JP2002167313A - Surfactant - Google Patents

Abstract

(57) [Problem] To provide an anionic surfactant having low irritation to skin and the like and having sufficient surface activity even at a low concentration. SOLUTION: The acyl group-containing composition represented by the following formula (1) exhibits excellent interface physical properties, and by using this, it has excellent surface activity at a low concentration and has low irritation to the skin and the like. Certain surfactants and cosmetic ingredients are obtained. Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides excellent interface properties at low concentrations and low irritation to skin, etc.
The present invention also relates to a novel surfactant capable of giving a favorable feeling to the skin and the like, an aqueous solution thereof, a cosmetic composition, and a production method thereof. This surfactant,
In particular, it is an anionic surfactant useful in the field of cosmetics such as detergents, quasi-drugs, and cosmetics.

[0002]

2. Description of the Related Art Various anionic surfactants useful as detergents and cosmetic raw materials have been known. Surfactants are required to have not only excellent surface active properties such as detergency and foaming, but also recently, irritation to the skin, etc., due to diversification of demands of consumers and high-quality products. In addition to a small amount, there are demands for effects such as good foaming properties and a favorable feeling on the skin. Further, from the viewpoint of load on the environment, there is a stronger tendency that it is desired that biodegradability is good and that a small amount has a surface active effect.

For example, alkyl sulfates, polyoxyethylene alkyl sulfates, alkyl benzene sulfonates and the like have been conventionally used. However, many of them have a problem that they are highly irritating to the skin when used. In addition, there is an N-long-chain acylamino acid salt as an anionic surfactant which is less irritating to the skin and is excellent in biodegradability. However, in this case, the surface activity at a low concentration is not yet sufficient. That is, in reality, there is no anionic surfactant which has a small amount of irritation to the skin and has a sufficient surface activity even at a low concentration.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, is excellent in surface activity even at a low concentration, is low irritating to the skin, etc., and is used as a raw material for cosmetics. It provides a useful surfactant.

[0005]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a surfactant having a specific structure exhibits excellent physical properties, in particular, a surfactant having a low concentration. The present invention was also found to be remarkably excellent in irritation to the skin and the like, and the present invention was completed. That is, the present invention is as follows. 1. A surfactant comprising an acyl group-containing composition containing at least one kind or two or more kinds of acyl compounds represented by the general formula (1).

[0006]

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(In the general formula (1), n Zs are bonding parts derived from m (m ≧ n) functional groups substituted by X, and each Z is independent, that is, may be the same or different. X is a spacer that is a linear, branched, or cyclic chain or an aromatic hydrocarbon chain having 0 to 40 carbon atoms which may have a substituent other than the above functional group. The substituents represented by n represented by the general formula (2) may be each independently, that is, they may be the same or different,
R ¹ CO represents a long-chain acyl group derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms, and R ² is hydrogen or a carbon atom which may be substituted by a hydroxyl group or a carboxyl group. A lower alkyl group having 1 to 3 atoms, Y represents a carboxyl group or a salt thereof,
j and k are each independently 0, 1, or 2,
And j and k are not simultaneously 0 and n is an integer of 2 to 20).

[0008]

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[0009] 2. In the acyl compound represented by the general formula (1), m functional groups substituted by X (m is m ≧ n,
And a hydroxyl group (—OH), a thiol group (—SH), an amino group (—NHR ³ ) (R ³ is hydrogen,
Or an alkyl group or alkenyl group or an aryl group or an alkylaryl group having 1 to 10 carbon atoms), wherein Z is -O- derived from a hydroxyl group, a thiol group or an amino group; -S-,
—NR ³ —. The surfactant according to the above. 3. In the acyl compound represented by the general formula (1), X
Is a substituent P other than the above functional group,
0 independent carboxyl groups, sulfonic acid groups,
1. It has a sulfate group, a phosphate group, or a salt thereof. Or 2. The surfactant according to the above.

[0010] 4. 1. The acyl compound represented by the general formula (1) is optically active. ~ 3. The surfactant according to any one of the above. 5. 1. It further comprises other surfactants. ~ 4. The surfactant according to any one of the above. 6. 4. The other surfactant is an N-long-chain acyl amino acid surfactant. A surfactant as described. 7. The above 1. ~ 6. The surfactant according to any one of the above.
001-80 wt% and water, and p of the aqueous solution
H is 3-12, The surfactant composition characterized by the above-mentioned.

8. A liquid or solid cosmetic composition comprising one or more surfactants or surfactant compositions according to any one of the above 1 to 7. 9. 0.001 of an acyl group-containing composition in a cosmetic composition
~ 80 wt%, and the pH of the cosmetic composition is 3 ~
7. It is characterized by being 8. A liquid or solid cosmetic composition according to the above. 10. M N-long-chain acyl acidic amino acids or derivatives thereof and one or more functional groups selected from a hydroxyl group, a thiol group and an amino group (m is an integer of 0 to 20)
A condensation reaction with a compound having the same.
~ 7. The method for producing a surfactant according to any one of the above.

11. The above compound is one or more compounds selected from a polyhydroxyl compound, a polyamine compound and a polymercaptan compound. ~ 7. The method for producing a surfactant according to any one of the above. 12. 9. The N-long-chain acyl acidic amino acid or derivative thereof is an N-long-chain acyl-L-acid amino acid or derivative thereof. Or 11. The method for producing a surfactant according to the above. 13. 9. The derivative of an N-long-chain acyl acidic amino acid is an N-long-chain acyl acidic amino acid anhydride represented by the general formula (3). ~ 12. The method for producing a surfactant according to any one of the above.

[0013]

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(Wherein R ¹ CO, R ² , j and k have the same meanings as described above)

14. 9. The derivative of an N-long-chain acyl acidic amino acid is an N-long-chain acyl acidic amino acid ester. ~ 13. The method for producing a surfactant according to any one of the above.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The surfactant described in the present invention is an anionic surfactant comprising an acyl compound having a plurality of acyl groups and a plurality of hydrophilic groups in a molecule as shown by the general formula (1). In the general formula (1), the acyl groups represented by R ¹ CO are independent, that is, they may be different or the same, and may be derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms. Anything may be used, and it may be linear, branched or cyclic.

Linear fatty acids such as, for example, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachiic acid; -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 -Ethyl octanoic acid, methyl docosanoic 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, butylethylnonanoic acid, methylpentadecanoic acid, ethyltetradecanoic acid, propyltridecanoic acid, butyldodecanoic acid, pentylundecanoic acid, hexyldecanoic acid, heptylnonanoic acid, dimethyltetradecanoic acid, butyl Pentylheptanoic acid, trimethyltridecanoic acid, methylhexadecanoic acid, ethylpentadecanoic acid, propyltetradecanoic acid, butyltridecanoic acid, pentyldodecanoic acid, hexylundecanoic acid, heptyldecanoic acid, methylheptylnonanoic acid,

