JP2006160687A - Water-in-oil type emulsified cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-in-oil type emulsified cosmetic having excellent stability of the cosmetic and slight irritation. <P>SOLUTION: The water-in-oil type emulsified cosmetic is characterized as comprising an ingredient (A): at least one kind of a multi-chain and multi-hydrophilic group type compound having &ge;2 long-chain hydrophobic groups and &ge;2 hydrophilic groups in the molecule, respectively and an ingredient (B): at least one kind of oily ingredient. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a water-in-oil type emulsified cosmetic comprising a multi-chain polyhydrophilic group type compound.

Conventionally, water-in-oil emulsified cosmetics (W / O type emulsified cosmetics) have lipophilic surfactants having an HLB value of 12 or less, for example, polyhydric alcohol fatty acid ester-based active agents such as sorbitan fatty acid esters as emulsifiers. Then, the activator was added to the oil phase and dissolved by heating, and then the aqueous phase was added and mixed to obtain a W / O emulsion. However, the W / O emulsion obtained in this manner has a drawback that it is difficult to obtain a system having excellent stability and usability as compared with an oil-in-water emulsion cosmetic.
In order to solve this problem, for example, in Patent Document 1, at least one selected from betaine, pyrrolidone carboxylate, and water-soluble alkyl carboxylate and a room temperature liquid lipophilic nonionic surfactant are used. A method for improving the stability is disclosed, and in Patent Document 2, a high-molecular weight polydimethylsiloxane having an average degree of polymerization of 5,000 to 20,000, trimethylglycine, sucrose fatty acid ester, and polyhydric alcohol is used. A method for improving is disclosed. However, these methods have a low degree of freedom in blending and are insufficient to obtain various product forms.
Thus, water-in-oil emulsified cosmetics having excellent cosmetic stability and low irritation have been eagerly desired.

Japanese Patent Laid-Open No. 09-301823 JP-A-10-139625

  The object of the present invention is to provide a water-in-oil emulsified cosmetic that is excellent in the stability of cosmetics and has little irritation.

As a result of intensive studies to solve the above problems, the present inventors have determined that a specific compound, that is, a compound having two or more long-chain hydrophobic groups and hydrophilic groups in the molecule, that is, a multi-chain poly-hydrophilic group. Focusing on the type compound, it has been found that by blending the compound, it becomes a water-in-oil emulsified cosmetic with excellent cosmetic stability and low irritation, and the present invention has been completed.
That is, the present invention is as follows.
1. A water-in-oil emulsified cosmetic comprising the following component (A) and component (B):
Component (A): At least one multi-chain polyhydrophilic group type compound having two or more long-chain hydrophobic groups and hydrophilic groups in the molecule.
Component (B): At least one oily component.
2. At least one of the multi-chain poly-hydrophilic group type compound, the long-chain hydrophobic group is a long-chain acyl group, and the hydrophilic group is a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group or a salt thereof The above 1. The water-in-oil emulsified cosmetic described in 1.
3. At least one of the multi-chain polyhydrophilic group type compounds has an amino acid residue in the molecule. Or 2. The water-in-oil emulsified cosmetic described in 1.

〔一般式（１）中、Ｘはｍ個の官能基、およびそれ以外の置換基を有していてもよい分子量１００万以下の直鎖または分枝鎖または環状鎖または芳香族炭化水素鎖であるスペーサーを示す。Ｘに結合しているｎ（ｍ≧ｎ）個のＱは、次の一般式（２）で表される置換基であり、それぞれ互いに同一でも異なっていてもよい。

（一般式（２）中、ＺはＸの有する官能基に由来する結合部であり、Ｒ¹ＣＯは炭素数８〜２０の飽和または不飽和の脂肪酸から誘導されるアシル基を示し、Ｒ²は水素であるか、またはヒドロキシル基またはカルボキシル基が置換していてもよい炭素数１〜３の低級アルキル基を示し、Ｙはカルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基またはそれらの塩の内のいずれかを示す。ｊ、ｋはそれぞれ独立に０、１、２のいずれかであり、かつｊ、ｋは同時に０ではない。ｎは２〜２０の整数を示す。また、ｍはｍ≧ｎである整数を示す。）〕 4). At least one of the multi-chain polyhydrophilic group type compounds is a compound represented by the following general formula (1): ~ 3. The water-in-oil emulsified cosmetic according to any one of the above.

[In General Formula (1), X is a linear, branched, cyclic, or aromatic hydrocarbon chain having a molecular weight of 1 million or less, which may have m functional groups and other substituents. A spacer is shown. N (m ≧ n) Qs bonded to X are substituents represented by the following general formula (2), and may be the same as or different from each other.

(In the general formula (2), Z is a bond unit derived from a functional group of X, R ¹ CO represents an acyl group derived from a saturated or unsaturated fatty acids having 8 to 20 carbon atoms, R ² Represents hydrogen, or a lower alkyl group having 1 to 3 carbon atoms which may be substituted by a hydroxyl group or a carboxyl group, and Y represents a carboxyl group, a sulfonic acid group, a sulfuric acid ester group, a phosphoric acid ester group or the like Wherein j and k are each independently 0, 1, or 2 and j and k are not 0 at the same time, and n is an integer of 2 to 20. m represents an integer satisfying m ≧ n.)]

5. At least one of the multi-chain polyhydrophilic group-type surfactant is a compound represented by the general formula (1), and in the general formula (1), X may have a substituent other than the functional group. 1. A spacer which is a straight chain, branched chain, cyclic chain or aromatic hydrocarbon chain having 1 to 40 carbon atoms. ~ 4. The water-in-oil emulsified cosmetic according to any one of the above.
6). Content of oily component is 0.1-80 mass%, said 1 characterized by the above-mentioned. ~ 5. The water-in-oil emulsified cosmetic according to any one of the above.
7). Furthermore, it contains at least one selected from component (C): anionic surfactant, nonionic surfactant, amphoteric surfactant, and cationic surfactant. ~ 6. The water-in-oil emulsified cosmetic according to any one of the above.
8). Furthermore, it contains at least one component (D): a polyhydroxyl compound. ~ 7. The water-in-oil emulsified cosmetic according to any one of the above.
9. Furthermore, it contains at least one selected from component (E): organic and / or inorganic electrolyte. ~ 8. The water-in-oil emulsified cosmetic according to any one of the above.
10. Above 1. ~ 9. A cosmetic method characterized by using the water-in-oil emulsified cosmetic according to any one of the above.

  According to the present invention, there is an effect that a water-in-oil emulsified cosmetic with excellent cosmetic stability and low irritation can be provided.

