlorine or fluorine, R1 is unsubstituted or substituted C1-C6-alkoxy, C1-C6-alkylamino, C6-C10-aryloxy or C6-Cio-arylamino; and t and z, independently from each other are 0; or 1; with the proviso that at least one oft or z isl.
Most preferred are of formula (1), wherein X1 is a bivalent radical selected from -N=N-; -CR8N-; and -NCR8-; T1 is phenylene; R5 is NR6R7; OR8; or SO2; R6 and R7 independently from each other are hydrogen; or C1-C12alkyl, which may be substituted by one or more hydroxyl; and R8 is hydrogen; or C1-C14alkyl.
The most preferred dyes according to the present invention correspond to formula
R
o -1+% (2a) or (2b) .N wherein
R
Q is C1 -C30al kylene; C2-C1 2alkenylene, -C5-C1 0arylene-, -C(O)-; or -C(O)-C2-C1 2al kenylene; R4 is hydrogen; C1-C16alkyl; or C1-C16alkoxy; R5 is NR6R7; and R6 and R7 independently from each other are hydrogen; or C1-C12alkyl, which may be substituted by one or more hydroxyl; and to formula (3) , wherein X1 is a bivalent radical selected from -N=N-; -CR8=N-; R5 is NR6R7; R8 is hydrogen; or C1-C14alkyl; and R6 and R7from each other are hydrogen; C1-C12alkyl; or phenyl; and to formula R4 1+ N-T-Q-NH 0 (4) [)__N" 1 wherein T1 is is a bivalent radical of an substituted or unsubstituted aromatic compound; Q is -C2-C12alkenylene, which may be interrupted by one or more than one -NR3-; R3 is hydrogen; or C1-C14alkyl; and R4 is hydrogen; or C1-C16alkyl.
Examples of the dyes of formula (1) are listed in the Table I below:
Table I s
CT-01 Br o H*N\ _ b
Table I \
CTO2 N N,N--N
N \
-S
CT-03 LL Y 0HH jNJ N_CJ_NH2
-S
CT-04 >-N llj N-Q-N S\J
S OH CT-05
NN
OH
S OH
CT-06 OOi: YN
NN
OH
H CT-07
NNJJ
N \
Table I
CT-08 H 1\
I H
CT-09 1+ NN cN.N) N\ <1ìIH /N All compounds of the present invention mentioned above can also exist as hydrates or solvates.
A further emodiment of the present inveintion relates to processes for the preparation of the dyes of formula (I).
Generally, the process comprises the reacing of dye intermediates with 3-amino-dihydro-thiophenone, which is a cyclic thioderivative according to the following reaction scheme: D An-+ Q + H2Ns DQ0 An The reaction is generally initiated by contacting, for example by mixing together the starting compounds or by dropwise addition of one starting compound to the other.
Customary, the temperature is in the range of 263-363. K, preferably in the range of 263-33Q K during the mixing of the starting compounds.
The reaction time is generally dependent on the reactivity of the starting compounds, on the selected reaction temperature and on the desired conversion. The reaction time is usually in the range fromi h to 3 days.
The selected reaction pressure is generally in the range from 10 kPa to 1 MPa, especially from 50 kPa to 150 kPa, and is more especially atmospheric pressure.
Preferably the reaction is carried out in the presence of a catalyst.
The molar ratio of compound of formula (1 b) to the catalyst is generally selected in the range from 10:1 to 1:5, especially in the range from 10:1 to 1:1.
Preferred are acid catalysts, HA and Lewis acids like Agor base catalysts as tertiary nitrogen bases In addition, the reaction may be carried out with or without a solvent, but is preferably carried out in the presence of a solvent, preferably organic solvents or solvent mixtures.
Preferred solvents are alcohols like methanol, ethanol, propariol, 2-propanol or butanol; nitnles like acetonitnl or propionitril; amides like dimethylformamide, dimethylacetamide or N- methylpyrolidone; halogenated hydrocarbons like chloroform, methylenechioride, trichloro-ethylene or chlorobenzene; or other solvents like dimethylsulfoxide or water or mixtures of the mentioned solvents.
The product prepared according to the process of the present invention may advantageously be worked up and isolated, and if desired be purified.
Customary, the work up starts by decreasing the temperature of the reaction mixture in the range from 350 to 273 K, especially in the range from 320 to 273 K. It may be advantageous to decrease the temperature slowly over a period of several hours.
In general, the reaction product is filtered off and subsequently dried.
Filtration is normally carried out in standard filtering equipment, for example Büchner funnels, filter presses, pressurised suction filters, preferably in vacuo.
The temperature for the drying is dependent on the pressure applied. Drying is usually carried out in vacuo at 50-200 mbar.
The drying is usually carried out at a temperature in the range from 313 to 363 K, especially from 323 to 353 K, and more especially in the range from 328 to 348 K. Advantageously the product is purified by recrystallisation after isolation.
The dyes of formula (I) according to the invention are suitable for dyeing organic materials, such as keratin-containing fibers, wool, leather, silk, cellulose or polyamides, cotton or nylon, and preferably human hair. The dyeings obtained are distinguished by their depth of shade and their good fastness properties to washing, such as, for example, fastness to light, shampooing and rubbing.
Gemerally, hair dyeing agents on a synthetic base may be classiefied into three groups: -temporary dyeing agents -semipermanent dyeing agents, and -permanent dyeing agents.
The multiplicity of shades of the dyes can be increased by combination with other dyes.
Therefore the dyes of formula (1) of the present invention may be combined with dyes of the same or other classes of dyes, especially with direct dyes oxidation dyes; dye precursor combinations of a coupler compound as well as a diazotized compound, or a capped dia-zotized compound; and/or cationic reactive dyes.
Direct dyes are of natural origin or may be prepared synthetically. They are uncharged, cationic or anionic, such as acid dyes.
The dyes of formula (1) may be used in combination with at least one single direct dye different from the dyes of formula (1).
Direct dyes do not require any addition of an oxidizing agent to develop their dyeing effect.
Accordingly the dyeing results are less permanent than those obtained with permanent dyeing compositions. Direct dyes are therefore preferably used for semipermanent hair dyeings.
Examples of direct dyes are described in "Dermatology", edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, p. 248-250, and in "Europäisches Inventar der Kosmetikrohstoffe", 1996, published by The European Commission, obtainable in diskette form from the Bundesver-band der deutschen Industrie-und Handelsuntemehmen für Arzneimiftel, Reformwaren und Körperpflegemittel e.V., Mannheim.
More preferred direct dyes which are useful for the combination with at least one single dye of formula (1), especially for semi permanent dyeing, are: 2-amino-3-nitrophenol, 2-amino-4-hydroxyethylamino-anisole sulfate, 2-amino-6-chloro-4-nitrophenol, 2-chloro-5-nitro-N-hydroxyethylene-p-phenylend iami ne, 2-hydroxyethyl-picramic acid, 2,6-diamino-3-((pyndine-3y1)-azo)pyndine, 2-nitro-5-glyceryl-methylanil., 3-methyl- amino-4-nitro-phenoxyethanol, 4-amino-2-nitrodiphenyleneamine-2'-carboxilic acid, 6-nitro-I,2,3,4,-tetrahydroquinoxal., 4-N-ethyl-I,4-bis(2'-hyd roxyethylamino-2-nitrobenzene hydrochloride, I -methyl-3-nitro-4-(2'-hydroxyethyl)-aminobenzene, 3-nitro-p-hydroxyethyl-aminophenol, 4-amino-3-nitrophenol, 4-hydroxypropylamine-3-nitrophenol, hydroxyanthryl-aminopropylmethyl morptili no methosulfate, 4-nitrophenyl-aminoethylurea, 6-nitro-p-toluidine, Acid Blue 62, Acid Blue 9, Acid Red 35, Acid Red 87 (Eosin), Acid Violet 43, Acid Yellow 1, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 12, Basic Blue 26, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Red 2, Basic Red 22, Basic Red 76, Basic Violet 14, Basic Yellow 57, Basic Yellow 9, Disperse Blue 3, Disperse Orange 3, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Fast Green FCF, HC Blue 2, HC Blue 7, HC Blue 8, HG Blue 12, HG Orange 1, HC Orange 2, HG Red 1, HG Red 10-Il, HG Red 13, HG Red 16, HG Red 3, HG Red BN, HG Red 7, HG Violet 1, HG Violet 2, HG Yellow 2, HG YellowS, HG Yellow 5, HG Yellow 6, HG Yellow 7, HG Yellow 9, HG Yellow 12, HG Red 8, hydroxyethyl-2-nitro-p-toluidine, N, N-Bis-(2-Hydroxyethyl)-2-nitro-p-phenylendiamine, HG Violet BS, Picramic Acid, Solvent Green 7.
Furthermore, the dyes of formula (1) may be combined with at least one cationic azo dye, for example the compounds disclosed in GB-A-2 319 776 as well as the oxazine dyes described in DE-A-299 12 327 and mixtures thereof with the other direct dyes mentioned therein, and even more preferred with cationic dyes such as Basic Yellow 87, Basic Orange 31 or Basic Red 51, or with cationic dyes as described in WO 01/66646, especially example 4, or with cationic dyes as described in WO 02/31056, especially example 6, the compound of formula 106; or the cationic dye of formula (3) as described in EP-A-714,954, or with a yellow cationic dye of formula (DDI) ,wherein R2 R1 and R2 are each independently of the other a C1-C8alkyl; or an unsubstituted or R3 is hydrogen; C1-C8alkyl; C1-C8alkoxy; cyanide; or halide; preferably hydrogen; and X is an anion; and preferably a compound of formula (DDI), wherein R1 is methyl; R2 is benzyl; R3 is hydrogen; and X is an anion; or wherein R1 is benzyl; R2 is benzyl; R3 is hydrogen; and X is an anion; or wherein R1 is benzyl; R2 is methyl; R3 is hydrogen; and X is an anion.
Furthermore, cationic nitroaniline and anthraquinone dyes are useful for a combination with a dye of formula (1) for example the dyes as described in the following patent specifications: US-5 298 029, especially in col 2, I. 33 to col 5, I. 38; US-5 360 930, especially in col 2, I. 38 to col 5, I. 49; US-5 169 403, especially in col 2, I. 30 to col 5, I. 38; US-5 256 823, especially in col 4, I. 23 to col 5, I. 15; US-5 135 543, especially in col 4, I. 24 to col 5, I. 16; EP-A-818 193, especially on p. 2, I. 40 to p. 3, I. 26; US-5 486 629, especially in ccl 2, I. 34 to col 5, I. 29; and EP-A-758 547, especially on p. 7, I. 48 to p. 8, I. 19.
The dyes of formula (1) may also be combined with acid dyes, for example the dyes which are known from the international names (Color index), or trade names.
Preferred acid dyes which are useful for the combination with a dye of formula (1) are described in US Patent 6,248,314. They include Red Color No. 120, Yellow Color No. 4, Yellow Color No. 5, Red Color No. 201, Red Color No. 227, Orange Color No. 205, Brown Color No. 201, Red Color No. 502, Red Color No. 503, Red Color No. 504, Red Color No. 506, Orange Color No. 402, Yellow Color No. 402, Yellow Color No. 406, Yellow Color No. 407, Red Color No. 213, Red Color No. 214, Red Color No. 3, Red Color No. 104, Red Color -14-No. 105(1), Red Color No. 106, Green Color No. 2, Green Color No. 3, Orange Color No. 207, Yellow Color No. 202(1), Yellow Color No. 202(2), Blue Color No. 202, Blue Color No. 203, Blue Color No. 205, Blue Color No. 2, Yellow Color No. 203, Blue Color No. 201, Green Color No. 201, Blue Color NO. 1, Red Color No. 230(1), Red Color No. 231, Red Color No. 232, Green Color No. 204, Green Color No. 205, Red Color No. 401, Yellow Color No. 403(1), Green Color No. 401, Green Color No. 402, Black Color No. 401 and Purple Color No. 401, especially Black Color No. 401, Purple Color 401, Orange Color No. 205.