Dipentylheptanoic acid, methylheptadecanoic acid, ethylhexadecanoic acid, ethylhexadecanoic acid,
Propylpentadecanoic acid, butyltetradecanoic acid, pentyltridecanoic acid, hexyldecanoic acid, heptylundecanoic acid, octyldecanoic acid, dimethylhexadecanoic acid, methyloctylnonanoic acid, methyloctadecanoic acid,
Branched fatty acids such as ethyl heptadecanoic acid, dimethyl heptadecanoic acid, methyl octyl decanoic acid, methyl nona decanoic acid, methyl nona decanoic acid, dimethyl octa decanoic acid, butyl heptyl nonanoic acid; octenoic acid, nonenic acid, decenoic acid, caproleic acid, undecylenic acid, Linear monoenoic acids such as lindelic acid, succinic acid, lauroleic acid, tridecenoic acid, tunic acid, myristoleic acid, pentadecenoic acid, hexedesenoic acid, palmitoleic acid, heptadecenoic acid, octadecenoic acid, oleic acid, nonadenoic acid, gondoic acid ; Methylheptenoic acid, methylnonenoic acid,
Branched monoenoic acids such as methylundecenoic acid, dimethyldecenoic acid, methyldodecenoic acid, methyltridecenoic acid, dimethyldodecenoic acid, dimethyltridecenoic acid, methyloctadecenoic acid, dimethylheptadecenoic acid, ethyloctadedecenoic acid;

Di- or trienoic acids such as linoleic acid, linoleic acid, eleostearic acid, linolenic acid, linolenic elaidic acid, pseudoeleostearic acid, parinaric acid, arachidonic acid; octic acid, noninic acid,
Descic acid, undesic acid, dodecic acid, tridesic acid,
Acetylene acids such as tetradecanoic acid, pentadecenoic acid, heptadecanoic acid, octadecinic acid, nonadecinic acid, dimethyloctadedecanoic acid; methylene octadecenoic acid, methylene octadecanoic acid, aleprolic acid, aleprestic acid, aleprilic acid, alepic acid, and hydronocarpnic acid ,
Acyl groups derived from cyclic acids such as scholmoog acid, gorulinic acid, α-cyclopentylic acid, α-cyclohexylic acid, and α-cyclopentylethyl acid are exemplified.

An acyl group derived from a fatty acid obtained from natural fats and oils may be used, and any acyl group derived from a mixed fatty acid containing 80% or more of the above-mentioned saturated or unsaturated fatty acid having 8 to 20 carbon atoms may be used. For example, coconut oil fatty acids, palm oil fatty acids, linseed oil fatty acids, sunflower oil fatty acids, soybean oil fatty acids, sesame oil fatty acids, castor oil fatty acids, olive oil fatty acids,
Examples include acyl groups derived from camellia oil fatty acid, rapeseed oil fatty acid, palm kernel oil fatty acid, and the like. R ¹ C in the molecule
O is preferably the same.

In the general formula (1), R ² is hydrogen or a carbon which may be substituted by a hydroxyl group or a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group or a salt thereof. A lower alkyl group having 1 to 3 atoms; for example, methyl group, ethyl group, propyl group, isopropyl group, hydroxymethyl group, hydroxyethyl group, hydroxy (iso) propyl group, dihydroxy (iso) propyl group, carboxymethyl group; Group, carboxyethyl group, carboxypropyl group, sulfoethyl group and the like.

In the general formula (1), the n substituents (formula (2)) attached to X are independent, that is, they may be different or the same. The formula (2) represents a so-called N-acylated acidic amino acid, and it does not matter whether it is an optical isomer, for example, a D-form, an L-form, or a racemic form. Examples of the acidic amino acids include, for example, glutamic acid, aspartic acid, lanthionine, β-methyllanthionine, cystathionine, diencholic acid, ferrinin, aminomalonic acid, β-oxyaspartic acid, α-
Amino-α-methylsuccinic acid, β-oxyglutamic acid, γ-oxyglutamic acid, γ-methylglutamic acid, γ-methyleneglutamic acid, γ-methyl-γ-oxyglutamic acid, α-aminoadipate, α-amino-
γ-oxyadipic acid, α-aminopimelic acid, α-amino-γ-oxypimelic acid, β-aminopimelic acid,
α-aminosuberic acid, α-aminosebacic acid, pantothenic acid and the like.

The n substituents represented by X (formula (2)) are preferred when the acidic amino acid is an L-acidic amino acid molecule, since the surfactant of the present invention is excellent in biodegradability.
Among them, the substituents are preferably the same. In the general formula, n Zs attached to X are m substituted for X (m ≧ m)
n and an integer from 2 to 20) a functional group (hydroxyl group, amino group, thiol group) derived from a bonding moiety (—O
—, —NR ³ —, and —S—), each being independent, that is, they may be the same or different. Here, R ³ is hydrogen, an alkyl group or alkenyl group having 1 to 10 carbon atoms, an aryl group, or an alkylaryl group.

In the general formula (1), X is a straight or branched chain having 0 to 40 carbon atoms and having m functional groups of one or more selected from a hydroxyl group, an amino group and a thiol group. Or, it is a spacer which is a cyclic chain or an aromatic hydrocarbon chain, and X may have a substituent other than the above-mentioned hydroxyl group, amino group and thiol group. Preferred examples of the substituent other than the hydroxyl group, the amino group, and the thiol group include a carboxyl group, a sulfonic group, a sulfate group, a phosphate group, and salts thereof.

In the general formula (1), X is preferably a residue of an m-valent compound having 0 to 40 carbon atoms and having m functional groups of one or more selected from a hydroxyl group, an amino group and a thiol group. And is a compound residue which may have a substituent other than a hydroxyl group, an amino group and a thiol group. Here, the m-valent compound means that a bond derived from m functional groups can be formed. They may be optical isomers such as D-form, L-form and racemic form.

For example, amino acids such as serine, threonine, cysteine, cystine, cystine disulfoxide, cystathionine, methionine, arginine, lysine, tyrosine, histidine, tryptophan, oxyproline and the like; aminoethanol, aminopropanol, aminobutanol, aminopentanol , Aminohexanol,
Aminopropanediol, aminoethylethanolamine, aminoethylaminoethanol, aminocresol, aminonaphthol, aminonaphtholsulfonic acid,
Aminohydroxybenzoic acid, aminohydroxybutanoic acid, aminophenol, aminophenethyl alcohol,
Compounds having an amino group and a hydroxyl group in a molecule such as glucosamine; compounds having a thiol group and a hydroxyl group in a molecule such as mercaptoethanol, mercaptophenol, mercaptopropanediol, and glucothioose; aminothiophenol, aminotriazole thiol and the like Compounds having a thiol group and an amino group in the molecule of the above.

Further, X is a group having 1 to 20 carbon atoms selected from a hydroxyl group, an amino group and a thiol group in the molecule.
A compound residue having m kinds or two or more kinds of functional groups, each having 1 to 10 independent carboxyl groups, sulfonic groups, sulfate groups, phosphate groups, or salts thereof as substituents; Is preferable, because the surfactant of the present invention is excellent in solubility in a weak acid. Further, the case where X is in the L-form is preferable in that the surfactant of the present invention is excellent in biodegradability.

In the general formula (1), X preferably has 0 to 0 carbon atoms which may have a substituent other than a hydroxyl group.
It is a polyhydroxyl compound residue having an m value of 40 (m ≧ n). Here, an m-valent polyhydroxyl compound means that m ester bonds can be formed. They may be optical isomers such as D-form, L-form and racemic form.

