JP3497889B2 - Novel amine compounds, intermediates for producing the same, and methods for producing them - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel amine compound useful as a base for hair and skin cosmetics, a detergent, an emulsifier, a conditioning agent, etc., a salt thereof, a quaternary compound thereof, an intermediate for producing the same, and them. Manufacturing method.

[0002]

2. Description of the Related Art Conventionally, surfactants such as alkyl sulfates, polyoxyethylene alkyl sulfates and alkylbenzene sulfonates have been used as detergents.
However, many of them have a problem that the skin irritation is rather strong during use. From such problems,
BACKGROUND ART Surfactants such as alkyl phosphates and acylated amino acid salts, which have low skin irritation, have come to be used as a base for hair and skin cosmetics, an emulsifier, or a detergent for skin and the like. Furthermore, recently, with the diversification of consumer demands and the trend toward high-end products, in addition to having less irritation to the skin and the like, it has an effect that it has good foaming property and that it can impart a favorable feel to the skin and the like. Although there is a demand for products, none satisfy these requirements sufficiently.

[0003]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the above-mentioned problems, less irritation to the skin and the like, excellent in foaming property, and further capable of imparting a favorable feel to the skin and the like. And a compound useful as a base for skin cosmetics, a detergent, an emulsifier, a conditioning agent, and the like.

[0004]

Under such circumstances, as a result of intensive studies conducted by the present inventors, the novel amphoteric compound represented by the general formula (1) described below gives a favorable feeling to skin and the like with low irritation. The present invention has been completed by finding out that they have a good foaming property.

That is, the present invention provides the following general formula (1):

[0006]

[Chemical 14]

[Wherein R ¹ and R ² are the same or different and each represents a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms, which may be substituted with a hydroxyl group, and A is a hydroxyl group. Represents an optionally substituted linear or branched alkylene group having 1 to 6 carbon atoms, Y represents a carboxyl group or a sulfonic acid group, and Z represents a sulfoalkyl group or an amino group from an amino acid or a salt thereof. A group excluding is shown. ] It is related with the amine compound represented by these, its salt, or its quaternary compound, its manufacturing intermediate, and their manufacturing method.

As a compound having a structure close to that of the compound of the present invention, a compound having a 2-hydroxypropanediamine structure (US Pat. No. 3,654,158, West German Patent No. 3)
No. 607884, US Pat. No. 4,982000, JP-A-1-233264, JP-A-2-223515 and the like) are known, and these compounds have a diamine structure, a carboxyl group, Does not have anionic functional groups such as sulfonic acid groups and sulfuric acid residues,
The structure and function of the compound of the present invention, which is an amphoteric compound having a triamine structure, are greatly different.

In the general formula (1), specific examples of the linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms, which may be substituted by the hydroxyl groups represented by R ¹ and R ² , include: The following can be mentioned.

Examples of the linear alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, Henicosyl, docosyl, tricosyl and tetracosyl can be mentioned, and examples of the branched chain alkyl group include groups such as methylhexyl, ethylhexyl, methylheptyl, ethylheptyl, methylnonyl, methylundecyl, methylheptadecyl, hexyldecyl and octyldecyl. Can be mentioned.

Examples of the straight chain alkenyl group include ethenyl, propenyl, butenyl, pentenyl, hexenyl,
Heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,
Examples thereof include groups such as pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icosenyl, henicosenyl, docosenyl, tricosenyl, and tetracosenyl, and examples of the branched chain alkenyl group include, for example, methylhexenyl, ethylhexenyl, methylheptenyl, ethylheptenyl, methylnonenyl, methylnonenyl. Mention may be made of groups such as cenyl, methylheptadecenyl, hexyldecenyl, octyldecenyl and the like.

The linear or branched alkyl group substituted with a hydroxyl group is not particularly limited in the substitution position of the hydroxyl group, and examples thereof include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, Hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, hydroxyundecyl, hydroxydodecyl, hydroxytridecyl, hydroxytetradecyl,
Hydroxypentadecyl, hydroxyhexadecyl, hydroxyheptadecyl, hydroxyoctadecyl, hydroxynonadecyl, hydroxyicosyl, hydroxyhenicosyl, hydroxydocosyl, hydroxytricosyl, hydroxytetracosyl, hydroxymethylhexyl, hydroxyethylhexyl, hydroxymethyl Examples thereof include groups such as heptyl, hydroxyethylheptyl, hydroxymethylnonyl, hydroxymethylundecyl, hydroxymethylheptadecyl, hydroxyhexyldecyl, and hydroxyoctyldecylbutyl.