These acid dyes may be used either as single component or in any combination thereof.
Hair dye compositions comprising an acid dye are known. They are for example described in "Dermatology", edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, p. 248-250, especially on p. 253 and 254.
Hair dye compositions which comprise an acid dye have a pH of 2-6, preferably 2-5, more preferably 2.5-4.0.
The dyes of formula (1) according to the present invention may also readily be used in combination with acid dyes and/or adjuvants, for example -acid dyes and an alkylene carbonate, as described in US patent 6,248,314, especially in
examples I and 2;
-acid hair dye compositions comprising various kinds of organic solvents represented by benzyl alcohol as a penetrant solvent have good penetrability into hair, as described in Japanese Patent Application Laid-Open Nos. 210023/1 986 and 101841/1995; -acid hair dye compositions with a water-soluble polymer or the like to prevent the drooping of the hair dye composition, as described for example in Japanese Patent Application Laid-Open Nos. 87450/1998, 255540/1997 and 245348/1996; -acid hair dye compositions with a water-soluble polymer of aromatic alcohols, lower alkylene carbonates, or the like as described in Japanese Patent Application Laid-Open No. 53970/1 998 and Japanese Patent Invention No. 23911/1973.
The dyes of formula (1) may also be combined with uncharged dyes, for example selected from the group of the nitroanilines, nitrophenylenediamines, nitroaminophenols, anthra-quinones, indophenols, phenazines, phenothiazines, bispyrazolons, bispyrazol aza derivatives and methines.
Furthermore, the dyes of formula (1) may also be used in combination with oxidation dye systems.
Oxidation dyes, which, in the initial state, are not dyes but dye precursors are classified according to their chemical properties into developer and coupler compounds.
Suitable oxidation dyes are described for example in -DE 19959479, especiallyincol2, l.6tocol3, 1.11; -"Dermatology", edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 8, on p. 264 -267 (oxidation dyes); Preferred developer compounds are for example primary aromatic amines, which are substituted in the para-or ortho-position with a substituted or unsubstituted hydroxy-or amino residue, or diaminopyndine derivatives, heterocyclic hydrazones, 4-aminopyrazol derivatives, 2,4,5,6-tetraaminopynmidine derivatives, or unsaturated aldehydes as described in DE 19 717 224, especially on p. 2, I. 50 to I. 66 and on p. 3 I. 8 to I. 12, or cationic develop- per compounds as described in WO 00/43367, especially on p., 2 I. 27 to p. 8, I. 24, in par-ticular on p. 9, I. 22 to p. 11, I. 6.
Furthermore, developer compounds in their physiological compatible acid addition salt form, such as hydrochloride or sulfate can be used. Developer compounds, which have aromatic OH radicals are also suitable in their salt form together with a base, such as alkali metal-phenolates.
Preferred developer compounds are disclosed in DE 19959479, p. 2, I. 8-29.
More preferred developer compounds are p-phenylendiamine, p-toluylendiamine, p-, m-o- aminophenol, N, N-bis-(2-hydroxyethyl)-p-phenylenediamine sulfate, 2-amino-4-hydroxy-ethylaminoanisole sulfate, hydroxyethyl-3,4-methylenedioxyanil., I -(2'-hydroxyethyl)-2,5diaminobenzene, 2,6-dimethoxy-3,5-diamino-pyndine, hydroxypropyl-bis-(N-hyd roxyethyl-p- phenylenediamine) hydrochloride, hyd roxyethyl-p-phenylenediamine sulfate, 4-ami no-3-me- thylphenol, 4-methylaminophenol sulfate, 2-aminomethyl-4-aminophenol, 4,5-diamino-1-(2-hydroxyethyl)-I H-pyrazol, 4-amino-m-cresol, 6-amino-m-cresol, 5-amino-6-chloro-cresol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopynmidine or 4-hydroxy-2,5,6-triaminopyrimidine sulfate.
Preferred coupler compounds are m-phenylendiamine derivatives, naphthole, resorcine and resorcine derivatives, pyrazolone and m-aminophenol derivatives, and most preferably the coupler compounds disclosed in DE 19959479, p.1,1.33 to p.3, I. 11.
The dyes of formula (1) may also be used together with unsaturated aldehydes as disclosed in DE 19717224 (p. 2, I. 50 to I. 66 and on p. 31.8 to I. 12) which may be used as direct dyes or, alternatively together with oxidation dye precursors.
Further preferred for a combination with a dye of formula (1) are the following oxidation dye precursors: -the developer/-coupler combination 2,4,5,6-tetraaminopyrimidine and 2-methylresorcine for assessing of red shades; -p-toluenediamine and 4-amino-2-hydroxytoluene for assessing of blue-violet shades; -p-toluenediamine and 2-amino-4-hydroxyethylaminoanisole for assessing of blue shades; -p-toluenediamine and 2,4-diamino-phenoxyethynol for assessing of blue shades; -methyl-4-aminophenol and 4-amino-2-hydroxytleoluene for assessing of orange shades; -p-toluenediamine and resorcine for assessing of brown-green shades; -p-toluenediamine and 1-naphthol for assessing of blue-violet shades, or -p-toluenediamine and 2-methylresorcine for assessing of brown-gold shades.
Furthermore, autooxidizable compounds may be used in combination with the dyes of formula (1).
Autooxidizable compounds are aromatic compounds with more than two substituents in the aomatic ring, which have a very low redox potential and will therefore be oxidized when exposed to the air. The dyeings obtained with these compounds are very stable and resistant to shampoo.
Autooxidizable compounds are for example benzene, indol, or indol, especially 5,6-dihy-droxyindol or 5,6-dihydroxyindol derivatives as described in WO 99/20234, especially on p. 26, I. 10 to p. 28, I. 15, or in WO 00/28957 on p. 2, third paragraph.
Preferred autooxidizable benzene derivatives are I,2,4-tnhydroxybenzene, I -methyl-2,4,5- trihydroxybenzene, 2,4-diamnio-6-methylphenol, 2-amino-4-methylaminophenol, 2,5-dia-mino-4-methyl-phenol, 2,6-diamino-4-diethylaminophenol, 2,6-diamino-1,4-dihydroxy-benzene, and the salts of these compounds, which are accessible with acid.
Preferred autooxidizable indol derivatives are 5,6-d ihydroxyindol, 2-methyl-5,6-dihyd roxy- indol, 3-methyl-5,6-dihyd roxyindole, I -methyl-5,6-di hydroxyindol, 2,3-dimethyl-5,6-dihydroxy- indol, 5-methoxy-6-dihydroxyindol, 5-acetoxy-6-hydroixyindol, 5,6-diacetoxyindol, acid of 5,6-dihydroxyindol-2-carbonacid, and the salts of these compounds, which are accessible with acid.
The dyes of formula (1) may also be used in combination with naturally occurring dyes, such as henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, Rhamnus frangula bark, sage, campeche wood, madder root, catechu, sedre and alkanet root. Such dyeings are described, for example, in EP-A-404 868, especially on p. 3, I. 55 to p.4,1.9.
Furthermore, the dyes of formula (1) may also be used in combination with capped dia-zotised compounds.
Suitable diazotised compounds are for example the compounds of formulae (1) -(4) in WO 2004/01 9897 (bridging gages I and 2) and the corresponding watersoluble coupling components (I) -(IV) as disclosed in the same reference on p. 3 to 5.
Further preferred dyes or dye combinations which are useful for the combination with a dye of formula (1) according to the present invention are described in (DC-0I): WO 95/01772, wherein mixtures of at least two cationic dyes are disclosed, especially p. 2, I. 7 to p. 4, I. 1, preferably p. 4, I. 35 to p. 8, I. 21; formulations p. 11, last ≈-p. 28, I. 19; (DC-02): US 6,843,256, wherein cationic dyes are disclosed, especially the compounds of formulae (1), (2), (3) and (4) (col. I, I. 27-col. 3, I. 20, and preferably the compounds as prepared in the examples Ito 4 (col. 10, 1.42 to col. 13, I. 37; formulations col. 13, I. 38 to col. 15, I. 8; (DC-03): EP 970 685, wherein direct dyes are described, especially p. 2, I. 44 to p. 9, I. 56 and preferably p. 9, I. 58 to p. 48, I. 12; processes for dyeing of keratin-containing fibers especially p. 50, I. 15 to 43; formulations p. 50, I. 46 to p. 51, I. 40; (DC-04): DE-A-19 713 698, wherein direct dyes are described, especially p. 2, I. 61 to p. 3, I. 43; formulations p. 5, I. 26 to 60; (DC-05): US 6,368,360, wherein directd dyes (col. 4, I. I to col. 6, I. 31) and oxidizing agents (col. 6, I. 37-39) are disclosed; formulations col. 7, I. 47 to col. 9, I. 4; (DC-06): EP 1166 752, wherein cationic dyes (p. 3, I. 22 -p. 4, I. 15) and anionic UV-absorbers (p. 4, I. 27-30) are disclosed; formulations p. 7, I. 50-p. 9, I. 56; (DC-07): EP 998,908, wherein oxidation dyeings comprising a cationic direct dye and pyra-zolo-[1,5-a]-pynmidines (p. 2, I. 48 -p. 4, I. 1) are disclosed; dyeing formulations p. 47, 1.25 to p. 50,1.29; (DC-08): FR-2788432, wherein combinations of cationic dyes with Ananors are disclosed, especially p. 53, I. I to p. 63, I. 23, more especially p. 51 to 52, most especially Basic Brown 17, Basic brown 16, Basic Red 76 and Basic Red 118, and/or at least one Basic Yellow 57, and/or at least one Basic Blue 99; or combinations of arianoren and/or oxidative dyes, especially p. 2, I. 16 to p. 3, I. 16; dyeing formulations on p. 53, I. I to p. 63, I. 23; (DC-09): DE-A-1 9 713 698, wherein the combinations of direct dyes and permanent-wave fixing comprising an oxidation agent, an oxidation dye and a direct dye are disclosed; especially p. 4, I. 65 to p. 5, I. 59; (DC-10): EP 850 638, wherein developer compounds and oxidizing agents are disclosed; especially p. 2, I. 27 to p. 7, I. 46 and preferably p. 7, I. 20 to p. 9, I. 26; dyeing formulations p. 2, I. 3-12 and I. 30 to p. 14, and p. 28, I. 35 -p. 30, I. 20; preferably p. 30, 1.25-p. 32,1.30; (DC-lI): us 6,190,421 wherein extemporaneous mixtures of a composition (A) containing one or more oxidation dye precursors and optionally one or more couplers, of a compo-sition (B), in powder form, containing one or more direct dyes (col. 5, I. 40-col. 7, I. 14), optionally dispersed in an organic pulverulent excipient and/or a mineral pulverulent excipient, and a composition (C) containing one or more oxidizing agents are disclosed; formulations col. 8, I. 60-col. 9, I. 56; (DC-12): US 6,228,129, wherein a ready-to-use composition comprising at least one oxidation base, at least one cationic direct dye and at least one enzyme of the 2-electron oxidoreductase type in the presence of at least one donor for the said enzyme are disclosed; especially col. 8, I. 17-col. 13, I. 65; dyeing formulations in col. 2, I. 16 to col.
25, I. 55, a multi-compartment dyeing device is described in col. 26, I. 13 -24; (DC-I 3): WO 99/20235, wherein compositions of at least one cationic dye and at least one nitrated benzene dye with cationic direct dyes and nitro benzene direct dyes are described; onp.2, 1.1 top. 7,l.9,and p. 39,1.1 top.40l. II, preferablyp.8,l. I2top.
