JP2006225631A - Solid detergent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid detergent superior in foaming property, detergency on body washing and in use feeling during the washing and after the washing and also less in getting out of the shape at dissolution of the solid detergent and superior in flowability of fine particles of a powdery detergent. <P>SOLUTION: The solid detergent contains a multi-chain and multi-hydrophilic group type surfactant with at least two of each of a hydrophobic group and a hydrophilic group respectively in a molecule. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a solid detergent, especially a solid detergent for the body.

  Solid detergents are roughly classified into powdery detergents and solid detergents molded by molding methods such as extrusion, compression, rolling, and injection. Conventionally, soaps mainly composed of higher fatty acid salts have been most commonly used for solid detergents for body use, kitchen use and the like. However, due to the problem of irritation to the human body, N-acylamino acid surfactants that have excellent detergency and less irritation to the skin and hair are gaining attention. A solid detergent containing a main component or a solid detergent containing a higher fatty acid salt as a main ingredient and an N-acylamino acid surfactant has been used. However, N-acylamino acid surfactants are excellent in terms of irritation to skin and hair, but are improved in terms of feeling of use such as foaming power, slimy feeling, and creaking after washing of skin and hair. It was necessary.

  In addition, problems such as melting / disintegration as a problem inherent to a solid detergent composition, or problems such as transparency stability in a transparent product, and problems inherent to a powder detergent composition include scatterability and dispersibility in water There were problems such as solubility. Many proposals have been made for the purpose of these improvements. For example, Patent Document 1 and Patent Document 2 describe improvements in foam characteristics, feeling of use, etc., for example, Patent Document 3, Patent Document 4 and Patent Document 5 describe improvements in solidity, melting, and other improvements of solid detergents. Patent Document 6, Patent Document 7 and Patent Document 8 have proposals related to transparent solid detergents, and for example, Patent Document 9 and Patent Document 10 relate to powdered detergents. Improvements have been made. However, it is not sufficient in terms of improving the foaming power, feeling of use, melt-disintegrating property in the solid detergent and fluidity of the powder in the powder detergent, and further improvement is desired.

JP-A-11-172278 Japanese Patent Laid-Open No. 06-057289 JP-A-11-323378 Japanese Patent Laid-Open No. 04-050300 JP 03-059099 A JP 2003-306695 A JP-A-56-112998 JP 56-076499 JP 2002-129187 A JP 2001-152183 A

  The present invention is excellent in foaming property and cleaning property at the time of cleaning, a feeling of use at the time of cleaning and after cleaning, and in a solid state excellent in melt-disintegrating property in a solid cleaning agent and fluidity of powder in a powdered cleaning agent. An object is to provide a cleaning agent.

As a result of intensive studies to achieve the above object, the present inventors have obtained at least one kind of multi-chain polyhydrophilic group-type surfactant having two or more specific hydrophobic groups and hydrophilic groups in the molecule. It was found that the above-mentioned object was achieved by the inclusion, and the present invention was completed.
That is, the present invention is as follows.
1. A solid detergent containing the following component (A):
Component (A): One or more of a multi-chain polyhydrophilic group-type surfactant having two or more hydrophobic groups and hydrophilic groups in the molecule.
2. At least one of the multi-chain, multi-hydrophilic group type surfactant, the hydrophobic group is an acyl group, and the hydrophilic group is a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group and / or a salt thereof. 1. An anionic surfactant as described above, The solid cleaning agent according to 1.
3. At least one of the multi-chain poly-hydrophilic group type surfactant has an amino acid residue in the molecule. Or 2. The solid cleaning agent according to 1.

（上記一般式（１）において、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、下記一般式（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。

該一般式（２）において、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２〜２０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 surfactant is a compound represented by the following general formula (1): ~ 3. A solid detergent according to any one of the above.

(In the above general formula (1), X is a linear, branched, cyclic or aromatic hydrocarbon chain having a molecular weight of 1,000,000 or less, which may have m functional groups and other substituents. The n (m ≧ n) Q bonded to X are substituents represented by the following general formula (2), which may be the same as or different from each other.

