CA2107796A1 - Hair colorants with substantive dyes - Google Patents
Hair colorants with substantive dyesInfo
- Publication number
- CA2107796A1 CA2107796A1 CA002107796A CA2107796A CA2107796A1 CA 2107796 A1 CA2107796 A1 CA 2107796A1 CA 002107796 A CA002107796 A CA 002107796A CA 2107796 A CA2107796 A CA 2107796A CA 2107796 A1 CA2107796 A1 CA 2107796A1
- Authority
- CA
- Canada
- Prior art keywords
- hair
- dyes
- dyeing
- dye
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/418—Amines containing nitro groups
-
- 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
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen 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
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/42—Colour properties
- A61K2800/43—Pigments; Dyes
- A61K2800/432—Direct dyes
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Cosmetics (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Coloring (AREA)
Abstract
Hair colourants based on direct-acting hair dyes containing a combination of two or more hair dyes dye even damaged hair particularly uniformly by reductive and oxidative hair treatment if this combination contains at least one nitrodiphenyl amine dye of the formula (I) in which one of the groups R3 to R7 is a -SO3H
or a -COOH- group, or one of its water-soluble salts besides other direct-acting dyes.
or a -COOH- group, or one of its water-soluble salts besides other direct-acting dyes.
Description
7 ~ ~
HAIR COLORANTS WITH SUBSTANTIVE DYES
This invention relates to hair-dyeing preparations containing at least two different substantive hair dyes which are distinguished by particularly uniform dye absorption, even on damaged hair.
In addition to oxidation dyes, which are formed through the oxidative coupling s of one or more primary intermediate components with one another or with one or more coupler components, substantive hair dyes play a particularly important part in the dyeing of hair. Substantive hair dyes have the advantage that they may be used without the addition of oxidizing agents. The substanLive dyes used are primarily compounds belonging to the group of nitrobenzene derivatives.
o Good hair-dyeing preparations have to form the desired shades of color in suf-2 ~ 7 ~ ~
~Icient intensity. In addition, they must readily be absorbed by human hair without excessive staining of the scalp. The hair colors produced with them must show high stability to light, heat, perspiration, shampoos and ~he chemicals used in the permanent waving of hair. Finally, ~hey should be both toxicologically and dcrmatologically safe.
5 Unfortunately, many substantive hair dyes have the disadvantage that they are un evenly absorbed onto the hair, the more seriously damaged hair ends generally being colored more intensively than the younger and less damaged hair roots. For this rea-son, many basically good dyes are unsuitable for practical application.
It has now been found that combinations of two or more substantive dyes pro-10 vide for the much more uniforrn dyeing even of hair which has been damaged by re-ductive and oxidative treatments, for example by permanent waving and bleaching, if the combination contains at least one nitrodiphenylamine dye corresponding to formula 1.
Accordingly, the present invention relates to hair-dyeing preparations contain-15 ing at least two substantive dyes in a cosmetic carrier, characterized in that they con-tain a first substantive dye (A) corresponding to forrnula I:
R~ R; ( I ) 25 in which R~ and R2 are hydrogen, C,4 alkyl groups or C2, hydroxyalkyl groups and one of the moieties R3 to R7 is an -SO3H or a -COOH group and the other moietiesare hydrogen, chlorine, Cl.,, alkyl groups, C" alkoxy groups or groups of the formula -NR8R9, where R8 and R9 are hydrogen, C,~ alkyl groups, C2 ~ hydroxyalkyl groupsor, together with the nitrogen atom, forrn a piperidine, morpholine, piperazine or 30 pyrrolidine ring, or one of its water-soluble salts and at least one second substantive dye (B) having a different stNcture.
The substantive dyes (A) corresponding to forrnula I are known from European Patent Application EP 0 280 187 Al. Through the presence of these dyes, the uni-~s forrnity of absorption of the many other substantive dyes is distinctly better than could 21~7~3~
,~'` ~
have been expec[ed from the absorption of the individual dyes of lhe combination.
In most cases, lhe combination of dye (A) corresponding to formula I and a sccond dye (B) shows more uniform absorption than the components (A) and (B) on their own. At the vcry least, however, the uniformity of dye absorption is higher than cor-s responds to the mixture rule.
Substantive dyes varying in structure may be used as the second dye (B). Sub-stantive dyes from the group of aromatic nitro compounds or anthraquinone com-pounds are particularly preferred. However, the effect according to the invention of improved uniformity of absorption by combinaticn with dyes corresponding to formula 10 I is also observed with other substantive dyes, for example azo dyes, triphenylmethane dyes or indophenols.
Particularly suitable substantive dyes (B) are mentioned in the Exarnples, par-ticularly under B1 to B9.
Particularly suitable substantive nitrodiphenylamine dyes (A) corresponding to formula I are A1: 2-nitro-4-aminodiphenylamine-2'-carboxylic acid and A2: 2-nitro-4-amino-4'-dimethylaminodiphenylamine-2'-carboxylic acid.
Further examples can be found in European Patent Application EP 0 280 187 20 Al.
The hair-dyeing preparations according to the invention are also distinguished by improved fastness to washing. Hair colors produced with a combina~ion of a nitro-diphenylamine dye (A) corresponding to formula I and a second substantive dye (B) of a different structure are lightened to a lesser extent after washing of the hair than 26 hair colors obtained with dye (B) in the absence of a dye corresponding to formula I.
The hair-dyeing preparations according to the invention may also contain two different dyes (A) of formula I and one or more other dyes (B).
Finally, the hair-dyeing preparations according to the invention may also con-30 tain oxidalion dye precursors.
