DE2151789C3 - Process for the non-permanent coloring of human hair - Google Patents

Description

v j - "* - Tr

^ T

Dye at least one compound of the general formula

Y-Ar ₁ -N = Ar ₈ = X (i)

or a corresponding tautomeric form or a salt thereof is used, where in this formula Ar _x and Ar ₂ , which are identical or different, represent a phenyl or pyridyl chain which is optionally replaced by one or more amino, acylamino, hydroxy, alkoxy - Or alkyl groups or is substituted by one or more halogen atoms, Y is a hydroxyl group or a group of the formula

-N

(II) is

'represents in which Ri and R ₄ , which are identical or different, are a hydrogen atom, or an alkyl, hydroxyalkyl or aminoalkyl radical, the amine function of which is optionally substituted by an acetyl or mesyl radical, or R _{1 is} a carbamylmethyl and R ₈ represents an ethyl radical and X represents an oxygen atom or an imine or iminium group, which is characterized in that a dye solution is used which has been prepared from the solid, anhydrous, powdered dye immediately before use.

The basic structure of these compounds with the, rings Ar ₁ and Ar ₂ is as follows:

The indamines in the invention ^ Procedures that can be used include, for example

N - [(4'-dimethylamino) phenyl] -3-amino-

ö-methylbenzoquinone dimine hydrochloride,

N - [(4'-Amino-2'-methoxy-5'-methyl) -phenyl] -

2-aza-3-amino-benzoquinonediimine monoacetate,

the double chloride of zinc and

N- [4 '- (Ethyl- / 3-acetylaminoethyl) -amino-phenyl] -

3-amino-6-methoxy-benzoquinonediimine,

N - [(4'-Amino-2'-methoxy-5'-methyl) -phenyl] -

S-amino-o-methyl-benzoquinonediimine monoacetate

and the double chloride of zinc and

N- [4 '- (Ethyl - ^ - acetylamitioäthyI) -amino-phenyl] -

S-hydroxy-benzoquinommine-N '^' - diethyl-

iminium.

The indoanilines that can be used in the process of the invention include for example

N-t (4'-dimethylamino) phenyl] -2,6-dimethyl-

benzoquinone imine,

N - [(4'-dimethylarnino> -phenyl] -2,5-dimethyl-

benzoquinone imine,

N - [(4'-Amino-2'-methoxy-3 ', 5'-dimethyl) -phenyl] -

2,6-dimethyl-benzoquinone imine,

N - [(4'-Amino-2'-methoxy-3 ', 5'-dimethyl) -phenyl] -

2,5-dimethyl-benzcquinonixnine,

N - [(4'-D !! i! Ethyi3mmo) -plienyl] -3-amino-

6-methylbenzoquinone imine,

N - [(4'-Amino-2 '"methoxy) -phenyl] -3-amino-

6-methy 1-benzochi nonimin,

N "[(4'-Amino-2 '" methoxy «5'« methyl) -phenyl] -

S-acetylamino-G-methylbenzoquinone imine,

N - [(4'-Hydroxy) -phenyl) -3-amino-6-methoxy-

benzoquinonediimine,

N - [(4'-Hydroxy) -phenyl] -3-amino-benzo-

quinondumine,

N - [(4'-Amino-3'-chloro) -phenyl] -3-amino-

2,6-dimethyl-benzoquinone imine.

The indophenols that can be used in the process of the invention include for example

N - [(4'-hydroxy) phenyl] -2,6-dimethyl-

benzocbinonimine,

N - [(4'-hydroxy) phenyl] -2,5-dimethyl-

benzoquinone imine,

N - [(4'-Hydroxy) phenyl] -3-amino-6-methyl-

benzoquinone imine and

N - [(4'-Hydroxy-3 ', 5'-dimethyl) phenyl] -

2,6-dimethyl-benzoquinone imine.

According to the invention, the indamines, indoanilines

as and indophenol in powder or tablet form be used. For the sake of simplicity, in describing the present invention, the Designation "powder" for both the powder itself and also used for the tablets made from these powders. It is beneficial if the Powders are as finely divided as possible so that their dissolution is quick and easy. This powder are kept with complete exclusion of moisture until the moment of use.

The powders used in the process according to the invention can also contain other direct dyes, in particular azo dyes, anthraquinone dyes or aromatic nitro derivatives or also lyophilisates of oxidation products of oxidation bases or

of mixtures of couplers and oxidation bases. These lyophilisates are in German Patent application P 21 09 850 described.

The powders used in the process according to the invention can also be cosmetic resins, optical bleaches or other additives commonly used in hair cosmetics, such as thickeners, Wetting agents, surfactants, swelling agents, penetrants or sun filters, include.

The indamines, indoanilines or indophenols can simply be present in these powders in crystallized or in microencapsulated form. They can also be provided with a protective coating.
The dye or dyes are dissolved at the moment of use by mixing the powder with a suitably selected amount of an aqueous solution of a suitable composition.

The aqueous solution used can simply consist of; Water, if necessary with a suitable *

th amount of acid or base is added to bring the pH of the end product to a value between 4 and 10 to adjust. It can also contain one or more low molecular weight alcohols such as ethanol or isopropanol, dyeing auxiliaries such as butyl glycol

or benzyl alcohol, surfactants, sun filters such as benzylidene camphor, optical bleaches, Antioxidants such as butylated hydroxyanisole and / or commonly used in hair cosmetics

I.

Contain additives such as thickeners, wetting agents, swelling agents, penetrants or perfumes,

In a special embodiment of the five According to the method, the aqueous solution contains hydrogen peroxide in a proportion of 1 to 6% by weight, and the end product, which is produced immediately before application to the hair, represents a decolorizing colorant.

In another special embodiment of the invention In the process, the powder and / or the aqueous solution contain one or more cosmetic Resins, such as polyvinylpyrrolidone or crotonic acid ■ vinyl acetate mixed polymers, inylpyrrolidone / vinyl acetate copolymers or maleic anhydride / butyl vinyl ether copolymers in a proportion that this resin makes up 1 to 3% by weight of the end product. In this case! is the end product that is immediate Before applying to the hair is made a colored water wave lotion. ap

As mentioned earlier, the pH of the agent is that

immediately before application to the hair by mixing the powder and the aqueous solution

"is made, usually between 4 and 10, where

adjust this pH by adding an appropriate% amount of an acid or base to the aqueous solution 'receives. With some dyes, however, it is possible - - to work at lower pH values, up to 2.5.

