JPH0696499B2 - Hair cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a hair cosmetic composition. More specifically, the present invention relates to a hair cosmetic composition which is attracted to hair and has durability such as glossiness, suppleness, smoothness, moisturizing feeling, easy brushing and antistatic property.

[Conventional technology and its problems]

Conventionally, hair is susceptible to mechanical damage due to combs, brushes, hair washes, etc. and physical and chemical damage due to sunlight, dryers, permanent waves, etc.For the purpose of protecting hair, vegetable oils such as camellia oil and olive oil, lanolin. , Animal oils such as beef tallow, mineral oils such as petrolatum and paraffin, and synthetic oils have been used directly or after being dissolved in emulsion or solvent.

In recent years, since organopolysiloxane gives hair gloss, suppleness, smoothness and moisturizing feeling, attention has been paid to it, and various hair cosmetics using the same have been proposed and put into practical use. For example, a hair cosmetic comprising dimethylpolysiloxane and a diol derivative or a branched aliphatic alcohol (JP-A-52-47923), a hair comprising a polyorganosiloxane-polyoxyalkylene block copolymer and hydrous ethanol or anhydrous ethanol. Hair composition comprising a composition composition (Japanese Patent Laid-Open No. 55-136214), (aminoalkyl) methylpolysiloxane, a cationic surfactant and an aqueous carrier (Japanese Patent Laid-Open No. 56-45406).
(Japanese Patent Laid-Open No. 55-66506), and cosmetics using a quaternary nitrogen-containing cationic organopolysiloxane.

However, the one using dimethylpolysiloxane has a defect that dust adhesion and hair fly phenomenon easily occur due to static electricity generation. The one using the organopolysiloxane-polyoxyalkylene block copolymer can prevent the generation of static electricity, but has a drawback that it is easily dissolved in water and easily falls off by swimming or washing hair. Those using (aminoalkyl) methylpolysiloxane are good in terms of durability, but have a drawback that static electricity is easily generated. Further, the one using the quaternary nitrogen-containing cationic organopolysiloxane has a slightly good durability and antistatic property, but has a drawback that it is not enough. As described above, although conventional hair cosmetics have succeeded in providing gloss, suppleness, smoothness, and moisturizing feeling, their durability is problematic or durable. However, due to problems with antistatic properties, it has not been possible to obtain satisfactory processing effects and durability.

In addition, the hair dye in hair cosmetics includes so-called "hair dyeing" for coloring white hair in a black or brown color tone, and so-called "wash dyeing" for coloring black hair in a light brown color tone. And both are used for cosmetic purposes. It is required for all of these hair dyes to surely conceal the color of the hair or the part of the hair to be dyed, and to finish the hair without giving a strange feeling. However, in existing hair dyes, the dye / pigment that is the dyeing base is different from the pigment component (melanin) of the hair itself, and the addition amount of dye / pigment in the composition is small, so There is a drawback that the hiding power and dyeing power are weak due to the fact that the subsequent hair does not have a deep color tone and there is a discomfort without being dyed in a natural color tone, and it is still satisfactory. Well then.

As a means for solving such a drawback, there is a method of increasing the concentration of the dye / pigment in the hair dye. For example, for the oxidation type hair dye, in recent years, the harmlessness of the oxidation dye / cutler, which is the dye component, It is unfavorable to increase the concentration of these because of a number of reports that question them, and the fact that the use of these substances is being regulated in advanced countries is increasing. When was dispersed in a dispersion medium such as alcohol or water, the dispersion solution is easily separated and it is difficult to keep the product stable for a long period of time. Furthermore, when the concentration of the dye / pigment in the hair dye is increased, it is necessary to add a large amount of polymer resin, spreading agent, etc. to prevent discoloration after hair dyeing. As a result, the hair after dyeing has a hard and stiff feel, or the comb and brush do not pass easily, causing deterioration of the feel of the hair and damage to the hair.