For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexane Diol, 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, dihydroxytartaric acid, mevalonic acid, 3,4-dihydroxycinnamic acid,
Divalent hydroxyl compounds such as 3,4-dihydroxyhydrocinnamic acid, hydroxybenzoic acid, dihydroxystearic acid, dihydroxyphenylalanine and the like and isomers thereof; glycerin, trioxyisobutane, 1,2
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-heptantriol,
2,4-dimethyl-2,3,4-pentanetriol,
1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane, diethanolamine, triethanolamine,
Trivalent polyhydroxyl compounds such as trihydroxystearic acid;

Pentaerythritol, erythritol,
1,2,3,4-pentane tetrol, 2,3,4,5
Tetravalent polyhydroxyl compounds such as hexane tetrol, 1,2,4,5-pentane tetrol, 1,3,4,5-hexane tetrol, diglycerin and sorbitan;
Pentavalent polyhydroxyl compounds such as adonitol, arabitol, xylitol, and triglycerin; divalent erythritol, sorbitol, mannitol, iditol, inositol, darcitol, talose, allose, and other hexavalent polyhydroxyl compounds; Is mentioned.

Also, saccharides such as tetroses such as erythrose, threose and erythrulose; pentoses such as ribose, arabinose, xylose, licose, xylulose and ribulose; allose, altrose, glucose, mannose, gulose, idose, galactose and talose , Monosaccharides such as hexoses such as fructose, sorbose, psicose and tagatose; maltose, isomaltose, cellobiose, gentiobiose, melibiose, lactose, turanose, trehalose, saccharose, mannitolose, cellotriose, gentianose, raffinose, meletitose, meletitose, And the like.

Further, other saccharides such as heptose,
Deoxy sugar, amino sugar, thio sugar, seleno sugar, aldon sugar, uronic acid, sugar acid, ketoaldonic acid, anhydro sugar,
It may be a residue such as an unsaturated sugar, a sugar ester, a sugar ether, or a glycoside, or a residue obtained by hydrolyzing a polysaccharide such as starch, glycogen, or cellulose. Moreover,
X is an m-valent polyhydroxyl compound residue having 1 to 20 carbon atoms, and each having 1 to 10 independent carboxyl groups, sulfonic acid groups, sulfate groups, phosphate groups, or salts thereof as substituents When the surfactant is contained, the surfactant of the present invention is preferred in that it has excellent solubility in a weak acid. Further, the case where X is in the L-form is preferable in that the surfactant of the present invention is excellent in biodegradability.

In the general formula (1), X is preferably an m-valent polyamino compound residue having 0 to 40 carbon atoms 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. They are optical isomers such as D-form and L-form.
It does not matter whether it is a body or a racemic body. For example, hydrazine,
N, N′-dimethylhydrazine, ethylenediamine,
N, N'-dimethylethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, diaminodecane, diaminododecane, diaminoadipic acid, diaminopropanoic acid, diaminobutanoic acid and each isomer thereof Aliphatic diamines such as a body; diethylenetriamine, triaminohexane, triaminododecane, 1,8-diamino-4-aminomethyl-octane,
2,6-diaminocapric acid-2-aminoethyl ester, 1,3,6-triaminohexane, 1,6,11-
Aliphatic triamines such as triaminoundecane, di (aminoethyl) amine and their respective isomers;

Alicyclic polyamines such as diaminocyclobutane, diaminocyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine and triaminocyclohexane; diaminobenzene, diaminotoluene, diaminobenzoic acid, diaminoanthraquinone, diaminobenzene Aromatic polyamines such as sulfonic acid, diaminobenzoic acid, and their respective isomers; diaminoxylene, di (aminomethyl) benzene, di (aminomethyl) pyridine, di (aminomethyl) naphthalene, and each isomer thereof Araliphatic polyamines such as diaminohydroxypropane and the residues of polyamines substituted with a hydroxyl group such as their respective isomers.

X is a m-valent polyamino compound residue having 1 to 20 carbon atoms, and 1 to 10 independent carboxyl groups, sulfonic groups, sulfate groups, and phosphate groups as substituents. In the case of containing a group or a salt thereof, the surfactant of the present invention is preferable in that it has excellent solubility in a weak acid. Further, the case where X is in the L-form is preferable in that the surfactant of the present invention is excellent in biodegradability. In the general formula (1), X is preferably an m-valent polythiol compound residue having 0 to 40 carbon atoms which may have a substituent other than a thiol group. Here, an m-valent polythiol compound means that m thioester bonds can be formed. They are optical isomers such as D-
It does not matter whether it is in the form, L-form, or racemic form. For example, residues of dithiol compounds such as dithioethylene glycol, dithioerythritol, dithiothreitol and the like can be mentioned.

Further, X is an m-valent polythiol compound residue having 1 to 20 carbon atoms, and 1 to 10
It is preferable that the surfactant of the present invention contains a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, a salt thereof, or the like, each of which has excellent solubility in a weak acid. Further, the case where X is in the L-form is preferable in that the surfactant of the present invention is excellent in biodegradability. In the general formula (1), the carboxyl group represented by Y and the carboxyl group, sulfonic acid group, sulfate group, phosphate group and the like which can be contained in X form salts with various basic substances. Can be formed.

Such salts include, for example, alkali metal salts, alkaline earth metal salts, ammonium salts, organic amine salts, basic amino acid salts and the like. Specific examples include alkali metals such as sodium, potassium and lithium. Alkaline earth metals such as calcium and magnesium, metals such as aluminum and zinc, ammonia, organic amines such as monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine, arginine,
A salt with one or two or more arbitrarily selected from basic amino acids such as lysine. Among these, sodium salts, potassium salts, organic amine salts and basic amino acid salts are preferred.

The acyl group-containing composition containing at least one or more of the acyl compounds represented by the general formula (1) can be produced, for example, by the following method. For example, a compound having an N-long-chain acyl acidic amino acid and one or two or more m functional groups selected from a hydroxyl group, an amino group, and a thiol group in a molecule, or a polyhydroxyl compound, a polyamino compound, or a polythiol compound And a reaction at room temperature to 250 ° C. for several hours without a solvent or in the presence of an inert solvent to obtain a surfactant comprising an acyl group compound represented by the general formula (1).

Here, the N-long-chain acyl acidic amino acid is, for example, one obtained by acylating an acidic amino acid with a saturated or unsaturated fatty acid residue having 8 to 20 carbon atoms, whether linear, branched or cyclic. The amino group may be an N-methyl form or an N-ethyl form. Optical isomers, ie, D-
It does not matter whether it is in the form, L-form, or racemic form. For example, N
Long chain acylglutamic acid, aspartic acid, lanthionine, β-methyllanthionine, cystathionine, diencholate, ferrinin, aminomalonic acid, β-oxyaspartic acid, α-amino-α-methylsuccinic acid, β
-Oxyglutamic 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-aminosuberic acid Aminosebacic acid, pantothenic acid and the like. Among these, the case where the acidic amino acid is an L-acidic amino acid is preferable because the obtained surfactant of the present invention has particularly excellent biodegradability.

Here, the compound having one or more kinds of m functional groups selected from a hydroxyl group, an amino group and a thiol group in the molecule means a substituent other than a hydroxyl group, an amino group and a thiol group. 0 to 40 carbon atoms having one or more functional groups selected from a hydroxyl group, an amino group and a thiol group in the molecule.
M-valent compound. Here, the m-valent compound is
It means that a bond derived from m functional groups can be formed. They do not matter whether they are optical isomers, that is, D-form, L-form and racemic form.