The content of indamines, indoanilines or indophenols in the ready-to-use agent can "due to the great coloring power of these compounds! be extremely low. This content varies in general between 0.0005 and 2% by weight.

The dyeing of hair according to the method according to the invention is preferably carried out by simply applying the agent obtained by mixing the dye powder with the aqueous solution, and then twisting and / or drying the hair, without this before -t 'the Screw in or dry, rinsed or washed. In another embodiment of this method, it is possible to wash or hair before screwing or drying to flush _u.

■ _w The process has the advantage of being non-permanent dyes can achieve that with respect to reflections and transparency have the advantages of permanent stains that are realized with ioffen Oxydationsfart ", without the disadvantages. to bring the use of Oxydationsfarbstoffen ^f with it to contact the generally applied in the presence of hydrogen peroxide.

The method according to the invention also allows the use of long-term unstable ! Dispersions of indamines, indoanilines and indophenols in a higher concentration than the upper solubility limit of these dyes. This in combination with the possibility of using extremely low concentrations of these dyes, gives the additional advantage that a particularly wide range of nuances can be obtained. The following examples are intended to explain the present invention further, but not to limit it.

B is ρ ie 1 1 ^6s

A dye is prepared by mixing ⁸ cm of solution S containing the following compositions:

Powder P,

^^ pmyjpy] 3-ammO "6-methy l-bcnzoquinone ·

diimine hydrochloride 2.5 g

Polyvinylpyrrolidone, as much as necessary for 100 g

Solution S,

Vinyl pyrrolidone / vinyl acetate mixed

polymer 70/30 2 g

Triethanolamine as much as required

for pH 9

Water as much as necessary for. ,, 100 cm ³

This means of water wave lotion is applied to naturally black hair. After drying the hair has a very bright blue tinge.

Example 2

A coloring agent is prepared by mixing, at the time of use, 0.1 g of powder P ₂ and 25 cm ³ of solution S _{2 of the} following compositions:

Powder P ₂

Double chloride of zinc and
N - [[4 '- (Ethyl - /? - acetylaminoethyl) -amino] -phenyl] -3-hydroxy-benzoquinoneimine-N'.N'-diethyliminium ... 5.0 g N - [(4'-Hydroxy ) -phenyl] -

2,6-dimethyl-benzoquinoneimine 1.0 g

Polyvinylpyrrolidone as much as necessary for 100 g

Solution S ₁

Crotonic acid / vinyl acetate

Copolymer 90/10 2.0 g

Ethyl alcohol 50 g

Triethanolamine as much as required

for pH 7

Water as much as necessary for ... 100 cm ³

This agent is applied to naturally blonde hair as a water wave lotion. After drying the hair has a very nice ash reflex.

Example 3

A coloring agent is prepared by mixing, at the time of use, 0.1 g of a powder P ₃ and cm ^{3 of} a solution S _{3 of the} following compositions:

Powder P ₃

bar VOr% aCr rnSWvAXUwsig v ₉ vZ * s% vjüvS & üiVCrS P] UH double chloride of zinc and

N- [4 '- (ethyl - /? - acetylaniinoethyl) -amino-phenyl] -3-hydroxy-benzo- quinonimine-N ', N'-diethyliminium.

N - [(4'-Amino-2'-methoxy-3 ', 5'-dimethyl) -phenyl] -2,6-dimethyl-

benzoquinone imine

Vinyl pyrrolidone / vinyl acetate copolymer 70/30 as much as necessary for 100 g

• 1.0g

• 2.0 g

Solution S ₃

Vinyl pyrrolidone / vinyl acetate mixed

polymer 2.0 g

N-acetylethanolamine 0.15 g

Water as much as necessary for ... 100 cm ³

Citric acid as much as needed

for pH 5

This agent is applied to naturally white hair as a water wave lotion. After drying the hair has a very luminous ash-silver shimmer. They are also easy to comb.

Example 4 ^IS

A coloring agent is prepared by mixing, at the time of use, 0.1 g of powder P ₄ and cm ³ of solution S _{4 of the} following compositions:

Powder P ₄

N - [(4'-Amino-2'-methoxy-5'-methyl) -phenyl] -2-aza-3-amino-benzoquinone- * 5

diimine monoacetate 1.0 g

N - [(4'-Dimethylamino) -phenyl] -S-amino-ö-methyl-benzoquinonediimine-

hydrochloride 5.0 g

Vinyl pyrrolidone / vinyl acetate mixed 3 <> polymer 70/30 as much as required for 100 g

Solution S _s

Crotonic acid / vinyl acetate mixed

polymer 90/10 2.0 g

Ethanol, 50 g

Benzylidene camphor 0.2 g

Triethanolamine as much as required

for pH 6.5

Water as much as necessary for ... 100 g

This agent is applied as a water wave lotion to previously bleached and very light blonde hair on. After drying, the hair has a very bright and particularly beautiful beige-ash color Shine.

Example 6

A coloring agent is prepared by mixing 0.1 g of powder P ₆ and cm ³ of solution S _{6 of the} following compositions at the time of application:

Powder P ₈

N - [(4'-hydroxy) phenyl] -2,5-dimethyl-

benzoquinone imine 0.7 g

N - [(4'-Dimethylamino) phenyl] -

2,6-dimethyl-benzoquinoneimine 0.3 g

Vinyl pyrrolidone / vinyl acetate copolymer as much as necessary for 100 g

Solution S ₄

35 vinyl pyrrolidone / vinyl acetate mixed

polymer 70/30 2 g

Butyl Cellosolve 0.2 g

Ethanol 50 g

N-acetylethanolamine 0.15 g

Benzylidene camphor 0.2 g

Butyl hydroxyanisole 0.15 g

Water as much as necessary for ... 100 g

This agent is applied to naturally white hair as a water wave lotion. After drying the hair has a very shiny silver shimmer.