Hereinafter, the present invention will be specifically described.
The component (A) used in the water-in-oil emulsified cosmetic of the present invention is structurally one kind of multi-chain polyhydrophilic group type compound having two or more long-chain hydrophobic groups and hydrophilic groups in the molecule. It is a composition comprising the above, and any compound may be used as long as it has this structure, and a compound known so far may be used.
In the water-in-oil type emulsified cosmetic of the present invention, as the multi-chain polyhydrophilic group-type compound, each of the long-chain hydrophobic groups is independently a saturated or unsaturated linear or branched chain having 8 to 20 carbon atoms. , Having a hydrophobic group consisting of a cyclic chain, and each of the hydrophilic groups is independently a carboxyl group, a sulfonic acid group, a sulfuric acid residue, a phosphoric acid residue or a salt thereof, or an oxyalkylene group, a polyethylene glycol group, etc. Alternatively, it has an amino group, a quaternary ammonium group, a pyridinium group, a sulfonium group, or a salt thereof.
Examples of the long-chain hydrophobic group of the multi-chain polyhydrophilic group type compound include n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n -Residues such as hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, etc., and branched isomers thereof, and corresponding one, two or three unsaturated moieties And unsaturated residues having.
In addition, the long-chain hydrophobic group of the multi-chain polyhydrophilic group-type compound is a long-chain acyl group derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms. That is, they may be different or the same, and those derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms are preferred, regardless of whether they are linear, branched or cyclic.

For example, linear fatty acids such as caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid;
2-butyl-5-methylpentanoic acid, 2-isobutyl-5-methylpentanoic acid, dimethyloctanoic acid, dimethylnonanoic acid, 2-butyl-5-methylhexanoic acid, methylundecanoic acid, dimethyldecanoic acid, 2-ethyl- 3-methylnonanoic acid, 2,2-dimethyl-4-ethyloctanoic acid, methyldocosanoic acid, 2-propyl-3-methylnonanoic acid, methyltridecanoic acid, dimethyldodecanoic acid, 2-butyl-3-methylnonanoic acid, methyltetradecanoic acid , Ethyltridecanoic acid, propyldodecanoic acid, butylundecanoic acid, pentyldecanoic acid, hexylnonanoic acid, 2- (3-methylbutyl) -3-methylnonanoic acid, 2- (2-methylbutyl) -3-methylnonanoic acid, butylethylnonane Acid, methylpentadecanoic acid, ethyltetradecanoic acid, propyltri Canic acid, butyldodecanoic acid, pentylundecanoic acid, hexyldecanoic acid, heptylnonanoic acid, dimethyltetradecanoic acid, butylpentylheptanoic acid, trimethyltridecanoic acid, methylhexadecanoic acid, ethylpentadecanoic acid, propyltetradecanoic acid, butyltridecanoic acid, pentyldodecane Acid, hexylundecanoic acid, heptyldecanoic acid, methylheptylnonanoic acid, dipentylheptanoic acid, methylheptadecanoic acid, ethylhexadecanoic acid, ethylhexadecanoic acid, propylpentadecanoic acid, butyltetradecanoic acid, pentyltridecanoic acid, hexyldodecanoic acid, heptyl Undecanoic acid, octyldecanoic acid, dimethylhexadecanoic acid, methyloctylnonanoic acid, methyloctadecanoic acid, ethylheptadecanoic acid, dimethylheptadecanoic acid, Octyl decanoic acid, Mechirunonadekan acid, Mechirunonadekan acid, dimethyl octadecanoic acid, branched fatty acids such as butyl heptyl nonanoic acid;
Octenoic acid, nonenoic acid, decenoic acid, caproleic acid, undecylenic acid, Lindellic acid, touric acid, lauroleic acid, tridecenoic acid, tuzuic acid, myristoleic acid, pentadecenoic acid, hexedenoic acid, palmitoleic acid, heptadecenoic acid, octadecenoic acid, Linear monoenoic acids such as oleic acid, nonadecenoic acid, gondoic acid;
Such as methylheptenoic acid, methylnonenoic acid, methylundecenoic acid, dimethyldecenoic acid, methyldodecenoic acid, methyltridecenoic acid, dimethyldodecenoic acid, dimethyltridecenoic acid, methyloctadecenoic acid, dimethylheptadecenoic acid, ethyloctadecenoic acid Branched monoenoic acid;
Di- or trienoic acids such as linoleic acid, linoleic acid, eleostearic acid, linolenic acid, linolenic elaidic acid, pseudoeleostearic acid, parinaric acid, arachidonic acid;
Acetylene acids such as octinoic acid, nonic acid, decinic acid, undecinic acid, dodecinic acid, tridecinic acid, tetradecinic acid, pentadecinic acid, heptadesinic acid, octadecinic acid, nonadesinic acid, dimethyloctadesinic acid;
Of methyleneoctadecenoic acid, methyleneoctadecanoic acid, aleprolic acid, alepresinic acid, allepuric acid, alepuric acid, hydnocarpic acid, shoulmuccinic acid, gorulic acid, α-cyclopentylic acid, α-cyclohexylic acid, α-cyclopentylethylic acid And an acyl group derived from such a cyclic acid.

Moreover, the acyl group derived from the fatty acid obtained from natural fats and oils may be sufficient, and the acyl group derived from the mixed fatty acid containing 80% or more of the above saturated or unsaturated fatty acid having 8 to 20 carbon atoms is preferable. For example, acyl groups derived from coconut oil fatty acid, palm oil fatty acid, linseed oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, castor oil fatty acid, olive oil fatty acid, camellia oil fatty acid, rapeseed oil fatty acid, palm kernel oil fatty acid, etc. Etc. Two or more of these acyl compounds may be used in combination.
In the case of using a multi-chain polyhydrophilic group type compound as a salt, examples thereof include alkali metal salts, alkaline earth metal salts, polyvalent metal salts, ammonium salts, organic amine salts, basic amino acid salts, and the like. Includes alkali metals such as sodium, potassium and lithium, alkaline earth metals such as calcium and magnesium, metals such as aluminum, zinc, iron, cobalt, titanium and zirconium, ammonia, monoethanolamine, diethanolamine, triethanolamine, It is a salt with one or more kinds arbitrarily selected from organic amines such as triisopropanolamine, basic amino acids such as arginine and lysine. Among these, sodium salts, potassium salts, organic amine salts, and basic amino acid salts are particularly preferable.