For example, amino acids such as serine, threonine, cysteine, cystine, cystine disulfoxide, cystathionine, methionine, arginine, lysine, tyrosine, histidine, tryptophan, oxyproline; aminoethanol, aminopropanol, aminobutanol, aminopentanol , Aminohexanol,
Aminopropanediol, aminoethylethanolamine, aminoethylaminoethanol, aminocresol, aminonaphthol, aminonaphtholsulfonic acid,
Aminohydroxybenzoic acid, aminohydroxybutanoic acid, aminophenol, aminophenethyl alcohol,
Compounds having an amino group and a hydroxyl group in a molecule such as glucosamine; compounds having a thiol group and a hydroxyl group in a molecule such as mercaptoethanol, mercaptophenol, mercaptopropanediol, and glucothioose; aminothiophenol, aminotriazole thiol and the like Compounds having a thiol group and an amino group in the molecule thereof.

A compound having two or three of a hydroxyl group, an amino group and a thiol group in a molecule is a compound having 1 to 20 carbon atoms and having 1 as a substituent.
When containing 10 to 10 independent carboxyl groups, sulfonic acid groups, sulfate ester groups, phosphate ester groups or salts thereof, etc., the surfactant of the present invention is preferred in that it has excellent solubility in weak acidity. . Further, when the compound having any two or three of a hydroxyl group, an amino group and a thiol group in the molecule is an L-form, the surfactant of the present invention is more excellent in biodegradability. Is preferred.

The term "polyhydroxy compound" as used herein means a m2 having a carbon number of 2 to 40 having a linear, branched or cyclic chain or an aromatic hydrocarbon chain which may be substituted by a hydroxyl group.
Is a polyhydroxyl compound having a valency (m ≧ n), and it does not matter whether it is an optical isomer, that is, a D-form, an L-form, or a racemic form. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 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, dihydroxytartaric acid, mevalonic acid, 3,4-dihydroxycinnamic acid, 3,4- Dihydroxyhydrocinnamic acid, hydroxybenzoic acid, dihydroxystearic acid,
Dihydric hydroxyl compounds such as dihydroxyphenylalanine and the isomers thereof; glycerin, trioxyisobutane, 1,2,3-butanetriol,
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-2,3,4-pentanetriol, 1,2,4
-Butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane,
Trivalent polyhydroxyl compounds such as diethanolamine, triethanolamine and trihydroxystearic acid;
Pentaerythritol, erythritol, 1,2,3
4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,
Tetravalent polyhydroxyl compounds such as 3,4,5-hexanetetrol, diglycerin and sorbitan; pentavalent polyhydroxyl compounds such as adonitol, arabitol, xylitol and triglycerin; dipentaerythritol, sorbitol, mannitol, iditol, inositol, Hexavalent polyhydroxyl compounds such as dalcitol, talose and allose; and dehydration condensates thereof.

Also, saccharides such as tetroses such as erythrose, threose and erythrulose; pentoses such as ribose, arabinose, xylose, licose, xylulose and ribulose; allose, altrose, glucose, mannose, gulose, idose, galactose and talose , Monosaccharides such as hexoses such as fructose, sorbose, psicose, and tagatose; maltose, isomaltose, cellobiose, gentiobiose, melibiose, lactose, turanose, trehalose, saccharose, mannitolose, cellotriose, gentianose, raffinose, meletothose, meletitose, And the like.

Also, other saccharides such as heptose,
Deoxy sugar, amino sugar, thio sugar, seleno sugar, aldon sugar, uronic acid, sugar acid, ketoaldonic acid, anhydro sugar,
Unsaturated sugars, sugar esters, sugar ethers, glycosides and the like may be used, and those obtained by hydrolyzing polysaccharides such as starch, glycogen and cellulose may be used. The polyhydroxy compound is an m-valent polyhydroxyl compound having 1 to 20 carbon atoms, and each having 1 to 10 independent carboxyl groups, sulfonic groups, sulfate groups, phosphate groups, or salts thereof as substituents. When the surfactant is contained, the surfactant of the present invention is preferred in that it has excellent solubility in a weak acid. Further, when the polyhydroxy compound is in the L-form,
The surfactant of the present invention is preferable in that it has excellent biodegradability.

Here, the polyamino compound is a polyamino compound having 0 to 40 carbon atoms and an m value (m ≧ n) which may have a substituent other than an amino group, and is an optical isomer, that is, a D-form. It does not matter whether it is an L-form or a racemic form. For example, hydrazine, N, N'-dimethylhydrazine, ethylenediamine, N, N'-dimethylethylenediamine,
Aliphatic diamines such as diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, 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 their isomers;

Alicyclic polyamines such as diaminocyclobutane, diaminocyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine and triaminocyclohexane; diaminobenzene, diaminotoluene, diaminobenzoic acid, diaminoanthraquinone, diaminobenzene Aromatic polyamines such as sulfonic acid, diaminobenzoic acid, and their respective isomers; diaminoxylene, di (aminomethyl) benzene, di (aminomethyl) pyridine, di (aminomethyl) naphthalene, and each isomer thereof Araliphatic polyamines such as diaminohydroxypropane and polyamines substituted by a hydroxyl group such as isomers thereof.

Further, X is a polyamino compound residue having 1 to 20 carbon atoms, and 1 to 10 independent carboxyl groups, sulfonic groups, sulfate groups, phosphate groups, or When the surfactant of the present invention is contained, the surfactant of the present invention is preferred in that it has excellent solubility in a weak acid. Further, the case where X is in the L-form is preferable in that the surfactant of the present invention is excellent in biodegradability. The polyamino compound is an m-valent polyamino compound having 1 to 20 carbon atoms, and each having 1 to 10 independent carboxyl groups, sulfonic groups, sulfate groups, phosphate groups, or salts thereof as substituents. When the surfactant is contained, the surfactant of the present invention is preferable in that it has excellent solubility in a weak acid. Further, the case where the polyamino compound is in the L-form is preferable in that the surfactant of the present invention is excellent in biodegradability.

Here, the polythiol compound is defined as a m-carbon compound having 0 to 40 carbon atoms which may have a substituent other than a thiol group.
Polythiol compounds, and optical isomers, ie, D-
It does not matter whether it is in the form, L-form, or racemic form. For example, dithiol compounds such as dithioethylene glycol, dithioerythritol, dithiothreitol and the like can be mentioned. For example, dithioethylene glycol or a polythiol compound is an m-valent polythiol compound having 1 to 20 carbon atoms, and has 1 to 10 independent carboxyl groups, sulfonic groups, sulfate groups, or phosphate groups as substituents. In the case of containing a salt thereof or the like, the surfactant of the present invention is preferable in that it has excellent solubility in a weak acid.
Further, when the polythiol compound is in the L-form,
The surfactant of the present invention is preferable in that it has excellent biodegradability.

The composition containing an acyl group may be a mono-lower ester of an N-long-chain acyl acidic amino acid (for example, a methyl ester or an ethyl ester) and a polyhydroxyl compound, a polyamino compound or a polythiol compound, or a hydroxyl group, an amino group or an amino group. And a compound having any two or three of the thiol groups are dissolved in an appropriate solvent such as dimethylformamide, a catalyst such as potassium carbonate is added, and the mixture is heated and reacted at -5 ° C to 250 ° C under reduced pressure. It can also be obtained by removing the reaction solvent after the reaction.