In the general formula (2), Z is a bond derived from a functional group of X, R ¹ CO represents an acyl group derived from a saturated or unsaturated fatty acid having 2 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 Of any of the salts. j and k are each independently 0, 1, or 2, and j and k are not 0 at the same time. n shows the integer of 2-20. 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. A solid detergent according to any one of the above.
6). Furthermore, the above-mentioned 1. characterized by containing a component (B). ~ 5. A solid detergent according to any one of the above.
Component (B): One or more selected from anionic surfactants, amphoteric surfactants, and cationic surfactants.
7). Furthermore, the above-mentioned 1. characterized by containing a component (C). ~ 6. A solid detergent according to any one of the above.
Component (C): One or more polyhydroxyl compounds.
8). Furthermore, the above-mentioned 1. characterized by containing a component (D). ~ 7. A solid detergent according to any one of the above.
Component (D): One or more selected from organic and inorganic electrolytes.

  The present invention is excellent in foaming property and cleaning property at the time of cleaning, a feeling of use at the time of cleaning and after cleaning, and in a solid state excellent in melt-disintegrating property in a solid cleaning agent and fluidity of powder in a powdered cleaning agent. There is an effect of providing a cleaning agent.

The present invention will be specifically described below.
The solid detergent of the present invention is a composition comprising at least one multi-chain polyhydrophilic group type compound having two or more hydrophobic groups and hydrophilic groups in the molecule. Any known compound may be used.
In the solid detergent of the present invention, the multi-chain polyhydrophilic group-type compound is independently composed of a saturated or unsaturated straight chain, branched chain or cyclic chain having 2 to 20 carbon atoms as the hydrophobic group. It has a hydrophobic group, 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, an oxyalkylene group, a polyethylene glycol group, or the like, or an amino group, 4 It has a quaternary ammonium group, a pyridinium group, a sulfonium group and / or a salt thereof.

Examples of the hydrophobic group of the multi-chain polyhydrophilic group compound include n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, Residues such as n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, etc. and their branched isomers, and corresponding ones, two or three unsaturated bonds. Examples include saturated residues.
In addition, the hydrophobic group of the multi-chain polyhydrophilic group type compound is an acyl group derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms, and each acyl group is independently, that is, each They may be different or the same, and those derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms are preferred, regardless of whether they are linear, branched or cyclic.

Examples of the acyl group include linear chains 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, and arachidic acid. fatty 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, shoulmuric acid, gorulic acid, α-cyclopentylic acid, α-cyclohexylic acid, α-cyclopentylethylic acid Cyclic acids such as;
An acyl group derived from is mentioned.

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 saturated or unsaturated fatty acid having 2 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.
When using a multi-chain polyhydrophilic group type compound as a salt, for example, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an organic amine salt, a basic amino acid salt and the like can be mentioned. Alkaline metals such as potassium and lithium, alkaline earth metals such as calcium and magnesium, metals such as aluminum and zinc, organic amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine, arginine and lysine It is a salt with one or more kinds arbitrarily selected from basic amino acids and the like. 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 type compounds contained in the solid detergent 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 2 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 (formula (2)) bonded to X may be different from each other or the same. Moreover, Formula (2) shows what is called an acidic amino acid N-acylated, and it does not ask | require whether they are optical isomers, for example, D-form, L-form, and a racemate.
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 (formula (2)) bonded 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,
Dimerdiol, dimethylolpropionic acid, dimethylolbutanoic acid, tartaric acid, dihydroxytartaric acid, mevalonic acid, 3,4-dihydroxycinnamic acid, 3,4-dihydroxyhydrocinnamic acid, hydroxybenzoic acid, dihydroxystearic acid, dihydroxyphenylalanine And divalent hydroxyl compounds such as each of these isomers;

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-2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2, Trivalent polyhydroxyl compounds such as 4-pentanetriol, trimethylolethane, trimethylolpropane, diethanolamine, triethanolamine, trihydroxystearic acid;
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, erythrulose;
Pentoses such as ribose, arabinose, xylose, lyxose, xylulose, ribulose;
Monosaccharides such as hexose such as allose, altrose, glucose, mannose, guylose, idose, galactose, talose, 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.
In addition, 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 residue, and may be a polysaccharide such as starch, glycogen, cellulose, chitin, or chitosan, 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 has 1 to 20 carbon atoms. X is preferably a naturally occurring type from the viewpoint of excellent biodegradability.

In general formula (2), the carboxyl group, sulfonic acid group, sulfate ester group, phosphate ester group represented by Y and the carboxyl group, sulfonate group, sulfate ester group, 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, ammonium salts, organic amine salts, basic amino acid salts, polyvalent metal 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.