In the present invention, it is preferable that at least one of the multi-chain polyhydrophilic group compounds contained in the water-in-oil emulsion cosmetic is an acyl compound represented by the general formulas (1) and (2).
The term “acyl compound” as used herein refers to a structure in which compounds having at least one acyl group and a hydrophilic group in the molecule are linked with an appropriate spacer as shown in the general formulas (1) and (2). belongs to.
In the general formula (2), the acyl groups represented by R ¹ CO are independent, that is, they may be different or the same, and are derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms as described above. Anything can be used as long as it is linear, branched or cyclic.
In general formula (2), R ² is hydrogen, or a hydroxyl group or a carboxyl group, a sulfonic acid group, a sulfuric ester group, a phosphoric ester group or a salt thereof, which may be substituted, 3 lower alkyl groups, for example, methyl group, ethyl group, propyl group, isopropyl group, hydroxymethyl group, hydroxyethyl group, hydroxy (iso) propyl group, dihydroxy (iso) propyl group, carboxymethyl group, carboxyethyl Group, carboxypropyl group, sulfoethyl group and the like.
In the general formula (1), n substituents Q (groups represented by the formula (2)) bonded to X may be different from each other or the same. In addition, the group represented by the formula (2) represents a so-called acidic amino acid obtained by N-acylation, and they are optical isomers, for example, D-form, L-form, and racemate. It doesn't matter.
The acidic amino acid is a monoaminodicarboxylic acid having 2 and 1 carboxyl groups and 1 amino group, respectively, in the molecule, and the amino group may be an N-methyl group or an N-ethyl group. It does not matter whether it is an optical isomer, for example, D-form, L-form, or racemate.

Examples of acidic amino acids include glutamic acid, aspartic acid, lanthionine, β-methyllanthionine, cystathionine, diencholic acid, ferrinin, aminomalonic acid, β-oxyaspartic acid, α-amino-α-methylsuccinic acid, β-oxy Glutamic acid, γ-oxyglutamic acid, γ-methylglutamic acid, γ-methyleneglutamic acid, γ-methyl-γ-oxyglutamic acid, α-aminoadipic acid, α-amino-γ-oxyadipic acid, α-aminopimelic acid, α-amino -Γ-oxypimelic acid, β-aminopimelic acid, α-aminosuberic acid, α-amino sebacic acid, pantothenic acid and the like.
The n substituents (groups represented by formula (2)) attached to X are preferable because the acidic amino acid is an L-acidic amino acid molecule because it is excellent in biodegradability.
In the general formula (2), Z is a bonding part (—O) derived from m functional groups (hydroxyl group, amino group, thiol group) substituted with X (m ≧ n and an integer of 2 to 20). -, -NR < ³ >-, -S-). Here, R ³ is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group, or an alkylaryl group.
In general formula (1), X is a linear or branched or cyclic chain having a molecular weight of 1 million or less and having m functional groups consisting of one or more selected from a hydroxyl group, an amino group and a thiol group. It is a spacer which is an aromatic hydrocarbon chain, and X may have a substituent other than the hydroxyl group, amino group and thiol group.
In the general formula (1), X is preferably a residue of an m-valent compound having a molecular weight of 1 million or less and having m functional groups of one kind or two or more kinds selected from a hydroxyl group, an amino group and a thiol group. , A compound residue that may have a substituent other than a hydroxyl group, an amino group, or a thiol group. Here, the m-valent compound means that a bond derived from m functional groups can be formed. It does not matter whether they are optical isomers, for example, D-form, L-form, or racemate.

Examples of such m-valent compounds include amino acids such as serine, threonine, cysteine, cystine, cystine disulfoxide, cystathionine, methionine, arginine, lysine, tyrosine, histidine, tryptophan, and oxyproline;
Aminoethanol, aminopropanol, aminobutanol, aminopentanol, aminohexanol, aminopropanediol, aminoethylethanolamine, aminoethylaminoethanol, aminocresol, aminonaphthol, aminonaphtholsulfonic acid, aminohydroxybenzoic acid, aminohydroxybutanoic acid Compounds having an amino group and a hydroxyl group in the molecule such as aminophenol, aminophenethyl alcohol, glucosamine;
Compounds having a thiol group and a hydroxyl group in the molecule such as mercaptoethanol, mercaptophenol, mercaptopropanediol, glucothiose;
Compounds having a thiol group and an amino group in the molecule such as aminothiophenol and aminotriazole thiol;
Is mentioned.
Further, proteins, peptides, etc., or those obtained by hydrolyzing them may be used.
In the general formula (1), X is preferably an m-valent (m ≧ n) polyhydroxyl compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than a hydroxyl group. Here, the m-valent polyhydroxyl compound means that m ester bonds can be formed. It does not matter whether they are optical isomers, for example, D-form, L-form, or racemate.

Examples of such m-valent polyhydroxyl compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, pentanediol, 1,6-hexanediol, cyclohexanediol, dimethylolcyclohexane, neopentyl glycol, 1,8-octanediol: 2,2,4-trimethyl-1,3-pentanediol, isoprene glycol, 3 -Methyl-1,5-pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F: dimer diol, dimethylolpropionic acid, dimethylolbutanoic acid, tartaric acid, The Dorokishi tartaric, mevalonate, 3,4-dihydroxy cinnamic acid, 3,4-dihydroxy-hydro cinnamic acid, hydroxy benzoic acid, dihydroxy stearic acid, dihydroxyphenylalanine, and the like, and divalent hydroxyl compounds such as isomers thereof;
Glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol: 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl Trivalents such as -2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane, diethanolamine, triethanolamine, trihydroxystearic acid Polyhydroxyl compounds;
Pentaerythritol, erythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexane Tetravalent polyhydroxyl compounds such as tetrol, diglycerin and sorbitan;
Pentavalent polyhydroxyl compounds such as adonitol, arabitol, xylitol, triglycerin;
Hexavalent polyhydroxyl compounds such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, allose;
Or these dehydration condensates; polyglycerol; etc. are mentioned.

Sugars such as tetroses such as erythrose, sreose and erythrulose; pentoses such as ribose, arabinose, xylose, lyxose, xylulose and ribulose: allose, altrose, glucose, mannose, gurose, idose, galactose, talose, Monosaccharides such as hexoses such as fructose, sorbose, psicose, tagatose;
And oligosaccharides such as maltose, isomaltose, cellobiose, gentiobiose, melibiose, lactose, turranose, trehalose, saccharose, mannitolose, cellotriose, gentianose, raffinose, meretitose, cellotetorose, stachyose and the like.
Residues of other saccharides such as heptose, deoxy sugar, amino sugar, thio sugar, seleno sugar, aldone sugar, uronic acid, sugar acid, ketoaldonic acid, anhydro sugar, unsaturated sugar, sugar ester, sugar ether, glycoside, etc. It may be a group, and may be a polysaccharide such as starch, glycogen, cellulose, chitin, chitosan or the like, or a hydrolyzed product thereof.
In general formula (1), X is preferably an m-valent polyamino compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than an amino group. Here, an m-valent polyamino compound means that m acid amide bonds can be formed. It does not matter whether they are optical isomers, for example, D-form, L-form, or racemate.