To produce the hair-dyeing preparations according to the invention, the substan-tive hair dyes (A) corresponding to formula I and the other dyes (B) are incorporated 2:~77~
,,, in a suitable cosmetic carrier, for example in creams, emulsions, gels or even surfact-ant-containing foaming solutions, for example in sham~oos, foarn aerosols or other preparations suitable for application to the hair.
Standard ingredients of cosmetic preparations such as these are, for example, wetting agents and emulsifiers, such as anionic, nonionic, cationic, zwitterionic and ampholytic surfac~n~. Preferred surfactants are, for example, fatty alcohol sulfates, fatty alcohol polyglycol ether sulfa~.es, n-alkanesulfonates, a-olefln sulfonates, ethylene oxide adducts with fatty amines, with fatty acids, with fatty alcohols, with aL~yl phe-nols, with fatty acid partial glycerides, with sorbitan fatty acid esters and with fatty o acid aL~anolarnides.
Other standard ingredients are water-soluble thickeners such as, for example, mcthyl or hydroxyethyl cellulose, starch and water-soluble starch derivatives, biopol-ymers, water-soluble synthetic polymers and copolymers, for example those of acrylic and methacrylic acid. For formulation as dyeing creams, fatty components such as, 15 for example, fatty alcohols, fatty acids, fatty acid partial glycerides, esters, paraffins and waxes in emulsified forrn are used as carriers. In addition, the hair-dyeing prepa-rations may contain known hair-care additives such as, for example, water-soluble cat-ionic polymers, water-soluble proteins and protein derivatives, pantothenic acid, vita-mins, plant extracts and fragrances, pH regulators (buffers), electrolytes and water.
The constituents of the carrier are used in the usual quantities for producing the hair-dyeing preparations according to the invention. For example, wetting agents and emulsifiers are used in quantities of 0.5 to 30 % by weight while thickeners are used in concentrations of 0.1 to 10 % by weight, based on the hair-dyeing preparation as a whole.
In one preferred embodiment, the carrier is an emulsion containing 1 to 5 %
by weight of a Cl~.22 fatty alcohol, 5 to 20 % by weight of an adduct of 5 to 20 moles of ethylene oxide with 1 mole of a linear, terminal C,2.22 alkyl amine, based on the weight of the hair-dyeing preparation as a whole.
The substantive dyes (A and B) are used in the hair-dyeing preparations ac-20 cording to the invention in a total quantity of 0.05 to 5 % by weight and preferably in a total quantity of 0.2 to 2 % by weight, based on the hair-dyeing preparation as a whole. The quantity ratio of the dyes tA) corresponding to forrnula I to the dyes 21~779~
(~) of different structure may bc in the range from 1:9 to 9:1 and is pre~rably in ~he range from 3:7 to 7:3.
Where the hair-dyeing preparation according to the invention conlaillS oxidationdye precursors, it is advisable addi~ionally to incorpor~e a small quantity of a rcduc-ing agent, for example 0.5 to 2.0 % by weigh~ of sodium sulfite, to stabilizc thc oxida-tion dye precursors. In this case, an oxidizing agent is added to the hair-dyeing prepa-ration before it is applied to initiate the oxidative development of the oxidation dye precursors. Suitable oxidizing agents are, in particular, hydrogen peroxide or adducts thereof with urea, melamine or sodium borate and also mixtures of such hydrogen per-oxide adducts with potassium peroxysulfate.
Irrespective of the nature of the cosmetic composition, the hair-dyeing prepara-tions according to the invention may be used, for example, in the form of creams, gels or shampoos in a mildly acidic, neutral or alkaline medium. The hair-dyeing prepara-tions are preferably used at a pH value in the range from 6 to 10. They may be ap-plied at temperatures in the range from 15 to 40 C. After a contact time of about 30 minutes, the hair-dyeing preparation is removed by rinsing out from the hair to be dyed. The hair is then rewashed in a mild shampoo and dried. There is no need for rewashing with a shampoo in cases where a carrier of high surfactant content, for ex-ample a dye shampoo, has been used.
Hair colors of high intensity and good fastness properties, including in particu-lar good fastness to washing and high stability to fading and changes in color during shampooing, can be obtained with the hair-dyeing preparations according to the inven-tion. The following examples are intended to illustrate the invention without limiting it in any way.
~E Examples 1. Improving levelling power 1.1 Production of the hair-dyeing preparations Hair-dyeing preparations of the following composition were prepared:
Tallow al~yl amine(C8-CI8)polyglycol (8 EO) ether 9.0 g so Oleic acid polyglycerol ester 2.5 g Ce~yVoleyl alcohol polyglycol ether (5 EO) 3.0 g 2:~77g6 -~ 1,3-Propylene glycol 5.0 g Substantive dye (or combination of substantivc dyes) 1.0 g Fragrance 0-3 g (NH.,)2SO4 1.0 g Ammonia (conc. in H2O) to pH = 9 Water ad 100 g The followin~ dyes were used as the substan~ive dyes corresponding to formula I:
A1 : 2-nitro-4-amino-2'-carboxydiphenylamine A2 : 2-nitro-4-amino-2'-carboxy-4'-dimethylaminodiphenylamine The following other substantive dyes were used:
B I : 1,2,3,4-tetrahydro-6-nitroquinoxaline B 2 : picrarnic acid (2-amino-4,6-dinitrophenol) B 3 : 1-amino-2-nitro-4-(2,3-dihydroxypropylamino)-5-chlorobenzene B 4 : 1-amino-2-nitro-4-(2-hydroxyethylamino)-5-chlorobenzene B 5 : 1,4-bis-(B-hydroxyethylamino)-2-nitrobenzene B 6 : 4-(3-hydroxypropyl)-amino-3-nitrophenol B 7 : 1-(2-hydroxyethyl)-amino-4-methyl-2-nitrobenzene B 8 : 6-chloro-4-nitro-2-aminophenol B 9 : 1-(2-hydroxyethyl)-amino-2-nitro-4-bis-(2-hydroxyethyl)-aminobenzene B 10 : 1-(2-hydroxyethyl)-amino-2-nitro-4-aminobenzene B 11 : 2-nitro-p-phenylenediamine B12 : 1-amino-2-nitro-4-bis-(2-hydroxyethyl)-aminobenzene B13 : 2-amino-4-nitrophenol B 14 : 1 -amino-2-(2-hydroxyethyl)-amino-5-nitrobenzene B 15 : 1-amino-2-nitro-4-(2-hydroxyethyl)-aminobenzene B16 : 1,4,5,8-tetraminoanthraquinone B 17 : 1-amino-4-methylaminoanthraquinone B18 : 1,4-diamino-5-nitroanthraquinone B 19 : 1-methylamino-4-(2-hydroxyethyl)-arninoanthraquinone B20 : 1,4-diaminoanthraquinone .~ . . .
