JPH0623084B2 - Water-in-oil emulsion hair cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention imparts excellent gloss, smooth feel, and moist and supple finish to hair, and excellent stability in water-in-oil emulsion (hereinafter, referred to as Abbreviated as W / O.) Hair cosmetics.

[Prior Art] Oils such as silicone oil, ester oil, and hydrocarbon oil have been conventionally solubilized, emulsified, and dissolved in hair cosmetics for the purpose of imparting gloss and smoothness to hair. In particular, silicone oil has been widely used in recent years because it has a low surface tension, is excellent in conformity to hair, and has good gloss. However, with these oils, there is a limit to the oil content, and when used in large amounts, or when consumers use it for a long time,
There was a defect that the squeaky feeling of the hair increased and it became greasy. Further, although a cationic surfactant is often used for the purpose of imparting smoothness, it has a drawback that it does not give a desired gloss and that a large amount of it is not preferable in terms of safety.

[Problems to be Solved by the Invention] In view of such circumstances, the present inventors have given the hair an excellent luster, a smooth feel, a firm and supple finish, and stability. As a result of diligent research to obtain an excellent hair cosmetic, a W / O hair cosmetic of a specific composition containing a high molecular weight silicone was found to be extremely effective, and the present invention was completed.

[Means for Solving the Problems] That is, the present invention provides a high molecular weight silicone represented by the following general formula [I], a low boiling point oil and / or a low viscosity silicone oil, a water-swelling clay mineral, a quaternary ammonium salt type. The present invention provides a water-in-oil type emulsion hair cosmetic containing a cationic surfactant and a lipophilic surfactant.

(R ₁ represents a methyl group or a part thereof is a phenyl group, R ₂ represents a methyl group or a hydroxyl group, and n is 3,
Represents an integer from 000 to 20,000. ) Hereinafter, the configuration of the present invention will be described.

The high molecular weight silicone used in the present invention is represented by the above general formula [I], and the value of n in the formula is 3,000 to 20,
It is 000, and exhibits a soft rubber-like property at room temperature. Specific examples include dimethylpolysiloxane, methylphenylpolysiloxane, terminal hydroxyl group-containing dimethylpolysiloxane, terminal hydroxyl group-containing methylphenylpolysiloxane, and the like.

The blending amount of the high molecular weight silicone used in the present invention is 0.1 to 50% by weight, preferably 1.0 to 25% by weight in the hair cosmetic composition. If it is less than 0.1% by weight, a sufficient effect cannot be obtained, and if it exceeds 50% by weight, the effect of the present invention is not enhanced.

The low boiling point oil used in the present invention has a boiling point of 260 at atmospheric pressure.
What is below ℃. The low-viscosity silicone oil refers to one having a viscosity at room temperature of 50 cps or less.

Specific examples of the low boiling point oil include low boiling point chain silicones such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and hexadecamethylheptasiloxane,
Low-boiling cyclic silicone oils such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and tetradecamethylcycloheptasiloxane, Isopar (registered trademark) A, C, D, E, G, and G manufactured by Exxon Co. H, the same K, the same L, the same M, Shell Sol (registered trademark) 71 manufactured by Shell Co., Saltol (registered trademark) 100 manufactured by Phillip Co., or 130, 220, etc., and the boiling point at atmospheric pressure is 60 to Examples thereof include low-boiling isoparaffin hydrocarbon oils in the range of 260 ° C., and fluorochloro-substituted products of hydrocarbons such as trichlorotrifluoroethane and tetrachlorodifluoroethane. Among these low boiling oils,
Isoparaffinic hydrocarbons are particularly preferred.

Specific examples of the low-viscosity silicone oil used in the present invention include dimethylpolysiloxane (10 to 50 cps) and methylphenylpolysiloxane (10 to 50 cps). As the low boiling point oil and the low viscosity silicone oil, any one kind or two or more kinds may be used, and the total blending amount is preferably 1 to 50 times (weight) with respect to the high molecular weight silicone.

The water-swellable clay mineral used in the present invention is a layered silicate mineral belonging to the genus Smectite, and generally includes montmorillonite, hydelite, nontronite, saponite, and hectorite, which are natural or synthetic products. Either may be used. Commercially available products include Kunipia, Smecton (both Kunimine Industries), Veegum (Vanderbilt), Laponite (Laporte), Fluorotetrasilicon mica (Topy Industries) and the like. These water-swellable clay minerals may be used alone or in combination of two or more, and the compounding amount thereof is 0.2 to 3.0% by weight in the hair cosmetic composition. If it is less than 0.2% by weight, the temperature stability may be insufficient,
If the amount is more than 3.0% by weight, the viscosity of the hair cosmetic composition may increase, and a smooth feeling of use may not be obtained.