251. 6, p. 26, I. 7 top. 30, I. 15; p. 1, 1.25 top. 8, I. 5, p. 30, I. 17 top. 34 1.25, p. 8, I. 12 to p. 25 I. 6, p. 35, I. 21 to 27, especially on p. 36, I. I to p. 37; (DC-14): Wa 99/20234, wherein compositions comprising at least one direct cationic dye and at least one autooxidisable dye, especially benzene, indol and indol. derivatives are described, preferably direct dyes on p. 2, I. 19 to p. 26, I. 4, and autooxidisable dyes as dislosed especially on p. 26, I. 10 to p. 28, I. 15; dyeing formulations especially on p. 34, l.5top. 35, Ii 18; (DC-15): EP 850 636, wherein oxidation dyeing compositions comprising at least one direct dye and at least one meta-aminophenol derivative as coupler component and at least one developer compound and an oxidizing agent are disclosed, especially p. 5, I. 41 to p. 7, I. 52, dyeing formulations p. 19, I. 50 -p. 22, I. 12; (DC-16): EP-A-850 637, wherein oxidation dyeing compositions comprising at least one oxidation base selected from para-phenylenediamines and bis(phenyl)alkylenediamines, and the acid-addition salts thereof, at least one coupler selected from meta-diphenols, and the acid-addition salts thereof, at least one cationic direct dye, and at least one oxidizing agent are disclosed, especially p. 6, I. 50 to p. 8, I. 44 are discioseded; dyeing formulations p. 21, I. 30 -p. 22, I. 57; (DC-i 7): WO 99/48856, wherein oxidation dyeing compositions comprising cationic couplers are disclosed, especially p.9,1. 16-p. 13, 1.8, and p. 11, 1.20-p. 12, I. 13; dyeing formulations p. 36, I. 7-p. 39, I. 24; (DC-i8): DE 197 172 24, wherein dyeing agents comprising unsaturated aldehydes and coupler compounds and primary and secondary amino group compounds, nitrogen-containing heterocyclic compounds, amino acids, oligopeptids, aromatic hydroxy -20 -compounds, and/or at least one CH-active compound are disclosed p. 3, I. 42 -p. 5 I. 25; dyeing formulations p. 8, I. 25 -p. 9, I. 61.
In the dye combinations disclosed in the references (DC-UI -DC-18) above, the dyes of formula (1) according to the present invention may be added to the dye combinations or dyeing formulations or one or more of the dye components may be replaced with at least one dye of formula (I).
The present invention also releates to formulations, which are used for the dyeing of organic materials, preferably keratin-containing fibers, and most preferably human hair, comprising at least one dye of formula (1).
Preferably the dyes of formula (1) are incorporated into the composition for treating organic material, preferably for dyeing in amounts of 0.001 -5% by weight (hereinafter indicated merely by "%"), particularly 0.005 -4%, more particularly 0.2 -3%, based on the total weight of the composition.
The formulations may be applied on the keratin-containing fiber, preferably the human hair in different technical forms.
Technical forms of formulations are for example a solution, especially a thickened aqueous or aqueous alcoholic solution, a cream, foam, shampoo, powder, gel, or emulsion.
Customary the dyeing compositions are applied to the keratin-containing fiber in an amount of5OtolUOg.
Preferred forms of formulations are ready-to-use compositions or multi-compartment dyeing devices or kits' or any of the multi-compartment packaging systems with compartments as described for example in US 6,190,421, col 2, I. l6to 31.
The pH value of the ready-to-use dyeing compositions is usually from 2 to 11, preferably from 5 to 10.
The dyeing compositions of the present invention are applied on the hair in a temperature range of 25 to 200, preferably 18 to 80, and most preferably from 20 to 40 C.
One preferred embodiment of the present invention relates to the formulation of dyes, wherein the dyes of formula (1) are in powder form.
Powder formulations are preferably used if stability and/or solubility problems as for example described in DE 197 13698, p.2, 1.26 to 54 and p.3, 1.51 top. 4, 1.25, and p.4, 1.41 to p.5 I. 59.
Suitable cosmetic hair-care formulations are hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pre-treatment preparations or leave-on products such as sprays, creams, gels, lotions, mousses and oils, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for per- manent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-selling preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colorants, preparations containing self-oxidizing dyes, or natural hair colorants, such as henna or camomile.
For use on human hair, the dyeing compositions of the present invention can usually be incorporated into an aqueous cosmetic carrier. Suitable aqueous cosmetic carriers include, for example W/O, O/W, OIW/O, W/O/W or PIT emulsions and all kinds of microemulsions, creams, sprays, emulsions, gels, powders and also surfactant-containing foaming solutions, e.g. shampoos or other preparations, that are suitable for use on keratin-containing fibers.
Such forms of use are described in detail in Research Disclosure 42448 (August 1999). If necessary, it is also possible to incorporate the dyeing compositions into anhydrous carriers, as described, for example, in US-3 369 970, especially coIl, I. 70 to col 3, I. 55. The dyeing compositions according to the invention are also excellently suitable for the dyeing method described in DE-A-3 829 870 using a dyeing comb or a dyeing brush.
The constituents of the aqueous carrier are present in the dyeing compositions of the present invention in the customary amounts; for example emulsifiers may be present in the dyeing -22 -compositions in concentrations from 0.5 to 30 % by weight and thickeners in concentrations of from 0.1 to 25 % by weight of the total dyeing composition.
Further carriers for dyeing compositions are for example described in "Dermatology", edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch.
Zviak, The Science of Hair Care, chapter 7, p. 248-250, especially on p. 243, I. I to p. 244, I. 12.
If the dyes of formula (1) are used together with oxidation dyes and/or the addition salts thereof with an acid, they may be stored separately or together. Preferably the oxidation dyes and the direct dyes which are not stable to reduction are stored separately.
The dyes of formula (I) may be stored in a liquid to paste-like preparation (aqueous or non-aqueous) or in the form of a dry powder.
When the dyes are stored separately, the reactive components are intimately mixed with one another directly before use. In the case of dry storage, a defined amount of hot (from 50 to 80 C) water is usually added and a homogeneous mixture prepared before use.
The dyeing compositions according to the invention may comprise any active ingredients, additives or adjuvants known for such preparations, like surfactants, solvents, bases, acids, perfumes, polymeric adjuvants, thickeners and light stabilisers.
The following adjuavents are preferably used in the hair dyeing compositions of the present invention: -non-ionic polymers, for example vinylpyrrolidone/vinyl acrylate copolymers, polyvinyl-pyrrolidone and vinylpyrrolidone/vinyl acetate copolymers and polysiloxanes; -cationic polymers, such as quaternised cellulose ethers, polysiloxanes having quatemary groups, dimethyldiallylammonium chloride polymers, copolymers of d imethyldiallyl-ammonium chloride and acrylic acid, as available commercially under the name Merquat 280 and the use thereof in hair dyeing as described, for example, in DE-A-4 421 031, especially p. 2, I. 20 to 49, or EP-A-953 334, especially p. 27, I. 17 to p. 30, I. 11; -23 --acrylamide/dimethyldiallylammonium chloride copolymers, diethyl-sulfate-quaternised di- methylaminoethyl methacrylate/vinylpyrrolidone copolymers, vinylpyrrolidone/imidazoli-nium methochioride copolymers; -quaternised polyvinyl alcohol: -zwitterionic and amphoteric polymers, such as acrylamido-propyltnmethylammonium chloride/acrylate copolymers and octylacrylamide/methyl methacrylate/tert-butyl-aminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers; -anionic polymers, such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert-butyl acrylamide terpolymers; -thickeners, such as agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean flour, linseed gums, dextrans, cellulose derivatives, e.g. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives, such amylose, amylopectin and dextrins, clays, e.g. bentonite or fully synthetic hydro-colloids such as, for example, polyvinyl alcohol; -structunng agents, such as glucose and maleic acid; -hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin, cephalins, silicone oils, and conditioning compounds, such as those described in DE-A-19 729 080, especially p. 2, I. 20 to 49, EP-A-834 303, especially p. 2, I. 18 -p. 3, 1.2, orEP-A-312 343, especially p.2,1.59-p. 3,1.11; -protein hydrolysates, especially elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolysates, condensation products thereof with fatty acids and also quatemised protein hydrolysates; -perfume oils, dimethyl isosorbitol and cyclodextrins, -solubilisers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, -anti-dandruff active ingredients, such as piroctones, olamines and zinc Omadine, -substances for adjusting the pH value; -panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extracts and vitamins; -cholesterol; -light stabilisers and UV absorbers as listed in Table below: Table 1: UV absorbers which may be use in the dyeinçj compositions of the present invention No Chemical Name CAS No. 1 (+1-)-1,7, 7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo-36861-47-9 -[2.2.1]heptan-2-one ____________ 2 1,7, 7-tnmethyl-3-(phenylmethylene)bicyclo[2.2.1]heptan-2-one 15087-24-8 3 (2-Hydroxy-4-methoxyphenyl)(4-methylphenyl)methanone 1641-17-4 4 2,4-dihydroxybenzophenone 131-56-6 -2,2',4,4'-tetrahydroxybenzophenone 131-55-5 -2-Hydroxy-4-methoxy benzophenone; 131-57-7 7 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 131-54-4 8_ 2,2'-Dihydroxy-4-methoxybenzophenone 131-53-3 9 1 -[4-( 1,1 -dimethylethyl)phenyl]-3-(4-methoxyphenyl)propane-1,3-70356-09-1 dione ____________ 3,3,5-Trimethyl cyclohexyl-2-hydroxy benzoate 118-56-9 Ii Isopentyl p-methoxycinnamate 71617-10-2 12 Menthyl-o-aminobenzoate 134-09-8 13 Menthyl salicylate 89-46-3 14 -Ethylhexyl 2-cyano,3,3-diphenylacrylate 197-30-4 -ethylhexyl 4-(dimethylamino)benzoate 1245-02-3 16 -ethylhexyl 4-methoxycinnamate 466-77-3 17 -ethylhexyl salicylate 118-60-5 18 Benzoic acid, 4, 4', 4"-(l, 3, 5-tnazine-2, 4,6-tnyltriimino)tns-,tns(2-88122-99-0 ethylhexyl)ester; 2,4,6-Tnanilino-(p-carbo-2'-ethylhexyl-l -oxi)- -1,3,5-triazine ____________ 19 Benzoic acid, 4-amino-, ethyl ester, polymer with oxirane 113010-52-9 2-Propenamide, N-[4-[(4, 7,7-trimethyl-3-oxobicyclo[2.2.1 Jhept-2-147897-12-9 -Iidene)methyl]phenyl]methyl]-, homopolymer ____________ 21 Triethanolamine salicylate 2174-16-5 22 2,2'-Methylene-bis-[6-(2H-benzotnazol-2-yl)-4-( 1,1,3,3-tetramethyl-103597-45-1 -butyl)-phenol] _____________ 23 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-187393-00-6 -methoxyphenyl)-(1,3,5)-triazine (Tinosorb S) ____________ 24 Benzoic acid, 4,4'-[6-[4-[(1,1-dimethylethyl)amino]carbonyl]-154702-15-5 phenyl]amino] I,3,5-tnazine-2,4-diyl]diimino]bis-, bis(2-ethylhexyl)ester _____________ Phenol, 2-(2H-benzotnazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-155633-54-8 -tetramethyl-1 -[(tnmethylsilyl)oxy]disiloxanyl]propyl] _____________ 26 Dimethicodiethylbezalmalonate 207574-74-1 27 Benzoic acid, 2-[4-(diethylamino)-2-hydroxybenzoylj-, hexyl ester 302776-68-7 28 1,3, 5-Triazine, 2,4,6-tns(4-methoxyphenyl)-7753-12-0 29 1,3,5-Triazine, 2,4,6-tns[4-[(2-ethylhexyl)oxy]phenylj-208114-14-1 2-Propenoic acid, 3-(1 H-imidazol-4-yl)-104-98-3 31 Benzoic acid, 2-hydroxy-, [4-(1 -methylethyl)phenyl]methyl ester 94134-93-7 32 1,2, 3-Propanetriol, I -(4-aminobenzoate) 136-44-7 33 Benzeneacetic acid, 3,4-dimethoxy-a-oxo-4732-70-1 34 2-Propenoic acid, 2-cyano-3,3-diphenyl-, ethyl ester 5232-99-5 -25 -Table 1: UV absorbers which may be use in the dyeing compositions of the present invention N Chemical Name CAS No. Anthralinic acid, p-menth-3-yl ester 134-09-8 36 1,3, 5-Triazine-2,4,6-tnamine, N, N'-bis[4-[5-( 1,1 -dimethylpropyl)-2-288254-16-0 benzoxazolyl]phenyl]-N"-(2-ethylhexyl)-or Uvasorb K2A 37 2-Hydroxy-4-methoxy benzophenone-5-sulfonic acid 4065-45-6 38 Alpha-(2-oxobom-3-ylidene)toluene-4-sulphonic acid and its salts 56039-58-8 39 Methyl N,N, N-trimethyl-4-[(4,7, 7-tnmethyl-3-oxobicyclo[2 2,1]hept-52793-97-2 -2-ylidene)methyl]anilinium sulphate; _____________ 4-aminobenzoic acid 150-13-0 41 2-phenyl-I H-benzimidazole-5-sulphonic acid 27503-81-7 42 3, 3'-(1, 4-phenylenedimethylene)bis[7, 7-dimethyl-2-oxo-90457-82-2 -bicyclo[2.2. I]heptane-1-methanesulfon ic acid] _____________ 43 1 H-Benzimidazole-4,6-disulfonic acid, 2,2'-(l,4-phenylene)bis-, 180898-37-7 -disodium salt ______________ 44 Benzenesulfonic acid, 3-(2H-benzotnazol-2-yl)-4-hydroxy-5-(1 -92484-48-5 -methylpropyl)-, monosodium salt _____________ 1 -Dodecanaminiu m, N-[3-([4-(dimethylamino)benzoyl]amino]-156679-41-3 - ropyl]N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1) ____________ 46 1 -Propanaminium, N,N, N-trimethyl-3-[( I -oxo-3-phenyl-2-propenyl)-177190-98-6 -amino]-, chloride ____________ 47 1 H-Benzimidazole-4,6-disulfonic acid, 2,2'-(l,4-phenylene)bis-170864-82-1 48 1 -Propanaminium, 3-[3-[3-(2H-benzotriazol-2-yl)-5-( 1,1 -dimethyl-340964-15-0 ethyl)-4-hydroxyphenyl]-1 -oxopropyl]amino]-N, N-diethyl-N-methyl-, -methyl sulfate (salt) ______________ 49 2,2'-bis(l,4-phenylene)-1 H-benzimidazole-4,6-disulphonic acid mo-349580-12-7, no sodium salt or Disodium phenyl dibenzimidazole tetrasulfonate -or Neoheliopan AP ____________ The use of UV absorbers can effectively protect natural and dyed hair from the damaging rays of the sun and increase the wash fastness of dyed hair.