[Means for solving problems]

As a result of diligent studies to improve the above-mentioned drawbacks, the present inventor has found that when a specific modified polysiloxane is blended, the hair has excellent gloss, suppleness, smoothness, moisturizing feeling, ease of brushing, and prevention of static electricity. Hair cosmetics, in particular, for hair dyes, which have durability and are capable of sustaining their treatment effect because they are adsorbed on the hair, and especially for hair dyes, hiding power without increasing the concentration of dyes and pigments in the composition. The present invention has been completed by finding that a hair dye having excellent dyeing and coloring power and capable of giving depth to the color tone of dyed hair can be obtained.

That is, the present invention provides a hair cosmetic containing a specific modified polysiloxane.

The specific modified polycyclosiloxane used in the present invention has the following formula (I): ▲ R ¹ _a ▼ ▲ R ^{2 b} ▼ Y _c Z _d SiO _{1/2 (4-abcd)} (I) [wherein R ^{1 is} : A substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms (hereinafter referred to as a monovalent hydrocarbon group) R ² : a monovalent hydrocarbon group or OX (X is a hydrogen atom or a monovalent hydrocarbon group) Y : (R ³ is a hydrogen atom, an organic group having a monovalent hydrocarbon group or an amino group, R ⁴ is an organic group having an amino group), (R ⁵ and R ⁶ are organic groups having an amino group), (R ⁸ is a hydrogen atom, a monovalent hydrocarbon group, or an organic group having an amino group or an ammonium group, R ⁹ and R ¹⁰ are monovalent hydrocarbon groups or an organic group having an amino group or an ammonium group, M is a halogen, Inorganic acid or organic acid anion) or (R ¹¹ , R ¹² and R ¹³ are organic groups having an amino group or an ammonium group, M is a halogen, an inorganic acid or an organic acid anion) Z: (R ⁷ is a hydrogen atom or a monovalent hydrocarbon group, p, q and r are 0
To 50) a, b, c, d: 0 <a ≦ 3, 0 <b ≦ 3, 0 <c ≦ 1, 0 <d
≤1 and 0 <a + b + c + d <3].

Examples of particularly preferred modified polysiloxanes include compounds represented by the following general formula (II).

[Wherein Y and Z have the same meanings as in formula (I), 1 is 1 to 300, m is 1 to 30, and n is a number of 1 to 10] These modified polysiloxanes (I) Is produced by a known method. These modified polysiloxanes can be used alone or in combination of two or more, and the compounding amount thereof varies depending on the kind of cosmetics, but usually 0.01 to 10% by weight based on the total amount of hair cosmetics. Is preferred.

In the present invention, the hair cosmetics include all cosmetics applied to the hair, and among them, for example, pre-shampoo treatment, shampoo, hair rinse, aftershampoo, conditioner, hair conditioner, set. Lotion, Brow Styling Lotion, Hair Spray, Hair Dye, Bleach, Permanent Wave No. 1 Agent, Permanent Wave No. 2 Agent
Hair styling agents such as agents, hair dyes, hair liquids, hair nicks, etc. are included.

The hair cosmetic composition of the present invention is produced by appropriately blending the above-mentioned essential components as well as the above-mentioned known components for hair cosmetic compositions depending on the application. Also, the dosage form of the hair cosmetic composition may be various forms such as an aqueous solution, an ethanol solution, emulsion, suspension, gel, solid, aerosol, and powder depending on the application.

Examples of the hair cosmetic composition of the present invention are as follows.

(1) Shampoo: Other known shampoo composition constituents are appropriately used according to a conventional method except that one or more anionic surfactants or amphoteric surfactants and the above-mentioned essential components are added as necessary components in the composition. It is manufactured by blending.

Among the anionic surfactants which are the bases of the shampoo, the following are exemplified as preferable ones.