Examples of such m-valent polyamino compounds include N, N′-dimethylhydrazine, ethylenediamine, N, N′-dimethylethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, and diaminononane. , Aliphatic diamines such as diaminodecane, diaminododecane, diaminoadipic acid, diaminopropanoic acid, diaminobutanoic acid and isomers thereof;
Diethylenetriamine, triaminohexane, triaminododecane, 1,8-diamino-4-aminomethyl-octane, 2,6-diaminocapric acid-2-aminoethyl ester, 1,3,6-triaminohexane, 1,6 , 11-triaminoundecane, aliphatic triamines such as di (aminoethyl) amine and isomers thereof;
Alicyclic polyamines such as diaminocyclobutane, diaminocyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, triaminocyclohexane;
Aromatic polyamines such as diaminobenzene, diaminotoluene, diaminobenzoic acid, diaminoanthraquinone, diaminobenzenesulfonic acid, diaminobenzoic acid, and their respective isomers;
Araliphatic polyamines such as diaminoxylene, di (aminomethyl) benzene, di (aminomethyl) pyridine, di (aminomethyl) naphthalene, and their isomers;
And polyamines substituted with hydroxyl groups such as diaminohydroxypropane and isomers thereof.

In the general formula (1), X is preferably an m-valent polythiol compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than a thiol group. Here, an m-valent polythiol compound means that m thioester bonds can be formed. It does not matter whether they are optical isomers, for example, D-form, L-form, or racemate.
Examples of such m-valent polythiol compounds include dithiol compounds such as dithioethylene glycol, dithioerythritol, and dithiothreitol.
X is preferably a group having 1 to 40 carbon atoms among the residues of the compounds listed above, and more preferably X is a case having 1 to 20 carbon atoms. X is preferably a naturally occurring type from the viewpoint of excellent biodegradability.
In general formula (2), a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group represented by Y and a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, etc. that can be contained in X are: Salts can be formed with various basic substances.
Examples of such salts include alkali metal salts, alkaline earth metal salts, polyvalent metal salts, ammonium salts, organic amine salts, basic amino acid salts, and the like. Specific examples include sodium, potassium, lithium and the like. Alkaline metals, alkaline earth metals such as calcium and magnesium, metals such as aluminum, zinc, iron, cobalt, titanium and zirconium, organic amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine, arginine, It is a salt with one or more kinds arbitrarily selected from basic amino acids such as lysine.

（一般式（３）中、Ｒ¹ ＣＯ、Ｒ² 、ｊ、ｋは、一般式（２）中と同じである。） The method for producing the acyl compound represented by the general formula (1) is selected from an N-acyl acidic amino acid anhydride represented by the following general formula (3) and a hydroxyl group, an amino group, and a thiol group in the molecule. By reacting a compound having one or more kinds of m functional groups with water and / or a mixed solvent of water and an organic solvent, or tetrahydrofuran, benzene, toluene, xylene, carbon tetrachloride, It can be obtained by reacting using an inert solvent such as chloroform or acetone, or by mixing at -5 ° C to 200 ° C at a temperature equal to or higher than any melting point without solvent.

(In general formula (3), R ¹ CO, R ² , j, and k are the same as in general formula (2).)

Alternatively, the acyl compound represented by the general formula (1) is an N-acyl acidic amino acid mono-lower ester such as methyl ester, ethyl ester and polyhydroxyl compound or polyamino compound or polythiol compound, or hydroxyl group, amino group, A compound having any two or three of the thiol groups is dissolved in a suitable solvent such as dimethylformamide, a catalyst such as potassium carbonate is added, and the mixture is heated at -5 ° C to 250 ° C under reduced pressure. It can be obtained by removing the post-reaction solvent. Alternatively, the acyl compound can be obtained by melting with heating without a solvent, adding a catalyst such as sodium hydroxide, and performing a transesterification reaction at room temperature to 250 ° C.
The blending amount of the water-in-oil emulsified cosmetic of the present invention is not particularly limited, but the content of the multi-chain polyhydrophilic group type compound (A) is preferably 0.001 to 20% by mass, depending on the purpose. More preferably, it is 0.01-10 mass% in a composition, More preferably, it is 0.01-5 mass%. If the content of the multi-chain polyhydrophilic group type compound is less than the above range, the stability of the cosmetic may not be sufficient. Further, when the amount is larger than the above range, stickiness or the like may occur.

The oil component of the component (B) used as the oil phase in the water-in-oil emulsified cosmetic of the present invention is not particularly limited, and is avocado oil, turtle oil, corn oil, almond oil, olive oil, cacao oil, Sesame oil, safflower oil, soybean oil, camellia oil, persic oil, castor oil, grape seed oil, macadamia nut oil, mink oil, cottonseed oil, owl, coconut oil, egg yolk oil, palm oil, palm kernel oil, glycerin triisooctanoate, tri 2-ethylhexanoic acid glyceryl cholesterol fatty acid ester, wheat germ oil, sasanqua oil, flaxseed oil, evening primrose oil, enoy oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagyl oil, Japanese kiri oil, jojoba oil, germ Oil, glyceryl trioctanoate, glycerin triisopalmitate, horse oil, hardened palm oil, beef tallow, beef leg fat, sheep fat, hardened beef , Lard, beef bone fat, Japan wax kernel oil, hardened oil, Japan wax, fats such as hydrogenated castor oil;
Hydrocarbons such as liquid paraffin, petrolatum, ceresin, microcrystalline wax, isoparaffin, ozokerite, squalene, pristane, squalane;
Beeswax, whale wax, lanolin, carnauba wax, candelilla wax, cotton wax, bayberry wax, ibotarou, montan wax, nukarou, lanolin, cabbage wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, lauryl hexyl, reduced lanolin, jojoba wax Waxes such as hard lanolin, shellac wax, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, polyoxyethylene hydrogenated lanolin alcohol ether and derivatives thereof;
Lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, behenic acid, undecylenic acid, lanolin fatty acid, hard lanolin fatty acid, soft lanolin fatty acid, linoleic acid, linolenic acid, eicosapentaenoic acid, 12-hydroxystearic acid Higher fatty acids such as;