For example like this

A coloring agent is prepared by mixing, at the time of application, 0.1 g of a powder P ₆ and cm ^{3 of} a solution S _{5 of the} following compositions:

Powder P ₅

N - [(4'-Amino-2'-methoxy-5'-methyl) -phenyl] -3-acetylamino-6-methyl-

benzoquinone imine ₆ · ■ · ·· ^ O g

N- (4'-hydroxyphenyl) -3-amino-

6-methyl-benzoquinone imine 2.0 g

N-t (4'-hydroxy) phenyl] -2,6-dimethyl-

benzoquinone imine 1.5 g

Vinyl pyrrolidone / vinyl acetate copolymer 70/30 as much as

required for 100 g

Solution S "

Crotonic acid / vinyl acetate mixed

polymer 2.0 g

Ethanol 55 g

Hydrogen peroxide with 20 volumes as much as 5 g of orthophosphoric acid

required for pH 3

Water as much as necessary for 100 g

This decolorizing water wave lotion is applied to naturally light brown hair. After screwing in and drying, the hair is slightly lightened and also has a very luminous and very transparent mother-of-pearl shimmer.

Example 7

A coloring agent is prepared by mixing 0.1 g of powder P ₇ and 25 cm ³ of solution S _{7 of the} following compositions at the time of application:

60 powder P ₇

N - [(4'-Amino-2'-methoxy) -phenyl] -3-amino-6-methyl-benzoquinoneimine .. 0.3 g of N - [(4'-Amino-2'-methoxy-3 ', 5'-dimethyl) -phenyl] -2,5-dimethyl-

benzoquinone imine 0.6 g

Vinyl pyrrolidone / vinyl acetate mixed polymer 70/30 as much as

required for 100 g

709 616/176

Solution S ₇

Vinyl pyrrolidone vinyl acetate mixed

polymer 70/30 2.0 g

Ethanol 50 g

Optical brightener for keratin fibers 0.060 g Triethanolamine as much as required

for pH 7

Water as much as necessary for 100 g

This agent is applied as a water wave lotion to blonde hair with freshly bleached strands. After drying, a particularly beautiful and luminous ash-mother-of-pearl shimmer is observed.

Example 8

A coloring agent is prepared by mixing at the time of application 25 cm ³ of the solution S ₂ described in Example 2 and 0.1 g of a powder P ₈ ^ of the following composition:

Powder P ₈

N - [(4'-Dimethylamino) phenyl] -3-amino-6-methyl-benzoquinone imine .. 8.0 g of N - [(4'-Dimethylamino) phenyl] -

2,5-dimethyl-benzoquinoneimine 1.0 g

Vinyl pyrrolidone / vinyl acetate copolymer 70/30 as much as necessary for 100 g

Have nen 10 the hair has a very bright mahogany VioIett Shimmer and easy to comb.

Example 10

A coloring agent is prepared by mixing 25 cm ^{3 of} the solution S ₆ according to Example 5 and 0.1 g of a powder P _{10 of the} following composition at the time of application:

Powder P ₁₀ . ; - _: ,.

N - [(4'-Amino-2'-methoxy-5'-methyl) -phenyl] -3-amino-6-methyl-

benzoquinonediimine monoacetate 3 g

N - [(4'-Hydroxy-3 ', 5'-dimethyl) -phenyl] -2,6-dimethyI-benzoquinoneimine .. 10 g vinylpyrrolidone / vinyl acetate copolymer 70/30 as much as
required for 100 g

This agent is applied as a water wave lotion to previously bleached and blonde-dyed hair. To When dry, the hair has a very bright beige-mother-of-pearl shade.

Example 11

A coloring agent is prepared by mixing at the time of application 25 cm ^{3 of} the solution S ₆ according to Example 5 and 0.015 g of a powder P _{n of the} following composition:

This agent is applied as a water wave lotion to hair that has previously been dyed light brown. After When drying, the hair has a very luminous ash reflex.

Example 9

A coloring agent is prepared by mixing, at the time of use, 0.15 g of a solid P ₉ in the form of a tablet and 25 cm ^{3 of} a solution S _{0 of the} following compositions:

Powder P _n

N - [(4'-Hydroxy) phenyl] -

2,5-dimethyl-benzoquinoneimine 8.0 g

4-methyl-8-di- / S-hydroxyethylaminomorpholino- [2,3-b] -phenoxazonium bromide 20 g

You apply this agent as a water wave lotion bleached and dark brown hair. After drying, you can see a very luminous one

Tablet P ₀

N - [(4'-hydroxy) phenyl] -3-amino-

6-methyl-benzoquinonediimine 8.0 g

Double chloride of zinc and

N - [[4 '- (ethyl- / 9-acetylaminoethyl) -amino] -phenyl] -3-amino-6-methoxy-

benzoquinonediimine 4.0 g

Vinyl pyrrolidone / vinyl acetate copolymer 70/30 as much as

required for 100 g

Solution S ₀

Crotonic acid / vinyl acetate mixed

polymer 90/10 2.0 g

Ethanol 50 g

Benzylidene camphor 0.2 g

Butyl hydroxyanisole 0.1 g

Triethanolarain as much as required

for pH 7

Water as much as necessary for, ... 100 cm ³

This agent is applied to chestnut-colored hair as a water wave lotion. After the dry A ~ _A U «~ a ~ .. Γ \! _ TT f-lDWXitIlGÄ \ JVZ Π

easy to comb.

45

55

Example 12

A coloring agent is prepared by mixing 0.2 g of powder P ₁₃ and 30 cm ³ of solution S _{12 of the} following compositions at the time of application:

Powder P ₁₂ '"'

Colored lyophilisate, prepared as described below (according to *

P 21 09 850) 99.8 g

N-t (4'-hydroxy) phenyl] -3-amino-

6-niethyl-benzoquinonediimine 0.2 g \

ö> Solution S ₁₂ ''

Hydroxyethyl cellulose, water-soluble 0.4 g vinylpyrrolidone / vinyl acetate mixed "■ '

polymer; ... 0.3 g

Ethanol 10 g

Citric acid as much as required ■

for pH 4.5

V / ater as much as necessary for .... * 100 g

You use this agent as a rinse on freshly bleached hair, which you then insert. To When dry, the hair has a light blonde shade with a mother-of-pearl shimmer.