Furthermore, the following UV absorbers or combinations may be used in the dyeing compositions according to the invention: -cationic benzotriazole UV absorbers as for example described in WO 01/36396 especially on p. 1, I. 20 to p. 2, I. 24, and preferred on p. 3 to 5, and on p. 26 to 37; -cationic benzotriazole UV in combination with antioxidants as described in Wa 01/36396,especiallyon p.11,1. l4top. 18; -UV absorbers in combination with antioxidants as described in US Patent 5 922 310, especially in col 2, I. I to 3; -26 - -UV absorbers in combination with antioxidants as described in US Patent 4 786 493, especially in coIl, 42 to col 2, I. 7, and preferred in col 3, 43 to col 5, I. 20; -combination of UV absorbers as described in US Patent 5 830 441, especially in col 4, I. 53 to 56; -combination of UV absorbers as described in WO 01/36396, especially on p. 11, I. 9 to 13; or -tnazine derivatives as described in WO 98/22447, especially on p. 1, I. 23 to p. 2, I. 4, and preferred on p. 2, I. 11 to p. 3, I. 15 and most preferred on p. 6 to 7, and 12 to 16.
Suitable cosmetic preparations may usually contain 0.05 to 40 % by weight, preferably from 0.1 to 20 % by weight, based on the total weight of the composition, of one or more UV absorbers; -consistency regulators, such as sugar esters, polyol esters or polyol alkyl ethers; -fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters; -fatty alkanolamides; -polyethylene glycols and polypropylene glycols having a molecular weight of from 150 to 000, for example such as those described in EP-A-801 942, especially p. 3, I. 44 to -complexing agents, such as EDTA, NTA and phosphonic acids, -swelling and penetration substances, such as polyols and polyol ethers, as listed extensively, for example, in EP-A-962 219, especially p. 27, I. 18 to 38, for example glycerol, propylene glycol, propylene glycol monoethyl ether, butyl glycol, benzyl alcohol, carbonates, hydrogen carbonates, guanidines, ureas and also primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole; -opacifiers, such as latex; -pearlising agents, such as ethylene glycol mono-and di-stearate; -propellants, such as propane-butane mixtures, N20, dimethyl ether, Ca2 and air; -antioxidants; -sugar-containing polymers, as described in EP-A-970 687, especially p. 28, I. 17 to p. 29, I. 23; -quatemary ammonium salts, as described in Wa 00/1 0517, especially p. 44, I. 16 to p. 46, I. 23.
-27 - -Bacteria inhibiting agents, like preservatives that have a specific action against gram- positive bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,44'-trichlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorising agent of interest is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,1O-dodecatrien-1-oI), which is present in lime blossom oil. Glycerol monolaurate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhibiting agents present is usually from 0.1 to 2 % by weight, based on the solids content of the preparations; The dyeing compositions according to the present invention generally comprise at least one surfactant. Suitable surfactants are zwitterionic or ampholytic, or more preferably anionic, non-ionic and/or cation ic surfactants.
Suitable anionic surfactants in the dyeing compositions according to the present invention include all anionic surface-active substances that are suitable for use on the human body.
Such substances are characterised by an anionic group that imparts water solubility, for example a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having approximately from 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and also hydroxy groups may be present in the molecule. The following are examples of suitable anionic surfactants, each in the form of sodium, potassium or ammonium salts or mono-, di-or tri-alkanolammonium salts having 2 or 3 carbon atoms in the alkanol group: -linear fatty acids having 10 to 22 carbon atoms (soaps), -ether carboxylic acids of formula R-O-(CH2-CH2-O)-CH2-COOl-I, in which R is a l.ar alkyl group having 10 to 22 carbon atoms and x = 0 or from I to 16, -acyl sarcosides having 10 to 18 carbon atoms in the acyl group, -acyl taurides having 10 to 18 carbon atoms in the acyl group, -acyl isothionates having 10 to 18 carbon atoms in the acyl group, -sulfosuccinic mono-and di-alkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and from I to 6 oxyethyl groups, -linear alkane sulfonates having 12 to 18 carbon atoms, -28 - -linear a-olefin sulfonates having 12 to 18 carbon atoms, -c-sulfo fatty acid methyl esters of fatty acids having 12 to 18 carbon atoms, -alkyl sulfates and alkyl polyglycol ether sulfates of formula R'-O(CH2-CH2-O)-SO3H, in which R' is a preferably l.ar alkyl group having 10 to 18 carbon atoms and x' = 0 or from ltol2, -mixtures of surface-active hydroxysulfonates according to DE-A-3 725 030, especially p. 3, I. 40 to 55, -sulfated hydroxyalkylpolyethylene and/or hydroxyalkylenepropylene glycol ethers according to DE-A-3 723 354, especially p. 4, I. 42 to 62, -sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and I to 6 double bonds according to DE-A-3 926 344, especially p. 2, I. 36 to 54, -esters of tartaric acid and citric acid with alcohols which are addition products of approximately from 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols having from 8 to 22 carbon atoms, or -anionic surfactants, as described in WO 00/1 051 8, especially p. 45, I. 11 to p. 48, I. 3.
Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and also especially salts of saturated and especially unsaturated C8-C22carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.
Surface-active compounds that carry at least one quatemary ammonium group and at least one -C00 or -S03 group in the molecule are terminated zwittenonic surfactants. Preference is given the so-called betaines, such as the N-alkylN,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazol. having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name cocoami-dopropyl betaine.
Ampholytic surfactants are surface-active compounds that, in addition to a C8-C18-alkyl or -acyl group and contain at least one free amino group and at least one -COOH or -SO3H group in the molecule and are capable of forming internal salts. Examples of suitable -29 -ampholytic surfactants include N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each having approximately from 8 to 18 carbon atoms in the alkyl group. Ampholytic surfactants to which special preference is given are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C1 2-C18acylsarcosine.
Suitable non-ionic surfactants are described in WO 00/1 0519, especially p. 45, I. 11 to p. 50, I. 12. Non-ionic surfactants contain as hydrophilic group, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example: -addition products of 2 to 30 mol of ethylene oxide and/or 0 to 5 mol of propylene oxide with l.ar fatty alcohols having 8 to 22 carbon atoms, with fatty acids having 12 to 22 carbon atoms and with alkylphenols having 8 to 15 carbon atoms in the alkyl group, -C12C22 fatty acid mono-and di-esters of addition products of I to 30 mol of ethylene oxide with glycerol, -C8-C22aIkyl-mono-and -oligo-glycosides and ethoxylated analogues thereof, -addition products of 5 to 60 mol of ethylene oxide with castor oil and hydrogenated castor oil, -addition products of ethylene oxide with sorbitan fatty acid esters, -addition products of ethylene oxide with fatty acid alkanolamides.
The surfactants which are addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of such addition products may either be products having a "normal" homologue distribution or products having a restricted homologue distribution. "Normal" homologue distribution are mixtures of homologues obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Restricted homologue distributions, on the other hand, are obtained when, for example, hydrotalcites, alkali metal salts of ether carboxylic acids, alkali metal oxides, hydroxides or alcoholates are used as catalysts.
The use of products having restricted homologue distribution may be preferred.
-30 -Examples of cationic surfactants that can be used in the dyeing compositions according to the invention are especially quatemary ammonium compounds. Preference is given to ammonium halides, such as alkyltnmethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethy-lammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetyl-methylammonium chloride. Further cationic surfactants that can be used in accordance with the invention are quatemised protein hydrolysates.
Also suitable are cationic silicone oils, such as, for example, the commercially available pro-ducts Q2-7224 (manufacturer: Dow Corning; a stabilised tnmethylsilylamodimethicone), Dow Coming 929 emulsion(comprising a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manu-facturer: Wacker) and also Abil-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquatemary polydimethylsiloxanes, quatemium-80), or silicones, as described in WO 00/1 2057, especially p. 45, I. 9 to p. 55, I. 2.
Alkylamidoamines, especially fatty acid amidoamines, such as the stearylamidopropyldi-methylamine obtainable under the name Tego Amid(18 are also preffered as surfactants in the present dyeing compositions. They are distinguished not only by a good conditioning action but also especially by their good biodegradability.
An example of a quatemary sugar derivative that can be used as cationic surfactant is the commercial product Glucquatw100, according to CTFA nomenclature a "lauryl methyl gluceth-lO hydroxypropyl dimonium chloride".
The alkyl-group-containing compounds used as surfactants may be single substances, but the use of natural raw materials of vegetable or animal origin is generally preferred in the preparation of such substances, with the result that the substance mixtures obtained have different alkyl chain lengths according to the particular starting material used.
