JPS62209015A - Method of dyeing keratine substance - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing keratin, and more particularly to a method for dyeing human hair.

Human hair is made up of fibers with layers of flat phosphorus layers that point from the root to the tip.The individual phosphorus layers are thin, but the phosphorus layers are long and overlap each other to form a continuous multi-layered protective layer around the fibers. Form. Within this protective layer is the hair cortex, which constitutes the main body of the hair. Dispersed throughout the cortex are pigment particles called melamine. The number and distribution pattern of melamine determines hair color.

Hair consists almost entirely of keratin, a cystine-containing protein. It should be understood that the main protein categories of 2FJ are low-sulfur proteins and high-sulfur proteins. The low-sulfur category consists of high molecular weight and highly molecularly organized (alpha-helix) proteins, while the high-sulfur proteins consist of proteins with low Both proteins, which are molecular weight proteins and do not exhibit regular secondary structures, are involved in the filament-matrix tissue complex that is the main component of the hair cortex. The filament is composed of low-sulfur proteins, and the surrounding matrix is composed of high-sulfur proteins.
The chemical composition of w4 debris is different from that of fibers (filaments), and the cells of the phosphorus layer clearly do not contain low-sulfur proteins9 The exposed parts of the individual phosphorus layers are highly cross-linked by cystine. This fact, together with the multi-layer protective layer effect, allows the phosphorus layer to form a barrier against the penetration of chemicals into the inside of the hair fiber.

The color tone of human hair has been changed by using dye-containing hair dyes.

For convenience, these hair dyes can be classified into those that perform "permanent dyeing,""semi-permanentdyeing," or "temporary dyeing.""Permanentdyeing" means that the dyeing result remains resistant to the effects of shampooing, perspiration, sunlight and mechanical abrasion until the hair grows out. "Semi-permanent dyeing" means that the dyeing result remains resistant to the effects of shampoo, perspiration, sunlight and mechanical abrasion for about 6 to 10 shampoo washes. "Temporary dyeing" means that the dyeing result can be removed with one to three shampoo washes.

In permanent hair dyeing, the dyes used (at least until recent years) are mainly of the oxidative type, so that water-insoluble dyes are deposited inside the hair fiber as a result of the oxidation of colorless intermediates that penetrate the cortex. A nine-color production reaction that produces a colored substance is carried out using a first intermediate, a second intermediate, and an oxidizing agent. The first intermediate is, for example, p-phenylenediamine, 9
-) Luenediamine, p-aminodiphenylamine, o
+G'-aminophenol, p-amino-O-cresol, toluene 2.5 diamine, N-phenyl-p-phenylenediamine, pyrogallol, 4.4'-diaminodiphenylene-diamine, p-methylaminophenol,
0-phenylenediamine, toluene-3゜4-diamine, p-chloro-O-phenylenediamine, O-chloro-
Includes p-phenylenediamine and 2°6-diamitubiridine. A second intermediate, known as a coupling or modifying agent, is also used in conjunction with the first intermediate to make the dye. The second intermediates are e.g. steel-aminophenol, resorcinol, m-phenylenediamine, hydroquinone, resorcinol, toluene-2,4-diamine, 1-naphthol, 4-methoxylr-phenylene-diamine, α-naphthol and polyhydroxyphenol diamine. For example, the initial oxidation product of p-phenylenediamine appears to be benzoquinone diimine. Although benzoquinone diimines can be reacted with p-phenylene diamine to form dyes, benzoquinone diimines react very quickly with second intermediates to form a variety of dyes.

By choosing appropriate intermediates, various colors can be created. A-forming agents (otherwise known as m-tinting agents) such as hydrogen peroxide, sodium perborate, urea peroxide or sodium percarbonate are usually mixed with the dye intermediate immediately before use. In addition to its oxidizing effect on dye intermediates, hydrogen peroxide has a slight effect on hair dyeing by bleaching melamine, and the use of autooxidizing dyes also avoids adding oxidizing agents separately. It is proposed to do so.