Higher alcohols such as lauryl alcohol, cetanol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldodecanol;
Isopropyl myristate, butyl stearate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, stearic acid Isocetyl, isocetyl isostearate, cholesteryl 12-hydroxystearylate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, monoisostearate N-alkyl glycol, neopentyl glycol dicaprate, diisostearyl malate, di- 2-glyceryl 2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate Bread, pentaerythritol tetra-2-ethylhexylate, glycerol tri-2-ethylhexylate, trimethylolpropane triisostearate, cetyl-2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2- Heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleic oil, cetostearyl alcohol, acetoglyceride, palmitic acid-2-heptylundecyl, adipic acid diisopropyl, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, adipine Di-2-heptyl undecyl acid, ethyl laurate, di-2-ethylhexyl sepatate, 2-hexyl decyl myristate, 2-hexyl decyl palmitate, adipine 2-hexyl decyl, Sebachiru acid diisopropyl succinate 2-ethylhexyl, ethyl acetate, butyl acetate, amyl acetate, ester oils such as triethyl citrate;
Metal soap, dimethylpolysiloxane, polyether-modified silicone, alcohol-modified silicone, methylphenylpolysiloxane, epoxy-modified silicone, fluorine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, amino-modified silicone, volatile silicone and other silicones Volatile and non-volatile oils;
Can be used, but the oil component is vegetable oils and fats, vegetable waxes, vegetable hydrocarbons, vegetable higher fatty acids, vegetable higher alcohols, plant esters, squalene and its It is particularly effective when it is at least one selected from the analogs, squalane and analogs thereof, dimethylpolysiloxane and derivatives thereof. In a preferred embodiment of the present invention, the oil component (B) is preferably blended in an amount of 0.1 to 80% by mass, more preferably 5 to 60% by mass.

The surfactant of component (C) blended in a preferred embodiment of the present invention can be used as an auxiliary emulsifier. Examples of the component (C) anionic surfactant to be blended in a preferred embodiment of the present invention include the following carboxyl group-containing ones.
For example, higher fatty acid salts (soaps) that are higher fatty acids having 8 to 20 carbon atoms in the hydrophobic group or salts thereof are used, and these are also used as mixed fatty acids.
Further, the N-acyl amino acid type anionic surfactant, the constituent acyl group includes those having 8 to 20 carbon atoms as described above, and examples of the constituent amino acid include glutamic acid and aspartic acid. Glycine, alanine, valine, leucine, isoleucine, proline, methionine, cysteine, tryptophan, tyrosine, phenylalanine, asparagine, glutamine, serine, threonine, oxyproline, β-aminopropionic acid, γ-aminobutyric acid, Anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid and the like can be mentioned.
Moreover, alkyl ether carboxylate, amide ether carboxylate, etc. are mentioned.

Moreover, as an anionic surfactant of the component (C) mix | blended in the preferable aspect of this invention, things other than the following carboxyl group containing are mentioned.
For example, alkane sulfonates, alpha-olefin sulfonates (AOS), alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfonates (SAS), sulfonates of higher fatty acid esters, alpha-sulfonated fatty acid salts, Higher fatty acid amide sulfonate, N-acyl-N-alkyltaurine salt, dialkylsulfosuccinate, sulfated oil, alkyl sulfate ester (AS), alkyl ether sulfate, sulfate of higher fatty acid ester, higher fatty acid alkyl Rollamide sulfate, polyoxyalkylene alkyl ether sulfate (AES), polyoxyalkylene styrenated phenyl ether sulfate, alkyl phosphate, alkyl ether phosphate, polyoxyethylene alkyl ether phosphate, Polyoxyethylene alkyl phenyl ether phosphates, naphthalenesulfonic acid salt formalin condensates and the like. Here, the counter ions of the salts of these anionic surfactants are arbitrarily selected from alkali metals, alkaline earth metals, ammonium ions, and organic ammonium ions. In a preferred embodiment of the present invention, the anionic surfactant is preferably blended in an amount of 0.01 to 5% by mass, and two or more types may be mixed and used. Among these, soaps, N-acyl amino acid salts, N-acyl alkyl taurine salts, sulfosuccinates, and polyoxyethylene alkyl ether sulfates are preferably blended.

The nonionic surfactant of component (C) to be blended in a preferred embodiment of the present invention includes polyhydric alcohols such as alkyl polyglucoside, (poly) glycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, and fatty acid ester such as sho Ester, polyoxyethylene alkyl ether (AE), polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid alkanolamide, polyoxyalkylene alkyl glucoside, polyoxyalkylene hydrogenated castor oil, polyoxyalkylene alkylamine, poly Oxyalkylene alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene alkyl Ethers, polyoxyethylene polyoxypropylene glycol, ethylene oxide condensation type, fatty acid alkanolamides and the like, sugars Amin'ashiru products, triethanolamine fatty acid partial esters, alkyl amine oxides, and the like. In a preferred embodiment of the present invention, the nonionic surfactant is preferably blended in an amount of 0.01 to 5% by mass, and two or more kinds may be mixed and used.
Examples of the amphoteric surfactant to be blended as component (C) in a preferred embodiment of the present invention include alkylbetaines, alkylamidobetaines, alkylsulfobetaines, imidazolinium betaines, and lecithins. Examples thereof include lauric acid amidopropyl betaine. In a preferred embodiment of the present invention, the amphoteric surfactant is preferably blended in an amount of 0.01 to 5% by weight, and two or more kinds may be mixed and used.

The cationic surfactant of component (C) to be blended in a preferred embodiment of the present invention includes primary to tertiary fatty amine salts, alkylammonium chlorides, tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridinium salts. And cationic surfactants such as alkylhydroxyethyl imidazolinium salt, dialkylmorpholinium salt, alkylisoquinolium salt, benzethonium salt, benzalkonium salt, and counterions of these include chlorine, iodine, bromine, etc. Organic anions such as halogen ions, methosulfate, ethosulfate, methophosphate, ethophosphate. In a preferred embodiment of the present invention, the cationic surfactant is preferably blended in an amount of 0.01 to 5% by mass, and two or more kinds may be mixed and used.
Examples of the component (D) polyhydroxyl compound to be blended in a preferred embodiment of the present invention include bivalent or higher polyhydroxyl compounds as described above. These polyhydroxyl compounds are preferably blended in an amount of 0.1 to 30% by mass, more preferably 1 to 20% by mass, and two or more kinds may be mixed and used.
The organic and / or inorganic electrolyte of component (E) blended in a preferred embodiment of the present invention includes sodium chloride, potassium chloride, lithium chloride, ammonium chloride, sodium sulfate, potassium sulfate, lithium sulfate, ammonium sulfate, sodium carbonate, carbonic acid. Potassium, lithium carbonate, ammonium carbonate, sodium acetate, potassium acetate, lithium acetate, ammonium acetate, sodium citrate, potassium citrate, lithium citrate, ammonium citrate, sodium malate, potassium malate, lithium malate, malic acid Examples thereof include ammonium, sodium glutamate, potassium glutamate, lithium glutamate, ammonium glutamate, and betaines. These organic and / or inorganic electrolytes are contained in an amount of 0.01 to 10% by mass. It is preferable that may be used in combination of two or more.
Moreover, in this invention, it is preferable that a water | moisture content is 20-80 mass% of cosmetics.
In addition, the water-in-oil emulsified cosmetic of the present invention can be used in a wide pH range of preferably 3 to 12 by adjusting the neutralization rate with a basic substance, and more preferably the composition has a pH of 4 It can be used in the range of 5-11. More preferably, it can be used in the range of pH 5-8.