The above lyophilizate is produced as follows:

The following solution is 7 mm thick and is poured into "penicillin" flasks for 20 minutes at around 20 ° C leave the open air:

2,4-diaminoanisole hydrochloride 4.22 g

(0.02MoI)

Polypeptide LSN anhydrous 5 g

Ammonia with 22 ° Be 5 cm ³

Hydrogen peroxide with 20 volumes of 50 cm ³
fill up with water to 100 cm ³

according to Example 2 and 0.1 g of a powder P _{16 of the} following composition:

Powder P _{16 s}

N - [(4'-hydroxy) phenyl] -3-amino-

6-methyl-benzoquinone imine 10 g

l-methylamino-4-y-aminopropyl-

amino-anthraquinone 5.0 g

Vinyl pyrrolidone / vinyl acetate copolymer 70/30 as much as

required for 100 g

This agent is applied as a water wave lotion to previously bleached and light brown colored hair. After drying, a very luminous ash-mother-of-pearl cutter is observed.

The reaction is cooled to - stopped 60 ⁰ C, then the reaction mixture in a Lyophilizer at a temperature of -40 ao ⁰ C and a pressure of 0.05 mm Hg is lyophilized for 24 hours, followed by desorption at +25 ⁰ C connects.

When the lyophilizate is chromatographed on a layer of silicon dioxide, no 2,4-diaminoanisole is obtained detected.

Example 13

A coloring agent is prepared by mixing 0.05 g of the powder according to Example 1 and 30 cm ^{3 of} a solution S _{13 of the} following composition at the time of application:

Solution S ₁₃

Hydroxyethyl cellulose 0.4 g

Citric acid as much as needed

for pH 4

Water as much as necessary for 100 cm ³

One uses this remedy as a rinse for natural dark brown hair with some white hair. After drying it is observed that these white hairs are camouflaged by a very luminous, slightly ashy shade.

45 Example 14

A coloring agent is prepared by mixing at the time of application 25 cm ^{3 of} the solution S ₄ according to Example 4 and 0.1 g of a powder P _{14 of the} following composition:

Powder P ₁₄

N - [(4'-Dimethylamino) phenyl] -

2,6-dimethyl-benzoquinoneimine 10.0 g

Nitro-p-phenylenediamine 5.0 g

Vinyl pyrrolidone / vinyl acetate mixed

polymerisat 70/30 as much as

required for 100 g

60

This agent is applied to nut-brown colored hair as a water wave lotion. After drying the hair has a slightly purple and very bright copper shimmer.

\ Example 15 ^6s

A colorant is prepared by adding 25 cm ^{3 of} the solution S ₁

Example 16

A coloring agent is prepared by mixing 50 cm ^{3 of} the solution S ₁₁ according to Example 12 and 0.00045 g of a powder P _{1 with the} following composition at the time of application:

Powder P _H

N - [(4'-hydroxy) phenyl] -3-amino-

6-methyl-benzoquinone imine 98 g

N - [(4'-Amino-2'-methoxy-3 ', 5'-dimethyl) -phenyl] -2,6-dimethylbenzoquinoneimine 2 g

This agent is applied to light-colored, freshly bleached hair. After the water wave and drying the hair has a very transparent and very luminous, very light golden blonde shade with a mother-of-pearl shimmer.

Example 17

A coloring agent is produced by mixing 0.45 g of powder P ₁₂ according to Example 12 and 25 cm ³ of solution S ₄ according to Example 4 at the time of application.

This solution is applied as a water wave lotion bleached and medium brown hair. After the water wave and drying, the hair shows which are shiny and easy to comb, a particularly uniform chestnut-golden brown shade.

Example 18

A coloring agent is prepared by mixing 0.02 g of powder P ₄ according to Example 4 and 25 cm 'of a solution S _{18 of the} following composition at the time of application:

Solution S ₁₈

Hydroxyethyl cellulose 0.3 g

Condensation product of coconut

amine with 5 moles of ethylene oxide 0.1 g

Citric acid as much as needed

for ...., pH3.5

Water as much as necessary for 100 cm ³

This agent is used as a conditioner for bleached and very light blonde hair. After When dry, the hair has an extraordinarily luminous and transparent very 'light ash blonde Nuance.

Example 19

A coloring agent is prepared by mixing 0.4 g of a powder P ₁₂ , described in Example 12, and 50 g of a gelled solution S _{19 of the} following composition at the time of application:

Solution p ₁₉

Crotonic acid / vinyl acetate mixed

polymer 90/10 2 g

Ethyl alcohol 20 g

Carboxyvinyl polymer with very

high molecular weight 0.5 g

Triethanolamine 0.8 g

Γ Water as much as necessary for 100 g

This gel is applied to dark blonde hair that contains 10% white hair. After Drying shows the hair a uniform, golden chestnut brown shade.

Example 20

A coloring agent is prepared by mixing 0.10 g of a P ₂₀ powder of the following composition and 25 cm ^{3 of} the S ₂ solution according to Example 2 at the time of application.

Powder P ₂₀

N - [(4'-Hydroxy) -phenyI] -2,6-di-

methyl benzoquinone imine 9.0 g

N - [(4'-hydroxy) phenyl] -3-amino-

6-methyl-benzoquinone imine 4.0 g

Butyl hydroxyanisole 25 g

Optical brightener for keratin fibers 15 g vinyl pyrrolidone / vinyl acetate copolymer 70/30 as much as
required for 100 g

This agent is applied as a water wave lotion to bleached and golden brown hair. To When it dries, the hair has a very shiny look.