In fact, permanent hair dyes include nitro dyes that dye hair without oxidation, such as nitro derivatives of aminophenols and benzenediamines, such as nitro-p-phenylenediamine, p-nitro-〇-phenylenediamine, etc. Diamine, 4
-nitro-〇-fluorinated diamine, 2-amino-4-
It is common practice to include nitrophenol, 2-amino-5-nitrophloenol, picramic acid, 1,4-diaminoanthraquinone and picric acid. Also,
Nitro dyes, anthraquinone dyes and azobenzene dyes are commonly used in semi-permanent dyes.

For example, nitrophenyl diamines and nitroaminophenols give colors in the yellow, orange, red and violet range, while aminoanthraquinones give a blue color. Dyes that can be used in permanent or semi-permanent hair dyeing systems include, for example, vegetable hair dyes, such as dyes derived from henna, walnut or soybean, and metallic hair dyes, such as iron, copper, lead, manganese, Includes dyes using insoluble salts of nickel or cadmium.

Permanent hair dye compositions and semi-permanent hair dye compositions contain not only water and dyes or dye intermediates, but also surfactants (to increase wetting, detergency, dispersibility and viscosity control). For example, it is common practice to also include ammonium oleate, alkanolamides, aliphatic alkyl sulfates, thickeners such as carboxymethylcellulose, substances that promote the diffusion of the dye into the hair, and substances for solubilizing the dye. . It may also contain conditioning agents.

Temporary hair dyes usually use high molecular weight dyes that do not penetrate significantly into the hair structure and are deposited on the hair surface. Dyes that can be used in temporary hair dye systems include oxidative dyes, azo dyes, quinoline dyes, acridine dyes, azine dyes,
Includes oxazine dyes, indigoid dyes, anthraquinone dyes, stilbene dyes and thiazole dyes. - Temporary hair dyeing systems can also use pigments such as iron oxide, titanium oxide or carbon black, and
Binders such as methacrylate, acrylate, vinyl acetate or vinyl pyrrolidone polymers or copolymers can be used to facilitate the binding of the hair dye to the hair and also improve the ease of application of the dye and the dyed hair. dispersion medium such as water, acetone, ionic surfactants, nonionic surfactants,
Lower alcohols, polyhydric alcohols, higher alcohols, fatty acids and liquid hydrocarbons can be used.

Care of human hair involves increasing the desired qualities of the hair, such as ease of combing, resistance to tangles, density, shine, texture, straightening of split ends, prevention of static electricity build-up, and general ease of handling. Applying a so-called conditioner composition 0
It has been proposed to include various silicone products in conditioner compositions, including, for example, emulsions of the amino silicone polymer amodimethicone. EP 95,238 discloses certain siloxanes containing siloxane units having certain amine, carboxyl, amide or quaternized amino groups, and which is suitable for use as a conditioner for application to hair after shampooing. Discloses the substances used as For several years, it has been common practice to apply conditioner compositions, which may contain, for example, one or more silicone polymers, to the hair after the hair dyeing operation has been completed.

We now use hydroxyl-functional silicones in combination with hair wash systems to improve the depth of tone of keratinous substances treated with hair dyes and to improve the number of hair washes in which the tone is completely retained by the keratinous substances. We have found that it can be increased in some cases.

In one aspect, the present invention provides for the dyeing of keratin materials with hair dye systems (i) having the general formula % [wherein R is a monovalent hydrocarbon group each having from 1 to 12 carbon atoms] or alkoxy group or alkoxyalkoxy group (each alkoxy group having up to 7 carbon atoms), a having a value of 1 or 2] The other siloxane units that may be present in the polysiloxane are (ii) general formula % formula % where Z is a monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group or an alkoxyalkoxy groups (alkoxy groups each having up to 7 carbon atoms)
and C has a value of 0, 1, 2, or 3.] Using polysiloxane, which is a siloxane unit represented by The object of the present invention is to provide a method of using a polysiloxane which enhances the holding power of a polysiloxane.