The water-in-oil emulsified cosmetic of the present invention can be used in combination with various base materials depending on the application and purpose as long as the object of the present invention is not impaired.
Specifically, natural rubbers such as gum arabic and tragacanth, glucosides such as saponin, cellulose derivatives such as methylcellulose, carboxycellulose, and hydroxymethylcellulose, natural polymers such as lignin sulfonate and shellac, polyacrylates, Styrene-acrylic acid copolymer salt, vinyl naphthalene-maleic acid copolymer salt, β-naphthalene sulfonic acid formalin condensate sodium salt, anionic polymer such as phosphate, polyvinyl alcohol, polyvinyl pyrrolidone, Dispersants such as nonionic polymers such as polyethylene glycol;
Polymeric surfactants such as sodium alginate, starch derivatives, tragacanth gum;
Natural surfactants such as phospholipids, lecithin, lanolin, cholesterol, saponins;
Moisturizers such as trimethylglycine, sorbitol, raffinose, pyrrolidone carboxylates, lactates, hyaluronates, ceramides;
Cationized cellulose derivative, cationic starch, cationized guar gum derivative, diallyl quaternary ammonium salt / acrylamide copolymer, quaternized polyvinylpyrrolidone derivative, quaternized vinylpyrrolidone / vinylimidazole polymer, polyglycol / amine condensate, Cationic compounds such as quaternized collagen polypeptides, polyethyleneimine, cationic silicone polymers, adipic acid / dimethylaminohydroxypropyldiethylenetriamine copolymers, polyaminopolyamides, cationic chitin derivatives, cationic polymers such as quaternized polymers;

Hydroxyethylcellulose, carboxymethylcellulose, hydroxyethylcellulose hydroxypropyltrimethylammonium chloride ether, methylcellulose, ethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, soluble starch, carboxymethylstarch, methylstarch: alginate propylene glycol ester, polyvinyl alcohol, polyvinylpyrrolidone, Polyvinyl methyl ether, carboxyvinyl polymer, polyacrylate, guar gum, locust bin gum, quince seed, carrageenan, galactan,: gum arabic, pectin, mannan, starch, xanthan gum, dextran, succinoglucan, curdlan, hyaluronic acid, gelatin The casei , Albumin, collagen, methoxyethylene maleic anhydride copolymer, amphoteric methacrylate copolymer, poly (dimethylmethylenepiperidinium chloride), polyacrylate copolymer, polyvinyl acetate, nitrocellulose, silicone resin, etc. And oil-soluble polymers;
Thickening and foam increasing components such as polyethylene glycol fatty acid ester, polyoxyethylene fatty acid ester methyl glycoside, tetradecene sulfonate;
Sequestering agents such as ethylenediaminetetraacetic acid and its salts, hydroxyethylenediaminetriacetic acid and its salts, phosphoric acid, ascorbic acid, succinic acid, gluconic acid, polyphosphates, metaphosphates, hinokitiles;
Preservatives such as paraoxybenzoates, benzoic acid and its salts, phenoxyethanol, hinokitile;

PH adjusters such as citric acid, malic acid, adipic acid, glutamic acid, aspartic acid;
Other anti-dandruff and itching agents such as trichlorolcarbanilide, salicylic acid, zinc pyrithione and isopropylmethylphenol;
Benzophenone derivatives, paraaminobenzoic acid derivatives, paramethoxycinnamic acid derivatives, salicylic acid derivatives and other UV absorbers;
Blood circulation promoters such as assembly extract, cephalanthin, vitamin E and its derivatives, gamma oryzanol;
Local stimulants such as pepper tincture, ginger tincture, cantharis tincture, nicotinic acid benzyl ester;
Nutrients such as various vitamins and amino acids;
Female hormone agent;
Hair root activator;
Anti-inflammatory agents such as glycyrrhetinic acid, glycyrrhizic acid derivatives, allantoin, azulene, aminocaproic acid, hydrocortisone;
Astringents such as zinc oxide, zinc sulfate, allantoin hydroxyaluminum, aluminum chloride, zinc sulfocolate, tannic acid;
Refreshing agents such as menthol and camphor;
Antihistamines;
Antihistamines such as diphenhydramine hydrochloride, chlorpheniramine maleate, glycyrrhizic acid derivatives;
Silicone materials such as high molecular silicones and cyclic silicones;
Antioxidants such as tocopherols, BHA, BHT, gallic acid, NDGA;
Sebum inhibitors such as estradiol, estrone, ethinyl estradiol;
Exfoliating / dissolving agents such as sulfur, salicylic acid, resorcin;
Α-hydroxy acids such as glycolic acid, lactic acid, malic acid, tartaric acid, citric acid;