A further embodiment of the present invention relates to the dyeing of keratin-containing fibers.
The processes comprises (a) treating the keratin-containing fiber with at least one dye of formula (1) and (b) leaving the fiber to stand and then rinsing the fiber.
The dyes of formula (1) are suitable for all-over dyeing of the hair, that is to say when dyeing the hair on a first occasion, and also for re-dyeing subsequently, or dyeing of locks or parts of the hair.
The dyes of formula (1) are applied on the hair for example by massage with the hand, a comb, a brush, or a bottle, or a bottle, which is combined with a comb or a nozzle.
In the processes for dyeing according to the invention, whether or not dyeing is to be carried out in the presence of a further dye will depend upon the color shade to be obtained.
Further preferred is a process for dyeing keratin-containing fibers which comprises treating the keratin-containing fiber with at least one dye of formula (1), a base and an oxidizing agent.
A preferred embodiment for dyeing keratin-containing fibers, in particular human hair, with a dye of formula (1) and an oxidizing agent, comprises a1) treating the keratin-containing fiber with the oxidizing agent, which optionally contains at least one dye of formula (1), bi) treating the keratin-containing fibe with an oxidizing agent free composition, which optionally contains at least one dye of formula (1); or alternatively a2) treating the keratin-containing fiber with an oxidizing agent free composition, which optionally contains at least one dye of formula (1); b2) treating the keratin-containing fiber with an oxidizing agent, which optionally contains least one dye of formula (1), with the proviso that at least in one of the process steps a1), a2), b1) or b2) a dye of formula (1) is present.
In general, the oxidizing agent containing composition is left on the fiber for 0 to 45 minutes, in particular for 15 to 30 minutes at 15 to 45 C.
-32 -The oxidizing agent free composition usually comprises customary adjuvants and additives.
Preferred are those, which are described in German Patent Application, in col 3, I. 17 to I. 41.
In general, the dye of formula (1) and the oxidizing agent free composition are left on the fiber for 5 to 45 minutes, in particular for 10 to 25 minutes at 15 to 50 C.
One preferred embodiment of the process is to wash the hair after dyeing with a shampoo and/or a weak acid, such as citric acid or tartrate acid.
The dyes of formula (1)which are stable to reduction can be stored together with the oxidizing agent free compositions and may be applied as a single composition.
Advantageously the compositions comprising a dye of formula (1) which are not stable to reduction are prepared with the oxidizing agent free composition just before the dyeing process.
In a further embodiment, the dye of formula (1) and the oxidizing agent free composition may be applied simultaneously or in succession.
Customary, the oxidizing agent containing composition is evenly applied in a sufficient amount related to the amount of hair, usually in amounts of 30 to 200 g.
Oxidizing agents are for example persulfate or dilute hydrogen peroxide solutions, hydrogen peroxide emulsions or hydrogen peroxide gels, alkaline earth metal peroxides, organic per-oxides, such as urea peroxides, melamine peroxides, or alkalimetalbromat fixations are also applicable if a shading powder on the basis of semi-permanent, direct hair dyes is used.
Further preferred oxidizing agents are -oxidizing agents to achieve lightened coloration, as described in WO 97/20545, especially p. 9, I. 5 to 9, -oxidizing agents in the form of permanent-wave fixing solution, as described in DE-A-19 713 698, especially p. 4, I. 52 to 55, and I. 60 and 61 or EP-A-1 062940, especially p. 6, I. 41 to 47 (and in the equivalent WO 99/40895).
-33 -Most preferred oxidizing agent is hydrogen peroxide, preferably used in a concentration from about 2 to 30 %, more preferably about 3 to 20% by, and most preferably from 6 to 12% by weight the corresponding composition.
The oxidizing agents may be present in the dyeing compositions according to the invention preferably in an amount from 0.01 % to 6 %, especially from 0.01 % to 3 %, based on the total dyeing composition.
In general, the dyeing with an oxidative agent is carried out in the presence of a base, for example ammonia, alkali metal carbonates, earth metal (potassium or lithium) carbonates, alkanol amines, such as mono-, di-or triethanolamine, alkali metal (sodium) hydroxides, earth metal hydroxides or compounds of the formula R3\ N-R-N, wherein R( R6 R is a propylene residue, which may be substituted with OH or C1-C4alkyl, R3, R4, R5 and R6 are independently or dependently from each other hydrogen, C1-C4alkyl or hyd roxy-(C1-C4)alkyl.
The pH-value of the oxidizing agent containing composition is usually about 2 to 7, and in particular about 2 to 5.
One preferred method of applying formulations-comprising the dyes of formula (1) on the keratin-containing fiber, preferably the hair is by using a multi-compartment dyeing device or "kit" or any other multi-compartment packaging system, as described for example in WO 97/20545 on p.4,1. 19 to 1.27.
The first compartment contains for examle at least one dye of formula (1) and optionally further direct dyes and a basifying agent, and in the second compartment an oxidizing agent; or in the first compartment at least one dye of formula (1) and optionally further direct dyes, in the second compartment a basiflying agent and in the third compartment an oxidizing agent.
Preferably, a ready-to-use composition is prepared according to a first preferred embodiment by a process which comprises a preliminary step which involves separately storing, on the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one developer compound, especially selected from para-phenylenediamines and bis(phenyl)- alkylenediamines, and the acid-addition salts thereof, at least one coupler, especially selec-ted from meta-phenylenediamines and the acid-addition salts thereof, and at least one dye of formula (I), on the other hand, a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent and mixing (A) and (B) together immediately before applying this mixture to the keratin-containing fibers.
According to a second preferred embodiment for the preparation of the ready-to-use dye composition, the process includes a preliminary step which involves separately storing, on the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one developer compound, especially selected from para-phenylenediamines and bis(phenyl)alkylenediamines, and the acid-addition salts thereof, at least one coupler compound, especially selected from meta-phenylenediamines and the acid-addition salts thereof; on the other hand, a composition (A') comprising, in a medium which is suitable for dyeing, at least one dye of formula (1), and finally, a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent as defined above, and mixing them together at the time of use immediately before applying this mixture to the keratin-containing fibers.
The composition (A') used according to this second embodiment may optionally be in powder form, the cationic dye(s) of formula (1) (themselves) constituting, in this case, all of the composition (A') or optionally being dispersed in an organic and/or inorganic pulverulent excipient.
When present in the composition A', the organic excipient may be of synthetic or natural origin and is selected in particular from crosslinked and non-crosslinked synthetic polymers, polysacchandes such as celluloses and modified or unmodified starches, as well as natural products such as sawdust and plant gums (guar gum, carob gum, xanthan gum, etc.).
When present in the composition (A'), the inorganic excipient may contain metal oxides such as titanium oxides, aluminium oxides, kaolin, talc, silicates, mica and silicas.
A very suitable excipient in the dyeing compositions according to the invention is sawdust.
-35 -The powdered composition (A') may also contain binders or coating products in an amount which preferably does not exceed approximately 3% by weight relative to the total weight of composition (A'). These binders are preferably selected from oils and liquid fatty substances of inorganic, synthetic, animal or plant origin.
The composition (A') may optionally contain other adjuvants, in powdered form, in particular surfactants of any kind, hair conditioners such as, for example, cationic polymers, etc. Generally the hair is rinsed after treatment with the dyeing solution and/or permanent-wave solution.
A further preferred embodiment of the present invention relates to a method of dyeing hair with oxidative dyes, which comprises a. mixing at least one dye of formula (1) and optionally at least one coupler compound and at least one developer compound, and an oxidizing agent, which optionally contains at least one further dye, and b. contacting the keratin-containing fibers with the mixture as prepared in step a.
For adjusting the pH-value organic or inorganic acids, as for example described in DE 199 59479, col 3, I. 46 to I. 53 are suitable.
Furthermore, the present invention relates to a process of dyeing of keratin-containig fibers of the dyes of formula (1) with autooxidable compounds and optionally further dyes.
The process comprises a. mixing at least one autooxidable compound and at least one developer compound and at least one dye of formula (1) and optionally further dyes, and b. treating the keratin-containing fiber with the mixture prepared in step a.
Furthermore, the present invention relates to a process for dyeing keratin-containig fibers with the dyes of formula (1) and capped diazotised compounds, which comprises, a. treating the keratin-containing fibers under alkaline conditions with at least one capped diazotised compound and a coupler compound, and optionally a developer compound -36 -ad optionally an oxidizing agent, and optionally in the presence of a further dye, and optionally with at least one dye of formula (1), and b. adjusting the pH in the range of 6 to 2 by treatment with an acid, optionally in the presence of a further dye, and optionally at least one dye of formula (1), with the proviso that at least in one step a. or b. at least one dye of formula (1) is present.
The capped diazotised compound and coupler compound and optionally the oxidizing agent and developer compound can be applied in any desired order successively or simultaneously.
Preferably, the capped diazotised compound and the coupler compound are applied simultaneously, in a single composition.
"Alkaline conditions" denotes a pH in the range from 8 to 10, preferably 9-10, especially 9.5- 10, which are chieved by the addition of bases, for example sodium carbonate, ammonia or sodium hydroxide.
The bases may be added to the hair, to the dye precursors, the capped diazotised compound and/or the water-soluble coupling component, or to the dyeing compositions comprising the dye precursors.
Acids are for example tartaric acid or citric acid, a citric acid gel, a suitable buffer solution with optionally an acid dye.
The ratio of the amount of alkal. dyeing composition applied in the first stage to that of acid dyeing composition applied in the second stage is preferably about from 1:3 to 3:1, especially about 1:1.
The alkaline dyeing compositions of step a. and the acid dyeing compositions of step b. are left on the fiber for 5 to 60 minutes at 15 to 45 C, in particular for 5 to 45 minutes at 20 to 30 C.
Furthermore, the present invention relates to a process for dyeing keratin-containig fibers with the dyes of formula (1) and at least one acid dye.
-37 -The following examples serve to illustrate the processes for dyeing without limiting the processes thereto. Unless specified otherwise, parts and percentages relate to weight. The amounts of dye specified are relative to the material being dyed.
Furthermore, the present invention relates to a process for dyeing keratin-containig fibers with the dyes of the present invention and at least one acid dye.
The following Examples serve to illustrate the processes for dyeing without limiting the processes thereto. Unless specified otherwise, parts and percentages relate to weight. The amounts of dye specified are relative to the material being coloured.
n the dyeing is carried out in presence of a reducing agent.
-38 -Preparation Examples A
Example Al: Br
(101) HN)\\/ 1. Formation of the Hydrazone 14 g sulfuric acid are added to 42g water and cooled to 20 C.
Then 24g N-methyl-phenyl hydrazine (100%) are added with stirring.
24.5g 4-pyndine-aldehyde are dropped in during 15mm and stirring is continued for lh.
The pH is raised to 2.2 by adding a solution of 36% sodium hydroxide in water.
2.7g sodium chloride are added at the temperature of 60 C, and one more h stirred at this temperature.
The slurry is separated by filtration, the filter cake dried at 70 C in vacuum to yield 42g of an orange powder.
2. Alkylating aQent A mixture of 52.Og of racemic 3-amino-dihydro-thiophenone in 120m1 chloroform and 74.lg pyndine are cooled with stirring to 0 C and then 58.Og bromo acetic acid chloride are added in small amounts maintaining the temperature.
After completion of the addition the mixture is left overnight in the refrigerator and the reaction is finished.
The reaction mixture is mixed with a water/chlorhidnc acid and ice slurry, the phases are separated, washed with water and dried, the solvent is evaporated to dryness to the product used as such in the following step 3.Alkylation The foregoing hydrazone is dissolved in chloroform by stirring with the equivalent amount of alkylating agent at a temperature of 20 C.
-39 -The temperature is maintained at 20 C during the following 48h. Crystals separated in the slurry are filtered off.