The linear or branched alkenyl group substituted with a hydroxyl group is not particularly limited in the substitution position of the hydroxyl group, and examples thereof include hydroxyethenyl, hydroxypropenyl, hydroxybutenyl, hydroxypentenyl, hydroxyhexenyl and hydroxy. Heptenyl, hydroxyoctenyl, hydroxynonenyl, hydroxydecenyl, hydroxyundecenyl, hydroxydodecenyl, hydroxytridecenyl, hydroxytetradecenyl, hydroxypentadecenyl, hydroxyhexadecenyl, Hydroxyheptadecenyl, hydroxyoctadecenyl, hydroxynonadecenyl, hydroxyicosenyl, hydroxyhenicosenyl, hydroxydocosenyl, hydroxytricosenyl, hydroxytetracosenyl, hydroxy Groups such as methylhexenyl, hydroxyethylhexenyl, hydroxymethylheptenyl, hydroxyethylheptenyl, hydroxymethylnonenyl, hydroxymethylundecenyl, hydroxymethylheptadecenyl, hydroxyhexyldecenyl, hydroxyoctyldecenyl. Can be mentioned.

Of these, R ¹ and R ² are linear or branched alkyl groups or alkenyl groups having 6 to 24 carbon atoms, and further linear or branched alkyl groups having 6 to 12 carbon atoms, especially carbon atoms. A linear alkyl group of the number 6 to 10 is preferable.

In the general formula (1), the linear or branched carbon number 1 to which the hydroxyl group represented by A may be substituted is 1 to 1.
The following can be mentioned as specific examples of the alkylene group of 6.

Examples of the alkylene group include methylene group, ethylene group, trimethylene group, tetramethylene group,
Examples thereof include a pentamethylene group, a hexamethylene group, a methylethylene group and an ethylethylene group. Of these, those having 1 to 4 carbon atoms are preferable, those having 1 to 3 carbon atoms are more preferable, and methylene group, ethylene group, trimethylene group, and particularly methylene group are preferable.

The hydroxy-substituted alkylene group is 1
-Hydroxyethylene group, 2-hydroxyethylene group,
1,2-dihydroxyethylene group, 1-hydroxytrimethylene group, 2-hydroxytrimethylene group, 3-hydroxytrimethylene group, 1,2-dihydroxytrimethylene group, 1,3-dihydroxytrimethylene group, 1,
2,3-trihydroxytrimethylene group, 1-hydroxytetramethylene group, 2-hydroxytetramethylene group, 3-hydroxytetramethylene group, 4-hydroxytetramethylene group, 1,2-dihydroxytetramethylene group, 1,3 -Dihydroxytetramethylene group, 1,4
-Dihydroxytetramethylene group, 2,3-dihydroxytetramethylene group, 2,4-dihydroxytetramethylene group, 3,4-dihydroxytetramethylene group, 1,
2,3-trihydroxytetramethylene group, 2,3,4
-Trihydroxytetramethylene group, 1,3,4-trihydroxytetramethylene group, 1,2,3,4-tetrahydroxytetramethylene group, and the like. Of these, 1,2-dihydroxyethylene group, 1- A hydroxyethylene group, a 2-hydroxyethylene group, a 2-hydroxytrimethylene group, and particularly a 2-hydroxytrimethylene group is preferable.

In the general formula (1), Z represents a sulfoalkyl group or a group obtained by removing one amino group from an amino acid or a salt thereof, and specific examples of the amino acid include asparagine,
Aspartic acid, alanine, arginine, isoleucine, glycine, glutamine, glutamic acid, cystine,
Cysteine, serine, tyrosine, tryptophan, threonine, valine, histidine, hydroxyproline, hydroxylysine, phenylalanine, proline, methionine, lysine, leucine, β-alanine, α-aminobutyric acid, isoserine, ornithine, glutathione, glycylglycine, γ -Aminobutyric acid, ε-aminocaproic acid, citrulline and the like can be mentioned. Of these, Z is preferably a sulfoalkyl group or a group in which one amino group is removed from an amino acid or β-alanine or its salt constituting a protein, particularly a sulfoethyl group and a carboxymethyl group.