Straight-chain or branched-chain alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16 having a straight-chain or branched alkyl group having an average carbon number of 8 to 20 and having an average of 0.5 to 8 mol in one molecule. Polyoxyalkylene alkyl sulphate salt having ethylene oxide and / or propylene oxide added thereto Alkyl sulphate salt having an alkyl group having an average carbon number of 10 to 20 Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule Alkane sulfonate having an average of 10 to 20 carbon atoms in one molecule Alkyl ethoxycarboxylate having an alkyl group having an average of 10 to 20 carbon atoms and adding an average of 0.5 to 8 mol of ethylene oxide in one molecule (In the formula, R ¹⁴ represents an alkyl group or an alkenyl group having 6 to 20 carbon atoms, and X ₁ and Y ₁ each represent an ion.) A succinic acid derivative represented by sodium is used as a counter ion of these anionic surfactants. , An alkali metal ion such as potassium: an alkaline earth metal ion such as calcium or magnesium: an ammonium ion, and an alkanol group having 2 or 3 carbon atoms
Alkanolamines having three (eg monoethanolamine, diethanolamine, triethanolamine,
Triisopropanolamine).

Among these exemplified anionic surfactants, particularly preferable ones are linear or branched alkyl sulfate ester salts having an average carbon number of 10 to 16, or polyoxyethylene alkyl having an average carbon number of an alkyl group of 8 to 20. Examples thereof include sulfuric acid ester salts (average number of moles added: 0.5 to 8), olefin sulfonates having an average number of carbon atoms of 10 to 16, and the like.

Preferred examples of the amphoteric surfactant include the following.

Alkylamine oxide represented by the following formula (In the formula, R ¹⁵ is an alkyl group or an alkenyl group having 10 to 20 carbon atoms, and R ¹⁶ and R ¹⁷ are alkyl groups having 1 to 3 carbon atoms, which may be the same or different) ^It is preferable that ¹⁵ has 12 to ¹⁶ carbon atoms and R ¹⁶ and R ¹⁷ are methyl groups.

(In the formula, R ¹⁹ represents an alkyl group or an alkenyl group having 10 to 20 carbon atoms, R ²⁰ and R ²¹ are alkyl groups having 1 to 4 carbon atoms,
t is an integer of 1 to 3, X ₂ represents a COO or —SO ₃ group) Among these, those in which R ¹⁹ has 12 to 16 carbon atoms, R ²⁰ and R ²¹ are methyl groups, and t is 3 are preferable.

Imidazoline type compound represented by the following formula [In the formula, R ²² is a fatty acid root having an average carbon number of 10 to 20, R ²³ is hydrogen, Na or CH ₂ COOMe (Me: H, Na, organic base), and R ²⁴ is COOM.
e, CH ₂ COOMe or (Me is the same as the above), R ²⁵ represents a hydroxyl group, an acidic group, an anionic surface-active sulfate or sulfate.] Of these, R ²² preferably has 12 to 16 carbon atoms.

In the shampoo of the present invention, the total amount of the anionic surfactant or amphoteric surfactant is preferably 5 to 30% by weight (hereinafter simply referred to as%), particularly 10 to 25%, and the total amount is balanced with water.

Other constituents that can be added to the shampoo of the present invention include nonionic surfactants, cationic surfactants in an amount that does not impair the effects of the present invention, and further solubilizers such as propylene glycol, glycerin, and urea: ethyl. alcohol,
Viscosity modifiers such as isopropyl alcohol, hydroxyethyl cellulose, methyl cellulose, higher alcohols: fragrances, dyes, ultraviolet absorbers, antioxidants, preservatives,
A pearling agent, a rosing agent and the like can be mentioned, and these can be blended as necessary.

The shampoo of the present invention thus obtained has good foaming and slipperiness, has a low combing force, and is unlikely to cause hair fly.

Hair rinse, hair conditioner, hair treatment The modified polysiloxane of the present invention is blended with water, hydroalcohol or the like in the form of a liquid or a lotion, oils,
It can be used in the form of an emulsion or cream when used together with a surfactant and water.

These hair rinses, hair conditioners and the like of the present invention can be blended with known components generally used in these compositions, such as cationic surfactants, anionic surfactants, nonionic surfactants and The surfactant selected from the amphoteric surfactants is used as an emulsifier for oil components described later or as a hair conditioning agent.

Suitable anionic surfactants and amphoteric surfactants include those exemplified in the section of Shampoo.