Example 21

A coloring agent is prepared by mixing, at the time of use, 0.0003 g of a powder Ρ _2ί and 25 cm ^{s of} a solution S _{11 of the} following compositions:

Example 22

A colored water wave lotion is produced by mixing 0.038 g of a powder P _{22 of the} following composition and 25 cm ^{3 of} the solution S ₂ according to Example 2 at the time of application:

Powder P ₂₂

Metal-containing dye »acid

red 184 "C.I. No. 15 685 94.8g

N - [(4'-Dimethylamino) phenyl] -S-amino-O-methyl-benzoquinonediimine hydrochloride 5.2 g

Applied to blonde hair, this water wave lotion gives the hair a particularly beautiful pearly blonde Nuance.

Example 23

A colored Wasserwelloibai h "is made by mixing 0.12 g of d.io.powder P ₂₃ and 25 cm ^{3 of} a solution S _{23 of the} following compositions at the time of application:

Powder P ₂₃

N - [(4'-Amino-2'-methoxy-3 ' , u -dimethyl) -phenyl] -2,6-dimethyl-

benzoquinone imine Ig

Vinyl pyrrolidone / vinyl acetate copolymer 70/30 as much as

required for 100 g

Solution S ₂₃

Ethanol % g

Water as much as necessary for 100 g

Powder P ₂₁

N - [(4'-Dimethylamino) -phenyl] -S-amino-o-methyl-benzoquinone-

diimine hydrochloride 20 g

N - [(4'-Hydroxy) phenyl] -3-amino-6-methyl-benzoquinone imine 80 g

Solution S ₁₁

Carboxymethyl cellulose 0.2 g

Triethanolamine as much as required

for pH 9

Water as much as necessary for 100 cm ^a

,. This means is applied to very light blonde hair on. After drying, the hair has a very bright emerald green sheen.

This lotion is applied to graying hair. After drying, the hair is white the hair has a particularly shiny and beautiful shimmer of silver.

Example 24

A coloring agent is prepared by mixing at the time of application 25 cm ^{3 of} the solution S ₂ according to Example 2 and 0.1 g of a powder P _{24 of the} following composition:

Powder P ₂₄

N - [(4'-Hydroxy) -phenyl] -2,6-dimethyl-benzoquinoneimine 2 g

N - [(4'-Dimethylamino) phenyl] -

2,5-dimethyl-benzoquinoneimine 0.5 g

N - [(4'-Dimethylamino) -phenylJ-

2,6-dimethyl-benzoquinoneimine 0.3 g

Vinyl pyrrolidone / vinyl acetate mixed

polymerisat 70/30 as much as

required for 100 g

This agent is applied to bleached and blond-dyed hair as a water wave lotion. After When dry, the hair has a very shiny mother-of-pearl shimmer.

Example 25

To set a colorant is prepared by mixing at the time of application of the solution ^a 25cm S ₀ according to Example 5 and 0.1 g of powder P "mixes of the following composition:

Powder P ₂₆

N - [(4'-Hydroxy) -phenyl] -2,6-dimethy | -benzoquinonimiri . ,,, N- [4'-Hydroxy) phenyl] -3-amino-

benzoquinonediimine

N - [(4'-Dimethylamino) -phenyI] -2,6-dimethyl-benzocbinonimine ,,,, vinylpyrrolidone / vinyl acetate copolymer 70/30 as much as
required for

Solution page ₂₈

■ ig . 2g

.. 0.5 g

, 100 g

Butyl cellosolve, 8 g

Propylene glycol, 8 g

Polyethylene from nonylphenol

and 4 moles of Ethyicnoxyd 22 g

Polyethoxyether of nonylphenol

and 9 moles of ethylene oxide 22 g

Water as much as necessary for - 100 g

IO

This means is brought to discolored and medium brown colored ones Hair up. After drying, the hair has a particularly beautiful mahogany shimmer,

Example 26

If 50 g of water are added to 50 g of the solution thus prepared, a gel is obtained which is decolorized Brings up hair. After 30 minutes the hair is rinsed and dried. One receives a very light beige shade,

Example 29

"> You make a colorant by going to Man making a water wave lotion by

Time of application 25 cm ^{3 of} the solution S ₂ 20 immediately before application 0.100 g of a PuI-

according to Example 2 and 0.075 g of a powder P ₂₀ fol- vers P ₂₀ and 25 cm ^{3 of} a solution S _{29 of the} following

gender mixes composition: mixes compositions:

Powder P ₂₀

as N - [(4'-amino-3 ', 5'-dimethyl) -

phenyl] -3-acetylamino-6-methyl-

benzoquinone imine 3 g

N - [(4'-Amino-2'-methoxy-3 ', 5'-dimethyl) -phenyl] -2,5-dimethyl-

benzoquinone imine Ig

N - [(4'-hydroxy) phenyl] -3-amino-

6-methyl-benzoquinone imine 1.5 g

Polyvinylpyrrolidone as much as

required for 100 g

Solution S ₂₀

Crotonic acid / vinyl acetate mixed

rjlolymensat 90/10 2.0 g

Ethanol 50 cm ³

Triethanolamine as much as required

for pH 7

Water as much as necessary for ... 100 cm ³

This product is applied to natural hair that has a large percentage of white hair. After drying, the hair has a very shiny and particularly beautiful ash-silver shimmer.

Example 30

A water wave lotion is produced by mixing 0.100 g of a powder P ₃₀ and 25 cm ^{3 of} a solution S _{30 of the} following compositions immediately before use:

Powder P ₂₆

N - [(4'-Hydroxy) phenyl] -

2,6-dimethyl-benzoquinoneimine 2 g

N - [(4'-Dimethylamino) phenyl] -S-amino-o-methyl-benzoquinonediimine hydrochloride 0.1 g

If you apply this water wave lotion to bleached and very light blonde colored hair, it gives they have a very pretty shimmer of gold and mother-of-pearl.

Example 27

A coloring agent is prepared by mixing at the time of application 25 cm ^{3 of} the solution S ₄ according to Example 4 and 0.12 g of a powder P _{27 of the} following composition:

powder

N - [(4'-Amino-3'-chloro) -phenyl] -S-amino ^ .ö-dimethyl-benzoquinone-

imin 2 g

Vinyl pyrrolidone / vinyl acetate copolymer 70/30 as much as

required for 100 g

If you apply this agent as a water wave lotion Bleached and blonde-dyed hair on, it gives it a pretty, very shiny mother-of-pearl shimmer.