~ L ~ 7 r~ ~ ~
B21 : 1-(4'-bis-(2-hydroxye~hyl)-amino)-phenylazo-4'-aminoben-~ene 1.2 Hair dyeing Grey hair tresses weighing 2 g for a length of 16 to 18 cm were treale~ at the s hair ends (upper half) with a cold wave preparation (aqueous solution of ammonium thioglycolate) for 30 minutcs at 27 C, rinsed with warm water, treaLed with 10 ml of a fixing solution (potassium bromate solution) and rerinsed. The same half was then bleached for 30 minutes at 27 C with an aqueous preparation of hydrogen peroxide and ammonium peroxydisulfate. It was then trealed once more with the cold-wave preparation and the fixing solution. Finally, the tresses as a whole were bleached once. In this way, two regions damaged to different extents were obtained, namely seriously damaged hair ends and less damaged hair roots.
The tresses thus pretreated were dyed with the hair-dyeing preparations accord-ing to 1.1, the dyes or dye combinations listed in Table I being used as the substantive dyes. The dyeing solutions were left on the hair tresses for about 20 minutes at 27 C, subsequently washed out with a typical shampoo, rinsed with water and dried.
1.3 Determination of uniformity of dyeing (color difference values (DE) between hair ends and hair roots) Each hair tress was measured at eight places (4 in the region of the hair roots and 4 in the region of the hair ends) using a Datacolor color measuring system~ To this cnd, the sample to be measured was fixed to the spectral photometer in a clamp and the reflectance spectrometry values were measured over the visible light range from 390 to 700 nm at intervals of 10 nm and processed in a computer (HP 2113 E
Minicomputer). The computer program determined the standard color values in ac-cordance with DIN 5033 corresponding to the CIE (Commission Internationale de l'Eclairage) systern and converted them into color differences according to DIN 6174.
The color difference values (DE) for hair colors obtained with individual dyes and with dye combinations according to the invention are shown in Table I. The color difference values of the hair colors obtained with the dye combinations according to the invention (substantive dye A + substantive dye B) are also shown in the Table.
h 1 ~3 i [~1) ;
Table I
~ Color dif-Substantive dye, Color tone ference quantity Hair end Hair xoot DE
Al : 1 g Grey-red Violet-brown 12.57 A2 : 1 g Grey-indigo Indigo 21.1 B1 : 1 g Brown-red Orange 18.35 B1 (0.5g) + Al (0.5g) Red-brcwn R~d-brcwn 6.25 B2 : 1 g Tight orange- Brown-orange 10.2 brown B2 (0.5g) + Al ~0.5g) Red-brownRed-brown 6.14 B3 : 1 g Red-brcwn Grey-red 9.4 B3 (0.5g) + Al (0.5g) Garnet-brown Grey-red 2.8 E4 : 1 g Raspberry red Brcwn-red 5.8 B4 (0.5g) + Al (0.5g) Red-brcwnGrey-red 5.0 B5 : 1 g Dark purple Grey-magenta 16.7 B5 (0.5g) + Al (0.5g) Ruby Grey-red 10.5 _ B5 : 1 g Dark purple Grey-magenta 16.7 B5 (0.5g) + A2 (0.5g) Grey-magenta Magenta 4.8 B6 : 1 g Coral red Lobster red 4.3 B6 (0.5g) + Al (0.5g) Pcmpeian red Grey red 3.5 B7 : 1 g Yellow-orange Buttercup11.8 yellow B7 (0.5g) + Al (0.5g) Cinnamon brown Fox red 12.7 _ B8 : 1 g Red-orange Melon orange 18.1 B8 (0.5g) + Al (0.5g) terra di Siena Copper red 8.4 B9 : 1 g Grey-magenta Grey-ruby 5.75 B9 (0.5g) + Al (0.5g) Grey-ru~yDull violet 5.80 B10 : 1 g Dull red Grey-red 12.56 B10 (0.5g) + Al (0.5g) Violet-brown Violet-brown 3.5 l .
B11 : 1 g Red-brown Orange-brcwn 19.9 B11 (0.5g) ~ Al (0.5g) Brown-red Brown-red 3.88 . ......
B12 : 1 g Grey-magenta Light krcwn 11.75 B12 (0.5g) ~ Al (0.5g) Grey-red-brcwn Red-brown 8.87 50 ___ .......... . .