Talc, kaolin, sericite, calcium carbonate, zinc oxide, aluminum oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, barium sulfate, chromium oxide, chromium hydroxide, tar dyes, mica, (synthetic) sericite , Silicon carbide, boron nitride, titanium dioxide, black titanium oxide, conger, red iron oxide, black iron oxide, yellow iron oxide, ultramarine, titanium coated mica, bismuth oxychloride, bengara, caking pigment, gunjo pink, gunjo Violet, chromium hydroxide, mica titanium, chromium oxide, aluminum cobalt oxide, carbon black, silicic anhydride, magnesium silicate, bentonite, (synthetic) mica, zirconium oxide, magnesium (meth) silicate aluminate, aluminate silicate Calcium, polye Len powder, nylon powder, polymethyl methacrylate, polyethylene terephthalate-polymethyl methacrylate laminated powder, acrylonitrile-methacrylic acid copolymer powder, vinylidene chloride-methacrylic acid copolymer powder, wool powder, silk powder, crystalline cellulose, N-acyl lysine, poly Methyl silsesquioxane powder, plant fruit or skin powder, bismuth oxychloride, mica titanium, iron oxide coated mica, iron oxide mica titanium, organic pigment treated mica titanium, aluminum powder, fine titanium oxide, fine particles Zinc oxide, fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium, barium sulfate coated mica titanium, carmine, β-carotene, chlorophyll, sunset yellow FCF, Ponceau SX, eosin YS, tetrab Lomofluorescein, rhodamine B, quinoline yellow SS, quinoline yellow WS, alizanin cyanine green, quinizarin green, resolbin BCA, resolbin BCA, permaton red, herringdon pink CN, phthalocyanine blue, β-apo-8-carotenal, Capsanthin, lilopine, bixin, crocin, canthaxanthin, shisonin, raphanin, ninocyanin, calsamine, safrole yellow, rutin, quercetin, cacao dye, lipoflavin, lacainate, carminic acid, kermesic acid, alizanin, shikonin, alkanine, niquinochrome, hemoglobin, Cosmetic colorants such as curcumin and betanin:
Others, oyster extract, N-methyl-L-serine, whey, nicotinamide, diisopropylamine dichloroacetic acid, mevalonic acid, γ-aminobutyric acid (including γ-amino-β-hydroxybutyric acid), altea extract, aloe extract, Apricot kernel extract, turmeric extract, oolong tea extract, seawater dried product, hydrolyzed wheat powder, hydrolyzed silk, carrot extract, cucumber extract, gentian extract, yeast extract, rice germ oil, comfrey extract, savanna extract, ginger extract, lion extract , Birch extract, Atlantic mint extract, assembly extract, bisabolol, propolis, loofah extract, bodaiju extract, hop extract, marronnier extract, muroji extract, melissa extract, eucalyptus extract, yukinoshita extract, rosemary extract, Over Ma chamomile extract, royal jelly extract, seaweed, rice bran, licorice, citrus unshiu peel, angelica, pulverized Momonoha, sphingolipids, guaiazulene, vitamin C; can be contained and the like.

The water-in-oil emulsified cosmetic of the present invention includes all cosmetics such as makeup removers, creams, foundations, suncare agents, and detergents applied to the outer skin, and the form thereof may also be a water-in-oil emulsified emulsion. For example, it is not limited to a product having an external appearance such as a milky lotion or cream, and includes a product having a solid appearance regardless of whether it is cloudy or transparent, or has fluidity.
The water-in-oil emulsified cosmetic of the present invention can be produced by a conventional method by a method using an apparatus equipped with a usual stirrer, mixer, disperser and the like. Also, a method of preparing an aqueous solution of the component (A) in which all of the component (A) is dissolved in a part of water, mixing this with the oil component, and then mixing with the rest of the water, or a part of the water By preparing an aqueous solution of the component (A) in which a part of the component (A) is dissolved, mixing this with the oil component, and then mixing with the remainder of the water containing the remainder of the component (A), etc. Can also be manufactured.

Hereinafter, the present invention will be described more specifically using examples and the like, but the present invention is not limited to these examples and the like.
The evaluation means used in the examples of the present invention are as follows.
(Skin irritation test)
After applying 0.1 g of the sample to the forearm flexion skin of 5 healthy male panelists for 3 days, the presence or absence of skin irritation was evaluated. The determination result is indicated by a case where the average score of the following evaluation points is 0 point or more and less than 1 point: ◯, when 1 point or more and less than 2 points: Δ, when 2 points or more: ×.
Judgment criteria and score Erythema, edema, blisters (4 points)
Erythema, edema (3 points)
Erythema (2 points)
Minor erythema (1 point)
No erythema, no edema (0 points)
(Storage stability)
Stability over time (1): After the sample was stored at 40 ° C. for 1 month, the appearance was visually observed and evaluated according to the following criteria. Judgment criteria are shown as follows.
Good (O): Aggregation is not recognized for 3 months or more.
Slightly poor (Δ): Aggregation was observed from 1 month to 3 months.
Poor (x): Aggregation was observed in less than 1 month.

（式（４）中、Ｘは、各々独立にＨまたはＮａを表す。）
〔アシル化合物の製造例２〕
製造例１において、Ｎ−ラウロイル−Ｌ−グルタミン酸無水物３１．１ｇをＮ−ココイル−Ｌ−グルタミン酸無水物（０．１ｍｏｌ）とし、それ以外は、製造例１の方法と同じ条件で実施し、アシル化合物を含有する組成物を得た。
［実施例１〜９、比較例１〜２］
表１に示す各成分を、表１に示す配合量で使用し、油中水型乳化化粧料を作成した。各油中水型乳化化粧料について評価した結果を表１に示す。 [Production Example 1 of acyl compound]
9.1 g (0.05 mol) of L-lysine hydrochloride was mixed with 57 g of water. While this solution was adjusted to a pH range of 10 to 11 with a 25% aqueous sodium hydroxide solution and the reaction temperature was maintained at 5 ° C., 31.1 g of N-lauroyl-L-glutamic anhydride (0. 1 mol) was added over 2 hours to carry out the reaction. After further stirring for 2 hours, tertiary butanol was added to a concentration of 20% by mass in the liquid, 75% sulfuric acid was added dropwise to bring the pH value of the liquid to 2, and the liquid temperature to 65 ° C. It was adjusted. After completion of the dropwise addition, stirring was stopped and the mixture was allowed to stand at 65 ° C. for 20 minutes, so that the organic layer and the aqueous layer were separated, and the organic layer was separated therefrom. Tertiary butanol and water were added to the separated organic layer, the temperature was raised to 65 ° C., and the mixture was stirred for 20 minutes. After the stirring was stopped, the mixture was allowed to stand to separate into an organic layer and an aqueous layer. After repeating the same water washing operation for the obtained organic layer, the solvent was removed from the obtained organic layer and neutralized with sodium hydroxide to an aqueous solution having a solid content of 30% by mass and a pH of 6.5 (25 ° C.). After the preparation, this was dried to obtain a composition containing an acyl compound represented by the following formula (4).

(In formula (4), each X independently represents H or Na.)
[Production Example 2 of acyl compound]
In Production Example 1, 31.1 g of N-lauroyl-L-glutamic anhydride was changed to N-cocoyl-L-glutamic anhydride (0.1 mol), and the other conditions were carried out under the same conditions as in Production Example 1. A composition containing an acyl compound was obtained.
[Examples 1-9, Comparative Examples 1-2]
Each component shown in Table 1 was used in the blending amount shown in Table 1 to prepare a water-in-oil emulsified cosmetic. Table 1 shows the results of evaluation for each water-in-oil emulsified cosmetic.