Example 28

A coloring agent is prepared by mixing, at the time of application, 50 cm ^{3 of} a solution S ₂₈ and 0.03 g of a powder P _{28 of the} following compositions:

Powder P,

N - [(4'-Hydroxy) phenyl] -

2,6-dimethyl-benzoquinoneimine 67 g

N - [(4'-Dimethylamino) phenyl] -2,5-dimethyl-benzoquinone imine 33 g

Powder P ₃₀

N - [(4'-Hydroxy) phenyl] -

2,6-dimethyl-benzoquinoneimine 22 g

N - [(4'-Hydroxy) phenyl] -3-acetylamino-2,6-dimethyl-benzoquinoneimine 11 g N - [(4'-Hydroxy) -phenyl] -3-amino-

6-methyl-benzoquinoneimine 11g

N - [[N-4 '- (ethyl-carbamylmethyl) -amino-2'-methyl] -phenyl] -3-amino-

6-methyl-benzoquinone imine 0.5 g

Polyvinylpyrrolidone as much as

required for iüö g

709 615/176

21 5

Solution S ₃₀

Vinyl pyrrolidone / vinyl acetate mixed

polymer 70/30 2 g

Ethanol 50 cm ³

N-acetylethanolamine ,,,,,, ,, 0.15 g

Benzylidene-Kampfcr ,,,, 0.2 g

Butylhydroxyanisole , .. ,,,,. 0.15 g

Triethanolamine as much as

required for pH 7

Water as much as necessary for ,,,, 100 cm ³

This agent is applied to hair that has been dyed mahogany brown. After drying, they have Hair a much stronger and very beautiful mahogany copper shimmer,

Example 31

A water wave lotion is produced by mixing 0.100 g of a powder P ₃₁ and 25 cm ^{3 of} a solution S ₃ J of the following compositions immediately before use:

Powder P ₃ ,

N - [(4'-Hydroxy-2 ', 6'-dirnethyl) -phenyl] -2,6-dimethyl-benzoquinoneimine 5 g polyvinylpyrrolidone as much as necessary for 100 g

Solution S ₃ i

Crotonic acid / vinyl acetate mixed

polymer 90/10 2.0 g

Ethyl alcohol 40 cm ³

Triethanolamine as much as required

for pH 8

Water as much as necessary for 100 cm ³

// $

M "n applies this agent to dyed blonde hair. After drying, the hair has a very shining and very beautiful ash blonde nuancc,

Example 33

A water wave lotion is made by mixing 0.130 g of a powdered powder and 25 cm ^{3 of} a solution S _{33 of the} following compositions at the time of application:

Powder P ₃₃

N - [(4'-hydroxy) phenyl] -3-amino-

fi-methyl-benzoquinonediimine 3.8 g

N - [(4'-Dimethylamino) -phenyl] -S-acetylamino-o-methyl-benzoquinoß-

imin .., 1 »5 g

Polyvinylpyrrolidone as much as

required for 100 g

Solution S ₃₃

Crotonic acid / vinyl acetate mixed

polymer 90/10 2 g

Ethanol 50 cm ³

Benzylidene camphor 0.2 g

Triethanolamine as much as

required for , pH 7

Water as much as necessary for - 100 cm ³

This agent is applied to light brown colored hair. After drying, the hair has a very beautiful purple shimmer.

This agent is applied to freshly bleached and very light blonde-dyed hair. After drying the hair shows a particularly beautiful, very light blonde, slightly pearly shade.

Example 32

A water wave lotion is produced by mixing 0.100 g of a powder P ₃₂ and 25 cm ^{3 of} a solution S _{38 of the} following compositions immediately before use:

Powder P ₃₂

N - [(4'-Am! No-3 ', 5'-d! Methyl) -phenyl] -

2,6-dimethyl-benzoquinoneimine 4 g

N - [(4'-hydroxy) phenyl] -3-amino-

6-methyl-benzoquinone imine Ig

Polyvinylpyrrolidone as much as

required for 100 g

Solution p ₃₂

! Crotonic acid / vinyl acetate copolymer 90/10 2.0 g

Ethanol 50 cm ³

Benzylidene-kampfcr 0.2 g

Butyl hydroxyanisole 0.1 g

Triethanolamine as much as

required for pH 6.5

Water as much as necessary for 100 cm ³

Example 34

One puts one. Water roll lotion by mixing 0.120 g of a powder P ₃₄ and 25 cm ^{3 of} a solution S _{34 of the} following compositions immediately before use:

Powder P ₃₁

N - [(4'-hydroxy) phenyl] -3-amino-

6-methyl-benzoquinone imine 4.16 g

N - [(4'-Amino-2 ', 5'-dimethyl) -phenyl] -

2,6-dimethyl-benzoquinone imine 0.83 g

Polyvinylpyrrolidone as much as necessary for 100 g

Solution S ₃₄

Polyvinylpyrrolidone 1.5 g

Ethyl alcohol 50 cm ³

Butyl hydroxyanisole 0.1 g

Triethanolamine as much as

required for pH 7

Water as much as necessary for 100 cm ³

You bring this remedy to naturally blond ' Hair up. After drying, the hair has a slight ash-mother-of-pearl shimmer.

Example 35

A coloring agent is prepared by mixing 0.200 g of a powder P ₃₅ and 25 cm ^{8 of} a solution S _{35 of the} following compositions before use:

Powder P ₃₆

N - ((4'-Amino) -phenyIH, 6-dimethyl "

benzocbinonimine 5 g

Polyvinylpyrrolidone as much as necessary for 100 g

Solution p ₃₆

Hydrogen peroxide with?, 0 volumes of 5 cm ³ orthophosphoric acid as much as

required for pH 3

Ethyl alcohol 50 cm ³

Water as much as necessary for 100 cm ³

'This remedy is applied naturally as a conditioner light brown hair aaf. After drying are the

-.Hair lightened and also have one "very beautiful mother-of-pearl shimmer.