The present invention also provides a step of applying a hair dye system to a keratin material, and before, during or after application of the dye system, (i) the general formula % formula % [wherein each R is the number of carbon atoms] represents a monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group or an alkoxyalkoxy group (each alkoxy group has up to 7 carbon atoms), and a has a value of 1 or 2] A polysiloxane containing at least one siloxane unit, wherein other siloxane units that may be present in the polysiloxane are (ii> general formula % formula % [wherein Z has 1 to 12 carbon atoms a monovalent hydrocarbon group or an alkoxy group or an alkoxyalkoxy group (each alkoxy group having up to 7 carbon atoms)
and C has a value of 0 or 1 or 2 or 3] The present invention provides a method for dyeing a keratin material, which comprises applying a polysiloxane which is a siloxane unit represented by:

Polysiloxanes are characterized by the presence of at least one silicon-bonded hydroxyl group.

Depending on the value of a, the siloxane units (i) can be present in the polysiloxane as terminal units or as linking units of the polymer or both, provided that at least one S i OH group is present. The desired proportion of total siloxane units in the polymer can be provided below. Preferred siloxane units (i) are from about 0.1% to about 20% of the total siloxane units, more preferably from 1 to 5
%I will provide a. However, if desired, siloxane units (i) can provide 100% of the total units in the polysiloxane. The siloxane units that may remain in the polysiloxane are those represented by general formula (i).

In siloxane units (i) and (ii), R and Z
is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, propyl or butyl, or an aryl group, such as phenyl, or an unsaturated aliphatic or cycloaliphatic group, such as vinyl or cyclohexenyl, or an alkoxy group or an alkoxyalkoxy group having up to 7 carbon atoms, such as a methoxy, ethoxy, propoxy or methoxyethoxy group. Suitable R and Z substituents are selected from alkyl or alkoxy groups having 1 to 4 carbon atoms and phenyl groups. The value of C can be 0 or 1 or 2 or 3, so that the siloxane unit (ii) can provide a terminal unit, main chain or branched chain in the polysiloxane.

Polysiloxanes can be linear or branched, and can range in consistency from free-flowing liquids to resinous materials. Good results are 2X10-'~
This is obtained by using a material with a viscosity in the range of 1/2/sec. Preferred polysiloxanes have a=2;
A liquid alpha, omega hydroxy polydiorganosiloxane neck having two siloxane units (i) in which R is a methyl group and a number of siloxane units (ii) in which C is two.

Conveniently, the Z groups each represent a methyl group; suitable polysiloxanes have the average formula H○(R2Sio)nH(
In the formula, each R represents a methyl group, and n is 600 to 17
00).

Preferably, the polysiloxane is applied to the hair or pond keratinous material as an aqueous emulsion of fine particle size.

In the process of the invention, the polysiloxane may be any polysiloxane used in the process of the invention, although other polysiloxanes may be present if desired.
For example, if it is desired to further enhance the durability of the hair color, in addition to the above-mentioned polysiloxanes, groups having silicon-bonded hydroxyl and/or alkoxy groups and silicon-bonded active amine groups, such as = S i (CH2)3 N H2 and =SiCH2C
It is sometimes possible to achieve enhanced durability by using polysiloxanes with groups such as H2NH(CHz)zNHz. Among the amino group-containing polysiloxanes mentioned above are known and include, for example, amodimethicone.

In the method of the invention, the hair dye system can be any dye system normally used for temporary, semi-permanent or permanent dyeing as mentioned above. The hair dye system is usually aqueous anionic. The emulsion may consist of an aqueous nonionic emulsion, an aqueous nonionic emulsion or an aqueous cationic emulsion, and may contain the usual additives as mentioned above.