The cationic activator used in the present invention is not particularly limited, and all that can be blended in hair rinses, hair conditioners, etc. are used. (In the formula, R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ each represent a linear or branched long-chain alkyl group having 8 to 20 carbon atoms or a long-chain hydroxyalkyl group, and the remainder is A quaternary ammonium salt represented by the formula ( ₃ ) represents an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a benzyl group, and X ₃ represents a halogen atom or an alkylsulfate group having 1 to 2 carbon atoms, and particularly preferably
Distearyldimethylammonium chloride, stearyltrimethylammonium methosulfate, stearyltrimethylammonium chloride, stearyldimethylbenzylammonium chloride, lauryldiethylbenzylammonium chloride, lauryltrimethylammonium bromide, distearylmethylhydroxymethyl chloride, cetyltrimethylammonium chloride and the like are preferable. .

The nonionic surfactant is mainly used for the purpose of emulsification, and is selected from the following examples in consideration of HLB and the like.

It has a primary or secondary alkyl group or alkenyl group having an average carbon number of 8 to 20, and has a polyoxyethylene alkyl or alkenyl ether having an average of 8 to 12 carbon atoms to which 3 to 12 mol of ethylene oxide is added. And a polyoxyethylene alkylphenyl ether having 3 to 12 mol of ethylene oxide added thereto, a higher fatty acid alkanolamide represented by the following formula or an alkylene oxide adduct thereof. (In the formula, R ³⁰ represents H or CH ₃ , and R ³¹ has 10 to 20 carbon atoms.
Is an alkyl group or an alkenyl group. n is an integer of 1 to 3 and m is an integer of 0 to 3. ) These surfactants are added in the range of 0.01-10 in the hair rinse composition.
%, Preferably 0.5-5%, gives good results.

Further, the hair rinse, hair conditioner and the like of the present invention include, as optional components, hydrocarbons such as liquid paraffin, petrolatum and solid paraffin, esters such as isopropyl myristate, lanolin, purified lanolin and lanolin fatty acid. Lanolin derivative, polyethylene glycol, polypropylene glycol or a polymer thereof,
Oil agents such as polyoxyalkylene alkyl ether, polyoxyalkylene alkyl ether phosphoric acid; polymeric substances such as hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, cationized cellulose, cationized polymer, glycerin, propylene glycol, etc. Moisturizers; bactericides, preservatives, fragrances, dyes and the like can be added appropriately.

(3) Hair setting agent (settling agent, hair spray, etc.): Prepared by dissolving the above essential components in a polar solvent such as water, ethyl alcohol, propyl alcohol, etc., according to a conventional method. Further, a polymer compound used in a conventional hair setting agent or the like can be added. Examples of these polymer compounds include the following.

(A) Polyvinylpyrrolidone-based polymer compound For example, polyvinylpyrrolidone, a copolymer of vinylpyrrolidone and vinyl acetate, a copolymer of vinylpyrrolidone, vinyl acetate, an alkylaminoacrylate, and the like can be mentioned. Commercially available products are rubiscol K. , Rubiscol VA, Rubiflex D4101 (Okaka Verdice), PVPK, PVP / VA, E-735 (GAF).

(B) Acidic vinyl ether polymer compound For example, a lower alkyl half ester of a copolymer of methyl vinyl ether and maleic anhydride can be mentioned. Commercially available products are GANTREZ ES-225 and ES-335 (GAF).
and so on.

(C) Acidic Polyvinyl Acetate Polymer Compound For example, a copolymer of vinyl acetate and crotonic acid may be mentioned. Commercially available products include Resin 28-1310 (National Star).
ch company), Rubiset CE5055 (Okaka Verdishyu Co., Ltd.) and the like.

(D) Acidic acrylic polymer compound For example, a copolymer of acrylic acid and / or methacrylic acid and an alkyl acrylate and / or an alkyl methacrylate, and acrylic acid and an alkyl acrylate and an N-alkylacrylamide Examples thereof include copolymers. Examples of commercially available products include Plusside (Reciprocal Chemistry) and Ultrahold 8 (Ciba Geigy).