The compound (1) of the present invention comprises a sulfonic acid group (-S
Since it has O ₃ H) or a carboxyl group (—COOH), it can form a salt with various basic substances. Examples thereof include alkali metal salts, alkaline earth metal salts, amine salts, basic amino acid salts, ammonium salts and the like. Specifically, salts with sodium, potassium, lithium, magnesium, calcium, trimethylamine, triethylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, lysine, arginine, choline, ammonia and the like can be mentioned. Among them, alkali metal salts, especially sodium salts are preferable. In addition, since the compound (1) of the present invention has a tertiary amino group, a proton is coordinated on the nitrogen atom of the tertiary amino group, the tertiary amino group becomes an ammonium cation, and a sulfonic acid residue is obtained. Alternatively, it may have a quaternary salt structure in which a carboxyl group becomes a sulfonate anion or a carboxyl anion.

If necessary, the compound (1) of the present invention can be made into a quaternary compound. Specifically, all or part of the three nitrogen atoms in the formula (1) are quaternized. Examples of the compound include: Examples of the group capable of being bonded to the nitrogen atom for the quaternization include a hydroxyl group, a carboxyl group or an alkyl group having 1 to 6 carbon atoms which may be substituted with a sulfonic acid group, a benzyl group or-(R ⁴ O) _m H (where R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, and m is 1 to 5)
Group which represents the number of 0). Here, examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, a carboxyl group or a sulfonic acid group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group and a hexyl group. , Hydroxyethyl group,
1,2-dihydroxypropyl group, carboxymethyl group, 2-hydroxy-3-sulfopropyl group and the like can be mentioned. As the group represented by the group-(R ⁴ O) _m H, specifically,
Examples thereof include polyoxyethylene groups and polyoxypropylene groups, with m = 1 to 20 being preferred.

The amine compound (1) of the present invention can be produced, for example, according to the following reaction formula.

[0022]

[Chemical 15]

[Wherein R ¹ , R ² , A, Y and Z have the same meanings as described above, X ¹ and X ² represent a halogen atom, and R ³ is the same or different and is a hydrogen atom or a hydroxyl group. 1 straight or branched chain carbon atom which may be substituted
~ 24 alkyl groups or alkenyl groups are shown. ]

That is, a novel halohydrin compound (3) obtained by reacting aminoalkyl sulfonic acid or amino acid or a salt thereof (5) with epihalohydrin (6), or a novel halohydrin compound obtained by reacting this with a basic compound. The novel amine compound (2) is obtained by reacting the epoxy compound (4) with the amine compounds (7) and (7) '. The amine compound (1) of the present invention can be obtained by reacting the compound (8) with the amine compound (2) ′ in which R ³ is a hydrogen atom in the amine compound (2). The present invention also provides the above novel compounds (2), (3) and (4) which are intermediates for producing the amine compound (1) of the present invention.

Examples of the halogen atom of the epihalohydrin (6) used for the synthesis of the halohydrin compound (3), that is, X ¹ in the formula (6) include chlorine, bromine and iodine, preferably chlorine. The reaction of aminoalkylsulfonic acid or amino acid or a salt thereof (5) with epihalohydrin (6) can be carried out, for example, in a solvent inert to the reaction such as water or a lower alcohol or a mixture thereof,
Preferably -20 to 100 ° C, particularly preferably 0 to 60
It can be performed at ° C. The amount ratio of the compound (5) to the epihalohydroline (6) to be used can be appropriately set, but it is preferable to use the epihalohydrin (6) in an amount of 2 to 5 times the molar amount of the compound (5).

The obtained halohydrin compound (3) can be converted into an epoxy compound (4) by reacting a basic compound, and examples of the basic compound include alkali metal hydroxides and alkali metal carbonates. Salts, amines and the like are preferable, and sodium hydroxide and potassium hydroxide are particularly preferable. The reaction of the halohydrin compound (3) with the basic compound is carried out in a solvent inert to the reaction such as water or a lower alcohol or a mixture thereof, preferably at 0 to 80 ° C, particularly preferably at 20 to 60 ° C. You can Also used halohydrin compound (3)
The amount ratio of the basic compound and the basic compound can be appropriately set,
2 to the basic compound with respect to the halohydrin compound (3)
It is preferable to use a 5-fold molar amount.

Next, the obtained halohydrin compound (3)
Alternatively, the reaction between the epoxy compound (4) and the amine compounds (7) and (7) 'is preferably carried out in a solvent inert to the reaction, such as water, lower alcohol, ether or aromatic hydrocarbon, or a mixture thereof, preferably It can be carried out at 40 to 150 ° C, particularly preferably 70 to 120 ° C. Also,
The amount ratio of each compound used can be appropriately set,
Generally, the amine compounds (7) and (7) 'are added to the halohydrin compound (3) or the epoxy compound (4) in an amount of 2 to
It is preferable to use 20 times mol, particularly 2 to 10 times mol.