A variety of commercially available hair dye systems can be used in the method of the invention, such as Elida Gibbs
), Bristol Mye
Harmony (IlarmonF) and Grinz (C1i) from rs) and Flyroll (C1airol), respectively.
The dye systems supplied under the trademarks Claiol and Claiol can be used.

In the method of the invention, the polysiloxane can be applied to the keratinous material in a mixture with a dye system, but the shampoo used on the keratin material before or after the application of the dye system, e.g. It is preferred to apply the polysiloxane in a conditioner rinse applied to the keratin material during or after the application of the dye system.

The hair dyeing method according to the present invention first uses, for example, about 20% sodium lauryl ether sulfate. The hair is washed using a conventional shampoo composition containing % It, rinsed with water, dried to a towel-drying stage by patting the hair substantially dry with a towel, and then drying the hair to a towel drying stage. This can be accomplished by applying the selected polysiloxane in an aqueous emulsion while in this substantially dry state. After about 1 minute, the hair is dried again to the towel drying stage, the dye system is applied and left for about 15-20 minutes.The hair is then rinsed to remove any remaining dye and subjected to forced hot air treatment. It can be dried by

The method of the invention can be used to dye virgin hair or to dye hair that has been damaged, for example as a result of bleaching or permanent waving, to provide hair with enhanced intensity of tone. Also, by using suitable polysiloxanes, the method of the present invention can extend the retention of the imparted shade compared to other methods.

The present invention will be further explained below by referring to a working PA (hereinafter simply referred to as an "example" unless otherwise specified). In the following examples, the symbol Me represents a methyl group. All proportions stated in the examples are by weight unless otherwise specified.

In an example, various commercially available hair dye systems are used to dye European virgin hair inserts of bleached and unbleached parts exactly according to their suppliers' instructions, and the individual dyeings are A dyed standard sample of bleached virgin hair and a dyed standard sample of unbleached virgin hair were obtained.

Comparative samples of dyed hair were prepared from similar treatments of virgin hair and bleached virgin hair using control compositions or polysiloxane compositions, as well as treatments for commercial hair dye systems. The color of the bleached and dyed parts of the sample and the color of the non-bleached and dyed parts were observed and compared with the standard sample immediately after the dyeing operation and for some samples after washing several times. The various stain systems used were semi-permanent stain systems.

Bleaching of virgin hair was performed as follows. The ends of individual strands of virgin hair were dipped into a solution formed by mixing equal volumes of Solution A and Solution B for 2 hours at room temperature. Solution A was a 50% by volume aqueous solution of hydrogen peroxide. Mixed solution B was 13.5 parts by volume of ammonia (specific gravity 0.88), Empicol (Empic).
ol) ES83 (sodium lauryl ether sulfate)
The mixture consisted of 3 parts by volume and 83.5 parts by volume of water. After 2 hours, the hair was removed from the solution, rinsed with tap water, and then dried using air heated to 70°C.

Control composition 1 is cetalkonium chloride (ceLalk
It was a 0.35% solid aqueous solution of the quaternary ammonium salt of C. onium chloride. Control composition 2 has the average formula MesSiO(Me*SiO) x (MeR' Si
O) ysiMea [where R' is -CpHsO (Czll
<O)n (C11sC211iO)+*represents II]
It was a 0.35% solids aqueous solution of a polysiloxane polyalkylene copolymer represented by:

Polysiloxane 1 has the average formula 110(MezSiO)nH
The emulsion was an aqueous emulsion with a pH of about 7.2 containing 0.35% of a hydroxyl-terminated polydimethylsiloxane having a value of about 1100±100.

Polysiloxane 2 has the average formula 110(MezSiO)nl
0.35% of polydimethylsiloxane terminated with hydroxyl groups having a value of 1, where n has a value of approximately 20.
, water and Tergitol 7MN6 [
isolaureth-6 (isolaureth-6),
It was an aqueous emulsion formed from [surfactant].