(E) Amphoteric acrylic polymer compound For example, dialkylamimoethyl methacrylate, dialkylaminoethyl acrylate, diacetone acrylamide, etc. and acrylic acid, methacrylic acid, acrylic acid alkyl ester, methacrylic acid alkyl ester, etc. are copolymerized and halogenated. Examples include compounds that have been amphotericized with acetic acid, and commercially available products include Yukafumer AM-TS (Mitsubishi Yuka)
and so on.

Furthermore, the hair setting agent of the present invention further comprises optional components according to the purpose within the range that does not impair the effects of the present invention, for example, oily substances such as higher alcohols and higher fatty acid esters; Nonionic surfactants such as oxyethylene lauryl ether, polyoxyethylene sorbitan monolaurate, and polyoxyethylene hydrogenated castor oil; humectants such as glycerin and propylene glycol; fragrances, pigments, and the like can be added.

The hair setting agent of the present invention may be directly applied to the hair as it is, but may be applied as a mist using a pump spray or the like, or may be further filled in a container together with a propellant such as CFC gas, liquid hydrocarbon or carbon dioxide gas. Then, it can be applied as a mist or foam.

The hair set agent of the present invention thus obtained forms a uniform and tough film after drying, and has an excellent hair set power even under high humidity conditions, and at the same time, it is an anionic surfactant which is widely used at present. When the hair is washed with a shampoo containing an agent or the like, it can be easily removed from the hair, and therefore it is an excellent product that satisfies both the set power and the washability.

(4) Permanent Wave First Agent: It is prepared by incorporating the above-mentioned essential components into the composition of a permanent wave first agent based on a reducing substance.

As the reducing substance which is the base of the permanent wave first agent of the present invention, any conventionally used reducing substance can be used, and among them, the ammonium salt of thioglycolic acid and the hydrochloride salt of cysteine are particularly preferable.

The permanent wave first agent of the present invention comprises the above components,
It is produced by mixing and blending by a method known per se, but in addition, conventionally used dyes, fragrances, oil components, clouding agents, organic salts, urea and the like can be added according to the purpose.

(5) Permanent Wave Second Agent: It is prepared by incorporating the above-mentioned essential components into the composition of a permanent wave second agent based on an oxidizing substance.

The compounding amount of the oxidizing agent as the base in the permanent wave second agent of the present invention varies depending on whether or not the second agent is dissolved in a solvent and the dilution degree when diluted and used. ~
30%, especially 3 to 20% is preferable.

Further, as the oxidizing substance which is the base of the permanent wave second agent of the present invention, any of those generally used can be used, for example, alkali metal bromate such as sodium bromate, potassium bromate, etc., hydrogen peroxide. , Sodium percarbonate, sodium perborate, etc., among which alkali metal bromate is particularly preferred.

The permanent wave second agent of the present invention contains, in addition to the above essential components, an amount of anionic surfactant, amphoteric surfactant, nonionic surfactant, which does not impair the effects of the present invention.
Optional components such as a cationic surfactant, a cationic polymer compound, urea, an appropriate oil agent, a wetting agent, a fragrance, and a dye can be added and blended.

Among these optional components, examples of the cationic polymer compound include a cationic cellulose derivative, a cationic starch, a diallyl quaternary ammonium salt or a copolymer of diallyl quaternary ammonium salt and acrylamide, a polyglycol / polyamine condensate, and methacryloxy. Examples thereof include copolymers of ethyltrimethylammonium salt or methacryloxyethyltrimethylammonium salt and polyvinylpyrrolidone. Among them, cationic cellulose represented by the trade name “Polymer JR” and represented by the trade name “Mercoat 100”. The diallyl quaternary ammonium salt and the diallyl quaternary ammonium salt / acrylamide copolymer typified by the trade name "Mercoat 550" are particularly effective. The addition amount of these cationic polymer compounds is preferably 0.01 to 5%, and particularly preferably 0.05 to 2%.

The second agent thus obtained is adjusted so that the pH of its 5% aqueous solution is 9 or less, preferably 3.5 to 6.5.