The product is washed with 50m1 chloroform and dried in vacuum to obtain 59g of an orange solid product.
The product is recristallized twice from methanol.
The product is characterized by the following data: I H-NMR data in deuterated methanol (32 scans)/36OMHz 8,564 d 6,8 2,00 py 8,102 d 6,7 2,00 py 7,677 s -_______ 0,994 hydrazone 7,540 d________ 6,1 1,97 phe 7,414 _________ 6,1 2,025 phe 7,154 ________ 6,4 1,005 phe 5,356 s ___________ I,72 methylene 4,750 q 12; 7 1,00 thiolactone 3,615 s __________ 3,05 me-hydrazone 3,464 he ___________ 1,047 thiolactone 3,35 M, overlaid __________ thiolactone 2,672 m ___________ 1,02 thiolactone 2,326 s __________ 0,927 thiolactone
ExampleA2: \
N H
(102) NO 1. Monoazo 12.4g 4-fluoroaniline is added to a stirred solution of 25m1 water and 25m1 32% hydrochloric acid at295 K. Then the reaction mixture is cooled to 273K and I 9m1 36% sodium nitrite solution is dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K. After the addition of the sodium nitrite solution the mixture is stirred for one hour. If no excess of nitrite is detected during one hour (detection by using a potassium iodide paper) further amounts of sodium nitrite solution are added.
After this one hour the remaining excess of nitrite is reduced with sulfamic acid. -40 -
Then the obtained diazo solution is dropped to a 273 K cold solution of 7.4g imidazole in 30ml water, whereby the pH of the solution is maintained in the range of pH 10 to 11 by adding 36% sodium hydroxide solution.
After completing the diazo addition the obtained suspension is warmed up to 295K and the pH is adjusted to 10.5 with 36% sodium hydroxide solution.
After one hour stirring at this pH and temperature the suspension is filtered off and then washed twice with 50m1 water to obtain 55g of the humid product.
500m1 water are introduced into a reaction vessel, the filter cake from the previouse step is added and suspended by stirring. The addition of dimethyl sulphate is started and simultaneously that of sodium hydroxide maintaining the pH at 10-10.3 and the temperature at 25-30 C.
The amount of 3 equivalent of dimethyl sulphate (OMS) are added within ca. 5h.
It is held for one more hour to finish the hydrolysis of excess of DMS.
The disappearance of DMS is controlled.
Then lOOg sodium chlorideare and 50g potassium chloride are added and cooled to 0 C.
After 16h the product is separated by filtration and washed with a cold solution of sodium/potassium chloride.
Ca. 20g cake mole product is obtained with the following formula / (102a) - N\ N-Cj-F.
19,9 g of N,N'-dimethyl-ethylendiamine is added at 293 K under nitrogen atmosphere with stirring to I 20g isopropanol and the foregoing compound of the formula (1 02a).
Then the temperature is raised then to 333K and viscosity of the reaction mixture decreases.
The reaction mixture is stirred at this temperature during 25h.
Then the reaction mass is stirred for 4h while the temperature is decreased to 295K.
The reaction mass is filtered off and the filter residue is washed with 45m1 isopropanol. Then The material is dried in vacuum to obtain I 6g of product.
2. Alkylating agent A mixture of 52.Og of racemic 3-amino-dihydro-thiophenone as chlorohydrate in I 20m1 chloroform and 54. 1 g tnethylamine are cooled with stirring to 0 C and then 58.0 g of bromo acetic acid chloride are added in small amounts maintaining the temperature.
After completion of the addition the mixture is left overnight in the refrigerator and the reaction is finished.
The reaction mixture is mixed with a water/chlorhidnc acid and ice slurry, the phases are separated, washed with water, dried and the solvent evaporated to dryness the product used as such in the following step.
3. Alkylation One equivalent of the foregoing monoazo is dissolved by stirring into the solution of the equivalent alkylation agent in chloroform.
The temperature is raised to 60 C and during the following 20 hours.
Crystals separated in the slurry are filtered off.
The product is washed with 5ml chloroform and dried in vacuum to obtain 80g of a dark solid product.
The product is recnstallized twice from methanol.
The product is characterized by the following data:1 H-NMR data in deuterated methanol (32 scans)! 360MHz 8,046 d 7,3 2,00 phenylene 7, 605 S __________ 1,92 imidazole 7,102 d 7,8 2,06 phenylene 4,705 __________ 12;6 0,97 thiolactone 4,084 s __________ 6,06 dimethyl 3,86 t 6 2,02 methylene 3,595 s ___________ 1,982 methylene 3,26 ___________ ___________ 3,03 methyl 2,672 m __________ 1,01 thiolactone 2,259 s __________ 3,10 methyl 2,204 m ___________ 0,98 thiolactone -42 -
Example A3:
I
N N-< ,)-NH (103) H 2 1. Monoazo 50.Og 2-amino-thiazol are added to a stirred solution of 135m1 60% sulfuric acid at 293-310K.
Then the reaction mixture is cooled to 273K and 81 ml of a 40% nitrosilsulfuric acid is dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K by cooling.
After the addition the mixture is stirred for 4h.
The solution is dropped to a well-stirred water ice mixture (4009) containing 2.5g amido-sulfuric acid.
To the obtained diazo solution (at 273K, ice added if need) 45.5g aniline is dropped.
Then the pH of the solution is raised to the range of 5 to 6 by adding 36% sodium hydroxide solution.
After one hour stirring at this pH and temperature the suspension is filtered off and then washed twice with 5Oml water to obtain I 55g of the humid product.
After drying 90g monoazo dye is obtained.
2. Alkylatinci agent The same alkylating agent is used as in previous examples.
3. Alkvlation The foregoing monoazo (30g) is dissolved by stirring into I 5Oml methanol.
The equivalent amount of alkylating agent is added. The temperature is raised to 60 C.
The temperature is maintained during the following 30h.
Crystals separated in the slurry after cooling are filtered off.
The product is washed with 5Oml methanol and dried in vacuum to obtain 49g of an dark reddish solid product. T he product is recristallized twice from methanol.
The product is characterized by I H-NMR Data in deuterated methanol (128 scans)! 360MHz -43 - 8,244 d J = 8,6; 1,007 phenylene 7,848 d J=4,2 1,00 thiazol 7,761 d J = 8,5 1,10 phenylene 7,500 d J=4,3 0,98 thiazol 6,914 d J = 8,6 2,00 phenylene 5,320 s _________ 1,908 methylene 4,733 _________ 12; 7 1,01 thiolactone 3,426 He _________ 1,02 thiolactone 3,361 m overlaid 1,01 thiolactone 2,640 m _________ 1,00 thiolactone 2, 201 oct _________ 1,10 thiolactone
Example A4: (104)
1. Monoazo 50.Og 2-amino-thiazol are added to a stirred solution of 135ml 60% sulfuric acid at 293-310K.
Then the reaction mixture is cooled to 273K and 81 ml of a 40% nitrosilsulfuric acid is dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K by cooling.
After the addition the mixture is stirred for 4h.
The solution is dropped to a well-stirred water ice mixture (400g) containing 2.5g amido-sulfuric acid.
To the obtained diazo solution (at 273K, ice added if need) 60.5g di-methyl-aniline is dropped.
Then the pH of the solution is raised to the range of 5 to 6 by adding 36% sodium hydroxide solution.
After I h stirring at this pH and temperature the suspension is filtered off and then washed twice with 5Oml water to obtain 200g of the humid product.
After drying bOg monoazo dye is obtained.
2. Alkylating agent The same alkylating agent is used as in previous examples. -44 -
3.Alkylation The foregoing monoazo (28g) is dissolved by stirring into I 5Oml methanol. The equivalent amount of alkylating agent is added.
Temperature is raised to 60 C and maintained during the following 24h.
Crystals separated in the slurry after cooling are filtered off.
The product is washed with 5Oml methanol and dried in vacuum to obtain 45g of a dark violett solid product.
The product is recristallized twice from methanol.
The product is characterized by I H-NMR Data in deuterated methanol (128 scans)/36OMHz 8,242 d J = 8,6; 1,007 phenylene 7,818 d J=4, 2 1,00 Thiazol 7,786 d J=8,5 1,10 phenylene 7,505 d J=4,3 1,03 Thiazol 7, 273 d J = 8,6 2,00 phenylene 5,322 s _________ 1,908 methylene 4,738 _________ 12; 7 *1,01 thiolactone 3,448 He _________ 1,02 thiolactone 3,34 m overlaid 1,01 thiolactone 3,27 s __________ 6,05 methyl 2,364 _________ _________ 1,00 thiolactone 2,208 oct _________ 1,10 thiolactone
Example A5
-OH
(105) N N_-Q_ N 1. Monoazo 50.Og 2-amino-thiazol is added to a stirred solution of I 35m1 60% sulfuric acid at 293-310K.
Then the reaction mixture is cooled to 273K and 81 ml of a 40% nitrosilsulfuric acid is dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K by cooling.
After the addition the mixture is stirred for 4h.
The solution is dropped to a well-stirred water ice mixture (400g) containing 2.5g amido-sulfuric acid.
To the obtained diazo solution (at 273K, ice added if need) 90.5g di-hydroxiethyl-aniline is dropped.
Then the pH of the solution is raised to the range of 5 to 6 by adding 36% sodium hydroxide solution.
After 1 h stirring at this pH and temperature the suspension is filtered off and then washed twice with 50m1 water to obtain 255g of the humid product.
After drying 140g monoazo dye is obtained.
2. Alkylating agent A mixture of 52.Og of racemic 3-amino-dihydro-thiophenone in l2Oml chloroform and 74.lg pyridine are cooled with stirring to 0 C and then 58.Og bromo acetic acid chloride are added in small amounts maintaining the temperature.
After completion of the addition the mixture is left one in the refrigerator and the reaction is finished.
The reaction mixture is mixed with a water/chlorhidnc acid and ice slurry, the phases are separated, washed with water, dryed, the solvent is evaporated to dryness the product used as such in the following step.
3. Alkvlation The foregoing monoazo (30g) is dissolved by stirring into I 5Oml methanol.
The equivalent amount of alkylating agent is added. The temperature is raised to 60 C. The temperature is maintained at 60 C during the following 30h.
Crystals separated in the slurry after cooling are filtered off.
The product is washed with 50m1 methanol and dried in vacuum to obtain 59g of a dark violett solid product.
The product is recristallized twice from methanol.
The product is characterized by I H-NMR Data in deuterated methanol (128 scans)/36OMHz 8,214 d J = 8,6; 1,007 phenylene 7,871 d J=4, 2 1,00 Thiazol 7,781 d J=8,5 1,10 phenylene 7,520 d J = 4,3 0,98 Thiazol 7,267 d J = 8,6 2,00 phenylene -46 - 5,322 s _________ 1,908 methylene 4,738 _________ 12; 7 1,01 thiolactone 4,000 T 6 4,05 methylene 3,913 t 6 4,05 methylene 3,448 He _________ 1,02 thiolactone 3,34 m overlaid 1,01 thiolactone 2,364 m __________ 1,00 thiolactone 2,208 oct _________ 1,10 thiolactone
Example A6: 0 OH
(106) -"N N-_(J__N
OH
50.Og 2-amino-methoxy benzothiazole are added to a stirred solution of I 35m1 60% sulfuric acid at 293-310K.
Then the reaction mixture is cooled to 273K and 61 ml 40% nitrosilsulfuric acid are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276K by cooling. After the addition the mixture is stirred for 4h.
The solution is dropped to a well-stirred water ice mixture (400g) containing 2.5g amidosul- furic acid. To the obtained diazo solution (at 273K ice added if need) 50.5g dihydroxyethyl-aniline are dropped. Then the pH of the solution is raised to the range of 5 to 6 by adding 36% sodium hydroxide solution.