B13 : 1 g Brick red Yellow-orange 10.0 B13 (0.5g) + Al (0.5g) Brown-orange Henna red _ 2 ~
.i Tablel(conti)l~ed) Color dif-Sub6tantive dye, Color tone ference s quantity Hair end Hair root DE
B14 : 1 g Brown-orange Yellcw 13.64 Bl4 (0.5g) ~ Al (0-5g) Orange-brown Orange-krown 10.2 to B15 : 1 g ~ed-brown Dull red- 8.9 brown B15 (0.5g) ~ Al (0.5g) Red-brown Red-brown 8.4 B16 : 1 g Grey-green Dull green9.15 B16 t0.5g) + Al (0.5g) Grey-ruby Dull ruby 10.6 B17 : 1 g Purple-grey Dull violet 17.65 B17 (0.5g) + Al (0.5g) Grey-red Grey-red 6.6 B18 : 1 g Silver grey Violet-grey11.2 B18 (0.5g) + Al (0.5g) Grey-red Grey-red 2.30 B19 : 1 g Grey-green GFey-tur- 19.9 quoise B19 (0.5g) + Al (0.5g) Grey-ruby Grey-ruby 7.74 B20 : 1 g Grey-ruby Grey-magenta 9.01 B20 (0.5g) + Al (0.5g) Grey-red-brown Red-brcwn 2.0 ~o B21 : 1 g Yellcw Orange-yellow 10.0 B21 (0.5g) + Al (0.5g) Light brown Light brown 7.3 Al (0.33 g) B10 (0.33 g) Brown-violet Brcwn-violet 5.0 B17 (0.33 g) Al (0,33 g) B1 (0.33 g) lerracotta Red-brown 2.0 B4 (0.33 g) Al (0.33 g) B1 (0.33 g) Red-brown Red-brown 3.9 B5 (0.33 g) .
Al ~0.33 g) B5 (0.33 g) Violet-brown Violet-brown 2.4 B8 (0.33 g) Al (0.25 g) ~2 (0.25 g) B5 (0.25 g) Grey-magenta Grey-ruby3.8 B9 (0.25 g)
HAIR COLORANTS WITH SUBSTANTIVE DYES
This invention relates to hair-dyeing preparations containing at least two different substantive hair dyes which are distinguished by particularly uniform dye absorption, even on damaged hair.
In addition to oxidation dyes, which are formed through the oxidative coupling s of one or more primary intermediate components with one another or with one or more coupler components, substantive hair dyes play a particularly important part in the dyeing of hair. Substantive hair dyes have the advantage that they may be used without the addition of oxidizing agents. The substanLive dyes used are primarily compounds belonging to the group of nitrobenzene derivatives.
o Good hair-dyeing preparations have to form the desired shades of color in suf-2 ~ 7 ~ ~
~Icient intensity. In addition, they must readily be absorbed by human hair without excessive staining of the scalp. The hair colors produced with them must show high stability to light, heat, perspiration, shampoos and ~he chemicals used in the permanent waving of hair. Finally, ~hey should be both toxicologically and dcrmatologically safe.
5 Unfortunately, many substantive hair dyes have the disadvantage that they are un evenly absorbed onto the hair, the more seriously damaged hair ends generally being colored more intensively than the younger and less damaged hair roots. For this rea-son, many basically good dyes are unsuitable for practical application.
It has now been found that combinations of two or more substantive dyes pro-10 vide for the much more uniforrn dyeing even of hair which has been damaged by re-ductive and oxidative treatments, for example by permanent waving and bleaching, if the combination contains at least one nitrodiphenylamine dye corresponding to formula 1.
Accordingly, the present invention relates to hair-dyeing preparations contain-15 ing at least two substantive dyes in a cosmetic carrier, characterized in that they con-tain a first substantive dye (A) corresponding to forrnula I:
R~ R; ( I ) 25 in which R~ and R2 are hydrogen, C,4 alkyl groups or C2, hydroxyalkyl groups and one of the moieties R3 to R7 is an -SO3H or a -COOH group and the other moietiesare hydrogen, chlorine, Cl.,, alkyl groups, C" alkoxy groups or groups of the formula -NR8R9, where R8 and R9 are hydrogen, C,~ alkyl groups, C2 ~ hydroxyalkyl groupsor, together with the nitrogen atom, forrn a piperidine, morpholine, piperazine or 30 pyrrolidine ring, or one of its water-soluble salts and at least one second substantive dye (B) having a different stNcture.
The substantive dyes (A) corresponding to forrnula I are known from European Patent Application EP 0 280 187 Al. Through the presence of these dyes, the uni-~s forrnity of absorption of the many other substantive dyes is distinctly better than could 21~7~3~
,~'` ~
have been expec[ed from the absorption of the individual dyes of lhe combination.
In most cases, lhe combination of dye (A) corresponding to formula I and a sccond dye (B) shows more uniform absorption than the components (A) and (B) on their own. At the vcry least, however, the uniformity of dye absorption is higher than cor-s responds to the mixture rule.
Substantive dyes varying in structure may be used as the second dye (B). Sub-stantive dyes from the group of aromatic nitro compounds or anthraquinone com-pounds are particularly preferred. However, the effect according to the invention of improved uniformity of absorption by combinaticn with dyes corresponding to formula 10 I is also observed with other substantive dyes, for example azo dyes, triphenylmethane dyes or indophenols.
Particularly suitable substantive dyes (B) are mentioned in the Exarnples, par-ticularly under B1 to B9.