Alternatively, the surfactant of the present invention can be obtained by heating and melting without a solvent, adding a catalyst such as sodium hydroxide and subjecting it to a transesterification reaction at room temperature to 250 ° C.
The N-long-chain acyl acidic amino acid mono-lower ester used in this case is preferably an N-long-chain acyl-L-acid amino acid mono-lower ester. Alternatively, the acyl group-containing composition comprises an N-long chain acyl acidic amino acid anhydride represented by the formula (3) and a polyhydroxyl compound or a polyamino compound or a polythiol compound, or a hydroxyl group, an amino group or a thiol group in a molecule. Compounds having any two or three kinds are mixed at a temperature of any melting point or higher or using an inert solvent such as tetrahydrofuran, benzene, toluene, xylene, carbon tetrachloride, chloroform, acetone or the like for -5 to 200. It can also be obtained by mixing at ° C.

Since the reaction proceeds almost ideally, the above-mentioned polyhydroxyl compound, polyamino compound or polythiol compound or a compound having any two or three of hydroxyl group, amino group and thiol group in the molecule is excessively added. No need to use. The N-long-chain acyl acidic amino acid anhydride used in this case is also preferably N-long-chain acyl-L-acid amino acid anhydride.
Here, the N-long-chain acyl acidic amino acid anhydride can be obtained by reacting the N-long-chain acyl acidic amino acid with a dehydrating agent, for example, a carboxylic anhydride such as acetic anhydride. Alternatively, the acyl group-containing composition can also be obtained by reacting an N-long-chain acyl acidic amino acid with an epoxy compound such as epichlorohydrin in the presence of a base catalyst.

Further, by neutralizing the acyl group-containing composition obtained by the above method with an alkali, an alkali salt thereof can be obtained. The acyl group-containing composition obtained by these methods can be appropriately purified by a general purification method of the general formula (1).
Can be isolated. The surfactant of the present invention can be obtained by neutralizing the acyl group-containing composition with a basic substance, and can be used in a wide pH range by adjusting the neutralization ratio with the basic substance.

The surfactant of the present invention can be used as it is as a surfactant or the like depending on the intended use, but can also be used in the form of an aqueous solution. Depending on the properties of the composition, it may be difficult to handle it as a solid at room temperature. In this case, it is preferable to handle the composition as an aqueous solution. The aqueous solution containing the surfactant of the present invention can be prepared (neutralized) by forming a salt between the acyl group-containing composition and the basic substance, and can be prepared over a wide range by adjusting the neutralization rate at this time. PH range. For example, an aqueous solution containing the acyl group-containing composition can be used at pH 3 to 12. Preferably, the pH of the aqueous solution is adjusted to 5 to 8.5. The aqueous solution prepared in this way is a surfactant aqueous solution having low irritation to the skin and the like and having very excellent surface activity even at a low concentration.

The content of the acyl group-containing composition in the aqueous surfactant solution of the present invention is not particularly limited, and is 0.001 to 80 wt%, preferably 0.01 to 80 wt%, depending on the use.
It can be used within a concentration range having a surface activity of 50 wt%. Further, in the aqueous solution containing the acyl group-containing composition, further surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and other surfactants An agent may be appropriately contained. Among them, those containing an N-long-chain acylamino acid type surfactant as an anionic surfactant in the aqueous solution are preferable, and (A) an acyl group-containing composition and (B) an N-long-chain acyl An amino acid type surfactant is mixed with (A) / (B) in a mass ratio of 1/100 to 100/1.
What contains in the composition of is less irritating to the skin, etc.,
It is an excellent surfactant aqueous solution even at a low concentration.

The N-long-chain acylamino acid referred to in the present invention is one in which an acyl group derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms is introduced into the amino group of the amino acid. Amino acid residues in N-long chain acyl amino acids are various amino acids such as α-amino acids, β-amino acids, γ-amino acids and ω-amino acids, and the amino group is an N-methyl form,
It may be an N-ethyl form. It does not matter whether it is an optical isomer, that is, a D-form, an L-form, or a racemic form.

For example, glutamic acid, aspartic acid, glycine, alanine, lanthionine, β-methyllanthionine, cystathionine, diencholic acid, ferrinin,
Aminomalonic acid, β-oxyaspartic acid, α-amino-α-methylsuccinic acid, β-oxyglutamic acid, γ
-Oxyglutamic acid, γ-methylglutamic acid, γ-
Methyleneglutamic acid, γ-methyl-γ-oxyglutamic acid, α-aminoadipic acid, α, α′-diaminoadipic acid, β, β′-diaminoadipic acid, α-amino-γ-oxyadipic acid, α-aminopimelic acid , Α-
Amino-γ-oxypimelic acid, β-aminopimelic acid, α-aminosuberic acid, α-aminosebacic acid, and pantothenic acid.

The acyl group is not particularly limited as long as it is derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms, and may be linear, branched or cyclic. It is preferable that the N-long-chain acyl amino acid is an N-long-chain acyl-L-amino acid from the viewpoint of biodegradability. Representative examples of uses of the surfactant and the aqueous solution thereof of the present invention include, for example, industrial detergents and processing agent raw materials, household (clothing, kitchen, house, tableware, etc.) detergent raw materials, cosmetic raw materials, food products, pharmaceuticals , Emulsification (polymerization), pesticide, textile processing (refining agent, dyeing aid,
Softeners, water repellents), antifouling agents, admixtures for concrete, printing inks, lubricating oils, antistatic agents, antifogging agents, lubricants, dispersants, deinking agents and the like.

These applications can be said to be useful applications taking advantage of low irritation to the skin and the like, surface activity at low concentrations, and biodegradability, which are features of the product of the present invention. When used in these applications, the product of the present invention is prepared as a composition (detergent composition, cosmetic composition, etc.) depending on the application, but the amount of the product of the present invention in the composition. Is not particularly limited, and 0.001 to 80 w
t%, preferably in the range of 0.01 to 50 wt%. Further, the acyl group-containing composition of the present invention can adjust, for example, p
It can be used in a wide range of pH from H3 to 12, preferably at pH 5 to 8.5 of the composition. Preferably, the surfactant of the present invention and its aqueous solution are used as cosmetic ingredients.

The cosmetics in the present invention are a general term of quasi-drugs and cosmetics referred to in the Pharmaceutical Affairs Law. Specifically, quasi-drugs include mouth fresheners, axillary odor inhibitors, and powdered starches. , Hair restorer, hair remover, hair dye, permanent waving agent, bath agent, medicated cosmetics, medicated toothpaste, etc. can be listed. As cosmetics, toilet soap, face wash (cream / paste, liquid / Gel, granule / powder, aerosol, etc.), shampoo, rinse and other cleansing cosmetics; hair dyes, hair treatments (cream, mist, oil, gel and other forms, and split ends) ), Hair setting agents (hair oils, set lotions, curler lotions, pomades, tics, bottled oils, hair sprays, hair mist, hair liquids, hair foams, hair dyes) Le, water grease) for the hair, such as cosmetics;

General cream, milky lotion (cleansing cream, cold cream, burnishing cream, hand cream, etc.), shave cream (after shaving cream, shaving cream, etc.), lotion (hand lotion, general lotion, etc.), cologne, Basic cosmetics such as shaving lotions (after shaving lotion, shaving lotion, etc.), cosmetic oils, packs, etc .; whitening (cream whitening, solid whitening, powdery whitening, talcum powder, paste whitening, baby powder, body powder, water whitening, etc.) , Powder, foundation (cream, liquid, solid, etc.), makeup cosmetics such as blusher, mayuzumi, eye cream, eye shadow mascara;

Perfumes such as general perfumes, kneaded perfumes, powdered perfumes, etc .; sunburns such as tanning / sunscreen creams, tanning / sunscreen lotions, tanning / sunscreen oils, etc.
Sunscreen cosmetics; nail cosmetics such as nail creams, enamels, and enamel removers; eyeliner cosmetics; lip cosmetics such as lipsticks and lip balms; oral cosmetics such as toothpastes; bath cosmetics such as bath salts, bath oils, and bubble baths. Can be listed. Above all, the product of the present invention is often used in the above-mentioned cosmetics for cleaning, cosmetics for hair, and basic cosmetics, and is most suitable for use in cosmetics for cleaning.

