JPH03193718A - Water-in-oil type emulsion hair cosmetic - Google Patents

Abstract

PURPOSE:To obtain the title cosmetic providing the hair with excellent gloss, smooth touch and good setting retaining properties and having excellent stability, comprising an organic silicone resin, water-swelling clay minerals and a specific surfactant. CONSTITUTION:The title cosmetic comprising (A) an organic silicone resin composed of a unit shown by formula I (R is 1-8C hydrocarbon group or phenyl; n is 1.0-1.8), (B) water-swelling clay minerals, a layer silicate mineral belonging to the smectite, (C) a quaternary ammonium salt type cationic surfactant shown by formula II (R1 is 10-22C alkyl or benzyl; R2 is methyl or 10-22C alkyl; R3 and R4 are 1-3C alkyl or hydroxyalkyl; X is halogen or methyl sulfate residue) and (D) a lipophilic surfactant (e.g. polyglycerin ester) in the ratio of 0.1-50wt.% component A, 0.2-3.0wt.% component B, 60-140 milliequivalent based on 100g component B and 75-2,000g component D.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a highly stable water-in-oil emulsion (hereinafter referred to as (abbreviated as Wlo)) relates to hair cosmetics.

[Conventional technology]

Conventionally, oil components such as silicone oils, ester oils, and hydrocarbon oils have been solubilized, emulsified, or 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, blends well into hair, and provides good gloss. However, these oils have a limit of 3J.
When used for i or used by consumers for a long time,
The drawbacks were that the hair became more creaky and greasier. In addition, cationic surfactants are often used for the purpose of imparting a smooth surface, but they do not provide the desired gloss and have the disadvantage of being unfavorable from a safety standpoint if used in large amounts.

[Problem to be Solved by the Invention 8] In view of the above circumstances, the present inventors have developed a method that provides hair with excellent gloss, smooth feel, good set retention, and stability. As a result of intensive research to obtain an excellent hair cosmetic, it was discovered that a W10 hair cosmetic with a specific composition containing a silicone resin was extremely effective, and the present invention was completed.

[Means for Solving the Problems] That is, the present invention solves the problem using the average formula RnS i O<4-n>
72 (R represents a hydrocarbon having 1 to 6 carbon atoms or a phenyl group, and rl represents a value of 1.0 to 1.8); 1f contains a water-swellable clay mineral, a quaternary ammonium salt type cationic surfactant, and a lipophilic surfactant.
The present invention provides a water-in-oil emulsified hair cosmetic designated as ff'J.

The configuration of the present invention will be explained below.

The organic silicone resin used in the present invention is R35iO)
/2 units, R2S i OSRS f 03/2 units,
It consists of appropriate combinations of 5i02 units, the proportion of which is determined by the average formula RnS i O (+-n>72 (R is 1 carbon number)
Represents a hydrocarbon or phenyl group up to 6, where n is 1.0 to
Represents values up to 1.8. ), approximately 1
, 500 to 10,000. The above silicone resin is soluble in benzene and can be produced by various methods. - Examples: General formula RaS i X1R2S i X2, R31X3, Si
X4 (X is a hydrolyzable group, such as chlorine, bromine,
A compound represented by fluorine, alkoxy (such as methoxy, ethoxy, etc., or acyloxy group) is added to a suitable solvent such as toluene, benzene, xylene, etc. depending on the desired resin composition, and then this solvent is mixed with a suitable solvent. in a sufficient amount of water to obtain the desired hydrolysis and cocondensation in an acidic solvent. The aqueous phase is removed from the resulting two-phase system, the remaining resinous material is neutralized with a sufficient amount of sodium bicarbonate or other alkaline material, and the solvent is distilled off to obtain the desired organosilicone resin. can get.

The amount of the organic silicone resin used in the present invention is 0.1 to 50% by weight, preferably 1.0 to 50% by weight in the hair cosmetic.
It is 25% by weight. If it is less than 0.1% by weight, sufficient effects cannot be obtained, and if it exceeds 50% by weight, the effects of the present invention will not be enhanced.

The water-swellable clay mineral used in the present invention is a layered silicate mineral belonging to the genus smectite, and generally includes montmorillonite, beidellite, nontronite, sabonite, and hectorite, which may be either natural or synthetic. It may be. Commercially available products include Knivia, Smectone (all manufactured by Kunimine Industries), Veegum (Vanderbilt), Laponite (Laborte), and Fluorotetrasilicon Mica (Topie Industries). Any one kind or two or more kinds of these water-swellable clay minerals can be used, and the blending amount thereof is 0.2 to 3.0% by weight in the hair cosmetic.