Particularly suitable substantive nitrodiphenylamine dyes (A) corresponding to formula I are A1: 2-nitro-4-aminodiphenylamine-2'-carboxylic acid and A2: 2-nitro-4-amino-4'-dimethylaminodiphenylamine-2'-carboxylic acid.
Further examples can be found in European Patent Application EP 0 280 187 20 Al.
The hair-dyeing preparations according to the invention are also distinguished by improved fastness to washing. Hair colors produced with a combina~ion of a nitro-diphenylamine dye (A) corresponding to formula I and a second substantive dye (B) of a different structure are lightened to a lesser extent after washing of the hair than 26 hair colors obtained with dye (B) in the absence of a dye corresponding to formula I.
The hair-dyeing preparations according to the invention may also contain two different dyes (A) of formula I and one or more other dyes (B).
Finally, the hair-dyeing preparations according to the invention may also con-30 tain oxidalion dye precursors.
To produce the hair-dyeing preparations according to the invention, the substan-tive hair dyes (A) corresponding to formula I and the other dyes (B) are incorporated 2:~77~
,,, in a suitable cosmetic carrier, for example in creams, emulsions, gels or even surfact-ant-containing foaming solutions, for example in sham~oos, foarn aerosols or other preparations suitable for application to the hair.
Standard ingredients of cosmetic preparations such as these are, for example, wetting agents and emulsifiers, such as anionic, nonionic, cationic, zwitterionic and ampholytic surfac~n~. Preferred surfactants are, for example, fatty alcohol sulfates, fatty alcohol polyglycol ether sulfa~.es, n-alkanesulfonates, a-olefln sulfonates, ethylene oxide adducts with fatty amines, with fatty acids, with fatty alcohols, with aL~yl phe-nols, with fatty acid partial glycerides, with sorbitan fatty acid esters and with fatty o acid aL~anolarnides.
Other standard ingredients are water-soluble thickeners such as, for example, mcthyl or hydroxyethyl cellulose, starch and water-soluble starch derivatives, biopol-ymers, water-soluble synthetic polymers and copolymers, for example those of acrylic and methacrylic acid. For formulation as dyeing creams, fatty components such as, 15 for example, fatty alcohols, fatty acids, fatty acid partial glycerides, esters, paraffins and waxes in emulsified forrn are used as carriers. In addition, the hair-dyeing prepa-rations may contain known hair-care additives such as, for example, water-soluble cat-ionic polymers, water-soluble proteins and protein derivatives, pantothenic acid, vita-mins, plant extracts and fragrances, pH regulators (buffers), electrolytes and water.
The constituents of the carrier are used in the usual quantities for producing the hair-dyeing preparations according to the invention. For example, wetting agents and emulsifiers are used in quantities of 0.5 to 30 % by weight while thickeners are used in concentrations of 0.1 to 10 % by weight, based on the hair-dyeing preparation as a whole.
In one preferred embodiment, the carrier is an emulsion containing 1 to 5 %
by weight of a Cl~.22 fatty alcohol, 5 to 20 % by weight of an adduct of 5 to 20 moles of ethylene oxide with 1 mole of a linear, terminal C,2.22 alkyl amine, based on the weight of the hair-dyeing preparation as a whole.
The substantive dyes (A and B) are used in the hair-dyeing preparations ac-20 cording to the invention in a total quantity of 0.05 to 5 % by weight and preferably in a total quantity of 0.2 to 2 % by weight, based on the hair-dyeing preparation as a whole. The quantity ratio of the dyes tA) corresponding to forrnula I to the dyes 21~779~
(~) of different structure may bc in the range from 1:9 to 9:1 and is pre~rably in ~he range from 3:7 to 7:3.
Where the hair-dyeing preparation according to the invention conlaillS oxidationdye precursors, it is advisable addi~ionally to incorpor~e a small quantity of a rcduc-ing agent, for example 0.5 to 2.0 % by weigh~ of sodium sulfite, to stabilizc thc oxida-tion dye precursors. In this case, an oxidizing agent is added to the hair-dyeing prepa-ration before it is applied to initiate the oxidative development of the oxidation dye precursors. Suitable oxidizing agents are, in particular, hydrogen peroxide or adducts thereof with urea, melamine or sodium borate and also mixtures of such hydrogen per-oxide adducts with potassium peroxysulfate.
Irrespective of the nature of the cosmetic composition, the hair-dyeing prepara-tions according to the invention may be used, for example, in the form of creams, gels or shampoos in a mildly acidic, neutral or alkaline medium. The hair-dyeing prepara-tions are preferably used at a pH value in the range from 6 to 10. They may be ap-plied at temperatures in the range from 15 to 40 C. After a contact time of about 30 minutes, the hair-dyeing preparation is removed by rinsing out from the hair to be dyed. The hair is then rewashed in a mild shampoo and dried. There is no need for rewashing with a shampoo in cases where a carrier of high surfactant content, for ex-ample a dye shampoo, has been used.
Hair colors of high intensity and good fastness properties, including in particu-lar good fastness to washing and high stability to fading and changes in color during shampooing, can be obtained with the hair-dyeing preparations according to the inven-tion. The following examples are intended to illustrate the invention without limiting it in any way.