Example 36

A water wave lotion is prepared by mixing 0.018 g of a powder P _M and 25 cm ^{3 of} a solution S _{36 of the} following compositions immediately before use:

Powder P ₃ ,

N - [(4'-Amino-3'-methyl) -phenyl] -

2,6-dimethyl-benzoquinoneimine 10 g

N - [(4'-Hydroxy-2 \ 6'-dimethyl) -phenyl] -2,6-dimethyl-benzoquinoneimine 5 g of N - [(4'-hydroxy) phenyl] -3-acetylamino-2,6-dimethyl-benzoquinoneimine 3 g

Solution S ₃ ,

Crotonic acid / vinyl acetate mixed

polymer 90/10 2 g

Ethyl alcohol 50 cm »

Benzylidene camphor 0.2 g

Triethanolamine as much as

required for pH 8.5

Water as much as necessary for 100 cm ³

This agent is applied to hair that contains 90% white hair. One feels very much luminous blgulie ashy shade,

Example 38

Prepare a Wasserwellotion prepared by prior to application to 0.100 g of a powder directly P ₃₈ and 25cm ^a solution of a mixed S ₃₈ to the following compositions:

Powder P ₃₈

N - [(4'-Hydroxy) -phenylI-2,6-dimethyl-benzoquinoneimine 19 g

N- [(4'-Hydroxy) -phenylI-3-acetylamino-2,6-dimethyl-benzoquinoneimine 8 g of N - [(4'-hydroxy) phenyl] -3-amino-

6-methyl-benzoquinone imine 7 g

N - [(4'-Ainino-3 ', S'-dimethyl) -pheny! J-S-acetylamino-o-methyl-benzoquinone-

imin 4 g

Polyvinylpyrrolidone 63 g

Solution page ₃₈

as crotonic acid / vinyl acetate mixed

polymer 90/10 1.5 g

Ethyl alcohol 50 cm ³

Triethanolamine as much as

required for pH 7.5

Water as much as necessary for 100 cm ³

This agent is applied to hair that has been dyed medium brown. After drying, the hair shows a especially uniform and luminous mshagoni brown Nuance.

B e i s ρ i e 1 39

A water wave lotion is produced by mixing 0.100 g of a PuI-VersP ₃₉ and 100 cm ^{3 of} a solution S _{39 of the} following compositions immediately before use:

This product is applied to natural hair that contains 30% white hair. After drying the white hair has a bluish ash shimmer and is camouflaged in a special way.

B e i s ρ i e 1 37

A water wave lotion is produced by mixing 0.150 g of a powder Pg and 25 cm ^{3 of} a solution S _{37 of the} following compositions immediately before use:

Powder P ₃₇

N - [(4'-Amino-3'-methyl-6'-methoxy) -phenyl] -2,6-dimethyl-benzoquinoneimine 3.3 g of N - [(4'-Ammo-3 ', 5'-dimethyl) -phenyl] -3-amino-6-methyl-benzoquinoneimine .. 1.65 g of polyvinylpyrrolidone as much as

required for 100 g

Solution p ₃₇

Crotonic acid / vinyl acetate mixed

polymer 90/10 20 g

Ethyl alcohol 50 cm ³

Triethanolamine as much as

required for pH 6

Water as much as necessary for 100 cm ³

Powder P ₃₈

N - [(4'-Dimethylamino) phenyl] -S-aniino-o-methyl-benzoquinoneimine ..8g N - [(4'-Hydroxy> phenyl] -2,5-dimethyl-

benzoquinone imine 8 g

N - [(2 ', 4'-Diamino-5'-methyl) -phenyl] -

2-chloro-benzoquinone imine 12 g

Polyvinylpyrrolidone as much as necessary for 100 g

Solution S ₃ p

Crotonic acid / vinyl acetate mixed

polymer 90/10 1.5 g

Ethyl alcohol 50 cm ³

Triethanolamine as much as

required for pH 7.5

Water as much as necessary for 100 cm ^s

This agent is applied to freshly bleached hair. After drying, the hair has a very uniform and particularly beautiful shade of beige.

Example 40

A dye is produced by adding Ö, ÖÖ2 g of a Fuiver F ₁₀ and 25 cm ³

a solution S ₄₀ mixes the following compositions:

Powder P ₄₀

N - [(4 '»hydroxy) phenyl] -2,3-dimethyl-

benzoquinone imine 50 g

N- [tN-4 '- (ethyl- / 3-mesylaminoethyl) -amino-2'-methyl] -phenyl] -2,5-dimethyl-bijnzoquinoneimine 50 g

Solution S ₄₀

Ethyl alcohol 30 cm ³

Butyl cellosolve 10 cm ³

Triethanolamine as much as

required for pH 7

Water as much as necessary for ... 100 cm ³

This agent is applied to light blonde hair as a conditioner. After drying it has -Hair a very nice light ash blonde shade.

Example 41

A water wave lotion is produced by mixing 0.025 g of a powder P ₄₁ and cm ^{3 of} a solution S _{41 of the} following compositions before use:

Powder P ₄₁

N - [[4 '- (ethyl - /? - mesylaminoethyl> amino-2'-methyl] -phenyl] -

2,5-dimethyl-benzoquinoneimine 8 g

N - [(4 -'-Amino-2 ' ₎ 5'-dimethyl) -phenyl] -

2,6-dimethyl-benzoquinoneimine 20 g

Polyvinylpyrrolidone as much as

required for 100 g

Solution p ₄₁

Polyvinylpyrrolidone / vinyl acetate

Copolymer 2.0 g

Ethyl alcohol 50 cm ³

Ethyl cellosolve 5 cm ³

Triethanolamine as much as

required for pH 7

Water as much as necessary for 100 cm ³

This agent is applied to hair that has been dyed ash blonde. After drying, the hair is still m? very ash-colored. The hair is beautiful and shiny.