If it is less than 0.2% by weight, temperature stability may be insufficient, and if it is more than 3.0% by weight, the viscosity of the hair cosmetic may increase and a smooth feel may not be obtained. .

The quaternary ammonium salt type cationic surfactant used in the present invention has the following general formula (where R1 is an alkyl group having 10 to 22 carbon atoms or a benzyl group, and R2 is a methyl group or an alkyl group having 10 to 22 carbon atoms. , R3 and R4 are an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X is a halogen atom or a methyl sulfate residue. For example, dodecyltrimedelammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, arakyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyldimethylethylammonium chloride, cetyldimethylethylammonium chloride, stearyldimethylethylammonium Chloride, aracyldimethylethylammonium chloride, behenyldimethylethylammonium chloride, myristyldiethylmethylammonium chloride, cetyldimethylethylammonium chloride, stearyldiethylmethylammonium chloride,
Arakyldiethylmethylammonium chloride, behenyldiethylmethylammonium chloride, benzyldimethylmyristylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylbehenylammonium chloride, benzylmethylethylcetylammonium chloride, benzylmethylethylstearylammonium chloride , distearyldimethylammonium chloride, dibehenyldihydroxyedylammonium chloride, and corresponding bromides, and furthermore, civalmidelpropylethylammonium methyl sulfate and the like. In carrying out the present invention, one or more of these may be arbitrarily selected.

The content of the quaternary ammonium salt type cationic surfactant in the W10 hair cosmetic of the present invention is 100% of the water-swellable clay mineral.
It is preferably 60 to 140 milliequivalents (hereinafter abbreviated as layer eq), more preferably 80 to 12 milliequivalents per g.
It is 0meq. In addition, the quaternary ammonium salt type cationic surfactant and the water-swellable clay mineral may be added separately to the oil phase and water phase, respectively, during the preparation of the W10 hair cosmetic of the present invention, or they may be added as commercially available products (e.g. The reactants may be added to the oil phase after reacting both of them, including Bentone (National Red Co.), in a suitable solvent.

The lipophilic surfactant used in the present invention has an HLB value of 1 to 12, such as polyglycerin esters, glycerin pyroglutamic acid monofatty acid esters,
Examples include polyglycerin ethers, polyoxyethylene alkyl ethers, polyoxyethylene hydrogenated castor oil esters, sorbitan fatty acid esters, polyoxyethylene polyoxybrobylene phytostanol esters, and one or more selected from these. It is used as Among these, polyglycerin esters, glycerin pyroglutamic acid monofatty acid esters, and the like are preferred in terms of ease of emulsification, stability, and good feel. Specific substances include diglyceryl diisostearate, triglyceryl diisostearate, pyroglutamic acid monoglyceryl oleate, diglyceryl isostearyl ether, polyoxyethylene (2 moles) oleyl ether, and polyoxyethylene (7 moles) cured. Castor oil ester, polyoxyethylene (4 mol), hydrogenated castor oil ester, sorbitan monolaurate, polyoxyethylene (5 mol)
mol) polyoxybrobylene phytostanol ester, sorbitandiolate, etc. The blending amount is preferably 75 to 2,000 g, more preferably 100 to 1,500 g per 100 g of water-swellable clay mineral.

In the present invention, it is preferable to blend a low boiling point oil in order to dissolve the silicone resin. The low boiling point oil to be used is one having a boiling point of 200° C. or lower at normal pressure. Moreover, low viscosity silicone oil refers to one having a viscosity of 50 cps or less at room temperature.

Specific examples of low boiling point oils include low boiling point quenched silicones such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and hexadecamethylheptasiloxane;
Low-boiling cyclic silicone oils such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and tetradecamethylcycloheptasiloxane, Exxon's Isopar (registered trademark) A, C1, D1, E1, and G
1 Same H1 Same 1 Same as M1 Shell Sol (registered trademark Alli 71) manufactured by Shell Co., Ltd., Tsurutrol (registered trademark) 100 manufactured by Philips Co., Ltd., or 130, 220, etc., which have a boiling point of 60 at normal pressure. Examples include low boiling point isoparaffinic hydrocarbon oils in the range of ~260°C, fluorochloro-substituted hydrocarbons such as trichlorotrifluoroethane and tetrachlorodifluoroethane. Among these low boiling point 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). The above-mentioned low boiling point oil and low viscosity silicone oil can be used arbitrarily one or more kinds, and the total amount of organic silicone (H fat) is preferably 1 to 50 times (heavy II).

In addition to the above-mentioned ingredients, the W10 hair cosmetic of the present invention includes:
N-acyl amino acid ester, carboxydextrin, casein, methylcellulose, ethylcellulose, C
Stability can be improved by adding oil phase thickeners such as MC, hydroxyethylcellulose, hydroxypropylcellulose, sodium polyacrylate, dialkyldimethylammonium cellulose sulfate, dextrin fatty acid ester, polyvinyl isobutyl ether, polyvinylethyl ether, polybutadiene, and polyisobutylene. It is particularly preferable in terms of. The amount to be blended is preferably 0.1 to 5.0% by weight based on the total amount of the cosmetic, and preferably about 0.5 to 2.0% by weight. In addition, the W10 hair cosmetic of the present invention contains 0 of the ultraviolet absorbers exemplified below in the total amount of the cosmetic.
．． It can be blended in an amount of about 0.01 to 10%, preferably about 0.5 to 5%. What is important when blending a UV absorber is that the UV absorption effect lasts longer on the hair than ever before. Typical examples of ultraviolet absorbers are listed below.

Barraminobenzoic acid (hereinafter abbreviated as PABA), PA
BA monoglycerin ester, N,N-dipropoxy P
ABA ethyl ester, N,N-jethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, N,N
- Benzoic acid UV absorbers such as dimethyl PABA amyl ester, N,N-dimethyl PABA octyl ester, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, pendyl salicylate-1, p-isobrobanol phenyl salicylate Salicylic acid-based UV absorbers such as 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 -Cinnamic acid ultraviolet absorbers such as β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl dibaramethoxycinnamate, 2.4
-dimethoxybenzophenone, 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-
Benzophenone ultraviolet rays such as sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4-phenylbenzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc. Absorbent, 3-(4'
-methylbenzylidene)-d, L-camphor, 3-benzylidene-d, t-camphor urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzo Triazole, 2-(2'-hydroxy-5'-71octylphenyl)benzotriazole,
Examples include 2-(2°-hydroxy-5°-methylphenyl)benzotriazole, 4-methoxy-4°-butyldibenzoylmecne, and the like.

In addition, the W10 hair cosmetic of the present invention includes oils, moisturizers, thickeners, preservatives, antioxidants, which are commonly used in cosmetics,
Can be mixed with crude drugs, fragrances, etc.

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

Prior to Examples, stability evaluation and sensory evaluation will be explained.

W10 hair makeup t1 obtained in Example 1.2 and Comparative Examples 1 to 5
was filled into a glass bottle and left at 0°C, room temperature, and 50°C for one month, and then evaluated.

Stability evaluation was performed using the following three-level evaluation.

O: No separation observed △; Very slight oil separation ×: Significant oil separation observed 1 plate 2 ■ Hair condition (thickness, hardness, degree of damage) is almost the same Using hair, make hair bundles (length: 15 cm, width: 3 cm, 5 layers,
11.5g) was prepared, 0.5g of the sample was applied, and the following three-level sensory evaluation was performed on setting power, gloss, and suppleness.

A, Good B, Normal C1 Not good (1) to (6) are heated and mixed and dissolved at 70°C, and the oil phase is adjusted in advance. Next, (7) to (10) were dispersed and mixed at 70°C, and then gradually added to the oil phase while stirring with a disperser, sufficiently uniformly mixed and stirred, and cooled to obtain the desired hair cosmetic.

In Comparative Example 4, the desired hair makeup It was obtained by stirring and dissolving (1) and (2).

(The following is a blank space) Examples 1 and 2, Comparative Example 1.4 A test was conducted on W10 hair makeup t1 having the composition shown in Table 1. The results are also shown in Table 1. The manufacturing method was as follows.

As is clear from Table 1, Examples 1.2 and 2 were very superior in both stability and sensory evaluation compared to the comparative example.

Example 3 Hair cream (1) Isopar M (2) Dimethylpolysiloxane 20CS (3) Rn
S i O (4-n) i2 (R is methyl group, n = 1.0
) (4) Distearyldimethylammonium chloride (5) Diglyceryl diisostearate (6) Vitamin E acetate (7) Dextrin fatty acid ester (8) Fragrance (9) Purified water (10) Polyethylene glycol 6000 (11) Glycerin ( 12) Methylparaben (13) Keratin hydrolyzate 20.0 2.0 5.0 0.8 1.5 0.1 1.0 Appropriate amount remaining 1.0 5.0 0.2 0.1 (14) Smectone 1 .2 Manufacturing methods (1) to (8) are heated to 70°C, dissolved, and mixed to prepare the oil phase in advance. Next, (9) to (14) were dispersed and mixed at 70° C., and then gradually added to the oil phase while stirring with a disperser, sufficiently uniformly mixed and stirred, and cooled to obtain the desired hair cream.

Example 4 Hair conditioner (1) Octamedylcyclotetrasiloxane (2) Dimethylpolysiloxane 5cs (3) RnSiO(4-n)/2 (R phenyl group, n=1.8) (4) Behenyl Trimethylammonium chloride (5) Diglyceryl diisostearate (6) Dextrin fatty acid ester (7) Flavor (8) Purified water 20.0 5.0 15.0 0.4 2.0 2.0 Appropriate amount remaining (9) Polyethylene glycol (10001,5 (lO
) Propylene glycol 5.0 (11)
Ethylparaben 0.2 (12) Smectone 0.8 According to the manufacturing method Example 3, the desired hair conditioner was obtained.

Example 5 Sunguard Hair Cream (1) Isopar H (2) Decamethylcycbentasiloxane (3) Rn
S i O<4-nri2 (10% of R is a phenyl group and the rest is a methyl group, n = 1.3) (4) diglyceryl diisostearate (5) 2-hydroxy-4-methoxybenzophenone (6) Varaminobenzoic acid monoglycerol ester (7) Tocopherol 10.0 10.0 5.0 2.0 0.1 2.0 0.1 (8) Dextrin fatty acid ester 0.5 (9)
Fragrance Appropriate amount (10) Bentone 38 2.0 (11) Purified water
Remainder (12) Propylene glycol 1.0 (13) Polyethylene glycol 6000 1.0 (14) Colored pigment
0.3 Manufacturing method According to Example 3, the desired sun guard cream was obtained.

Example 6 Hair mousse (1) Isopar L (2) Dimethylpolysiloxane (5as) (3) Rn
S i O<4-n>12 (R is a methyl group, n=1.7
) (4) Stearyltrimethylammonium chloride (5) Diglyceryl diisostearate (6) Dextrin fatty acid ester 30.0 2.0 15.0 0.4°1.0 0.1 (7) Flavoring appropriate amount (8) i
, 1 water Residue (9) Glycerin 2.0 (10) Medylparaben 0.2 (11) Smectone 0.6 (12) n-Bukun 8.0 Using manufacturing methods (1) to (11), Example 3 An emulsion was obtained in the same manner. After putting this in an aerosol container and attaching a valve,
Fill (12).

Example 7 Hair mousse (1) Octamethyltrisiloxane 25.0 (2
) RnS i O+4-n)/2 (R is ethyl group,
n = 1.1) 25.0 (3) diglyceryl diisostearate 3.0 (4) Dextrin fatty acid ester 0.5 (5) 2-hydroxy-4-methoxybenzophenone 0.2 (6) Fragrance appropriate amount ( 7) Bentone 3.0 (8) Purified water Residual (9) Bu0 pyrene glycol 0.0 (10) Polyethylene glycol 0.5 (11) Quaternized collagen
0.1 (12) Colored pigment
0.1 (13) Liquid petroleum gas
5.0(14) dimethyl ether
An emulsion was obtained according to Example 3 using the 5.0 production methods (1) to (12). After putting this in an aerosol container and attaching a valve,
(13) Fill (14).

The hair cosmetics of Examples 3 to 7 provided excellent gloss, smooth feel and good setting power, and had excellent stability.

[Effects of the Invention] The W10 hair cosmetic of the present invention is a hair cosmetic that imparts excellent gloss, smooth feel and good setting power to hair, and has excellent stability.

Claims (1)

[Claims] (1) Average formula RnSiO_(_4_-_n_)_/_2
(R represents a hydrocarbon having 1 to 6 carbon atoms or a phenyl group, and n represents a value of 1.0 to 1.8); A water-in-oil emulsion hair cosmetic comprising a swellable clay mineral, a quaternary ammonium salt type cationic surfactant, and a lipophilic surfactant.