After one hour stirring at this pH and temperature the suspension is filtered off and then washed twice with 50m1 water to obtain 15 g of the humid product.
After drying 95g monoazo dye is obtained.
2. Alkylating agent A mixture of 52.Og of racemic 3-amino-dihydro-thiophenone in 120m1 chloroform and 74.lg pyridine is cooled with stirring to 0 C and then 58.Og of bromo acetic acid chloride are added in small amounts maintaining the temperature.
After completion of the addition the mixture is left one in the refrigerator and the reaction is finished. The reaction mixture i mixed with a water/chlorhidnc acid and ice slurry, the phases are separated,washed with water, dried, the solvent is evaporated to dryness the product used as such in the following step.
3. Alkylation The 39g foregoing monoazo is dissolved by stirring into the equivalent alkylation solution in I OOml methanol.
The temperature is raised to 60 C andmaintained during the following 60h. Crystals separated in the slurry are filtered off.
The product is washed with 50m1 chloroform and dried in vacuum to obtain 59g of a dark solid product.
The product is recristallized twice from methanol.
The product is characterized by I H-NMR Data in deuterated methanol (128 scans)/36OMHz 8,214 d J = 8,6; 1,007 -phenylene 7,871 d J=6,2 2,00 benzothiazol 7,781 d J=8,5 1,10 phenylene 7,520 d J 6,3 1,98 benzothiazol 7,267 d J = 8,6 2,00 phenylene 5,322 s _________ 1,908 methylene 4,738 q 12; 7 1,01 thiolactone 4,000 T 6 4,05 methylene 3,913 t 6 _4,05 methylene 3,448 He __________ I,02 thiolactone 3,34 m overlaid 1,01 thiolactone 2,364 m _________ 1,00 thiolactone 2,208 oct _________ 1,10 thiolactone
ExampleA7:
(107) YNNS 1. Monoazo 12.4g 4-fluoroaniline are added to a stirred solution of 25m1 water and 25ml of 32% hydrochloric acid at 295 K. Then the reaction mixture is cooled to 273K and 1 9m1 36% sodium nitrite solution are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K. After the addition of the sodium nitrite solution the mixture is stirred for I h. If no excess of nitrite is detected during I h (detection by using a potassium iodide paper) further amounts of sodium nitrite solution are added.
After this I h the remaining excess of nitrite is reduced with sulfamic acid.
Then the obtained diazo solution is dropped to a 273K cold solution of 7.4 g imidazole in 3Oml water whereby the pH of the solution is maintained in the range of p1-I 10 to 11 by adding 36% sodium hydroxide solution.
After completing the diazo addition the obtained suspension is warmed up to 29 K and the pH is adjusted to 10.5 with 36% sodium hydroxide solution.
After one hour stirring at this pH and temperature the suspension is filtered off and then washed twice with 50m1 water to obtain 55g of the humid product.
500ml water are introduced into a reaction vessel wherein the filter cake from the previouse step is added and suspend by stirring.
The addition of dimethyl sulphate is started and simultaneously that of sodium hydroxide maintaining the pH at 10-10.3 and the temperature at 25-30 C.
The amount of 3 equivalents of dimethyl sulphate (DMS) is added within ca. 5h.
It is held for I h to finish the hydrolysis of excess of DMS.
The disappearance of DMS is controlled.
Then bOg of sodium chloride and 50g of potassium chloride are add and cooled to 0 C.
After 16h the product is separated by filtration and washed with a cold solution of so-dium/potassium chloride.
Ca. 20g cake mole product of formula CH3 (107a) are obtained. -49 -
20.8g of racemic 3-amino-dihydro-thiophenone is added at 29 K under nitrogen atmosphere with stirring to I 20g isopropanol and the equivalent amount of triethylamine and the foregoing compound of the formula (1 07a).
Then the temperature is raised to 333K and viscosity of the reaction mixture decreases.
The reaction mixture is stirred at this temperature during 5h.
Then the reaction mass is stirred for 4h while the temperature is decreased to 295K.
The reaction mass is filtered off and the filter residue is washed with 4ml isopropanol.
Then the material is dried in vacuum to obtain 26g of product.
The product is characterized by the following data: I H-NMR data in deuterated chloroform (128 scans)/36OMHz 8,046 d 7,3 2,00 phenylene 7,605 S _________ 1,92 imidazol 7,102 d 7,8 2,06 phenylene 4,705 __________ 12;6 0,97 thiolacton 4,084 s __________ 12,06 dimethyl 3,86 t 6 2,02 methylene 3,595 s ___________ 1,982 methylene 3,26 ___________ ___________ 3,03 methyl 2,672 m _________ 1,01 thiolactone 2,259 s __________ 3,10 methyl 2,204 m __________ 0,98 thiolactone
Example A8: O(S (108)
1. Monoazo 12.4g 4-fluoroaniline are added to a stirred solution of 2 ml water and 25m1 of 32% hydrochloric acid at 29 K. Then the reaction mixture is cooled to 273K and 19m1 36% sodium nitrite solution are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276K. After the addition of the sodium nitrite solution the mixture is stirred for I h. If no -50 -excess of nitrite is detected during I h (detection by using a potassium iodide paper) further amounts of sodium nitrite solution are added.
After I h the remaining excess of nitrite is reduced with sulfamic acid.
Then the obtained diazo solution is dropped to a 273K cold solution of 7.4 g imidazole in 3Oml water whereby the pH of the solution is maintained in the range of pH 10 to 11 by adding 36% sodium hydroxide solution.
After completing the diazo addition the obtained suspension is warmed up to 295K and the pH is adjusted to 10.5 with 36% sodium hydroxide solution.
After I h stirring at this pH and temperature the suspension is filtered off and then washed twice with 50m1 water to obtain 55g of the humid product.
500 ml water are introduced into a reaction vessel, the filter cake from the previouse step is added and suspended by stirring.
The addition of dimethyl sulphate is started and simultaneously that of sodium hydroxide maintaining the pH at 10-10.3 and the temperature at 25-30 C.
The amount of 3 equivalents of dimethyl sulphate (DMS) is added within ca. 5h.
It is held for I h to finish the hydrolysis of excess of DMS.
The disappearance of DMS is controlled.
Then bOg sodium chloride and 50 g potassium chloride are added and cooled to 0 C.
After 16h the product is separated by filtration and washed with a cold solution of so-dium/potassium chloride.
Ca. 20g cake mole product offollowing formula / (108a) -
N
are obtained.
2. Amination 19.9 g ethylendiamine are added at 293K under nitrogen atmosphere with stirring to I 20g isopropanol and the foregoing compound of the formula (1 08a).
Then the temperature is raised to 333K and viscosity of the reaction mixture decreases. The reaction mixture is stirred at this temperature during 25h.
Then the reaction mass is stirred for 4h while the temperature is decreased to 295K.
The reaction mass is filtered off and the filter residue is washed with 45ml isopropanol.
-51 -Then the material is dried in vacuum to obtain 26g of product.
3. Derivatisation 25.9g of of racemic 3-amino-dihydro-thiophenone are added to I 20g toluene at 293K under nitrogen atmosphere with stirring.
Then phosgene is introduced below the surface of the liquid at 333 K. After completion of the addition the mixture is left I h and the reaction is finished.
The reaction mixture is mixed with a water/ hydorochloric acid and ice slurry the phases are separated, washed with water, dryed and the solvent is evaporated to dryness.
The product is used as such in the following step with the foregoing azo compound.
Both compounds are suspended in acetonitrile.
Then the temperature is raised then to 303K and viscosity of the reaction mixture decreases.
The reaction mixture is stirred at this temperature during 5h.
The reaction mass is filtered off and the filter residue is washed with 45m1 acetonitrile.
Then the material is dried in vacuum to obtain 36g of product.
The product is characterized by the following data: I H-NMR data in deuterated methanol (128 scans)/36OMHz 8,046 d 7,3 2,00 phenylene 7, 605 S _________ 1,92 imidazole 7,102 d 7,8 2,06 phenylene 4,705 __________ 12;6 0,97 thiolactone 4,084 s __________ 12,06 dimethyl 3,86 t 6 2,02 methylene 3,595 s __________ 1,982 methylene 2,672 m __________ 1,01 thiolactone 2,204 m ___________ 0,98 thiolactone B. Application Examples: For the application examples, the following hair types have been used: * blonde hair tress (VIRGIN white hair from IMHAIR Ltd., via G. Verga 8, It 90134 Palermo, Italy) * middle blond hair tress (UNA-Europ. nature hair, color middle blond from Fischbach & Miller, Postfach 1163, 88461 Laupheim, Deutschland) * bleached hair tresses (UNA-Europ. Naturhaar, Farbe wei1!gebleicht from Fischbach & Miller, Postfach 1163, 88461 Laupheim, Deutschland).
-52 -The washing fastness of the dyed hair is analyzed by the Grey scale according to Industrial organic pigments by Herbst&Hunger, 2nd ed. engl. S. 61) Nr 10: DIN 54 001-8-1982, l-lerstellung und Bewertung derAenderung der Farbe", ISO 105-A02-1 993.
In the following application examples compositions within the below given definitions are used: Solution I (permanent lotion, PH 8.2): Aqua, Ammonium Thioglycolate, Ammonium Bicarbonate, Ethoxydiglycol, Hexylene Glycol, Thioglycolic Acid; Thiolactic Acid, PEG-60 Hydrogenated Castor Oil, Glycine, Etidronic Acid, lsoceteth-20, Polysilicone-9, Styrene/PVP Copolymer, Tndeceth-1 2, Amodimethicone, Cetnmonium Chloride, Ammonium Hydroxide, Polyquatemium-6, Isopropyl Alcohol, Alcohol denat., Simethicone, Parfum.
Solution 2 (permanent fixation, PH 3.9): Based on: Aqua, Hydrogen Peroxide, Propylene Glycol, Lauryldimonium Hydroxypropyl Hydrolyzed Wheat Protein, PEG-5 Cocamide, Sodium Cocoamphoacetate, Polyquatemium-35, Coco-Betaine, Acetaminophen, Phosphoric Acid, Sodium Chloride, Parfum.
Solution 3 (dyeing solution): 0.1 % of the dye is dissolved in a 10 % solution of a non-ionic surfactant (Plantacare 200UP, Henkel) adjusted to pH 9.5 using citric acid or monoethanolamine.
Example BI:
5mg of compound of formula (101) according to example Al is dissolved in 20g ethanol and then 30g water is added: This blue dyeing solution is applied on the dry hair (two blond, two middle blond and two damaged hair strands) and allowed to stand for 20mm. at room temperature.
Then the strands are rinsed under tap water and dried 12 hours.
Washing fastness: 10 x washed with shampoo.
-53 -Results: Strand Colour result Washing fastness blond blue/good 2-3 middelblond blue/good 3-4 damaged blue/good 3
Example B2:
The 0.1%, by weight colouring material solution of example BI is applied on the dry hair (two blond, two middle blond, and two damaged hair strands) and allowed to stand for 20mm. at room temperature.
Then the strands are rinsed and the towel dry strands are treated with the solution 2 (permanent fixation) and allowed to stand for 10 mm.
Then the strands are rinsed under tap water and dried 12 hours at room temperature.
Washing fastness: 10 x washed with shampoo.
Results: Strand Colour result Washing fastness blond blue/good 2-3 middelblond blue/good 3-4 damaged blue/good 3
ExampleB3:
A solution I (permanent lotion) is applied on shampooed hair (two blond, two middle blond, and two damaged hair strands) and allowed to stand for 10 mm.
Then the strands are rinsed under tap water and the towel dry strands are treated with the 0.1 %, by weight colouring material solution of example BI allowed to stand for 20mm and then rinsed.
Then the towel dry strands are treated with the solution 2 (permanent fixation) and allowed to stand for 10 mm.