Of the amine compound (2) thus obtained, the amine compound (2) 'in which R ³ is a hydrogen atom is reacted with the compound (8) or a salt thereof to obtain the amine compound of the present invention ( 1) is obtained, and when a salt of the compound (8) is used here, salts of alkali metals, amines and the like, specifically, sodium salts, potassium salts, ammonium salts and the like can be mentioned. The reaction of the amine compound (2) ′ with the compound (8) or a salt thereof is carried out in a solvent inert to the reaction such as water or a lower alcohol or a mixture thereof, preferably 40 to 150 ° C., particularly preferably 70 to 150 ° C. It can be carried out at 100 ° C. while adjusting the pH of the reaction system to 8 to 10. The amount ratio of the amine compound (2) ′ to be used and the compound (8) or a salt thereof can be appropriately set, but generally, the compound (8) or a salt thereof is 2 to the amine compound (2) ′. It is preferable to use 20 times mol, particularly 2 to 10 times mol.

The amine compound (1) of the present invention is obtained as described above. Depending on the reaction conditions, other than these, salts of amine and acid, inorganic salts, unreacted compounds or salts thereof,
In each reaction, a by-product in which only one of the two reaction points has reacted, such as the following formula

[0030]

[Chemical 16]

The compound represented by and the like may remain as a by-product or remain. This reaction product can be used for various purposes as it is, but when higher purity is required, solvent fractionation method, dialysis method, recrystallization method, distillation method, partition chromatography method, gel filtration method It can be purified by a known method such as. The obtained target product may be isolated as a free base, or may be isolated in the form of a desired salt by salt exchange by a usual means such as neutralization with a desired base substance. As the basic substance, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, trimethylamine, triethylamine, tributylamine, alkanolamine (monoethanolamine, diethanolamine, triethanolamine, etc.), Lysine, arginine, choline and the like, preferably alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are used.

In the general formula (1) or (2), the compound of the present invention (1) is obtained by reacting this with a quaternizing agent.
A compound in which all or some of the three nitrogen atoms therein are quaternized is obtained. Examples of the quaternizing agent include alkyl halides having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, a carboxyl group or a sulfonic acid group, benzyl halides, alkylene oxides or salts thereof. Of these, alkyl halides are more preferable. Here, as the alkyl group, methyl group, ethyl group, n-propyl group, n-
Examples thereof include a butyl group and an isopropyl group, and examples of halogen include chlorine, bromine, and iodine. Of these, methyl chloride is particularly preferable.

Since the compound (8) is also a quaternizing agent, various quaternized compounds are produced by reacting the compound (8) with the compound (1) or (2) as exemplified below. To do.

[0034]

[Chemical 17]

The amine compound represented by the general formula (1) of the present invention has excellent detergency and foaming ability, and uses applications of these characteristics, for example, skin and hair cleaners, dishes. It can be used for various cleaning agents such as cleaning agents for clothes and detergents for clothes. In this case, the compounding amount of the compound (1) of the present invention is not particularly limited and may be 0.1 to 8 depending on its use.
It can be used in an amount of 0% by weight, particularly 1 to 50% by weight.

In the detergent composition, if necessary, various known surfactants, moisturizers, bactericides, emulsifiers, thickeners, pearlizing agents, divalent metal ion scavengers, alkali agents,
Inorganic salts, recontamination inhibitors, enzymes, effective chlorine scavengers, reducing agents, bleaching agents, fluorescent dyes, solubilizers, fragrances, anti-caking agents, enzyme activators, antioxidants, preservatives, dyes, A bluing agent, a bleaching activator, an enzyme stabilizer, a phase regulator, a penetrating agent and the like can be added.

As the surface active agent, an anionic surface active agent, a nonionic surface active agent, an amphoteric surface active agent or a cationic surface active agent can be used. The anionic surfactant is usually added for detergency, foaming power, and usability improvement, and examples thereof include higher fatty acid salts, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates,
α-olefin sulfonate, alkylbenzene sulfonate, alkanoyl isethionate, alkyl succinate, alkyl sulfosuccinate, N-alkanoyl sarcosinate, alkyl phosphate, alkyl ether phosphate, alkyl ether carboxylic acid Salt etc. are mentioned. The alkyl and acyl groups of these anionic surfactants usually contain 8 to 20 carbon atoms and may be unsaturated. 1 alkyl ether sulfate, alkyl ether phosphate and alkyl ether carboxylate per molecule
It may contain from 10 to 10 ethylene oxide or propylene oxide units, but preferably from 2 to 3 ethylene oxide units per molecule. Further, as salts of these anionic surfactants, sodium, magnesium,
Mention may be made of ammonium and mono-, di- and triethanolamine salts.