(6) Hair dye: It is prepared by blending the above-mentioned essential components with a hair dye base by a conventional method.

The hair dye base of the hair dye composition of the present invention is not particularly limited, and any known hair dye base can be used. For example, an oxidative hair dye and a temporary hair dye will be described below as an example.

(I) Oxidative hair dye A dye intermediate, an oxidizing agent and, if necessary, a kuppler or a modifier are added.

Examples of dye intermediates include p-phenylenediamine, toluene-2,5-diamine, N-phenyl-p-phenylenediamine, 4,4'-diaminodiphenylamine, p-aminophenol and p-methylaminophenol. , O-phenylenediamine, toluene-3,4-diamine, o-aminophenol, p-chloro-o-phenylenediamine,
p-amino-o-cresol, o-chloro-p-phenylenediamine, fluorogelsin, pyrogallol, 3,3 '
Examples include para or ortho components such as iminodiphenyl, diphenylamine, 2,6-diaminopyridine and p-aminophenylsulfamic acid. As the cutler (modifer), m-phenylenediamine, toluene-2,4-diamine, p-methoxy-m
-Phenylenediamine, m-aminophenol, .alpha.-naphthol, resorcin, hydroquinone, meta components such as catechol, and phenols can be mentioned. Hydrogen peroxide is usually used as the oxidizing agent, but sodium perborate, urea peroxide, sodium percarbonate, sodium peroxypolyphosphate triphosphate, sodium pyrophosphate pyrophosphate, sodium peroxyphosphate orthophosphate, sodium silicate peroxide Examples thereof include hydrogen adducts, sodium sulfate sodium chloride hydrogen peroxide adducts, and the like. Further, since it does not participate in the pigment formation reaction but affects the color tone of hair, direct dyes such as nitro-p-phenylenediamine and p-nitro-o-
Phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, 4-amino-
A nitro dye such as 2-nitrophenol and, if necessary, picramic acid, picric acid and 1,4-diaminoanthraquinone can be added.

Further, nonionic surfactants and cationic surfactants are used in an amount within a range that does not impair the effects of the present invention, solvents such as propylene glycol and glycerin, lower alcohols such as ethyl alcohol and isopropyl alcohol, hydroxyethyl cellulose, methyl cellulose. , Cationic polymer compounds, viscosity modifiers such as higher alcohols, wetting agents, protein denaturants such as urea, fragrances, dyes, ultraviolet absorbers,
Antioxidants, antiseptics, pearling agents, rosifying agents and the like can be added.

The oxidative hair dye in the present invention is a one-part agent or an oxidative dye used by mixing the above-mentioned components and the above-mentioned essential components by a conventional method to prepare a powder formulation or a cream-like formulation, which is used in addition to water or a shampoo base at the time of use. It is preferable to separate the oxidant and the oxidant, and mix the one or both of them with the above-mentioned essential components to prepare a powder preparation, a cream preparation, a liquid preparation, and a combined preparation to be mixed at the time of use.

(Ii) Temporary hair dyes The dyes and pigments are not particularly limited, but for example, pigments such as titanium oxide and carbon black, triphenylmethane dyes, azo dyes, quinoline dyes, zanthene dyes, acridine dyes, azine dyes, oxazine dyes, Examples include tar-based dyes such as indigoid dyes, anthraquinone dyes, stilbene dyes, and thiazole dyes.

Examples of the resin include copolymers of acrylic acid esters and methacrylic acid esters, copolymers of N, N′-dimethylaminoethyl methacrylate monochloroacetic acid amine salt modified products and methacrylic acid esters, vinylpyrrolidone acetic acid. A vinyl copolymer or the like is used.

The temporary hair dye is prepared by dissolving and dispersing the above essential components, resin, dye, pigment and the like in a dispersion medium such as water, amyl alcohol, isopropanol, ethanol and acetone. In addition, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, polyhydric alcohols such as propylene glycol, glycerin and polyethylene glycol, and higher alcohols such as isostearyl alcohol and oleyl alcohol. , Fatty acids such as lanolin fatty acid and coconut fatty acid, esters such as isopropyl myristate, hydrocarbons such as liquid paraffin, cationic polymer compounds, amines, fragrances, etc. It can be blended according to the purpose.