The product of the present invention can be used in combination with various base materials usually used in cosmetics. Specifically, fatty acid salt (soap), alkyl sulfate salt (AS), polyoxyethylene alkyl ether sulfate salt (AE
S), alpha-olefin sulfonate (AOS),
Alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfonate (SAS), dialkyl sulfosuccinate, alpha-sulfonated fatty acid salt, N-long chain acyl amino acid salt, N-acyl-N-methyltaurine salt, sulfated Fatty acids, anionic surfactants such as polyoxyethylene styrenated phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, and naphthalene sulfonate formalin condensate ;

Amphoteric surfactants such as alkylbetaines, alkylamidobetaines, alkylsulfobetaines, imidazolinium betaines; fatty acid alkylolamides, alkylamine oxides, polyoxyethylene alkyl ethers (AE), polyoxyethylene Alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid Ester, polyglycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, triethanolamine fat Nonionic surfactants such as partial esters; primary to tertiary fatty amine salts, alkyl ammonium chloride salts, tetraalkyl ammonium salts, trialkyl benzyl ammonium salts, alkyl pyridinium salts, alkyl hydroxyethyl imidazolinium salts, dialkyl morphos Cationic surfactants such as rhinium salts;

Sodium alginate, starch derivatives,
Polymeric surfactants such as tragacanth gum; natural surfactants such as lecithin, lanolin, cholesterol, saponin; avocado oil, almond oil, olive oil, cocoa oil, sesame oil, safflower oil, soybean oil, camellia oil, persic oil, castor oil, Mink oil, cottonseed oil, mole, palm oil,
Fats and oils such as egg yolk oil, palm oil, palm kernel oil and synthetic triglyceride; hydrocarbons such as liquid paraffin, petrolatum, ceresin, microcrystalline wax, isoparaffin; beeswax, spermaceti, lanolin, carnauba wax, candelilla wax and derivatives thereof. Wax; lauric acid,
Myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, behenic acid, undecylenic acid,
Higher fatty acids such as lanolin fatty acids, hard lanolin fatty acids, and soft lanolin fatty acids;

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, etc. Other ester oils; volatile and non-volatile oils such as silicones such as metal soaps, straight silicone oils and modified silicone oils; polyols such as glycerin, 1,3-butanediol, propanediol and polyethylene glycol;
Humectants such as trimethylglycine, sorbitol, pyrrolidone carboxylate, lactate, hyaluronate;
Hydroxyethylcellulose, carboxymethylcellulose, hydroxyethylcellulose hydroxypropyltrimethylammonium chloride ether, methylcellulose, ethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, soluble starch, carboxymethylstarch, methylstarch,

Propylene glycol alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer,
Polyacrylate, guar gum, locust bingham,
Quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum, dextran, succinoglucan, curdlan, hyaluronic acid, gelatin, casein, albumin, collagen, methoxyethylene maleic anhydride copolymer, amphoteric methacrylic acid Water-soluble and oil-soluble polymers such as ester copolymers, polydimethylmethylenepiperidinium chloride, polyacrylate copolymers, polyvinyl acetate, nitrocellulose, silicone resin; polyethylene glycol fatty acid esters, polyoxyethylene fatty acid esters Thickening and foaming components such as methylglycoside and tetradecenesulfonate; ethylenediaminetetraacetic acid and its salts, hydroxyethylenediaminetriacetic acid and its salts, phosphoric acid, ascorbic acid Acid, succinic acid, gluconic acid,
Sequestering agents such as polyphosphates, metaphosphates, hinokitols;

Preservatives such as paraoxybenzoic acid esters, benzoic acid and salts thereof, phenoxyethanol, hinokitol, etc .; pH adjusting agents such as citric acid, malic acid, adipic acid, glutamic acid, aspartic acid; other trichlororcarbanilide, salicylic acid , Zinc pyrithione,
Anti-dandruff and itching agents such as isopropylmethylphenol; benzophenone derivatives, paraaminobenzoic acid derivatives, paramethoxycinnamic acid derivatives, salicylic acid derivatives and other ultraviolet absorbers; whitening agents such as arbutin, kojic acid, ascorbic acid, hinokitol and derivatives thereof; Blood circulation enhancers such as extract, cepharanthin, vitamin E and its derivatives, gamma-oryzanol; local stimulants such as pepper tincture, showa tincture, cantharistin tincture, benzyl nicotinate;

Nutrients such as various vitamins and amino acids; female hormones; hair root activators; anti-inflammatory agents such as glycyrrhetinic acid, glycyrrhizic acid derivatives, allantoin, azulene, aminocaproic acid, hydrocortisone; zinc oxide, zinc sulfate, allantoin hydroxyaluminum ,
Astringents such as aluminum chloride, zinc sulfocarbonate and tannic acid; Cooling agents such as menthol and camphor; Antihistamines; Silicone-based substances such as polymeric silicone and cyclic silicone; tocopherols, oxidation of BHA, BHT, gallic acid, NDGA, etc. Inhibitor; purified water and the like.

In particular, the combined use with fatty acid diethanolamide, polyoxyethylene dioleate methylglucoside, polyethylene glycol distearate, tetradecene sulfonate, myristate, and myristyl dimethylamine increases viscosity and foaming power. It is useful, and is extremely useful in that the combined use with each zwitterionic surfactant further reduces irritation. In addition, those described in the standard of raw materials for cosmetics and the standard for blending ingredients according to cosmetic varieties can also be used.

Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the present invention is not limited to these examples and the like. Hereinafter, the method of the present invention will be described in detail with reference to examples. The evaluation means used in the examples of the present invention are as follows. (A) Skin irritation test (A-1) Skin irritation of surfactant aqueous solution 0.1 g of a 5 wt% sodium salt aqueous solution sample of an acyl group-containing composition was applied to the skin of the forearm bend of five healthy male panelists.
Was affixed with a 1-cm-diameter patch test bandage for 24 hours, and then evaluated for skin irritation. The judgment result is shown by the number of persons who became (±) or more in the following evaluation. Erythema, edema, blister (+++) Erythema, edema (++) Erythema (+) Minor erythema (±) No erythema, no edema (-)

(A-2) Skin Irritation of Combination Composition After five consecutive healthy male panelists used for one week, the presence or absence of skin irritation was evaluated. The evaluation criteria are described below.