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 the compound having one or more kinds of m functional groups in 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 by using an inert solvent such as chloroform, acetone, etc., or by mixing at −5 ° C. to 200 ° C. at a temperature equal to or higher than any melting point without solvent.

Alternatively, the acyl compound represented by the general formula (1) includes an N-acyl acidic amino acid mono-lower ester (for example, methyl ester, ethyl ester) and a polyhydroxyl compound, a polyamino compound, or a polythiol compound, or a hydroxyl group or an amino group in the molecule. , 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 reaction is performed at −5 ° C. to 250 ° C. under reduced pressure. Then, it can be obtained by removing the 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.
Although the compounding quantity of the solid detergent of this invention does not have a restriction | limiting in particular, it is preferable that a polychain polyhydrophilic group type compound content shall be 0.001-20 mass%, and can be adjusted according to the objective. 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.

Examples of the anionic surfactant of component (B) to be blended in the preferred embodiment of the solid detergent of the present invention include the following carboxyl group-containing ones.
For example, higher fatty acid salts (soaps); higher fatty acids having 2 to 20 carbon atoms in the hydrophobic group or salts thereof are used, and are also used as mixed fatty acids.
N-acyl amino acid type anionic surfactants; examples of acyl groups include those having 2 to 20 carbon atoms as described above, and examples of the constituent amino acids include acidic amino acids such as glutamic acid and aspartic acid Or 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, amino acids such as p-aminobenzoic acid, and the like.
Or alkyl ether carboxylate, amide ether carboxylate, etc. are mentioned.

In addition, examples of the anionic surfactant of the component (B) other than the component (A) to be blended in the preferred embodiment of the solid detergent of the present invention include those other than the following carboxyl group-containing.
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 the solid detergent of the present invention, the anionic surfactant is preferably blended in an amount of 0.01 to 5% by mass, and two or more kinds 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.

  Nonionic surfactants of component (B) blended in a preferred embodiment of the solid detergent of the present invention include alkyl polyglucosides, (poly) glycerin fatty acid esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acids such as sho Polyhydric alcohol ester such as 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, poly Oxyalkylene alkylamine, polyoxyalkylene alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxy B pyrene 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 the solid detergent 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.

In a preferred embodiment of the solid detergent of the present invention, the amphoteric surfactant to be blended as the component (B) includes alkylbetaines, alkylamidobetaines, alkylsulfobetaines, imidazolinium betaines, lecithins and the like. Specifically, lauramide amidopropyl betaine is exemplified. In the solid detergent of the present invention, the amphoteric 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 cationic surfactant of component (B) to be blended in the preferred embodiment of the solid detergent of the present invention include primary to tertiary fatty amine salts, alkylammonium chloride salts, tetraalkylammonium salts, and trialkylbenzyls. Cationic surfactants such as ammonium salts, alkylpyridinium salts, alkylhydroxyethyl imidazolinium salts, dialkylmorpholinium salts, alkylisoquinolinium salts, benzethonium salts, benzalkonium salts, and the like are used as counter ions. Examples include halogen ions such as chlorine, iodine and bromine, and organic anions such as methosulfate, ethosulfate, methophosphate and ethophosphate. In the solid detergent 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 (C) polyhydroxyl compound to be blended in the preferred embodiment of the solid detergent 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 in the solid detergent, and may be used in combination of two or more.
The organic and inorganic electrolytes of component (D) blended in the preferred embodiment of the solid detergent of the present invention include sodium chloride, potassium chloride, lithium chloride, ammonium chloride, sodium sulfate, potassium sulfate, lithium sulfate, ammonium sulfate, and carbonic acid. Sodium, potassium carbonate, 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 , Ammonium malate, sodium glutamate, potassium glutamate, lithium glutamate, ammonium glutamate, betaines, etc., and these organic and inorganic electrolytes are 0.01 to 10 quality. % I am preferable to blend, or may be used in combination of two or more.