In Examples 1 and 2, the control composition and polysiloxane 1
Bleached virgin hair and unbleached virgin hair inserts described above were dyed in the following manner using various hair dye systems with and without pre-treatment using 2 and 2.

The sample produced using pre-treatment was used as a standard sample, and the sample produced without pre-treatment was used as a comparison sample.
An aqueous composition of 0% active sodium lauryl ether sulfate was used to shampoo.

The hair was rinsed and dried to towel dry by patting it with a towel. Apply to bleached and unbleached areas of hair treated by covering the hair with the selected dye prepared according to the supplier's instructions for 20 minutes. Rinse the hair with tap water until the water is colorless. The dried hair was dried in air heated to 70° C. until the hair was dry. When using a control composition or a permanent with Polysiloxane 1, after the initial shampooing and rinsing step, after drying the hair by patting it dry, the bleached and unbleached areas of the hair were compared. 1 in 1 composition or polysiloxane
Remove the hair from the control composition or polysiloxane 1 and dry it to a towel-dried layer by patting it with a towel.The selected dye is then applied to the hair and the hair is rinsed. , dried as described above. The color tone of the bleached and unbleached portions of the sample was observed and immediately after hot air drying, the color tone of the standard sample was compared.

Harmony Open (Ila) using the method described above.
Harmony Rich Chestnut
Elida Gibbs (Elida (estnut))
Control Compositions 1 and 2 and Polysiloxane 1 were evaluated as pre-treatment agents for hair dye systems using products supplied by: 1bbs). Polysiloxane 2 was evaluated using Harmony Open. By examining the samples stained with Harmony Lynch Chestnut, it was determined that the color intensity of the dyed bleached areas and the dyed unbleached areas of the samples made using Control Composition 2 was the same as that of the dyed areas. It was found that the color intensity of the bleached and unbleached areas was the same as that of the corresponding area of the standard sample, but control composition 1 had a slightly darker color intensity of the bleached and unbleached areas than the standard sample. .

Comparison of bleached and unbleached areas of samples made using Polysiloxane 1 with corresponding areas of dyed samples made using Control Composition 1 shows that The ones used had a darker color.

By examining the samples dyed using Harmony Open, it was found that the color intensity of the dyed bleached areas and the dyed unbleached areas of the samples made using control compositions 1 and 2 were similar to each other. It was found that the color was darker than that of the corresponding part of the standard sample. Comparing the bleached and unbleached areas of the samples run using Polysiloxane 1 with the corresponding areas of the samples run using Control Composition 1, the samples run using Polysiloxane 1. had a darker color than the samples run using Control Composition 1. In combination with Harmony Open and Harmony Rich Chestnut, etc., dyed bleached areas and dyed unbleached areas of samples made using Polysiloxane 1 were compared with corresponding areas of standard samples. showed a darker color. By using Polysiloxane 2 and Harmony Open, a slight improvement in color intensity was achieved when compared to the corresponding part of the standard sample.

[Bleached virgin hair and unbleached virgin hair were implanted into Harmony Open and Harmony Rich with and without pretreatment with Polysiloxane 1 and the control composition using the method described above. It was stained with chest oak l-. The stained sample was washed in a 20% active aqueous solution of sodium lauryl ether TiQ acid, rinsed with clean water, washed twice in 20% active sodium lauryl ether TiQ acid, and washed for two days. A hair washing cycle was carried out consisting of 2 rinses with normal water followed by drying with air heated to 70°C. After each hair wash cycle, examine the individual samples and record the color. Please note that some color from the individual samples was washed out, the bleached and unbleached areas of each comparative sample. The washing cycle was repeated until the color of the area was the same as the color of the corresponding area of the washed standard sample counterpart.The number of washing cycles performed before a 0 color match was obtained is listed in the table below. : Control Composition 1 2 5 Control Composition 2 3 0 Polysiloxane 1 2 7 These results indicate that the hair samples dyed according to the method of the invention were not subjected to any pretreatment using a polysiloxane having units of general formula (i). This shows that the hair retains its color even after shampooing more times than hair dyed.