The quaternary ammonium salt type cationic surfactant used in the present invention has the following general formula: (In the formula, R ₁ is an alkyl group having 10 to 22 carbon atoms or a benzyl group, R ₂ is a methyl group or an alkyl group having 10 to 22 carbon atoms, R _2
3 and R ₄ represent an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and X represents a halogen atom or a methylsulfate residue. ) Is represented by. For example, dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride,
Stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyldimethylethylammonium chloride, cetyldimethylethylammonium chloride, stearyldimethylethylammonium chloride, aralkyldimethylethylammonium chloride,
Behenyldimethylethylammonium chloride, myristyldiethylmethylammonium chloride, cetyldiethylmethylammonium chloride, stearyldiethylmethylammonium chloride, aralkyldiethylmethylammonium chloride, behenyldiethylmethylammonium chloride, benzyldimethylmyristylammonium chloride, benzyldimethylcetylammonium chloride, benzyl Dimethylstearyl ammonium chloride, benzyldimethylbehenylammonium chloride, benzylmethylethylcetylammonium chloride, benzylmethylethylstearylammonium chloride, distearyldimethylammonium chloride, dibehenyldihydroxyethylammonium chloride, and corresponding bromide, etc. Etc. Further dipalmityl propyl ethyl ammonium methyl sulfate and the like.
In carrying out the present invention, one kind or two or more kinds are arbitrarily selected from these.

The content of the quaternary ammonium salt type cationic surfactant in the W / O hair cosmetic composition of the present invention is 100 g of water-swelling clay mineral.
It is preferably 60 to 140 meq. (Hereinafter abbreviated as meq), more preferably 80 to 120 meq. or,
The quaternary ammonium salt type cationic surfactant and the water-swelling clay mineral may be added separately to the oil phase and the water phase at the time of preparation of the W / O hair cosmetic composition of the present invention, or commercially available products (for example, Benton: National Red Co., Ltd.) may be reacted in advance in a suitable solvent, and then the reaction product may be added to the oil phase.

The lipophilic surfactant used in the present invention has an HLB value of 1 to 12, and examples thereof include polyglycerin esters,
Glycerin pyroglutamic acid monofatty acid esters, polyglycerin ethers, polyoxyethylene alkyl ethers, polyoxyethylene hydrogenated castor oil esters, sorbitan fatty acid esters, polyoxyethylene polyoxypropylene phytostanol esters, and the like. More than one kind or two or more kinds are selected and used. Among them, polyglycerin esters, glycerin pyroglutamic acid monofatty acid esters, and the like are preferable in terms of ease of emulsification, stability, and good feel. Specific substances include diglyceryl diisostearate, triglyceryl diisostearate, monoglyceryl pyroglutamate oleate, diglyceryl isostearyl ether, polyoxyethylene (2 mol) oleyl ether,
Polyoxyethylene (7 mol) hydrogenated castor oil ester,
Polyoxyethylene (4 mol) hydrogenated castor oil ester,
Sorbitan monolaurate, polyoxyethylene (5 mol) polyoxypropylene phytostanol ester,
Examples thereof include sorbitandiolate. The blending amount is preferably 75 to 2000 g, and more preferably 100 to 1500 g based on 100 g of the water-swelling clay mineral.

In addition to the above-mentioned essential components, the W / O hair cosmetic composition of the present invention contains N-acyl amino acid ester, carboxydextrin, casein, methyl cellulose, ethyl cellulose, CMC, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium polyacrylate, dialkyldimethyl. Ammonium sulfate cellulose, dextrin fatty acid ester, polyvinyl isobutyl ether,
It is particularly preferable to add an oil phase thickener such as polyvinyl ethyl ether, polybutadiene or polyisobutylene in terms of stability. The blending amount is preferably 0.1 to 5.0% by weight, more preferably 0.5 to 2.0% by weight, based on the total amount of the cosmetic. In the W / O hair cosmetic composition of the present invention, the ultraviolet absorbers exemplified below are added in an amount of 0.01 to 10 in the total amount of the cosmetic composition.
%, Preferably about 0.5 to 5%. What is important in blending the ultraviolet absorber is that the durability of the ultraviolet absorbing effect on the hair is unprecedented and good.
Typical examples of the ultraviolet absorber are shown below.