Further, the solid detergent of the present invention can be used in a wide pH range of preferably 3 to 12, more preferably by adjusting the neutralization rate with a basic substance, and more preferably pH 4.5 to 4 of the composition. 11 can be used. More preferably, it can be used at pH 5-8.
The solid detergent of the present invention can be produced by a method using an apparatus equipped with a normal stirrer, mixer, disperser and the like.
Moreover, in the solid cleaning agent of this invention, unless the objective of this invention is impaired, it can be used together with various base materials according to a use and the objective.
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;

Avocado oil, almond oil, olive oil, cacao oil, sesame oil, safflower oil, soybean oil, camellia oil, persic oil, castor oil, mink oil, cottonseed oil, owl, palm oil, egg yolk oil, palm oil, palm kernel oil, synthetic triglyceride, Fats and oils such as jojoba oil;
Hydrocarbons such as liquid paraffin, petrolatum, ceresin, microcrystalline wax, isoparaffin;
Waxes such as beeswax, whale wax, lanolin, carnauba wax, candelilla wax and derivatives thereof;
Higher fatty acids such as 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;
Higher alcohols such as lauryl alcohol, cetanol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldodecanol;

Other ester oils such as isopropyl myristate and butyl stearate;
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;
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,
Propylene glycol alginate, polyvinyl alcohol, polyvinyl pyrrolidone, 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, casein, albumin, collagen, methoxyethylene maleic anhydride copolymer, amphoteric methacrylate copolymer, polychlorinated Water-soluble and oil-soluble polymers such as dimethylmethylene piperidinium, polyacrylate copolymer, polyvinyl acetate, nitrocellulose, silicone resin;

Thickening and foam increasing components such as polyethylene glycol fatty acid ester, polyoxyethylene fatty acid ester methyl glycoside, tetradecene sulfonate;
Oil gelling agents such as dextrin fatty acid ester, glycerin fatty acid ester, hydroxystearic acid;
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 trichlorocarbanilide, salicylic acid, zinc pyrithione, 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;
Antioxidants such as silicone-based materials such as polymer silicone and cyclic silicone, tocopherols, BHA, BHT, gallic acid, NDGA;

Purified water, 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, dried sea water, hydrolyzed wheat powder, hydrolyzed silk, carrot extract, cucumber extract, gentian extract, yeast extract, rice germ oil, comfrey extract, savonso extract, Giant 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 Kiss, Roman chamomile extract, royal jelly extract, seaweed, rice bran, licorice, citrus unshiu peel, angelica, pulverized Momonoha, sphingolipids, guaiazulene, vitamin C,
Etc.
In particular, combined use with fatty acid diethanolamide, polyoxyethylene dioleic acid methyl glucoside, polyethylene glycol distearate, tetradecene sulfonate, myristic acid salts, myristyl dimethylamine is useful in terms of increasing viscosity and foaming power. In addition, the combined use with each amphoteric surfactant is extremely useful in terms of further reducing irritation.
The solid detergent of the present invention includes a detergent such as a makeup remover and a face wash applied to the outer skin. If the form is also solid, it is cloudy or transparent, and whether it is fluid or not. It doesn't matter.

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.
Various physical properties of the cleaning composition obtained in Examples and the like were measured by the following methods.
<Measurement of foaming power>
1 g of the sample detergent composition was taken as a solute and made up to 300 g with purified water, placed in a mixer and stirred with a mixer for 30 seconds, and the height of foam immediately after (mm) was taken as foaming power. The measurement temperature was 25 ° C. Moreover, the obtained result was determined according to the following criteria.
◎: Foaming force is 180 mm or more, ○: Foaming force is 170 mm or more and less than 180 mm, △: Foaming force is 160 mm or more and less than 170 mm, ×: Foaming force is less than 160 mm.
<Measurement of feeling of use>
Using the sample cleaning composition, a hand washing test was performed on 8 male and female panelists, and sensory evaluation was performed on each test item (a refreshing feeling and a feeling of being refreshed in hand washing). The results were indicated by ◎, ○, Δ, and × in order of increasing (good) score.

<Measurement of irritation>
The test was conducted using guinea pigs (5 per group), diluted with sterilized purified water to a concentration of 0.5%, and closed and applied for 4 hours. The temporary irritation index (PCI) was evaluated.
<Melting disintegration>
10 g of a solid sample detergent composition was cut into cubes, soaked in tap water for 1 hour, observed for dissolution of the solid detergent, and indicated by ○, ○, Δ, × in the order of less dissolution. .

(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 stirring for another 30 minutes, 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).

（式４において、Ｘは、各々独立にＨまたはＮａを示す。）

(In Formula 4, each X independently represents H or Na.)

(Production Example 2 of acyl compound)
The same procedure as in Production Example 1 was carried out except that 31.1 g of N-lauroyl-L-glutamic acid anhydride was changed to 31.1 g (0.1 mol) of N-cocoyl-L-glutamic acid anhydride in Production Example 1. Thus, a composition containing an acyl compound was obtained.
[Example 1]
The compounding ingredients shown in Table 1 were mixed using a roll at the ratio (mass%) shown in Table 1, extruded, then stamped to prepare a solid detergent composition. An appropriate amount of a pH adjusting agent (citric acid, sodium hydroxide) was used to adjust to a predetermined pH (value measured at 25 ° C. for a 1% aqueous solution). The obtained cleaning composition was evaluated, and the results are shown in the evaluation column of Table 1. The composition of the present invention had a pH of 4.5 to 9.0, and showed excellent results in foaming, feeling of use in hand washing, irritation, and meltability.

[Example 2]
A mixture of 97 g of the compound of Production Example 1 and 3 g of lauric acid was neutralized with a 30% aqueous sodium hydroxide solution to prepare Composition 1. The following composition was roll mixed, extruded, and then stamped to prepare a solid detergent composition having a pH of 5.5. The resulting cleaning composition was excellent in foaming properties, cleaning properties, and feeling during use, and was not easily melted and collapsed.
(mass%)
Composition 1 60 (solid content)
Lauric acid 7
Cetyl alcohol 8
Microcrystalline wax 8
Collagen, titanium oxide, EDTA, citric acid, small amount of water, residue [Example 3]
The following composition was heated and stirred at 80 to 85 ° C. to uniformly dissolve, then poured into a mold and left at room temperature (one month). A transparent solid detergent excellent in foaming and usability was obtained.
(mass%)
Compound of Production Example 1 62
Glycerin 10
Isopropanol 10
Urea 4
Water 14

[Example 4]
The following composition was heated, mixed and dissolved, poured into a mold, cooled and solidified, cut and left at room temperature for 1 month to obtain a transparent solid soap. The weight loss due to standing was about 20% by mass.
(mass%)
Mixed fatty acid sodium soap 40
Compound 7 of Production Example 2
Glycerin 10
Sorbitol 5
Sucrose 5
Ethanol 15
Water 18

  The solid detergent of the present invention is excellent in foaming, detergency, and feeling of use, and also has excellent meltability in the solid detergent and fluidity of the powder in the powder detergent. It can be suitably used in the field.

Claims (8)

A solid detergent containing the following component (A):
Component (A): One or more of a multi-chain polyhydrophilic group-type surfactant having two or more hydrophobic groups and hydrophilic groups in the molecule.   At least one of the multi-chain, multi-hydrophilic group type surfactant, the hydrophobic group is an acyl group, and the hydrophilic group is a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group and / or a salt thereof. The solid detergent according to claim 1, which is an anionic surfactant.   3. The solid detergent according to claim 1 or 2, wherein at least one of the multi-chain polyhydrophilic group type surfactant has an amino acid residue in the molecule. The solid detergent according to any one of claims 1 to 3, wherein at least one of the multi-chain polyhydrophilic group-type surfactant is a compound represented by the following general formula (1).

(In the above general formula (1), X is a linear, branched, cyclic or aromatic hydrocarbon chain having a molecular weight of 1,000,000 or less, which may have m functional groups and other substituents. The n (m ≧ n) Q bonded to X are substituents represented by the following general formula (2), which may be the same as or different from each other.

In the general formula (2), Z is a bond derived from a functional group of X, R ¹ CO represents an acyl group derived from a saturated or unsaturated fatty acid having 2 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 Of any of the salts. j and k are each independently 0, 1, or 2, and j and k are not 0 at the same time. n shows the integer of 2-20. 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 solid detergent according to any one of claims 1 to 4, which is a good spacer having a straight chain, branched chain, cyclic chain or aromatic hydrocarbon chain having 1 to 40 carbon atoms. Furthermore, a component (B) is contained, The solid cleaning agent in any one of Claims 1-5 characterized by the above-mentioned.
Component (B): One or more selected from anionic surfactants, amphoteric surfactants, and cationic surfactants. Furthermore, a component (C) is contained, The solid cleaning agent in any one of Claims 1-6 characterized by the above-mentioned.
Component (C): One or more polyhydroxyl compounds. Furthermore, a component (D) is contained, The solid cleaning agent in any one of Claims 1-7 characterized by the above-mentioned.
Component (D): One or more selected from organic and inorganic electrolytes.