Example 1, except that no pre-treatment was carried out, but post-treatment was carried out after the application of the dye and the accompanying rinsing step.
Polysiloxanes 1 and 2 were evaluated as post treatments for hair dye systems using Harmony Open using the method used in Example 2 and Example 2.

The dyed hair was dried by patting it with a towel. Post-treatment consisted of applying control composition 1 or polysiloxane to the hair by dipping the dyed hair into the given composition and then drying the hair in air heated to 70°C. Ta. This intensity of color 0 corresponds to the observed good color intensity of the bleached and unbleached areas of the hair in the samples without using polysiloxane 1 or 2 as post-treatment. The color depth was better than that of the standard sample product.

1- Samples prepared as described in Example 3 were subjected to the wash cycle and investigation described in Example 2. The number of hair washing cycles performed before the color of the bleached and unbleached areas of each comparison sample became similar to the color of the corresponding areas of the washed standard sample counterpart is listed in the table below: Until L1111 is formed, Sain Polysiloxane 14 Polysiloxane 21

Claims (1)

[Claims] 1. When dyeing keratin materials with a hair dye system, (i) the general formula R_a(HO)SiO_(_3_-_a_)_/_2[
In the formula, R each represents a monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group or an alkoxyalkoxy group (each alkoxy group has up to 7 carbon atoms), and a is 1 or 2. having a value of ], wherein the other siloxane units that may be present in the polysiloxane have the general formula Z_cSiO_(_4_-_c_)_/ ＿2 [in the formula, Z
represents a monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group or an alkoxyalkoxy group (each alkoxy group has up to 7 carbon atoms), and c
has a value of 0 or 1 or 2 or 3] Polysiloxane, which is a siloxane unit represented by Method of using polysiloxane consisting of strengthening. 2. Polysiloxane has the average formula HO(R_2SiO)_nH (where R is the number of carbon atoms
2. The method according to claim 1, wherein the material is a substantially linear substance represented by an alkyl group or a phenyl group having 600 to 1700. 3. The method of use according to claim 2, wherein n has a value of 1100±100. 4. The keratin material is human hair, the human hair is patted to a substantially dry state, the dye system is applied to the hair during this substantially dry state, and the polysiloxane is applied to the hair. The method of use according to any one of claims 1 to 3, which comprises applying the composition to the hair in the form of an aqueous emulsion before or after application. 5. Applying the hair dye system to the keratin material, and before, during or after applying the dye system, (i) having the general formula R_a(HO)SiO_(_3_-_a_)_/_2[
In the formula, R each represents a monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group or an alkoxyalkoxy group (each alkoxy group has up to 7 carbon atoms), and a is 1 or 2. having a value of ], wherein the other siloxane units that may be present in the polysiloxane have the general formula Z_cSiO_(_4_-_c_)_/ ＿2 [in the formula, Z
represents a monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group or an alkoxyalkoxy group (each alkoxy group has up to 7 carbon atoms), and c
has a value of 0 or 1 or 2 or 3] A method for dyeing a keratin material, comprising the step of applying polysiloxane, which is a siloxane unit represented by: 6. Polysiloxane has the average formula HO(R_2SiO)_nH (where R is the number of carbon atoms
6. The dyeing method according to claim 5, which is a substantially linear substance represented by an alkyl group or a phenyl group having ~6 alkyl groups or phenyl groups, where n has a value in the range of 600 to 1700. 7. The dyeing method according to claim 6, wherein n has a value of 1100±100. 8. The keratin material is human hair, the human hair is patted to a substantially dry state, the dye system is applied to the hair during this substantially dry state, and the polysiloxane is applied to the hair. The dyeing method according to any one of claims 5 to 7, wherein the dyeing method is applied to the hair in the form of an aqueous emulsion before or after application.