Example 42

A dye is provided! by mixing 25 cm ^{p of} the solution S ₈₆ gcmilß s Example 35 and 0.010 g of a powder P _{42 of the} following composition immediately before use:

Powder P ₄₂

N »[(4'-Hydroxy) phenyl] -

2,3-dimethyl-benzoquinone imine ,,,,,, 50g N - [(4'-Hydroxy-2 ', 6'-dimethyl) -phenyl] -2,6-dimethyl-benzoquinoneimine 50 g

This solution is applied as a conditioner to naturally dark blonde hair. Also after drying are the hair is lightened and also has a beautiful mother-of-pearl shimmer.

B e ί s ρ i e I 43

A water wave lotion is produced by mixing 0.100 g of a powder P ₄₃ and 25 cm ^{3 of} a solution S _{43 of the} following compositions immediately before use:

Powder P ₄₃

N - [(4'-Hydroxy-2 ', 6'-dimethyl) -phenyl] -2,6-dimethyl-benzoquinoneimine 4 g N - [(4'-Amino-3'-methyl) -phenyl] -

2,6-dimethyl-benzoquinoneimine 0.4 g

N - [(2 ', 4'-Diamino-5'-methyl) -phenyl] -

2-chloro-benzoquinone imine 0.4 g

Polyvinylpyrrolidone as much as necessary for 100 g

Solution p ₄₃

Polyvinyl pyrrolidone 2.0 g

Ethyl alcohol 40 cm ³

Butyl cellosolve 2 cm ³

Triethanolamine as much as

required for pH 7

Water as much as necessary for 100 cm ³

Applied to freshly bleached hair, this lotion gives the hair a particularly beautiful look Platinum shade.

Claims (6)

1 2 Lyophilisate of the product found in the Claims; Oxidation of an oxidation base or a mixture of coupler and oxidation base results, 1. contains a process for non-permanent dyeing, of human hair that is; an aqueous S 7. Process according to Claims X to 6, characterized "Dye solution, which has a pH value between that which is usually found in the hair 2.5 and 10 and which additives, if any, used in cosmetics »m anhydrous . one or more alcohols with a low dye powder are contained, Molecular weight usually for hair coloring, 8, process according to claims 1 to 7, characterized in that " direct dyes, dyeing auxiliaries used, ίο characterized in that a dye dispersion, surface-active agents, sun filters, optical ones are used, Bleaching agents, antioxidants and / or conventional additives used in hair cosmetics contains, applies to the hair and, given- «_—- if after subsequent washing or rinsing, 15
the hair twists and / or dries and with the
as a dye at least one compound of
J general formula γ _ Ar _ w - Ar - ν m There are two known types of hair coloring, . ι λγι in - λγ ₂ - λ w _{ao dje due to the nature of} the dyes used "■. Or a corresponding tautomeric form or and the result that can be achieved with it "A salt of it is used, being in this formula differentiate the permanent coloring and the not - Ar, and Ar ₂ , which are the same or different, have a permanent coloration, The permanent coloration that Represent phenyl or pyridyl nucleus, which is characterized in that it is a very good one if necessary by one or more amino, 25 wash resistance and repeated shampoo Acylamino, hydroxy, alkoxy or alkyl groups survive kidney, made with the help of dyes, , or by one or more halogen atoms sub- the oxidation dyes are called, d. h, color Y is a hydroxyl group or a loose compound that is under the action of a '' Group of the formula oxidizing agent develop a color in situ, 30 The non-permanent color is not so great / ^{Rl wash} resistance, but allows easy - n '(II) change in hair color. It takes place with \ _R help of direct dyes that are too very different ⁸ classes belong, like the azo dyes, the anthra represents, wherein R ₁ and R ₂ , the same or ver 35 quinone dyes or the aromatic Nitroderi- are different, a hydrogen atom, or a vaten. The up to now to achieve this not permanent Alkyl, hydroxyalkyl or aminoalkyl radical, the adhesive dyeings of which have the direct dyes used , Amine function optionally through an acetyl the disadvantage that it has nuances without transparency 'or mesyl radical is substituted, mean or R ₁ and result without reflections, which is therefore in comparison with - a carbamylmethyl and R ₂ an ethyl radical 40 the less obtained with oxidation dyes, represents and X represents an oxygen atom or an "attractive": 1min or iminium group means, thereby In the older German patent applications geke η η ζ eich η et that one a dye 20 28 846, 20 31 008, 21 17 363, 21 33 900, 2146 634, .-. solution used immediately before the 2146 635 and 2146 636 are new indoaniline, inddung from the solid, anhydrous, powdered amine and indophenol dyes used here Dye has been produced. The type and hair coloring agent made from it is described 2. The method according to claim 1, characterized in that in the usual manner, d, h. in the form of a solution, that the solid, anhydrous, powders, creams and gels are sold, shaped dye as a finely divided powder, as in addition, a certain number of Tablet form agglomerated powder, in simple 5 ° dyes from the indoaniline family, the crystallized form or in the form of micro-indamine and the indophenols known, their application encapsulated or coated crystals. dung for dyeing hair so far in particular 3. The method according to claims 1 and 2, because of the lack of stability of these dyes characterized in that the aqueous dye in solution could not be used commercially, solution of hydrogen peroxide in an amount of 55 It was now after the family of this ver-1 contains up to 6% by weight. bindings has been extended to a method of not 4. The method according to claims 1 and 2, found there- permanent dyeing of human hair, characterized in that the aqueous dye in which one is an aqueous dye solution which solution and / or the anhydrous dye has a ^ pH between 2.5 and 10 and powders contain at least one cosmetic resin, which may contain one or more alcohols or contains, with low molecular weight usually for 5. The method according to claims 1 to 4, characterized in that hair coloring used direct dyes, dye marked, that the aqueous dye solution auxiliaries, surface-active agents, sun filters, contains between 0.0005 and 2% by weight of dye. optical bleaches, antioxidants and / or 6. The method according to claims 1 to 5, characterized in 65 conventional additives used in hair cosmetics characterized in that the anhydrous dye contains, applies to the hair and, optionally powders that are usually used to color hair after washing or rinsing the hair applied direct dyes and or, or a screwing in and / or drying and in which one as