~E Examples 1. Improving levelling power 1.1 Production of the hair-dyeing preparations Hair-dyeing preparations of the following composition were prepared:
Tallow al~yl amine(C8-CI8)polyglycol (8 EO) ether 9.0 g so Oleic acid polyglycerol ester 2.5 g Ce~yVoleyl alcohol polyglycol ether (5 EO) 3.0 g 2:~77g6 -~ 1,3-Propylene glycol 5.0 g Substantive dye (or combination of substantivc dyes) 1.0 g Fragrance 0-3 g (NH.,)2SO4 1.0 g Ammonia (conc. in H2O) to pH = 9 Water ad 100 g The followin~ dyes were used as the substan~ive dyes corresponding to formula I:
A1 : 2-nitro-4-amino-2'-carboxydiphenylamine A2 : 2-nitro-4-amino-2'-carboxy-4'-dimethylaminodiphenylamine The following other substantive dyes were used:
B I : 1,2,3,4-tetrahydro-6-nitroquinoxaline B 2 : picrarnic acid (2-amino-4,6-dinitrophenol) B 3 : 1-amino-2-nitro-4-(2,3-dihydroxypropylamino)-5-chlorobenzene B 4 : 1-amino-2-nitro-4-(2-hydroxyethylamino)-5-chlorobenzene B 5 : 1,4-bis-(B-hydroxyethylamino)-2-nitrobenzene B 6 : 4-(3-hydroxypropyl)-amino-3-nitrophenol B 7 : 1-(2-hydroxyethyl)-amino-4-methyl-2-nitrobenzene B 8 : 6-chloro-4-nitro-2-aminophenol B 9 : 1-(2-hydroxyethyl)-amino-2-nitro-4-bis-(2-hydroxyethyl)-aminobenzene B 10 : 1-(2-hydroxyethyl)-amino-2-nitro-4-aminobenzene B 11 : 2-nitro-p-phenylenediamine B12 : 1-amino-2-nitro-4-bis-(2-hydroxyethyl)-aminobenzene B13 : 2-amino-4-nitrophenol B 14 : 1 -amino-2-(2-hydroxyethyl)-amino-5-nitrobenzene B 15 : 1-amino-2-nitro-4-(2-hydroxyethyl)-aminobenzene B16 : 1,4,5,8-tetraminoanthraquinone B 17 : 1-amino-4-methylaminoanthraquinone B18 : 1,4-diamino-5-nitroanthraquinone B 19 : 1-methylamino-4-(2-hydroxyethyl)-arninoanthraquinone B20 : 1,4-diaminoanthraquinone .~ . . .
~ L ~ 7 r~ ~ ~
B21 : 1-(4'-bis-(2-hydroxye~hyl)-amino)-phenylazo-4'-aminoben-~ene 1.2 Hair dyeing Grey hair tresses weighing 2 g for a length of 16 to 18 cm were treale~ at the s hair ends (upper half) with a cold wave preparation (aqueous solution of ammonium thioglycolate) for 30 minutcs at 27 C, rinsed with warm water, treaLed with 10 ml of a fixing solution (potassium bromate solution) and rerinsed. The same half was then bleached for 30 minutes at 27 C with an aqueous preparation of hydrogen peroxide and ammonium peroxydisulfate. It was then trealed once more with the cold-wave preparation and the fixing solution. Finally, the tresses as a whole were bleached once. In this way, two regions damaged to different extents were obtained, namely seriously damaged hair ends and less damaged hair roots.
The tresses thus pretreated were dyed with the hair-dyeing preparations accord-ing to 1.1, the dyes or dye combinations listed in Table I being used as the substantive dyes. The dyeing solutions were left on the hair tresses for about 20 minutes at 27 C, subsequently washed out with a typical shampoo, rinsed with water and dried.
1.3 Determination of uniformity of dyeing (color difference values (DE) between hair ends and hair roots) Each hair tress was measured at eight places (4 in the region of the hair roots and 4 in the region of the hair ends) using a Datacolor color measuring system~ To this cnd, the sample to be measured was fixed to the spectral photometer in a clamp and the reflectance spectrometry values were measured over the visible light range from 390 to 700 nm at intervals of 10 nm and processed in a computer (HP 2113 E
Minicomputer). The computer program determined the standard color values in ac-cordance with DIN 5033 corresponding to the CIE (Commission Internationale de l'Eclairage) systern and converted them into color differences according to DIN 6174.
The color difference values (DE) for hair colors obtained with individual dyes and with dye combinations according to the invention are shown in Table I. The color difference values of the hair colors obtained with the dye combinations according to the invention (substantive dye A + substantive dye B) are also shown in the Table.
h 1 ~3 i [~1) ;
Table I
~ Color dif-Substantive dye, Color tone ference quantity Hair end Hair xoot DE
Al : 1 g Grey-red Violet-brown 12.57 A2 : 1 g Grey-indigo Indigo 21.1 B1 : 1 g Brown-red Orange 18.35 B1 (0.5g) + Al (0.5g) Red-brcwn R~d-brcwn 6.25 B2 : 1 g Tight orange- Brown-orange 10.2 brown B2 (0.5g) + Al ~0.5g) Red-brownRed-brown 6.14 B3 : 1 g Red-brcwn Grey-red 9.4 B3 (0.5g) + Al (0.5g) Garnet-brown Grey-red 2.8 E4 : 1 g Raspberry red Brcwn-red 5.8 B4 (0.5g) + Al (0.5g) Red-brcwnGrey-red 5.0 B5 : 1 g Dark purple Grey-magenta 16.7 B5 (0.5g) + Al (0.5g) Ruby Grey-red 10.5 _ B5 : 1 g Dark purple Grey-magenta 16.7 B5 (0.5g) + A2 (0.5g) Grey-magenta Magenta 4.8 B6 : 1 g Coral red Lobster red 4.3 B6 (0.5g) + Al (0.5g) Pcmpeian red Grey red 3.5 B7 : 1 g Yellow-orange Buttercup11.8 yellow B7 (0.5g) + Al (0.5g) Cinnamon brown Fox red 12.7 _ B8 : 1 g Red-orange Melon orange 18.1 B8 (0.5g) + Al (0.5g) terra di Siena Copper red 8.4 B9 : 1 g Grey-magenta Grey-ruby 5.75 B9 (0.5g) + Al (0.5g) Grey-ru~yDull violet 5.80 B10 : 1 g Dull red Grey-red 12.56 B10 (0.5g) + Al (0.5g) Violet-brown Violet-brown 3.5 l .