Then the strands are rinsed under tap water and dried 12 hours at room temperature.
Washing fastness: 10 x washed with shampoo.
Results: Strand Colour Washing fastness blond blue/good 3-4 -54 -middeiblond blue/good 3-4 damaged blue/good 2-3

Claims (17)

  1. -55 -Claims: 1. Dyes of formula + D-NH o (1) wherein D is the radical
    of anthraquinone, acridine, azo, azomethine, hydrazomethine, benzodifuranone, coumanne, diketopyrrolopyrrol, dioxaxine, diphenylmethane, formazane, indigoid, indophenol, naphtalimide, naphthaquinone, nitroaryl, merocyanine, methine, oxazine, perinone, perylene, pyrenequinone, phtalocyanine, phenazine, quinoneimine, quinacridone, quinophtalone, stilbene, styryl, triphenylmethane, xanthene, thiazine dye and thioxanthene dye; Q is C1-C30alkylene, -C2-C1 2alkenylene, -C5-C1 0arylene-, -C5-C10cycloalkylene-or -C1-C10alkylene(C5-C10arylene)-which may be interrupted and/or terminated at one or both ends by one or more than one -0-, -5-, -N=, -N(R1)-, SO2, -(CH2CH2-O)15-, -(CH2CH2CH2-O)15-, -C(O)-, -C(O)-C1 -C1 2alkenylene, -C(O)O-, -OCO-, -N i-R1 -CON(R1)-, -C(NR1R2)2-, -(R1)NC(O)-, -CSR-or an optionally substituted, saturated or unsaturated, fused or non-fused aromatic or nonaromatic (hetero)cyclic) bivalent radical optionally comprising at least one heteroatom; -0-; -S-; -N(R1)-; SO2; -(CH2CH2-O)15-; -C(O)-; -C(O)-C1-C12alkenylene; -C(O)O-, -OCO-; -Nt-; -CON(R1)-; -C(NR1R2)2-; R1 -(R1)NC(O)-; CSR1; saturated or unsaturated, fused or non-fused aromatic or nonaro-matic bivalent radical optionally comprising at least one heteroatom; which is optionally substituted by C1-C30alkyI, C1-C30alkoxy, -C2-C12alkenyl, C5-C1 0aryl, C5-C10cycloalkyl, C1-C1 0alkyl(C5-Ci 0arylene), hydroxy or D; R1 and R2 independently from each other are hydrogen; or unsubstituted or substituted, straight-chain or branched, monocyclic or polycyclic, interrupted or uninterrupted C1-C14alkyl; C1-C14 hydroxyalkyl; C1-C14aminoalkyl; C2-C14alkenyl; C6-C10aryl; C6-C1oaryl-C1-C10aIkyl; or C5-C10alkyl(C5-C1oaryl).
  2. 2. Dyes according to claim 1, wherein in formula (1) -56 - D is the radical of anthraquinone, acndine, azo, azomethine, hydrazomethine, benzodifu-ranone, coumarine, diketopyrrolopyrrol, dioxaxine, diphenylmethane, formazane, indigoid, indophenol, naphtalimide, naphthaquinone, nitroaryl, merocyanine, methine, oxazine, perinone, perylene, pyrenequinone, phtalocyanine, phenazine, quinoneimine, quinacridone, quinophtalone, stilbene, styryl, triphenylmethane, xanthene, thiazine dye and thioxanthene dye; Q is -C2-C1 2alkenylene, -C5-C10arylene-, -C5-C1 0cycloalkylene-or -C1-C1 oalkylene(C5-C10arylene)-which may be interrupted by one or more than one -0-, -S-, -NR3-or SO2; -(CH2CH2-O)15-; -C(O)-; -C(O)-C1-C12alkenylene; -C(O)O-; -OCO-; -N(R1)-; -re--R1 -CON(R1)-; -C(NR1R2)2; -(R1)NC(O)-; -CSR1-; -0-; -S-; -CS-; -S(O)-; or-S(O)2-; and R1, R2 and R3 independently from each other are hydrogen; unsubstituted or substituted, straightchain or branched, monocyclic or polycyclic, interrupted or uninterrupted C1-C14alkyl; C2-C14alkenyl; C6-C10aryl; C6-C1 0aryl-C1 -C1 0alkyl; or C5-C1oalkyl(C5-Cioaryl).
  3. 3. Dyes according to claim I or 2, wherein D is selected from a nitroaryl, an anthraquinone, a naphthoquinone, a pyrenequinone, a phathylocyanine, a formazane, a methine, an azomethine, a dioxazine, a phenazine, an azo, an indophenol, a stilbene, a tnphenylmethane, a xanthene, a thioxanthene and a direct dye.
  4. 4. Dyes according to any of claims 1 to 3, wherein * D is a radical of form:a (Ia) *_N?i;, :: R5T1XTi4 An -or (Ic) *_NAfl; or (Id) -T1X--_1) An X1 is a bivalent radical selected from -N=N-; -CRN-; -NCR8-; -NR8-NCR9-; and -R8C=N-NR9-; -57 -T1 is a bivalent radical of a substituted or unsubstituted aromatic or heteroaromatic compound; G1 is N; or a radical CR10; G2 is -0-; or -S-; R and R5 independently from each other are hydrogen; halogen; C1-C16alkyI, which may be interrupted with heteroatoms; phenyl; a carboxylic acid radical; a sulfonic acid radical; hydroxy; nitrile; C1-C16alkoxy; (poly)-hydroxy-C2-C4-alkoxy; halogen; SO2NR6R7; SR6; NR6R7; OR6; SO2; COOR6; NR6COR7; or CONR; R6 and R7 independently from each other are hydrogen; C1-C12alkyl, which may be substituted by one or more C1-C5alkyl, C1-C5-alkoxy or hydroxyl; -(CO)-H; -(CO)-C1-C5alkyl; phenyl or phenyl-C1-C4alkyl, wherein the phenyl moiety may be substituted by one or more C,-C5alkyl, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkyl-amino, di-C1-C5alkylamino, -NO2, carboxy or hydroxy; R8 and R9 independently from each other are hydrogen; C1-C14alkyl; C2-C14aIkenyl; C5-C10aryl; C1-C10alkyl-C5-C10aryl; or C5-C10aryl-C1-C10alkyl; R10 is hydrogen; C1-C14alkyl; C2-C14alkenyl; C6-C10aryl; C5-C1oaryl-(C1-Cioalkyl); or -Ci-C1oalkyl(C5-Cioaryl); and An is an anion.
  5. 5. Dyes according to any of claims I to 4, wherein \ D is aradical of (Ia1) , (Ia) *-N An-I N-< ji An X-Tr--R5 N R4 +1 (1b1) R__T_XT') An; or (Ic1) ; *NGXTl..R, wherein X1, T1 R4, R5and An are defined as in claim 4.
  6. 6. Dyes according to any of claims I to 5, wherein Q is a bivalent radical of formula (Ia) -(T)1(Z)-, -58 -T is a radical selected from saturated or unsaturated, linear or branched -C1-C12alkylene; -C(O)-; -(CH2CH2-O)15-; -(CH2CH2CH2-O)15-; -C(O)O-; -OC(O)-; -N(Ri)-; -CON(R1)-; -(R1)NC(O)-; -0-; -S-; -S(0)-; -S(O)2-; -S(0)2-N(Ri)-; and -N(R1)(R2)-; * N * 7 is-(CH2)2-S02-; -CH2-CHR-CO-NR'-; or a biradical of formula (Ib) NJ -N (Ic) NRa;or(1d) Dia; D R and R' independently from each other are hydrogen; or C1-C6 alkyl; D is Ra; D1; or D2; a and b independently from each other are 1, 2 or 3; Ra is chlonne or fluorine, R is unsubstituted or substituted C1-C6-alkoxy, C1-C6-alkylamino, C6-C10-aryloxy or C6-C10-arylamino; and t and z, independently from each other are 0; or 1; with the proviso that at least one of t or z is 1.
  7. 7. Dyes according to any of claims I to 6, wherein X1 is a bivalent radical selected from -N=N-; -CR8=N-; and -N=CR8-; T is phenylene; R5 is NR6R7; OR6; or SO2; R6 and R7 independently from each other are hydrogen; or C1-C12alkyl, which may be substituted by one or more hydroxyl; and R8 is hydrogen; or C1-C14alkyl.
  8. 8. Dyes according to any of claims I to 7, which correspond to formula -59 -R4
    OHH
    (2a) I or (2b) , wherein R5 Q is C1-C30alkylene; C2-C12alkenylene, -C5-C10arylene-, -C(O)-; or -C(O)-C2-C12alkenylene; R4 is hydrogen; C1-C16aIkyI; or C1-C16alkoxy; R5 is NR6R7; and R6 and R7 independently from each other are hydrogen; or C1-C12aIkyl, which may be substituted by one or more hydroxyl.
  9. 9. Dyes according to any of claims I to 7, which correspond to formula (3) 0, wherein ri X is a bivalent radical selected from -N=N-; -CR8N-; R5 is NR6R7; and R6 and R7from each other are hydrogen; C1-C12alkyl; or phenyl; and R8 is hydrogen; or C1-C14alkyl.
  10. 10. Dyes according to any of claims I to 7, which correspond to formula R4 1+ N-T-Q-NH 0 (4) (\>-N" ,wherein T1 is is a bivalent radical of a substituted or unsubstituted aromatic compound; Q is -C2-C12alkylene, which may be interrupted by one or more than one -NR3-; R3 is hydrogen; or C1-C14aIkyl; and R4 is hydrogen; or C1-C16alkyl.
    -60 -
  11. 11. A method of dyeing keratin-containing fibers compnsing treating the fiber with a dye as defined in any of claims I to 10.
  12. 12. A method according to claim 11, wherein the dyeing is carried out in presence of a reducing agent.
  13. 13. A method according to claim 11 or 12, wherein the reducing agent is selected from thioglycol acid or salts therof, gycenne monothioglycolate, cystein, 2-mercaptopropionic acid, 2-mercaptoethylamine, thiolactic acid, thioglycenne, sodium sulfite, dithionithe, ammonium sulfite, sodium bisulfite, sodium metabisulfite and hydrochinon.
  14. 14. A method according to any of claims 11 to 13, comprising treating the keratin-containing fiber (a) optionally with a reduction agent, and (b) with a dye as defined in claim 1, and (c) optionally with an oxidizing agent.
  15. 15. A composition comprising a dye as defined in claim 1.
  16. 16. A composition according to claim 15 in form of a shampoo, conditioner, gel or emulsion.
  17. 17. A composition according to claim 15 or 16 comprising at least one dye as defined in claim I and a direct dye and/or a reactive dye.
GB0800663A 2008-01-16 2008-01-16 Cationic dyes comprising a 2-oxo-tetrahydrothiophen-3-ylamino substituent for dyeing keratin-containing fibres Withdrawn GB2446257A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4714763A (en) * 1985-07-11 1987-12-22 Viomedics Inc. Novel oxazine-ureas and thiazine urea chromophors as fluorescent labels
US6251687B1 (en) * 1993-09-24 2001-06-26 Biosite Diagnostics, Inc. Fluorescence energy transfer and intramolecular energy transfer in particles using novel compounds
EP1477158A1 (en) * 2003-05-16 2004-11-17 L'oreal Dithiols and their use to strenghten the hair

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4714763A (en) * 1985-07-11 1987-12-22 Viomedics Inc. Novel oxazine-ureas and thiazine urea chromophors as fluorescent labels
US6251687B1 (en) * 1993-09-24 2001-06-26 Biosite Diagnostics, Inc. Fluorescence energy transfer and intramolecular energy transfer in particles using novel compounds
EP1477158A1 (en) * 2003-05-16 2004-11-17 L'oreal Dithiols and their use to strenghten the hair

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