Para-aminobenzoic acid (hereinafter abbreviated as PABA), PAB
A monoglycerin ester, N, N-dipropoxy PA
BA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N
Benzoic acid type ultraviolet absorbers such as dimethyl PABA amyl ester and N, N-dimethyl PABA octyl ester, salicylic acid such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanolphenyl salicylate UV absorbers, octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate,
Propyl-p-methoxycinnamate, isopropyl-
p-methoxycinnamate, isoamyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β -Phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate and other cinnamic acid-based UV absorbers, 2,
4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenylbenzophenone-2-carboxylate, 2-hydroxy-4-n-
Benzophenone-based UV absorbers such as octoxybenzophenone and 4-hydroxy-3-carboxybenzophenone, 3- (4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanic acid, urocanine Acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2- (2 '
-Hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 4-methoxy-4'-t
-Butyldibenzoylmethane and the like can be mentioned.

In addition, the W / O hair cosmetic composition of the present invention includes oils, moisturizers, thickeners, preservatives, antioxidants, which are commonly used in cosmetics.
It can be mixed with crude drugs and fragrances.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. All compounding amounts are weight%.

Prior to the examples, stability evaluation and sensory evaluation will be described.

Stability Evaluation The W / O hair cosmetics obtained in Examples 1 and 2 and Comparative Examples 1 to 5 were filled in glass bottles and allowed to stand at 0 ° C., room temperature and 50 ° C. for one month, and then evaluated.

The stability evaluation was evaluated by the following three-stage evaluation.

◯: No separation was observed at all Δ: Very slight separation of oil was observed ×: Significant separation of oil was observed Sensory evaluation Hair with almost the same hair condition (thickness, hardness, degree of damage) Used, hair bundle (length 15 cm, width 3 cm, weight 1.5
g), apply 0.5 g of the sample, and feel smooth, gloss,
The following three-level sensory evaluation was performed for suppleness.

A. Good B. Ordinary C. Poor Examples 1 and 2, Comparative Examples 1 and 4 W / O hair cosmetic compositions having the compositions shown in Table 1 were tested. The results are also shown in Table 1. The manufacturing method was as follows.

(1) to (6) are heated to 70 ° C, mixed and dissolved to prepare an oil phase in advance. Next, (7) to (10) were dispersed and mixed at 70 ° C., then gradually added to the oil phase while stirring with a disper, mixed and stirred sufficiently uniformly, and cooled to obtain the intended hair cosmetic.

In Comparative Example 4, (1) and (2) were dissolved by stirring to obtain the desired hair cosmetic composition.

As is clear from Table 1, Examples 1 and 2 were very excellent in stability and sensory evaluation as compared with Comparative Examples.

Example 3 Hair Cream (1) Isopar M 20.0 (2) Dimethylpolysiloxane 20CS 2.0 (3) Dimethylpolysiloxane (R ₁ and R ₂ are methyl groups, n = 10,000) 5.0 (4) Distearyldimethylammonium chloride 0.8 ( 5) Diglyceryl diisostearate 1.5 (6) Vitamin E acetate 0.1 (7) Dextrin fatty acid ester 1.0 (8) Perfume proper amount (9) Purified water residue (10) Polyethylene glycol 6000 1.0 (11) Glycerin 5.0 (12) Methylparaben 0.2 (13) Keratin hydrolyzate 0.1 (14) Smecton 1.2 Preparation methods (1) to (8) are heated to 70 ° C, dissolved and mixed to prepare an oil phase in advance. Next, (9) to (14) were dispersed and mixed at 70 ° C., then gradually added to the oil phase while stirring with a disper, mixed and stirred sufficiently uniformly, and cooled to obtain a target hair cream.

Example 4 Hair Conditioner (1) Octamethylcyclotetrasiloxane 20.0 (2) Dimethylpolysiloxane 5cs 5.0 (3) Dimethylpolysiloxane (R ₁ is a methyl group, R ₂ is a hydroxyl group n = 20,000) 15.0 (4) Behenyltrimethylammonium Chloride 0.4 (5) Diglyceryl diisostearate 2.0 (6) Dextrin fatty acid ester 2.0 (7) Perfume proper amount (8) Purified water residue (9) Polyethylene glycol 6000 1.5 (10) Propylene glycol 5.0 (11) Ethylparaben 0.2 ( 12) Smecton 0.8 Manufacturing method According to Example 3, a target hair conditioner was obtained.