(7) Pre-Campoo Treatment Pre-Campoo Treatment is prepared by dissolving or suspending the above-mentioned essential components and known optional components as necessary in a medium such as water.

As the known optional components, oils and fats such as higher alcohols and fatty acid esters; nonionic surfactants such as polyoxyalkylene alkyl ethers that act as emulsifiers and solubilizers; moisturizers such as glycerin and pyrrolidonecarboxylic acid are used. By adding these, hair can be treated with the pre-shampoo treatment agent of the present invention, and the feeling of finish after washing can be adjusted arbitrarily. That is, a moisturizing finish by adding a liquid oil and fat component, a moisturizing finish by adding a humectant component, and a smoother finish by using a higher alcohol are obtained.

〔The invention's effect〕

The modified polysiloxane of the present application is obtained by introducing an amino group or an ammonium group, and an oxyalkylene group into polycyclosiloxane, and is water-soluble without impairing the effect that polysiloxane originally has on suppleness and smoothness of hair. It has improved adsorption retention on hair and can be widely applied to hair cosmetics. Especially when used for hair dye, it has a high adsorption residual property and is excellent in the effect of increasing the color depth.

〔Example〕

 Next, a synthesis example and an example will be described.

Synthesis Example 1 A reactor was charged with a polyoxyalkylene of the following formula. (P = q, average molecular weight 2300) 1898 g (0.83 mol), allyl glycidyl ether 28.5 g
(0.25 mol), isopropyl alcohol 2500 g, potassium acetate 0.5 g and chloroplatinic acid 0.01 g are charged and heated under reflux (temperature about 83 ° C.) to which methylhydrogenpolysiloxane of the following formula is added. 894 g (0.125 mol) was added dropwise over 2 hours, and heating under reflux (about 83 ° C.) was continued for 5 hours. Next, 150 g (2.5 mol) of ethylenediamine was charged into this reaction system at a temperature of 70 ° C., and the mixture was heated under reflux for 2 hours.

The reaction product thus produced was stripped and filtered to obtain 2552 g of polyoxyalkyleneaminopolysiloxane corresponding to the following formula (hereinafter referred to as modified polysiloxane I).

This product has a viscosity of 2500 centistokes (25 ° C) and a refractive index.
It was 1.4450 (25 ° C) and had an amine equivalent of 5100.

Synthesis Example 2 350 g (0.8 mol) of polyoxyalkylene CH ₂ ═CHCH ₂ O (CH ₂ CH ₂ O) _p Me (average molecular weight 438) of the following formula, 1000 g of toluene, and 0.1 g of potassium acetate were placed in a reactor.
And 2-ethylhexanol 3% solution of chloroplatinic acid.
Charge 1 g and heat to reflux (temperature approx. 115 ° C) to which methylhydrogenpolysiloxane of the formula below is added. 735 g (0.067 mol) was added dropwise over 1 hour, 23 g (0.2 mol) of allyl glycidyl ether was added dropwise, and heating under reflux (about 115 ° C.) was continued for 8 hours.

997 g (0.060 mol) of polyoxyalkylene epoxy polysiloxane obtained by stripping the above reaction mixture, 1 g of isopropyl alcohol and 12 g of ethylenediamine (0.2
(Mol) was charged in a reactor and reacted for 3 hours while heating under reflux (temperature about 83 ° C.).

The reaction product thus produced was stripped and filtered to obtain 950 g of a polyoxyalkyleneaminopolysiloxane corresponding to the following formula (hereinafter referred to as modified polysiloxane II).

This product has a viscosity of 640 centistokes (25 ° C) and a refractive index.
It showed 1.4355 (25 ° C) and an amine equivalent of 2800.

Synthesis Example 3 1683 g (0.1 mol) of modified polysiloxane II and 842 g of isopropyl alcohol were placed in a 3 l flask, and methyl iodide 85 was added.
g (0.6 mol) was added, and the mixture was reacted with heating under reflux for 2 hours. When the reaction product was stripped, 1670 g of a dark brown viscous modified polysiloxane III was obtained.