When there are 4 or more people who have no irritation ○ When 2 or 3 people have no irritation △ When 1 or less people have no irritation ×

(B) Biodegradability test The biodegradability test was carried out according to JIS biodegradability test method K-3363. The evaluation criteria are described below. Decomposition rate 70% or more ○ Decomposition rate 40% or more, less than 70% △ Decomposition rate less than 40% ×

(C) Critical micelle concentration (CMC) The surface tension of an aqueous solution of a sodium salt of a surfactant was measured by the Wilhelmy method at 25 ° C., from which the critical micelle concentration was determined. The evaluation criteria for the surfactant activity at low concentrations are shown below. CMC 0.05 wt% or less ○ CMC 0.05 wt% or more and less than 0.3 wt% △ CMC 0.3 wt% or more ×

[0080]

EXAMPLE 1 31.1 g (0.1 mol) of N-lauroyl-L-glutamic anhydride and 3.8 g (0.05 mol) of 1,3-propanediol were placed in an acetone solvent (90 wt% of acetone in the solution). And reacted for 3 hours under reflux with acetone at normal pressure. After acetone is distilled off from the reaction solution, it is purified by chromatography, and R ¹ CO, R ² , X,
24.4 g of an acyl group-containing composition having Y, n, j, and k as shown in Table 1 was obtained. The test was carried out at pH 7.5, since the 5 wt% aqueous sodium salt solution was completely dissolved only at pH 7 or higher. Table 1 shows the analysis and test results of the purified product.

[0081]

Example 2 41.3 g (0.1 mol) of N-stearoyl-D, L-glutamic acid and ethylene glycol 3.
1 g (0.05 mol) was placed in a reaction vessel, heated at 170 ° C. under a nitrogen atmosphere and reacted for 3 hours, cold water was added to the reaction solution, the pH was adjusted to 1 with sulfuric acid, and the precipitated crystals were filtered and washed with water. And dried. The resulting white solid is purified by chromatography to obtain R ¹ CO, R ² , X, Y, n,
7. an acyl group-containing composition in which j and k are as shown in Table 1.
5 g were obtained. Since the 5 wt% sodium salt aqueous solution was completely dissolved only at pH 7 or higher, the test was conducted at pH
Performed at 7.5. Table 1 shows the analysis and test results of the purified product.

[0082]

Example 3 In Example 2, N-stearoyl-
D, L-glutamic acid and its amount were determined by N-myristoyl-
The same procedure as in Example 2 was repeated except that D, L-aspartic acid was 34.3 g, ethylene glycol and the amount thereof were 4.5 g of 1,4-butanediol, and R ^{1 of the} formula (1) was used.
7.4 g of an acyl group-containing composition in which CO, R ² , X, Y, n, j, and k are shown in Table 1 was obtained. 5w of this thing
The test was carried out at pH 7.5, since the t% aqueous sodium salt solution was only completely dissolved at pH 7 and above. Table 1 shows the analysis and test results of the purified product.

[0083]

Example 4 In Example 1, N-lauroyl-L-
Glutamic anhydride and its amount were determined by adding N-palmitoyl-L-
Aspartic anhydride was 29.7 g, and 1,3-propanediol and its amount were 1,6-hexanediol 5.9.
g was carried out in the same manner as in Example 1 except that g was used.
23.1 g of an acyl group-containing composition having R ¹ CO, R ² , X, Y, n, j, and k shown in Table 1 was obtained. The test was carried out at pH 7.5, since the 5 wt% aqueous sodium salt solution was completely dissolved only at pH 7 or higher. Table 1 shows the analysis and test results of the purified product.

[0084]

Example 5 In Example 1, N-lauroyl-L-
The procedure was performed in the same manner as in Example 1 except that glutamic anhydride was changed to N-lauroyl-D-glutamic anhydride, and R ¹ CO, R ² , X, Y, n, j, and k of the formula (1) are represented in Tables. As a result, 24.3 g of an acyl group-containing composition shown as 1 was obtained. The test was carried out at pH 7.5, since the 5 wt% aqueous sodium salt solution was completely dissolved only at pH 7 or higher. Table 1 shows the analysis and test results of the purified product.

[0085]

In Example 6 Example 1, except that 1,3-butanediol and the the amount and dimethylol butanoic acid 7.4g were performed in the same manner as in Example 1, R ¹ C of formula (1)
26.0 g of an acyl group-containing composition having O, R ² , X, Y, n, j, and k shown in Table 1 was obtained. 5w of this thing
The test was carried out at pH 6.3, since the t% aqueous sodium salt solution was weakly acidic and completely dissolved. Table 1 shows the analysis and test results of the purified product.

[0086]

In Example 7 Example 1, 1,3-butane diol and the the amount except that the L- tartrate 7.5g were performed in the same manner as in Example 1, R ¹ CO of formula (1), R ² , X,
27.0 g of an acyl group-containing composition in which Y, n, j, and k were as shown in Table 1 was obtained. The test was carried out at pH 6.3 because the 5 wt% sodium salt aqueous solution was completely dissolved with weak acidity. Table 1 shows the analysis and test results of the purified product.

[0087]

Comparative Examples 1 and 2 Tests were conducted using sodium laurylbenzenesulfonate and sodium N-lauroyl-L-glutamate. Table 1 shows the results. Table 1 shows that the surfactant of the present invention has low skin irritation, is biodegradable, and has excellent surface activity at a low concentration.

[0088]

[Table 1]

[0089]

Example 8 Using the surfactants comprising the acyl group-containing compositions of Examples 1 to 7, shampoo-containing compositions shown in Table 2 were formulated. The skin irritation and feeling of use were confirmed.
Table 2 shows the results. All of the formulations prepared from the surfactant of the present invention had low skin irritation and good foaming.

[0090]

[Table 2]

[0091]

Example 9 31.1 g (0.1 mol) of N-lauroyl-L-glutamic anhydride was added to 400 mL of toluene, and dissolved by stirring at 95 ° C. To this, 3.7 g (0.05 mol) of 1,3-propanediamine was added dropwise. After completion of the addition, stirring was continued for 1 hour, and then the mixture was allowed to cool to room temperature. The precipitated crystals were filtered and further purified by chromatography to obtain an acyl group-containing composition in which R ¹ CO, R ² , R ³ , X, Y, n, j, and k of the formula (1) are shown in Table 3. 24.0 g were obtained. The test was carried out at pH 7.5, since the 5 wt% aqueous sodium salt solution was completely dissolved only at pH 7 or higher.
Table 3 shows the analysis and test results of the purified product.

[0092]

Example 10 In Example 9, N-lauroyl-L was used.
-Glutamic anhydride and its amount by N-myristoyl-L
-Aspartic anhydride to 32.5 g, 1,3-propanediamine and its amount to 1,4-butanediamine 4.4
g was carried out in the same manner as in Example 9 except that g was used.
26.6 g of an acyl group-containing composition having R ¹ CO, R ² , R ³ , X, Y, n, j, and k shown in Table 3 was obtained. The test was carried out at pH 7.5, since the 5 wt% sodium salt aqueous solution was completely dissolved only at pH 7 or higher. Table 3 shows the analysis and test results of the purified product.

[0093]

Example 11 In Example 9, N-lauroyl-L was used.
-Glutamic anhydride and its amount by N-palmitoyl-L
-Glutamic anhydride was 36.7 g, and 1,3-propanediamine and the amount thereof were changed to 3.0 g of ethylenediamine in the same manner as in Example 9 to obtain R ¹ C of the formula (1).
28.2 g of an acyl group-containing composition having O, R ² , R ³ , X, Y, n, j, and k shown in Table 3 was obtained. The test was carried out at pH 7.5, since the 5 wt% aqueous sodium salt solution was completely dissolved only at pH 7 or higher. Table 3 shows the analysis and test results of the purified product.