Example 5 Sunguard Hair Cream (1) Isopar H 10.0 (2) Decamethylcyclopentasiloxane 10.0 (3) Methylphenylpolysiloxane (10% of R ₁ is a phenyl group, the rest is a methyl group, R ₂ is a methyl group n = 15,000) 5.0 (4) Diglyceryl diisostearate 2.0 (5) 2-Hydroxy-4-methoxybenzophenone 0.1 (6) Para-aminobenzoic acid monoglycerin ester 2.0 (7) Tocopherol 0.1 (8) Dextrin fatty acid ester 0.5 (9) Fragrance Appropriate amount (10) Benton 38 2.0 (11) Purified water Residual (12) Propylene glycol 1.0 (13) Polyethylene glycol 6000 1.0 (14) Coloring pigment 0.3 Manufacturing method According to Example 3, the intended sun guard hair cream was obtained.

Example 6 Hair mousse  (1) Isopar L 30.0 (2) Dimethyl polysiloxane (5cs) 2.0 (3) Dimethyl polysiloxane (R₁And R_TwoIs a methyl group, n = 20,000) 15.0 (4) Stearyl trimethyl ammonium chloride 0.4 (5) Diglyceryl diisostearate 1.0 (6) Dextrin fatty acid ester 0.1 (7) Perfume proper amount (8) Purified water Residue (9) Glycerin 2.0 (10) Methylparaben 0.2 (11) Smecton 0.6 (12) n-Butane 8.0 Using the production methods (1) to (11), an emulsion was obtained according to Example 3. This
After putting this in the aerosol container and attaching the valve, (12)
Fill.

Example 7 Hair mousse  (1) Octamethyltrisiloxane 25.0 (2) Dimethylpolysiloxane (R₁And R_TwoIs a methyl group, n = 10,000) 25.0 (3) Diglyceryl diisostearate 3.0 (4) Dextrin fatty acid ester 0.5 (5) 2-hydroxy-4-methoxy benzophenone 0.2 (6) Perfume proper amount (7) Benton 3.0 (8 ) Purified water Residual (9) Propylene glycol 6.0 (10) Polyethylene glycol 0.5 (11) Quaternized collagen 0.1 (12) Colored pigment 0.1 (13) Liquid petroleum gas 5.0 (14) Dimethyl ether 5.0 Manufacturing method (1) to (12) Was used to obtain an emulsion in the same manner as in Example 3. This
After putting it in the aerosol container and installing the valve, (13) (1
Fill 4).

Example 8 Hair spray (1) Dimethyl polysiloxane 1.0 (R ₁ and R ₂ are methyl groups, n = 5,000) (2) Diglyceryl diisostearate 0.1 (3) Isopar M 10.0 (4) Benton 38 0.1 (5 ) Propylene glycol 1.0 (6) Ethanol 3.0 (7) Preservative proper amount (8) Perfume proper amount (9) Purified water Residual (10) Liquid petroleum gas 60.0 Manufacturing methods (1) to (4) are heated to 70 ° C, dissolved and mixed. Then, the oil phase is adjusted in advance. Next, (5), (7) to (9) are conducted at 70 ° C.
After being dispersed and mixed in, the mixture was gradually added to the oil phase while stirring with a disper, and further (6) was gradually added, mixed and stirred sufficiently uniformly, and cooled to obtain an emulsion. After putting this in an aerosol container and attaching a valve, (10) is filled.

The hair cosmetics of Examples 3 to 8 give excellent luster, give a smooth feel, moisturize and supple the hair,
And it was excellent in stability.

[Effects of the Invention] The W / O hair cosmetic composition of the present invention is a hair cosmetic composition that imparts excellent gloss to the hair, imparts a smooth feel to the hair, moisturizes the hair, and is excellent in stability. is there.

Claims (1)

[Claims] 1. A high molecular weight silicone represented by the following general formula [I], a low boiling point oil and / or a low viscosity silicone oil, a water-swelling clay mineral, a quaternary ammonium salt type cationic surfactant and a lipophilic surfactant. A water-in-oil type emulsified hair cosmetic containing an agent. (R ₁ represents a methyl group or a part thereof is a phenyl group, R ₂ represents a methyl group or a hydroxyl group, and n is 3,
Represents an integer from 000 to 20,000. )