B11 : 1 g Red-brown Orange-brcwn 19.9 B11 (0.5g) ~ Al (0.5g) Brown-red Brown-red 3.88 . ......
B12 : 1 g Grey-magenta Light krcwn 11.75 B12 (0.5g) ~ Al (0.5g) Grey-red-brcwn Red-brown 8.87 50 ___ .......... . .
B13 : 1 g Brick red Yellow-orange 10.0 B13 (0.5g) + Al (0.5g) Brown-orange Henna red _ 2 ~
.i Tablel(conti)l~ed) Color dif-Sub6tantive dye, Color tone ference s quantity Hair end Hair root DE
B14 : 1 g Brown-orange Yellcw 13.64 Bl4 (0.5g) ~ Al (0-5g) Orange-brown Orange-krown 10.2 to B15 : 1 g ~ed-brown Dull red- 8.9 brown B15 (0.5g) ~ Al (0.5g) Red-brown Red-brown 8.4 B16 : 1 g Grey-green Dull green9.15 B16 t0.5g) + Al (0.5g) Grey-ruby Dull ruby 10.6 B17 : 1 g Purple-grey Dull violet 17.65 B17 (0.5g) + Al (0.5g) Grey-red Grey-red 6.6 B18 : 1 g Silver grey Violet-grey11.2 B18 (0.5g) + Al (0.5g) Grey-red Grey-red 2.30 B19 : 1 g Grey-green GFey-tur- 19.9 quoise B19 (0.5g) + Al (0.5g) Grey-ruby Grey-ruby 7.74 B20 : 1 g Grey-ruby Grey-magenta 9.01 B20 (0.5g) + Al (0.5g) Grey-red-brown Red-brcwn 2.0 ~o B21 : 1 g Yellcw Orange-yellow 10.0 B21 (0.5g) + Al (0.5g) Light brown Light brown 7.3 Al (0.33 g) B10 (0.33 g) Brown-violet Brcwn-violet 5.0 B17 (0.33 g) Al (0,33 g) B1 (0.33 g) lerracotta Red-brown 2.0 B4 (0.33 g) Al (0.33 g) B1 (0.33 g) Red-brown Red-brown 3.9 B5 (0.33 g) .
Al ~0.33 g) B5 (0.33 g) Violet-brown Violet-brown 2.4 B8 (0.33 g) Al (0.25 g) ~2 (0.25 g) B5 (0.25 g) Grey-magenta Grey-ruby3.8 B9 (0.25 g)
Claims (4)
1. The use of a substantive dye (A) corresponding to formula I:
(I) in which R1 and R2 are hydrogen, C1-4 alkyl groups or C2-4 hydroxyalkyl groups and one of the moieties R3 to R7 is an -SO3H or a -COOH group and the other moietiesare hydrogen, chlorine, C1-4 alkyl groups, C1-4 alkoxy groups or groups of the formula -NR8R9, where R8 and R9 are hydrogen, C1-4 alkyl groups, C2-4 hydroxyalkyl groups or, together with the nitrogen atom, form a piperidine, morpholine, piperazine or pyrrolidine ring, or one of its water-soluble salts in hair-dyeing preparations containing at least one sec-ond substantive dye (B) of a different structure in a cosmetic carrier for improving the uniformity of hair dyeing, particularly the dyeing of hair damaged by reductive or oxi-dative hair treatments.
(I) in which R1 and R2 are hydrogen, C1-4 alkyl groups or C2-4 hydroxyalkyl groups and one of the moieties R3 to R7 is an -SO3H or a -COOH group and the other moietiesare hydrogen, chlorine, C1-4 alkyl groups, C1-4 alkoxy groups or groups of the formula -NR8R9, where R8 and R9 are hydrogen, C1-4 alkyl groups, C2-4 hydroxyalkyl groups or, together with the nitrogen atom, form a piperidine, morpholine, piperazine or pyrrolidine ring, or one of its water-soluble salts in hair-dyeing preparations containing at least one sec-ond substantive dye (B) of a different structure in a cosmetic carrier for improving the uniformity of hair dyeing, particularly the dyeing of hair damaged by reductive or oxi-dative hair treatments.
2. The use claimed in claim 1, characterized in that at least one second substan-tive dye (B) from the group of aromatic nitro compounds or anthraquinone compounds is present.
3. The use claimed in claim 1 or 2, characterized in that the substantive hair dyes are present in a total quantity of 0.05 to 5 % by weight, the ratio by weight of the dyes (A) corresponding to formula I to the other dyes (B) being 7:3 to 3:7.