[0094]

Example 12 In Example 9, N-lauroyl-L was used.
Glutamic anhydride and its amount are N-stearoyl-
38.1 g of D, L-aspartic anhydride, 1,3
-In the same manner as in Example 9 except that propanediamine and the amount thereof were changed to 5.8 g of 1,6-hexanediamine,
28.6 g of an acyl group-containing composition of the formula (1) in which R ¹ CO, R ² , R ³ , X, Y, n, j, and k are shown in Table 3 was obtained. The 5 wt% sodium salt aqueous solution of this
The test was performed at pH 7.5, since it was only completely dissolved above 7. Table 3 shows the analysis and test results of the purified product.

[0095]

EXAMPLE 13 In Example 9, N-lauroyl-L was used.
-Glutamic anhydride was changed to N-lauroyl-D-glutamic anhydride except that it was carried out in the same manner as in Example 9.
22.1 g of an acyl group-containing composition of the formula (1) in which R ¹ CO, R ² , R ³ , X, Y, n, j, and k are as shown in Table 3 was obtained. The 5 wt% sodium salt aqueous solution of this
The test was performed at pH 7.5, since it was only completely dissolved above 7. Table 3 shows the analysis and test results of the purified product.

[0096]

Example 14 The same procedure as in Example 9 was carried out except that 1,3-propanediamine and the amount thereof were changed to 7.3 g of L-lysine, and R ¹ CO, R ^{1 2} , R
³ , 25.0 g of an acyl group-containing composition having X, Y, n, j, and k shown in Table 3 was obtained. Since the 5 wt% sodium salt aqueous solution was completely dissolved with weak acidity, the test was conducted at pH
6.3. Table 3 shows the analysis and test results of the purified product.

[0097]

Example 15 The same procedure as in Example 9 was carried out except that 1,3-propanediamine and the amount thereof were changed to 5.2 g of L-serine, and R ¹ CO and R ^{1 of the} formula (1) were obtained. ² , R
³ , 23.5 g of an acyl group-containing composition having X, Y, n, j and k shown in Table 3 was obtained. Since the 5 wt% sodium salt aqueous solution was completely dissolved with weak acidity, the test was conducted at pH
6.3. Table 3 shows the analysis and test results of the purified product.

[0098]

[Table 3]

[0099]

Example 16 The same procedure as in Example 9 was carried out except that 1,3-propanediamine and the amount thereof were changed to 6.0 g of L-cysteine, and R ¹ CO of the formula (1)
24.1 g of an acyl group-containing composition having R ² , R ³ , X, Y, n, j, and k shown in Table 3 was obtained. 5w of this thing
The test was carried out at pH 6.3, since the t% aqueous sodium salt solution was weakly acidic and completely dissolved. Table 3 shows the analysis and test results of the purified product.

[0100]

Example 17 Examples 9 to 16 Shampoo-containing compositions shown in the table were prepared using acyl group-containing compositions. The skin irritation and feeling of use were confirmed. Table 4 shows the results.

[0101]

[Table 4]

[0102]

As described above, the present invention provides a surfactant having a low irritation to the skin and the like and having a sufficient surface activity even at a low concentration, an aqueous solution thereof, and a cosmetic composition containing the same. Can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 1/10 C11D 1/10 1/52 1/52 F term (Reference) 4C083 AC122 AC312 AC642 AC661 AC662 AC712 AD132 AD282 BB05 CC03 CC38 DD21 DD23 EE10 4D077 AB10 AB11 AC07 BA07 BA13 CA02 CA12 CA13 DC02X DC02Y DC04X DC04Y DC07Z DC15Z DC26X DC26Y DC26Z DC32X DC32Y DC43Z DC48X DC48Y DC50X DC50Y DC50Z DC54X DC04Y DC43Y DC04Y DC04Y 4H006 AA03 AB68 AB70 BN10 BS10 BT12 BV22

Claims (14)

[Claims] 1. A surfactant comprising an acyl group-containing composition containing at least one or two or more acyl compounds represented by the general formula (1). Embedded image (In the general formula (1), n Zs are bonding portions derived from m (m ≧ n) functional groups substituted by X, and each is independently, that is, they may be the same or different; Has 0 to 0 carbon atoms which may have a substituent other than the functional group.
A spacer which is 40 linear, branched or cyclic chains or aromatic hydrocarbon chains, and which is attached to X via Z
The substituents represented by the general formula (2) are each independently
That is, R ¹ CO may be the same or different, R ¹ CO represents a long-chain acyl group derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms, and R ² is hydrogen or a hydroxyl group or A carboxyl group represents a lower alkyl group having 1 to 3 carbon atoms which may be substituted, Y represents a carboxyl group or a salt thereof,
j and k are each independently 0, 1, or 2,
And j and k are not simultaneously 0 and n is an integer of 2 to 20). Embedded image 2. In the acyl compound represented by the general formula (1), m functional groups (m is m ≧ n and an integer of 2 to 20) substituted by X are a hydroxyl group (—OH), a thiol A group (—SH), an amino group (—NHR ³ ) (R ³ is hydrogen, or an alkyl group or an alkenyl group or an aryl group or an alkylaryl group having 1 to 10 carbon atoms) Wherein Z is -O-, -S-, derived from a hydroxyl group, a thiol group, or an amino group.
-NR ³ - surfactant of claim 1, characterized in that a. 3. In the acyl compound represented by the general formula (1), 1 to 10 independent carboxyl groups, sulfonic acid groups, and sulfate esters as X may have a substituent other than the above functional group. 3 or a phosphate ester group, or a salt thereof.
The surfactant according to the above. 4. The surfactant according to claim 1, wherein the acyl compound represented by the general formula (1) is optically active. 5. The surfactant according to claim 1, further comprising another surfactant. 6. The surfactant according to claim 5, wherein the other surfactant is an N-long-chain acylamino acid type surfactant.
A surfactant as described. 7. A surfactant composition comprising 0.001 to 80% by weight of the surfactant according to claim 1 and water, and wherein the pH of the aqueous solution is 3 to 12. object. 8. A liquid or solid cosmetic composition comprising one or more of the surfactants or surfactant compositions according to claim 1. . 9. The cosmetic composition according to claim 8, wherein the cosmetic composition contains 0.001 to 80% by weight of an acyl group-containing composition, and the cosmetic composition has a pH of 3 to 12. Liquid or solid cosmetic compositions. 10. An N-long-chain acyl acidic amino acid or a derivative thereof, and m (one or two or more) functional groups selected from a hydroxyl group, a thiol group and an amino group (m is an integer of 0 to 20). The method for producing a surfactant according to any one of claims 1 to 7, wherein the compound is subjected to a condensation reaction. 11. The surfactant according to claim 1, wherein the compound is one or more compounds selected from a polyhydroxyl compound, a polyamine compound, and a polymercaptan compound. Manufacturing method. 12. The N-long-chain acyl-acid amino acid or derivative thereof is an N-long-chain acyl-L-acid amino acid or derivative thereof.
2. The method for producing a surfactant according to 1. 13. The N-long-chain acyl acidic amino acid derivative according to claim 10, wherein the derivative of the N-long-chain acyl acidic amino acid is an N-long-chain acyl acidic amino acid anhydride represented by the general formula (3). A method for producing the surfactant according to the above. Embedded image (In the formula, R ¹ CO, R ² , j, and k have the same meanings as described above.) 14. The method for producing a surfactant according to claim 10, wherein the derivative of the N-long-chain acyl acidic amino acid is an N-long-chain acyl acidic amino acid ester.