[Example 10]
The following moisturizing cream was prepared. The evaluation results for the stability of cosmetics and skin irritation were both good.
(Composition) (Mass)
(1) PEG400 1
(2) Lactic acid Na 1
(3) BG 5
(4) Liquid paraffin 5
(5) Cetyl-2-ethylhexanoate 5
(6) Acylated product of Production Example 1 3
(7) Methylphenylpolysiloxane 4
(8) Decamethylcyclopentasiloxane 12
(9) Silicon SC9450N (manufactured by Shin-Etsu Silicone, HLB = 4.5)
1
(10) Zinc stearate 2
(11) Vitamin E-acetate 3
(12) Preservative appropriate amount (13) Fragrance appropriate amount (14) Purified water

[Example 11]
The following sunscreen cream was made. The evaluation results for the stability of cosmetics and skin irritation were both good.
(Composition) (Mass)
(1) 2-ethoxyethyl paramethoxycinnamate 4
(2) Glyceryl trioctanoate 20
(3) 2-Ethylhexyl p-methoxycinnamate 25
(4) Acrylic modified resin-treated fine particle titanium oxide 10
(5) Decamethylcyclopolysiloxane 10
(6) Polyoxyalkylene-modified organopolysiloxane surfactant
(KF-6015 manufactured by Shin-Etsu Chemical Co., Ltd.) 3
(7) Acyl compound of Production Example 2 1.5
(8) Preservative appropriate amount (9) Fragrance appropriate amount (10) Purified water

[Example 12]
The following make-up remover was prepared. The evaluation results for the stability of cosmetics and skin irritation were both good.
(Composition) (Mass)
(1) Liquid paraffin 25
(2) Vaseline 6
(3) Microcrystalline wax 0.5
(4) Lanolin 4
(5) Tri (capryl / capric acid) glyceryl 12
(6) White beeswax 1
(7) Glycerin 15
(8) Acyl compound 1 of Production Example 1
(9) Preservative appropriate amount (10) Fragrance appropriate amount (11) Purified water

[Example 13]
The following body emulsion was prepared. The evaluation results for the stability of cosmetics and skin irritation were both good.
(Composition) (Mass)
(1) Squalane 15
(2) Liquid paraffin 8
(3) Vaseline 6.5
(4) Microcrystalline wax 0.2
(5) Lanolin 4
(6) Lanolin Fatty Acid Cholestearyl 0.5
(7) Olive oil 12
(8) Bare beeswax 1.2
(9) Glycerin 15
(10) Production Example 2 Acyl Compound 1.5
(11) Decaglyceryl tristearate 0.5
(12) Preservative appropriate amount (13) Fragrance appropriate amount (14) Purified water

[Example 14]
The following lip balm was prepared. The evaluation results for the stability of cosmetics and skin irritation were both good.
(Composition) (Mass)
(1) Cetyl isooctanoate 25
(2) Liquid lanolin 25
(3) Polyisobutylene 2
(4) Dimethylpolysiloxane (100 cs) 10
(5) Polyoxyalkylene-modified organopolysiloxane surfactant
(Manufactured by Goldschmidt, ABILEM905) 5
(6) Acyl compound 2 of Production Example 1
(7) Preservative appropriate amount (8) Fragrance appropriate amount (9) Purified water

  INDUSTRIAL APPLICABILITY The present invention can be suitably used as a water-in-oil emulsified cosmetic with excellent cosmetic stability and low irritation.

Claims (10)

A water-in-oil emulsified cosmetic comprising the following component (A) and component (B):
Component (A): At least one multi-chain polyhydrophilic group type compound having two or more long-chain hydrophobic groups and hydrophilic groups in the molecule.
Component (B): At least one oily component.   At least one of the multi-chain poly-hydrophilic group type compound, the long-chain hydrophobic group is a long-chain acyl group, and the hydrophilic group is a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group or a salt thereof The water-in-oil emulsified cosmetic according to claim 1.   The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein at least one of the multi-chain polyhydrophilic group type compound has an amino acid residue in the molecule. The water-in-oil emulsion cosmetic according to any one of claims 1 to 3, wherein at least one of the multi-chain polyhydrophilic group type compound is a compound represented by the following general formula (1).

[In General Formula (1), X is a linear, branched, cyclic, or aromatic hydrocarbon chain having a molecular weight of 1 million or less, which may have m functional groups and other substituents. A spacer is shown. N (m ≧ n) Qs bonded to X are substituents represented by the following general formula (2), and may be the same as or different from each other.

(In the general formula (2), Z is a bond unit derived from a functional group of X, R ¹ CO represents an acyl group derived from a saturated or unsaturated fatty acids having 8 to 20 carbon atoms, R ² Represents hydrogen, or a lower alkyl group having 1 to 3 carbon atoms which may be substituted by a hydroxyl group or a carboxyl group, and Y represents a carboxyl group, a sulfonic acid group, a sulfuric acid ester group, a phosphoric acid ester group or the like Wherein j and k are each independently 0, 1, or 2 and j and k are not 0 at the same time, n is an integer of 2 to 20. m represents an integer satisfying m ≧ n.)]   At least one of the multi-chain polyhydrophilic group type surfactant is a compound represented by the general formula (1), and in the general formula (1), X may have a substituent other than the functional group. The water-in-oil emulsified cosmetic according to any one of claims 1 to 4, which is a spacer having a straight chain, branched chain, cyclic chain or aromatic hydrocarbon chain having 1 to 40 carbon atoms.   The water-in-oil emulsified cosmetic according to any one of claims 1 to 5, wherein the content of the oil component is 0.1 to 80% by mass.   Furthermore, at least 1 sort (s) chosen from component (C): anionic surfactant, nonionic surfactant, an amphoteric surfactant, and a cationic surfactant is included, The statement in any one of Claims 1-6 characterized by the above-mentioned. Water-in-oil emulsified cosmetic.   The water-in-oil emulsified cosmetic according to any one of claims 1 to 7, further comprising at least one component (D): a polyhydroxyl compound.   Furthermore, at least 1 sort (s) chosen from component (E): organic and / or inorganic electrolyte is contained, The water-in-oil type emulsion cosmetic in any one of Claims 1-8 characterized by the above-mentioned.   A cosmetic method comprising using the water-in-oil emulsified cosmetic according to any one of claims 1 to 9.