Example 1 An oxidative permanent hair dye having the following composition was produced, and the color tone of dyed hair when the hair was dyed with this was examined. The results are shown in Table 1.

Composition: (First agent) p-Phenylenediamine 1.0% Propylene glycol 10.0 Sodium edetate 0.3 Sodium sulfite 0.5 Perfume 0.1 Additive (Table 1) 1.0 Polyoxyethylene (6) stearyl ether 1.0 Water balance (pH is aqueous ammonia) Adjusted to 10.0) (Second agent) Hydrogen peroxide 6.0% Water 4.0 Hair dyeing method: Hair was dipped in an equivalent mixture of the first agent and the second agent for 30 minutes to dye hair. The hair was then thoroughly washed with a 1% sodium dodecyl sulphate aqueous solution, rinsed with running water and air dried.

Evaluation method: (1) Color measurement Using a colorimetric color difference computer ND-1010C type (manufactured by Nippon Denshoku Industries Co., Ltd.), the lightness of the hair after dyeing was measured. The L value in Table 1 indicates the lightness, and the smaller this value is, the deeper the color tone is.

Example 2 The shampoo composition shown in Table 2 was prepared by a conventional method and pH
Adjusted to 7.2. All of these shampoos exhibited good foaming and foam slippage when used, and hair washed and dried with these shampoos showed no hair fly,
Comb force was small and showed a supple feel.

Example 3 A hair rinse agent shown in Table 3 was prepared, adjusted to pH 5.0 and then adjusted to 100 with water. The hair treated with these rinses was excellent in moisturizing feeling after drying and smoothness, and gave a supple finish.

Example 4 The precision shampoo treatment shown in Table 4 was prepared by adding the water-soluble component heated to the same temperature to the oil-soluble component heated to 70 ° C., cooling, stirring and emulsifying. The hair treated with these treatments all had excellent moisturizing feeling and smoothness after drying, and had a low combing force.

Example 5 The hair setting agents shown in Table 5 were prepared according to a conventional method. All of them showed a good set-holding power, and gave a supple and smooth feel.

Example 6 A permanent wave first agent shown in Table 6 was prepared.
Both were adjusted to pH 8.5 with ammonia. The first of these
When the hair was permed with a second agent containing 5% of sodium bromate, a supple finish was obtained.

Example 7 Hair liquids shown in Table 7 were prepared. All of these had improved stickiness.

Claims (1)

[Claims] 1. A general formula: ▲ R ¹ _a ▼ ▲ R ² _b ▼ Y _c Z _d SiO _{1/2 (4-abcd)} [wherein R ^{1 is} a substituted or unsubstituted monovalent group having 1 to 20 carbon atoms]. Hydrocarbon group (hereinafter referred to as monovalent hydrocarbon group) R ² : a monovalent hydrocarbon group or OX (X is a hydrogen atom or a monovalent hydrocarbon group) Y: (R ³ is a hydrogen atom, an organic group having a monovalent hydrocarbon group or an amino group, R ⁴ is an organic group having an amino group), (R ⁵ and R ⁶ are organic groups having an amino group), (R ⁸ is a hydrogen atom, a monovalent hydrocarbon group, or an organic group having an amino group or an ammonium group, R ⁹ and R ¹⁰ are monovalent hydrocarbon groups or an organic group having an amino group or an ammonium group, M is a halogen, Inorganic acid or organic acid anion) or (R ¹¹ , R ¹² and R ¹³ are organic groups having an amino group or an ammonium group, M is a halogen, an inorganic acid or an organic acid anion) Z: (R ⁷ is a hydrogen atom or a monovalent hydrocarbon group, p, q and r are 0
A number of up to 50) a, b, c, d: 0 <a ≦ 3, 0 <b ≦ 3, 0 <c ≦ 1,
0 <d ≦ 1 and 0 <a + b + c + d <3]], and a hair cosmetic comprising one or more amino-modified polysiloxane or ammonium-modified polysiloxane.