4. The use claimed in claims 1 to 3, characterized in that the carrier is an emul-sion and contains 1 to 5 % by weight of a fatty alcohol containing 12 to 22 carbon atoms and 5 to 20 % by weight of an adduct of 5 to 20 moles of ethylene oxide with 1 mole of a linear terminal alkyl amine containing 12 to 22 carbon atoms, in each case based on the weight of the hair-dyeing preparation as a whole.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4110995A DE4110995A1 (en) | 1991-04-05 | 1991-04-05 | HAIR DRYER WITH DIRECT DYES |
| DEP4110995.3 | 1991-04-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2107796A1 true CA2107796A1 (en) | 1992-10-06 |
Family
ID=6428867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002107796A Abandoned CA2107796A1 (en) | 1991-04-05 | 1992-03-27 | Hair colorants with substantive dyes |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0578665B1 (en) |
| JP (1) | JPH06505984A (en) |
| KR (1) | KR100204550B1 (en) |
| AT (1) | ATE115853T1 (en) |
| CA (1) | CA2107796A1 (en) |
| DE (2) | DE4110995A1 (en) |
| DK (1) | DK0578665T3 (en) |
| ES (1) | ES2066609T3 (en) |
| FI (1) | FI104043B1 (en) |
| NO (1) | NO300953B1 (en) |
| PL (1) | PL170028B1 (en) |
| WO (1) | WO1992017156A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10042786C2 (en) | 2000-08-31 | 2002-10-24 | Wella Ag | N-heteroarylmethyl-p-phenylenediamine derivatives and hair dyes containing these compounds |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3537763A1 (en) * | 1985-10-24 | 1987-04-30 | Henkel Kgaa | HAIR DYE WITH DIRECT DRAWING NITRODIPHENYLAMINE DERIVATIVES |
| DE3706225A1 (en) * | 1987-02-26 | 1988-09-08 | Henkel Kgaa | HAIR DYE WITH DIRECT DRAWING NITRODIPHENYLAMINE DERIVATIVES |
-
1991
- 1991-04-05 DE DE4110995A patent/DE4110995A1/en not_active Withdrawn
-
1992
- 1992-03-27 DK DK92907054.8T patent/DK0578665T3/en active
- 1992-03-27 JP JP4506720A patent/JPH06505984A/en active Pending
- 1992-03-27 AT AT92907054T patent/ATE115853T1/en not_active IP Right Cessation
- 1992-03-27 PL PL92300775A patent/PL170028B1/en unknown
- 1992-03-27 CA CA002107796A patent/CA2107796A1/en not_active Abandoned
- 1992-03-27 ES ES92907054T patent/ES2066609T3/en not_active Expired - Lifetime
- 1992-03-27 EP EP92907054A patent/EP0578665B1/en not_active Expired - Lifetime
- 1992-03-27 WO PCT/EP1992/000681 patent/WO1992017156A1/en active IP Right Grant
- 1992-03-27 DE DE59201029T patent/DE59201029D1/en not_active Expired - Lifetime
- 1992-03-27 KR KR1019930702984A patent/KR100204550B1/en not_active IP Right Cessation
-
1993
- 1993-08-16 NO NO932907A patent/NO300953B1/en unknown
- 1993-10-01 FI FI934334A patent/FI104043B1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| FI104043B (en) | 1999-11-15 |
| EP0578665A1 (en) | 1994-01-19 |
| EP0578665B1 (en) | 1994-12-21 |
| FI934334A (en) | 1993-10-01 |
| JPH06505984A (en) | 1994-07-07 |
| FI104043B1 (en) | 1999-11-15 |
| NO932907L (en) | 1993-08-16 |
| NO300953B1 (en) | 1997-08-25 |
| FI934334A0 (en) | 1993-10-01 |
| PL170028B1 (en) | 1996-10-31 |
| NO932907D0 (en) | 1993-08-16 |
| DE59201029D1 (en) | 1995-02-02 |
| WO1992017156A1 (en) | 1992-10-15 |
| DE4110995A1 (en) | 1992-10-08 |
| ES2066609T3 (en) | 1995-03-01 |
| ATE115853T1 (en) | 1995-01-15 |
| KR100204550B1 (en) | 1999-06-15 |
| DK0578665T3 (en) | 1995-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3281386B2 (en) | Method for dyeing keratin-containing fibers | |
| US3578387A (en) | Dyeing hair while simultaneously lightening its color | |
| US5494489A (en) | Aqueous colorants for keratin fibers | |
| CN106659657B (en) | Improved decolorization of dyed keratin fibers | |
| EP0429855B1 (en) | Hair dye composition | |
| KR101364872B1 (en) | Hair dyeing composition | |
| JP5774052B2 (en) | Dyes containing thiol groups | |
| US4883656A (en) | Composition and method for the oxidative dyeing of hair | |
| US7429276B2 (en) | Composition for coloring of keratin fibers | |
| JP6791837B2 (en) | Improved decolorization of dyed keratin fibers | |
| KR100391696B1 (en) | Dyeing composition for keratinous fibres with direct cationic colouring agent and a quaternary ammonium salt | |
| MX2007016018A (en) | Cationic oligomeric azo dyes. | |
| ES2438222T3 (en) | Oxazine disulfide dyes | |
| US5032138A (en) | Chlorites as oxidants in hair coloring | |
| KR101322111B1 (en) | Hair dyeing composition | |
| ES2291359T3 (en) | METHOD FOR DYING FIBERS CONTAINING KERATIN. | |
| KR20050058415A (en) | Method of colouring porous material | |
| JP4511158B2 (en) | Rapid dyeing and decolorization method of human keratin fibers with direct dyes | |
| AU3431000A (en) | Phosphate-type tensides combined with hair conditioning agents in hair colouring compositions | |
| JPH04117322A (en) | Oxidative hair dye and hair dyeing method | |
| CA1100878A (en) | Methylenedioxy-benzene in oxydative dye | |
| JPS5967216A (en) | Hair dye | |
| JPH0662396B2 (en) | An oxidative hair dye comprising an emulsion dye carrier and an emulsion oxidant-containing composition | |
| EA002660B1 (en) | Dyes | |
| US20050204484A1 (en) | Hair colorants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |