JPH10265344A - Water-in-oil type emulsion hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject hair cosmetic having good emulsion stability by formulating a specific cationic polymer and further using a specific water swelling clay mineral, a quaternary ammonium salt type cationic surfactant and a hydrophobic surfactant. SOLUTION: This water-in-oil type emulsion hair cosmetic is obtained by combining (A) a cationic thickener obtained by copolymerizing a monomer composition for thickeners containing (preferably 15.0-85.0 wt.%) amino- containing (meth)acrylic monomer of formula I (R<1> is H or methyl; R<2> and R<3> are each H, methyl, etc.; A is O or NH; B is a 1-4C alkylene), (preferably 1.0-60.0 wt.%) (meth)acryloyl group-containing monomer and (preferably 0.1-20.0 wt.%) cross-linkable vinyl monomer with (B) an organic modified clay mineral containing a water-swelling clay mineral, a quaternary ammonium salt type cationic surfactant and a hydrophobic surfactant. The hair cosmetic provides excellent gloss, smooth feeling and good set retaining force to hair without sticking to hair.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a water-in-oil type (hereinafter referred to as W / O) which imparts excellent non-stickiness, excellent gloss, a smooth feel, good set holding power, and excellent stability to hair.
Abbreviated as type. ) It relates to emulsified hair cosmetics.

[0002]

2. Description of the Related Art Conventionally, hair cosmetics have solubilized, emulsified and dissolved oils such as silicone oil, ester oil and hydrocarbon oil for the purpose of giving gloss and smoothness to hair. Used. In particular, silicone oils have been widely used in recent years because they have low surface tension, are excellent in conformity to hair, and have good gloss. For the purpose of setting the hair, a high molecular compound such as a polyvinylpyrrolidone-based polymer, an acidic acrylic polymer, or a copolymer of ethylene and maleic anhydride is blended. However, oils represented by silicone oils have a limit of oil content, and have a drawback that when used in large amounts or when used by consumers for a long time, the feeling of squeaking of the hair increases and the hair becomes greasy. In addition, cationic surfactants are often used for the purpose of imparting smoothness, but they do not impart desirable gloss, and have a drawback that if they are incorporated in a large amount, safety is not preferable. On the other hand, the above-mentioned polymer compound formulated for the purpose of setting the hair also has excellent fixing properties, that is, setting power, but does not satisfy gloss and smoothness.

On the other hand, in recent years, as a technique for producing a W / O emulsion which can be emulsified in a small amount and has good storage stability over a wide temperature range, a quaternary ammonium salt type cationic surfactant and a nonionic type surfactant are used. An emulsifier composition comprising a water-swellable clay mineral treated with an emulsifier has been developed (Japanese Patent Publication No. 3-80531), and a hair cosmetic containing this emulsifier composition has also been obtained (JP-A-3-15731).
7, JP-A-5-246824). However, in the W / O type emulsified cosmetic using this emulsification technique, further improvement in emulsification stability has been desired.

Accordingly, an object of the present invention is to eliminate the above-mentioned drawbacks, to provide excellent emulsion stability, to have a sticky and spreadable usability, to impart a smooth feel, and to make the hair oily and An object of the present invention is to provide a W / O-type emulsified hair cosmetic composition which is free from squeaking and has good set holding power.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a specific water-swellable clay mineral and a quaternary ammonium salt have been added to a specific cationic polymer. When a W / O type emulsified composition is prepared using a cationic cationic surfactant and a lipophilic surfactant, not only the emulsion stability is improved, but also a sticky and sticky usability and a smooth feel are obtained. Have been found, and based on this finding, the present invention has been completed.

That is, the present invention is a water-in-oil type emulsified hair cosmetic comprising the following component (A) and component (B).

(A) A cationic thickener obtained by polymerizing a monomer composition for a thickener containing: General formula (I):

[0008]

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(Wherein R ¹ is a hydrogen atom or a methyl group,
R ² and R ³ each independently represent a hydrogen atom, a methyl group,
Ethyl group or t-butyl group, A represents an oxygen atom or -N
H-group and B represent a linear or branched alkylene group having 1 to 4 carbon atoms. Amine-containing (meta) represented by)
Acrylic monomer 15.0 to 85.0% by weight, General formula (III):

[0010]

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(Wherein, R ¹ and A have the same meanings as described above;
R ⁵ is a linear or branched alkylene group having 1 to 17 carbon atoms or a general formula (IV):

[0012]

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(Wherein, n is an integer of 1-4, and q is 1-25
Indicates an integer. ), R ⁶ represents a hydrogen atom or a methyl group. (Meth) acryloyl group-containing monomer represented by 1.0 to 60.0% by weight, crosslinkable vinyl monomer 0.1 to 20.0% by weight

(B) An organically modified clay mineral containing: Water-swellable clay mineral. Quaternary ammonium salt type cationic surfactant.

In the present invention, the monomer composition for a thickener of the component (A) preferably further contains the following. General formula (II):

[0016]

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(Wherein, R ¹ has the same meaning as described above, and R ⁴ has the general formula:

[0018]

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(Wherein p represents 3 or 4) or a group represented by the following formula:

[0020]

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The group represented by 3.0 to 80.0% by weight of a vinyl monomer represented by

Next, the configuration of the present invention will be described. First, the cationic thickener of the component (A) is as described above.
Or a polymer obtained by polymerizing a monomer composition for a thickener containing Hereinafter, each component constituting the cationic thickener will be described in detail.

The amine-containing (meth) acrylic monomer represented by the general formula (I) is obtained by neutralizing a copolymer obtained by copolymerizing a monomer composition for a thickener with an appropriate acid. Occasionally, it is a component having a role of giving the property of a cationic ion to the copolymer.

Representative examples of the amine-containing (meth) acrylic monomer include, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (Meth) acrylamide and the like,
The present invention is not limited to only such examples. In the present invention, the amine-containing (meth) acrylic monomers are used alone or in combination of two or more.

The ratio of the amine-containing (meth) acrylic monomer in the monomer composition for a thickener is 15.0.
To 85.0% by weight, preferably 25.0 to 75.0% by weight, more preferably 35.0 to 65.0% by weight. When the proportion of the amine-containing (meth) acrylic monomer is less than the above range, the amount of neutralization of the amine-containing (meth) acrylic monomer by the acid in the obtained copolymer is too small. If the viscosity exceeds the above range, the resulting cationic thickener loses the flexibility of the film formed after drying.

The vinyl monomer represented by the general formula (II) is a component that imparts flexibility, gloss and smoothness to a film formed after the cationic thickener is dried.

Representative examples of the vinyl monomer include, for example, N-vinylpyrrolidone, N-vinylpiperidone,
Examples thereof include acrylamide and methacrylamide, but the present invention is not limited only to such examples. In the present invention, the vinyl monomers are used alone or in combination of two or more.

The proportion of the vinyl monomer in the monomer composition for a thickener is 80.0% by weight or less, preferably 7% by weight.
It is prepared so as to be 5.0% by weight or less, more preferably 60.0% by weight or less. When the proportion of such a vinyl monomer exceeds the above upper limit, the gel viscosity of the resulting cationic thickener is significantly reduced. In addition, effects achieved by blending the vinyl monomer,
That is, in order to sufficiently impart flexibility, gloss, and smoothness to a film formed after the cationic thickener is dried, the ratio of the vinyl monomer in the thickener monomer composition is 3.0. % By weight or more, preferably 5.0% by weight or more, more preferably 20.0% by weight
It is desirable that this is the case.

The (meth) acryloyl group-containing monomer represented by the general formula (III) is used for improving the gloss of a film formed after the cationic thickener is dried, improving the gel viscosity, and various settings. It is a component for improving compatibility with the polymer.

Specific examples of the (meth) acryloyl group-containing monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, Stearyl (meth) acrylate, cyclohexyl (meth) acrylate, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) (T) acrylate, hydroxybutyl (meth) acrylate, polyoxyethylene (in the general formula (IV), n is 2 and q is an integer of 2 to 9)
(Meth) acrylate, methoxypolyethylene glycol (in the general formula (IV), n is 3 and q is an integer of 2 to 23)
Examples thereof include (meth) acrylates, but the present invention is not limited to only such examples. In the present invention, the (meth) acryloyl group-containing monomers are used alone or in combination of two or more.

The ratio of the (meth) acryloyl group-containing monomer in the monomer composition for a thickener is 1.0 to 6
It is adjusted to be 0.0% by weight, preferably 1.0 to 55.0% by weight, more preferably 2.0 to 30.0% by weight. When the proportion of the (meth) acryloyl group-containing monomer exceeds the above range, the proportion of the hydrophobic group in the obtained copolymer becomes large, and the solubility in water becomes small even after neutralization, It is difficult to obtain a smooth gel, and if the amount is less than the above range, the gel viscosity is reduced, so it is necessary to increase the amount of the cationic thickener used. The gloss of the film formed after the cationic thickener has dried is reduced.

The crosslinkable vinyl monomer is a compound having two or more carbon-carbon unsaturated double bonds in one molecule, and has a property of crosslinking with another monomer.

Representative examples of the crosslinkable vinyl monomer include, for example, ethylene glycol di (meth) acrylate, polyoxyethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and polypropylene. (Meth) having two or more carbon-carbon unsaturated double bonds in one molecule such as glycol di (meth) acrylate
Acrylic monomers; methylenebis (meth) acrylamide, 1,2-bis (meth) acrylamideethane,
1, such as 1,5-bis (meth) acrylamidopentane
(Meth) acrylamide monomers having two or more carbon-carbon unsaturated double bonds in the molecule; vinyl monomers having two or more carbon-carbon unsaturated double bonds in one molecule such as divinylbenzene; However, the present invention is not limited only to such an example. In the present invention, the crosslinkable vinyl monomers are used singly or as a mixture of two or more.

The proportion of the crosslinkable vinyl monomer in the monomer composition for a thickener is 0.1 to 20.0% by weight,
It is preferably prepared to be 1.0 to 10.0% by weight, more preferably 2.0 to 8.0% by weight. When the proportion of the crosslinkable vinyl monomer is less than the above range, the crosslink density of the obtained cationic thickener becomes too small, so that the viscosity of the cationic thickener cannot be increased, and If the above range is exceeded,
Although the viscosity of the cationic thickener increases, fine aggregates are formed in the gel, and it becomes difficult to obtain a uniform gel.

The polymerization reaction of the monomer composition for a thickener containing the amine-containing (meth) acrylic monomer, vinyl monomer, (meth) acryloyl group-containing monomer and crosslinkable vinyl monomer is carried out by a general solution polymerization method or the like. The polymerization can be performed by a bulk polymerization method, for example, by a precipitation polymerization method that is a polymerization method for obtaining a powder, and is usually performed by heating in a nonaqueous solvent under an inert gas atmosphere such as nitrogen gas. It is done while. Thus, the polymerization reaction is carried out in a non-aqueous solvent under an inert gas atmosphere,
This is for preventing the ester group present in the monomer or the formed copolymer from being hydrolyzed.

In the present invention, a good solvent alone or a mixed solvent of a good solvent and a poor solvent is used as the non-aqueous solvent.

In the present invention, a good solvent is used.
This is because the formation of a homopolymer due to the difference in reactivity of each monomer is suppressed, and a uniform copolymer is obtained. In the present specification, the good solvent means the good solvent 1 at 25 ° C.
A solvent in which a copolymer having a molecular weight of 10,000 or more is dissolved in an amount of 20 g or more per 00 ml and no turbidity is observed. Specific examples of the good solvent include, for example, methanol, ethanol, isopropanol, acetone,
Examples include ethyl acetate, benzene, toluene, xylene and the like. Among these good solvents, ethanol, isopropanol and benzene are particularly preferable since they can obtain a copolymer having a relatively high molecular weight. Since benzene and the like are harmful, ethanol and isopropanol are most preferable.

The reason why the poor solvent is used in the present invention is to easily precipitate the formed copolymer from the polymerization solution. The poor solvent means a solvent which dissolves a copolymer having a molecular weight of 10,000 or more in 5 g or less in 100 ml of the poor solvent at 25 ° C. Specific examples of the poor solvent include linear, branched or cyclic aliphatic hydrocarbons having 15 or less carbon atoms, such as n-pentane, n-hexane, and cyclohexane. Among these poor solvents, linear, branched or cyclic aliphatic hydrocarbons having a relatively high boiling point and 7 or less carbon atoms are preferred. Among them, straight-chain, branched-chain or cyclic aliphatic hydrocarbons having 6 or 7 carbon atoms are particularly preferable because of their high boiling points. Further, n-hexane, cyclohexane, and the like are preferable because they are inexpensive and industrially easy to handle.

In order to synthesize a cationic thickener without impairing the properties of the resulting cationic thickener, it is preferable to mix the good solvent and the poor solvent in appropriate ratios. If the proportion of the poor solvent is too large, the polymerization proceeds promptly, and a cationic thickener having desired physical properties tends to be obtained in a short time because the powder is precipitated in a short time. The ratio of the poor solvent to the mixed solvent of the good solvent and the poor solvent is 98% by weight or less, preferably 97% by weight or less, and the ratio of the good solvent is 2% by weight or more, preferably 3% by weight or more. It is desirable.

In order to efficiently obtain the cationic thickener from the reaction solution, it is preferable to use a reaction device for improving the stirring during the polymerization. When using a stirrer for solution polymerization generally used as such a reactor,
It is preferable to dilute with the solvent such that the concentration of the monomer composition for a thickener is 30% by weight or less. In addition,
At the time of the reaction, it is preferable to sufficiently stir using a stirrer or the like in order to prevent the reaction solution from stagnating. The polymerization reaction is preferably performed under heating at 50 to 100 ° C., and is generally performed at the reflux temperature of the solvent used in the reaction. The time required for the polymerization reaction is usually 1
0 hours or more. The polymerization reaction can be arbitrarily terminated when the amount of the remaining monomer becomes 10% by weight or less. In addition, the amount of the remaining monomer can be determined by, for example, adding sulfur to the double bond by a known method such as the PSDB method and measuring the double bond content.

Thus, a reaction solution containing a precipitate of the cationic thickener is obtained. The mixed solvent is removed, for example, by filtering the obtained precipitate of the cationic thickener,
It can be carried out by performing vacuum drying or distilling off under normal pressure or reduced pressure.

In the polymerization reaction, a polymerization catalyst may be used. Such polymerization catalysts include, for example, 2,2'-
Azobisisobutyronitrile, 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), azo compounds such as dimethyl-2,2'-azobisisobutyrate, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, and di-t-butylperoxide There are peroxides represented by dialkyl peroxides such as oxides, peroxycarbonates such as diisopropylperoxydicarbonate, and peroxyesters such as t-butylperoxypivalate. These catalysts are used alone or in combination of two or more. These are used in combination. In addition, the present invention is not limited only to such an example. When a large amount of an amine-based monomer is used in the monomer composition for a thickener, an excessive use of a peroxide catalyst may cause undesired side reactions such as an oxidation reaction at the same time, and may hinder polymerization. Be careful when using.
In general, it is preferable to mainly use an azo-based catalyst, but it depends on the boiling point of the solvent used. For example, when ethanol or benzene is used, 2,2′-azobisisobutyronitrile is not easily handled. Most preferred because it is good. The amount of the polymerization catalyst used is preferably 0.05 to 3.0% by weight, more preferably 0.1 to 1.0% by weight, based on the total weight of the monomers of the monomer composition for a thickener.

In the process of polymerizing the monomer,
Various aspects are exhibited. For example, when only the above-mentioned good solvent is used, the appearance is similar to that in the case where general solution polymerization is performed in the initial stage of the polymerization reaction, but the crosslinking reaction proceeds with the progress of the reaction, and the gel-like state is obtained. And a grease-like product without a precipitate is obtained as the reaction further proceeds.

Further, when a mixed solution of the above-mentioned good solvent and poor solvent is used, at the initial stage of the polymerization, the same aspect as when a general solution polymerization method is adopted is exhibited, but the reaction proceeds. As the reaction proceeds, the crosslinking reaction progresses and the mixture becomes gel-like. As the reaction further progresses, the obtained polymer can no longer be dissolved in the mixed solvent, becomes insoluble, and precipitates as a precipitate.

Thus, a cationic thickener is obtained,
The cationic thickener is described, for example, in JP-A-5-140531.
And Japanese Patent Application No. Hei 5-298659.
The cationic thickener itself is non-sticky and has a set holding power.
30.0% by weight, more preferably 0.1 to 10.0% by weight is blended. If it is less than 0.01% by weight, a sufficient emulsification stabilizing effect cannot be obtained, and if it exceeds 30.0% by weight, the effect of the present invention is not enhanced.

The water-swellable clay mineral used in the present invention is a kind of colloidal hydrous aluminum silicate having a three-layer structure and is represented by the following general formula (V), and specifically includes montmorillonite, saponite, hectorite and the like. (In this case, the (OH) group in the formula is replaced with fluorine) of a montmorillonite group (Vegum,
Kunipia, Laponite and the like. ) And synthetic mica known as sodium silicic mica, sodium or lithium teniolite (a commercially available product is Dimonite; Topy Industries, Ltd.).

[0047]

Embedded image (X, Y) _2-3 (Si, Al) ₄ O ₁₀ (OH) ₂ Z _1/3 · nH ₂ O (V)

Where X = Al, Fe ¹¹¹ , Mn ¹¹¹ , Cr ¹¹¹ Y = Mg, Fe ¹¹ , Ni, Zn, Li Z = K, Na, Ca

The quaternary ammonium salt type cationic surfactant used in the present invention is represented by the following general formula (VI).

[0050]

Embedded image

Wherein R ⁷ is an alkyl group or benzyl group having 10 to 22 carbon atoms, and R ⁸ is a methyl group or 1 carbon atom.
An alkyl group of 0 to 22, R ⁹ and R ¹⁰ represent an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and X represents a halogen atom or a methyl sulfate residue. )

Examples of such a quaternary ammonium salt type cationic surfactant include dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, and the like.
Stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyldimethylethylammonium chloride, cetyldimethylethylammonium chloride, stearyldimethylethylammonium chloride, aralkyldimethylethylammonium chloride, behenyldimethylethylammonium chloride, myristyldiethylmethylammonium chloride , Cetyl diethyl methyl ammonium chloride, stearyl diethyl methyl ammonium chloride, aralkyl diethyl methyl ammonium chloride, behenyl diethyl methyl ammonium chloride, benzyl dimethyl myristyl ammonium chloride, benzyl dimethyl cetyl ammonium chloride, Zyl dimethyl stearyl ammonium chloride, benzyl dimethyl behenyl ammonium chloride, benzyl methyl ethyl cetyl ammonium chloride, benzyl methyl ethyl stearyl ammonium chloride, dibehenyl dihydroxyethyl ammonium chloride, and the corresponding promide, and further dipalmityl propyl ethyl ammonium methyl sulfate, etc. can give. In practicing the present invention, one or more of these are arbitrarily selected.

The lipophilic surfactant used in the present invention has an HLB value (Note 1) in the range of 2 to 16, and 3 to 12
Are more preferred. For example, addition of 2 to 30 mol of polyoxyethylene (hereinafter abbreviated as POE (2 to 30)) oleyl ether, POE (2 to 35) stearyl ether, POE (2 to 20) lauryl ether,
POE (1-20) alkyl phenyl ether, POE
(6-18) behenyl ether, POE (5-25) 2
-Decyl pentadecyl ether, POE (3-30) 2
-Decyltetradecyl ether, POE (8-16) 2
Ether activators such as octyl decyl ether, POE (4-60) hydrogenated castor oil, POE (3-1)
4) Fatty acid monoesters, POE (6-30) fatty acid diesters, POE (5-20) sorbitan fatty acid esters and other ester-type activators, further POE (2-30) glyceryl monoisostearate, POE (10-60) Glyceryl triisostearate, POE (7-50) hydrogenated castor oil monoisostearate, POE (12-6)
0) Ethylene oxide addition type surfactant of ether ester type surfactant such as hydrogenated castor oil triisostearate,
And polyglycerol fatty acid esters such as decaglyceryl tetraolate, hexaglyceryl triisostearate, tetraglyceryl diisostearate, diglyceryl diisostearate, glycerin such as glyceryl monostearate, glyceryl monoisostearate and glyceryl monooleate. Nonionic surfactants such as fatty acid esters and the like can be mentioned.

Among these, polyglycerol fatty acid esters of triglycerin or higher such as decaglyceryl tetraolate, hexaglyceryl triisostearate, tetraglyceryl diisostearate, POE (2-12) oleyl ether, POE (3-12) ) Stearyl ether, POE (2-10) lauryl ether, POE (2
-10) Nonylphenyl ether, POE (6-15)
POE-added ether type activators such as behenyl ether, POE (5-20) 2-decylpentadecyl ether, POE (5-17) 2-decyltetradecyl ether, POE (8-16) 2-octyldecyl ether, and the like; POE (10-20) hydrogenated castor oil, POE (5-1)
4) POE addition ester type activators such as oleic acid monoester, POE (6-20) oleic acid diester, POE (5-10) sorbitan oleic acid ester, PO
E (3-15) glyceryl monoisostearate, PO
Particularly preferred are ethylene oxide addition type nonionic surfactants such as POE addition ether ester type surfactants such as E (10-40) glyceryl triisostearate.

In the practice of the present invention, one or more of these lipophilic surfactants are arbitrarily selected and used. (Note 1) The HLB value of a lipophilic surfactant is calculated by the Kawakami equation of the following equation (1).

[0056]

HLB = 7 + 11.7 · log (M _W / M _O )

(Here, M _W represents the molecular weight of the hydrophilic group, and M _O represents the molecular weight of the lipophilic group.) The organically modified clay mineral used in the present invention may be, for example, a low boiling point such as water, acetone, or a lower alcohol. Disperse and stir the water-swellable clay mineral, quaternary ammonium salt type cationic surfactant and lipophilic surfactant in a solvent, or prepare the water-swellable clay mineral and quaternary ammonium salt type cationic surfactant in advance. To obtain a cationically modified clay mineral by treating the agent with a low-boiling solvent, followed by treatment with a lipophilic surfactant, and then removing the low-boiling solvent.

When the quaternary ammonium salt type cationic surfactant and the lipophilic surfactant penetrate between the layers, the interlayer distance of the water-swellable clay mineral is widened.
The presence or absence of adsorption of the quaternary ammonium salt type cationic surfactant and the lipophilic surfactant can be confirmed by measuring the long plane spacing by line diffraction.

If the organically modified clay mineral is subjected to Soxhlet extraction using chloroform, ether or the like, the surfactant between the layers is washed away, and the extract is analyzed by gas chromatography, pyrolysis temperature measurement or pyrolysis amount measurement. (DTA-TG measurement) or the like can be used to confirm the presence of the surfactant.

The content of the quaternary ammonium salt type cationic surfactant in the organically modified clay mineral of the present invention is preferably 70 to 140 meq per 100 g of the water-swellable clay mineral. The content of the lipophilic surfactant in the organically modified clay mineral is 5 to 100 g of the water-swellable clay mineral.
-100 g is preferable, and 15-50 g is more preferable.
It is.

The amount of the treated organically modified clay mineral is as follows:
It varies depending on the type and amount of the oil component used, the amount of the aqueous phase to be emulsified, and the like, but it is 0.1 to 5.0% by weight, preferably 1.2 to 3.0% by weight in the total amount of the hair cosmetic of the present invention. .

Further, the W / O type hair cosmetic of the present invention is obtained by mixing an oil phase in which the above-mentioned organically modified clay mineral is dissolved, an aqueous phase containing a cationic thickener, and then neutralizing with a neutralizing agent. It is obtained by thickening.

The neutralizing agent used here is sulfuric acid,
Examples include mineral acids such as hydrochloric acid and phosphoric acid, and organic acids such as acetic acid, citric acid, lactic acid, amino acids, succinic acid, malic acid, dimethyl sulfate, and diethyl sulfate.

Further, the water-in-oil type emulsified hair cosmetic composition of the present invention may contain, in addition to the above-mentioned components, other optional components as long as the effects of the present invention are not impaired. Such optional ingredients include locust bean gum, xanthan gum,
Natural and synthetic high molecular substances such as cross-linked polyacrylic acid; glycerides such as avocado oil, jojoba oil, macadamian nut oil, olive oil; waxes such as beeswax and lanolin; hydrocarbons such as liquid paraffin, solid paraffin, isoparaffin and squalane Cetyl alcohol,
Linear and branched higher alcohols such as stearyl alcohol and 2-octyldodecanol; polyhydric alcohols such as propylene glycol, glycerin and sorbitol; esters such as isopropyl myristate and octyldodecyl myristate; diethanolamide oleate and laurin Amides such as acid diethanolamide;
Silicone derivatives such as dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone and amino-modified silicone; nonionic polymers such as polyvinylpyrrolidone, copolymer of vinylpyrrolidone and vinyl acetate; acrylic acid and / or methacrylic acid Anionic polymers such as copolymers with alkyl (meth) acrylates; protein derivatives such as collagen and keratin hydrolysates; plant extracts, crude drugs, vitamins, ultraviolet absorbers such as oxybenzone, parabens, etc. Preservatives, chelating agents such as EDTA-Na, dyes, pigments, fragrances and the like.

[0065]

Next, the present invention will be described in more detail with reference to examples. The present invention is not limited by this.
The compounding amount is% by weight. The effect was determined according to the following evaluation method.

Stability Evaluation A W / O type hair cosmetic was filled in a glass bottle,
After leaving at 50 ° C. for one month, the evaluation was performed. The stability evaluation is
The following three-step evaluation was performed. ：: No separation was observed. Δ: Oil is separated very slightly. X: Remarkable separation of oil components is observed.

Sensory Evaluation Using hair having almost the same hair condition (thickness, hardness and degree of damage), a hair bundle (length 15 cm, width 3 cm, weight 1.5 g) was prepared, and the sample 0.5 g was applied, and non-stickiness, smoothness, and gloss were evaluated by the following four stages by 15 professional judges. A: 12 or more out of 15 answered that they were good. Good: 8 to 11 out of 15 answered that they were good. Δ: 4 to 7 out of 15 answered that they were good. X: Three or less out of 15 answered that it was good.

Set Retention Strength Evaluation A hair bundle having a length of 25 cm and a weight of 2 g was wetted with water, 0.5 g of a hair setting agent composition was applied, wound around a rod having a diameter of 15 mm, and dried at 50 ° C. After drying, remove the rod from the curled hair bundle and place it in a constant temperature, constant humidity box (28 ° C, 90 ° C).
% RH) for 1 hour and the length of the curl was measured. The set holding force (A) was calculated from the length of the curl (l ₁ ) immediately after being removed from the rod and the length (l ₂ ) after leaving for 1 hour according to the following equation.

Set holding force = ｛(25−l ₂ ) / (2
5-l ₁ )｝ × 100 (%) Display of measurement result ：: Set holding force 80 to 100% ：: Set holding force 50 to 80% ×: Set holding force 0 to 50%

Examples 1 to 7, Comparative Examples 1 to 5 W / O type hair cosmetics having the compositions shown in Tables 1 and 2 were prepared by the following methods and evaluated. The results are shown in Tables 1 and 2.

[Production Method] Production Method of Cationic Thickener A three-necked flask equipped with a thermometer, a reflux tube and a nitrogen introduction tube was charged with 50 g of N, N-dimethylaminoethyl methacrylate as a monomer and N-vinylpyrrolidone 47 as a monomer. .5
g, 2.5 g of stearyl acrylate and 1.9 g of tripropylene glycol diacrylate, and a mixed solvent (mixing ratio (weight ratio) of 4:96) of 23.1 g of ethanol and 554.3 g of cyclohexane were added. While refluxing, the mixture was stirred for 2 hours under a nitrogen stream to degas. Next, 0.41 g of 2,2'-azobisisobutyronitrile was added to the three-necked flask, and polymerization was started at 80 ° C. After 45 minutes from the start of polymerization, 1.9 g of tripropylene glycol diacrylate was added.
After a lapse of minutes, 1.9 g of tripropylene glycol diacrylate was added. Approximately 1 while stirring under a nitrogen stream
After the polymerization reaction was performed for 0 hours, the obtained polymer slurry solution was filtered under reduced pressure, and the solid component was dried under reduced pressure.
The obtained dried polymer was pulverized with a pulverizer to obtain a white powdered cationic thickener.

Production method of W / O type hair cosmetics In Examples 1 to 7 and Comparative Examples 1 to 3, (2) to (6)
And dissolve in the mixture by heating to prepare an oil phase in advance. Next, if necessary, (1) or (12), and (7) to (10) are dispersed and mixed, and gradually added to the oil phase while stirring with a disper,
Mix and stir sufficiently uniformly. Thereafter, (13) or (11) was added as necessary, and the mixture was cooled by neutralization and thickening to obtain a desired W / O type hair cosmetic. Comparative Example 4 is (1)
~ (10) was stirred and dissolved to obtain the desired W / O type hair cosmetic.

[0073]

[Table 1] ─────────────────────────────────── Examples Examples Ingredients ────── {1 2 3 4 5 6 7} ─────── (1) Cationic thickener 0.05 0.1 3.0 10.0 30.0 40.0 1.5 (2) Volatile isoparaffin 10.0 10.0 10.0 10.0 10.0 10.0 20.0 (3) Distearyl dimethyl ammonium chloride ゛ 0.8 0.8 0.8 0.8 0.8 0.8 0.8 (4) Polyglyceryl diisostearate 2.0 2.0 2.0 2.0 2.0 2.0 2.0 (5) Dextrin fatty acid ester 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (6) Benton 38 ^{* 1)} ------1.5 (7) Deionized water Residual Residual Residual Residual Residual Residual (8) Glycerin 4.0 4.0 4.0 4.0 4.0 4.0 4.0 (9) Polyethylene glycol 6000 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (10) Ton ^{SA * 2) 1.2 1.2 1.2 1.2} 1.2 1.2 - (11) phosphoric acid 0.015 0.03 0.9 3.0 9.0 12.0 0.45 ──────────────────────────評 価 Stability evaluation 0 ℃ △ ○ ○ ○ ○ ○ ○ Room temperature ○ ○ ○ ○ ○ ○ ○ 50 ℃ ○ ○ ○ ○ ○ △ ○ Sensory evaluation Non-stickiness △ ◎ ◎ ◎ ◎ ○ ◎ Smoothness ◎ ◎ ◎ ◎ ◎ △ ◎ Gloss ○ ◎ ◎ ◎ ◎ ○ ◎ Set holding power ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ─────────────────────── ────────────

[0074]

[Table 2] 例 Comparative example Ingredients───────── １ 1 2 3 4 5 ──────────────────────────────── (1) Cationic Thickener---3.0-(2) Volatile isoparaffin 10.0 10.0 10.0-10.0 (3) Percyaryl dimethyl ammonium chloride--0.8--(4) Polyglyceryl diisostearate 2.0 2.0 2.0-2.0 (5) Dextrin Fatty acid ester 1.5 − 1.5 − 1.5 (6) Benton 38 ^{* 1)} − − − − − (7) Deionized water residue Residue Residue Residual residue (8) Glycerin 4.0 4.0 4.0 4.0 4.0 (9) Polyethylene glycol 6000 0.5 0.5 0.5 0.5 0.5 (10) Smecton SA ^{* 2)} --1.2--(11) Phosphoric acid---0.9-(12) Anionic thickener ^{* 3)} ---- 0.6 (13) Caustic soda − − − − 0.12 評 価 Stability evaluation 0 ℃ △ × ○ ○ ○ Room temperature × × ○ ○ ○ 50 ℃ × × △ ○ △ Sensory evaluation Non-stickiness △ △ △ ○ ○ Smoothness ◎ ◎ ◎ △ ◎ Luster ○ ○ △ △ ○ Set holding power × × × ◎ × ──── ────────────────────────────

* 1): Dimethyl distearyl ammonium hectorite, trade name of National Lead Co. * 2): Aluminum magnesium silicate, trade name of Kunimine Industries * 3): Carboxyvinyl polymer

Example 8 Hair Cream (1) Volatile Isoparaffin 20.0% by Weight (2) Dimethylpolysiloxane (20cs) 2.0 (3) Distearyldimethylammonium Chloride 0.8 (4) Diglyceryl diisostea Rate 1.5 (5) Vitamin E acetate 0.1 (6) Dextrin fatty acid ester 1.0 (7) Perfume appropriate amount (8) Purified water residue (9) Polyethylene glycol 6000 1.0 (10) Glycerin 5.0 ( 11) Methylparaben 0.2 (12) Keratin hydrolyzate 0.1 (13) Cationic thickener 5.0 (14) Smecton SA 1.2 (15) Lactic acid 1.5

[Production method] (1) to (7) were heated to 70 ° C.
Mix and prepare an oil phase in advance. Next, (8) to (14) were dispersed and mixed at 70 ° C., and gradually added to the oil phase with stirring with a disper. After sufficiently mixing and stirring, (15) was added to increase the neutralization. It was thickened to obtain the desired hair cream.

Example 9 Hair Conditioner (1) Octamethylcyclotetrasiloxane 20.0% by weight (2) Dimethylpolysiloxane (5cs) 5.0 (3) Behenyltrimethylammonium chloride 0.4 (4) Diglyceryldiiso Stearate 2.0 (5) Dextrin fatty acid ester 2.0 (6) Flavor appropriate amount (7) Purified water residue (8) Cationic thickener 0.5 (9) Polyethylene glycol 6000 1.5 (10) Propylene glycol 5.0 (11) Ethylparaben 0.2 (12) Smecton SA 0.8 (13) Phosphoric acid 0.15

[Production Method] A desired hair conditioner was obtained according to Example 8.

Example 10 Hair Mousse® (1) volatile isoparaffin 30.0% by weight (2) dimethylpolysiloxane (5cs) 2.0 (3) stearyltrimethylammonium chloride 0.4 (4) diglyceryldi Isostearate 1.0 (5) Dextrin fatty acid ester 0.1 (6) Perfume appropriate amount (7) Purified water residue (8) Cationic thickener 1.0 (9) Glycerin 2.0 (10) Methyl paraben 0. 2 (11) Smecton SA 0.6 (12) n-butane 8.0 (13) Stearic acid 0.45

[Production method] Using Example (1) to (11) and (13), Example 8
An emulsion was obtained according to the following procedure. This is put in an aerosol container, a valve is attached, and then (12) is filled.

Example 11 Hair Mousse® (1) Octamethyltrisiloxane 25.0% by weight (2) Diglyceryl diisostearate 3.0 (3) Dextrin fatty acid ester 0.5 (4) 2-hydroxy -4-methoxybenzophenone 0.2 (5) Fragrance appropriate amount (6) Benton 38 3.0 (7) Purified water residue (8) Cationic thickener 10.0 (9) Propylene glycol 6.0 (10) Polyethylene Glycol 0.5 (11) Quaternized collagen 0.1 (12) Color pigment 0.1 (13) Liquid petroleum gas 5.0 (14) Dimethyl ether 5.0 (15) Malic acid 5.0

[Production Method] Using Example (1) to (12) and (15), Example 8
An emulsion was obtained according to the following procedure. After putting this in an aerosol container and attaching a valve, (13) and (14) are filled.

The W / O type hair cosmetics of Examples 8 to 11
It gave an excellent gloss without stickiness, gave a smooth feel and good setting force, and was excellent in stability.

[0085]

As described above, the W / O type hair cosmetic of the present invention is superior in emulsification stability as compared with W / O emulsification by organically modified clay mineral alone, and is sticky to hair. And imparts excellent gloss and good set holding power.

Claims (3)

[Claims] 1. A water-in-oil type emulsified hair cosmetic comprising the following component (A) and component (B). (A) A cationic thickener obtained by polymerizing a monomer composition for a thickener containing: General formula (I): (Wherein R ¹ is a hydrogen atom or a methyl group, R ² and R ³
Each independently represents a hydrogen atom, a methyl group, an ethyl group or a t-butyl group, A represents an oxygen atom or a -NH- group, and B represents a linear or branched alkylene group having 1 to 4 carbon atoms. 15.0 to 85.0% by weight of an amine-containing (meth) acrylic monomer represented by the following formula (III): (Wherein, R ¹ and A have the same meanings as described above, and R ⁵ is a linear or branched alkylene group having 1 to 17 carbon atoms or a general formula (IV): (Wherein, n represents an integer of 1 to 4 and q represents an integer of 1 to 25), and R ⁶ represents a hydrogen atom or a methyl group. (B) An organically modified clay mineral containing the following (1): 1.0 to 60.0% by weight of a (meth) acryloyl group-containing monomer represented by the formula (1), and 0.1 to 20.0% by weight of a crosslinkable vinyl monomer. Water-swellable clay mineral. Quaternary ammonium salt type cationic surfactant. Lipophilic surfactant. 2. A water-in-oil type emulsified hair cosmetic comprising the following component (A) and component (B). (A) A cationic thickener obtained by polymerizing a monomer composition for a thickener containing: General formula (I): (Wherein R ¹ is a hydrogen atom or a methyl group, R ² and R ³
Each independently represents a hydrogen atom, a methyl group, an ethyl group or a t-butyl group, A represents an oxygen atom or a -NH- group, and B represents a linear or branched alkylene group having 1 to 4 carbon atoms. 15.0 to 85.0% by weight of an amine-containing (meth) acrylic monomer represented by the general formula (III): (Wherein, R ¹ and A have the same meanings as described above, and R ⁵ is a linear or branched alkylene group having 1 to 17 carbon atoms or a general formula (IV): (Wherein, n represents an integer of 1 to 4 and q represents an integer of 1 to 25), and R ⁶ represents a hydrogen atom or a methyl group. (Meth) acryloyl group-containing monomer represented by the following formula: 1.0 to 60.0% by weight, crosslinkable vinyl monomer 0.1 to 20.0% by weight General formula (II): (Wherein, R ¹ has the same meaning as described above, and R ⁴ has the general formula: (Wherein p represents 3 or 4) or a group represented by the following formula: Represents a group represented by ) Vinyl monomer
3.0 to 80.0% by weight, (B) an organically modified clay mineral containing: Water-swellable clay mineral. Quaternary ammonium salt type cationic surfactant. Lipophilic surfactant. 3. Component (A) is contained in an amount of 0.01 to 30.0% by weight.
The water-in-oil type emulsified hair cosmetic according to claim 1 or 2, comprising 0.1 to 5.0% by weight of the component (B).