Nonionic surfactants are usually used for improving detergency,
It is added to improve the usability, and examples thereof include polyoxyalkylene alkyl ethers, polyoxyalkylene phenyl ethers, mono- or dialkyl alkanolamides or alkylene oxide adducts thereof, alkyl polyglycosides, monoglycerides and the like. To be The alkyl or acyl groups of these nonionic surfactants usually contain from 8 to 20 carbon atoms and may be unsaturated. Examples of the polyoxyalkylene group include polyoxyethylene, polyoxypropylene and mixed types thereof, and the condensation degree thereof is usually 6 to 30.

Examples of the amphoteric surfactant include long-chain alkyldimethylcarboxymethyl betaine and sulfobetaine; examples of the cationic surfactant include long-chain alkyl trimethyl ammonium salt and di-long chain alkyl dimethyl annium salt. .

These surfactants are combined with the compound (1) of the present invention in an amount of 0.5 to 60% by weight in the detergent composition, and particularly 10 to 45 in the powdery detergent composition.
% By weight, 20 to 50% by weight for liquid detergent compositions
It is preferable to mix them. When the detergent is a bleaching detergent, the surfactant is generally added in an amount of 1 to 10% by weight, preferably 1 to 5% by weight.

As the moisturizer, glycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol or the like can be used.

As the thickener, polyacrylic acid, cross-linked polymer of acrylic acid, copolymer of acrylic acid and hydrophobic monomer, copolymer of carboxylic acid-containing monomer and acrylic acid ester, acrylic acid and acrylic acid ester, ester of ethylene glycol. Alternatively, a cross-linked copolymer with an ester of polyethylene glycol (for example, a fatty acid ester thereof), a heteropolysaccharide gum, or the like can be used.

The _pearling agent may be selected from C _16-22 fatty acids, C _16-22 esters of fatty acids and alcohols, C _16-22 fatty acid esters containing elements such as alkylene glycol units. Suitable alkylene glycol units include ethylene glycol and propylene glycol, but polyalkylene glycols can also be used. Suitable polyalkylene glycols may include polyethylene glycol and polypropylene glycol.

As the divalent metal ion scavenger, condensed polyphosphates such as tripolyphosphate, pyrophosphate, orthophosphate, aluminosilicates such as zeolite, synthetic layered crystalline silicate, nitrilotriacetate, Ethylenediaminetetraacetate, citrate, isocitrate, polyacetalcarboxylate and the like can be used. The divalent metal ion scavenger is 0 to 50% by weight, preferably 5 to
40% by weight is blended. It is more preferable to use a divalent metal ion scavenger containing no phosphorus.

As the alkaline agent and the inorganic salt, silicates, carbonates, sesquicarbonates, sulfates, alkanolamines and the like are used. These are blended in an amount of 0 to 80% by weight.

As the anti-redeposition agent, polyethylene glycol, polyacrylic acid salt, polyacrylic acid copolymer such as acrylic acid-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose and the like are used. Some anti-redeposition agents can also be used as divalent metal ion scavengers. The anti-redeposition agent is blended in an amount of 0 to 10% by weight, preferably 1 to 5% by weight.

As the enzyme, cellulase, α-amylase, pullulanase, lipase, hemicellulase, β-glycosidase, glucose oxidase, cholesterol oxidase, protease and the like can be used.

The scavengers of available chlorine in tap water are represented by ammonium sulfate, urea, guanidine hydrochloride, guanidine carbonate, guanidine sulfamate, thiourea dioxide, monoethanolamine, diethanolamine, triethanolamine, glycine, sodium glutamate and the like. Amino acids and proteins such as bovine serum albumin and casein, as well as protein hydrolysis, meat extract and fish meat extract. Examples of the reducing agent include alkali metal salts such as thiosulfates, sulfites, and nitrite salts, alkaline earth metal salts, and Rongalit C. Sulfite is particularly preferable and stabilizes the enzyme in the washing liquid.

Examples of the bleaching agent include percarbonate, perborate, sulfonated phthalocyanine zinc salt or aluminum salt, hydrogen peroxide and the like. When using as a bleaching detergent,
Sodium peroxide is particularly effective, and the compounding amount is 1-9.
5% by weight, further 5 to 95% by weight, especially 20 to 95% by weight
Is preferred.

Examples of the fluorescent dye include fluorescent dyes usually used in detergents. In the case of liquid detergents, lower alcohols such as ethanol, benzene sulfonate, p-
Solubilizing agents such as lower alkylbenzene sulfonates such as toluene sulfonate and polyols such as glycerin and propylene glycol may be blended.

The detergent composition of the present invention can be produced by combining the compound (1) of the present invention and the above-mentioned known components according to a conventional method. The form of the detergent can be selected according to the application, and can be liquid, powder, granules, or the like.

[0052]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 50 g (0.67 mol) of glycine and 70 parts of water were placed in a reaction vessel.
g and 27 g (0.67 mol) of sodium hydroxide were added and the mixture was cooled to 5 ° C. Then epichlorohydrin 12
4 g (1.34 mol) was added dropwise over 1 hour and 30 minutes, and the temperature was raised to room temperature. After stirring for 6 hours, the precipitated insoluble material was collected by filtration and dried to obtain 106 g of N, N-bis- (3-chloro-2-hydroxypropyl) glycine sodium salt as a white powder (isolated yield. 56%). Below ¹ H-NM
R data is shown.

[0054]

[Chemical 18]

Example 2 N, N-bis-obtained in the same manner as in Example 1 was placed in a reaction vessel.
40 g (0.14 mol) of (3-chloro-2-hydroxypropyl) glycine sodium salt, 100 g of methanol
And 181 g (1.4 mol) of octylamine were added, and 9
The temperature was raised to 0 ° C. After stirring for 10 hours, an aqueous solution of 11 g of sodium hydroxide was added. Then, methanol and water were distilled off under reduced pressure, and unreacted octylamine was distilled off at 100 ° C. and 0.5 mmHg. 700 ml of xylene in the residue
And 700 ml of water were added, and the xylene layer was separated and concentrated to give 13-carboxymethyl-11,15-dihydroxy-.
47 g (isolated yield 79%) of 9,13,17-triazapentacosane was obtained. The ¹ H-NMR data is shown below.

[0056]

[Chemical 19]

Example 3 N, N-bis-obtained in the same manner as in Example 1 was placed in a reaction vessel.
20 g (0.07 mol) of (3-chloro-2-hydroxypropyl) glycine sodium salt and 100 g of water were added, and the mixture was kept at 50 ° C. 35 ml of 4N sodium hydroxide aqueous solution was put into this, and after stirring for 30 minutes, the solvent was distilled off under reduced pressure, 100 ml of ethanol was added, and the insoluble portion was filtered off. Then, ethanol was distilled off under reduced pressure, and N, N-bis-
11 g of (2,3-epoxypropyl) glycine (isolated yield 84%) was obtained. The ¹ H-NMR data is shown below.

[0058]

[Chemical 20]

Example 4 13-Carboxymethyl-11,15-dihydroxy-9,13,17 obtained in the same manner as in Example 2 was placed in a reaction vessel.
-26.5 g (0.06 mol) of triazapentacosane and 40 g of ethanol were added, and the temperature was raised to 50 ° C. To this, a solution prepared by dissolving 40 g (0.34 mol) of sodium monochloroacetate in 80 g of water and 20 g of ethanol was added, and while maintaining the pH at 8 to 10 with an aqueous sodium hydroxide solution, 30
Reacted for hours. After the reaction was completed, ethanol was distilled off under reduced pressure, the residue was redissolved in 500 ml of water, and the produced inorganic salt and unreacted sodium chloroacetate were removed by electrodialysis, and the aqueous solution was freeze-dried. Dihydroxy-9,13,17-triaza-9,13,17
22 g of tricarboxymethylpentacosane was obtained as a white powder (isolated yield 65%). The ¹ H-NMR data is shown below.

[0060]

[Chemical 21]

Example 5 30 g (0.24 mol) of taurine and 30 g of water were placed in a reaction vessel.
And 9.65 g of sodium hydroxide were added and the mixture was cooled to 10 ° C. 44.7 g (0.48 mol) of epichlorohydrin was added dropwise over 30 minutes, and the temperature was raised to room temperature. After reacting for 5 hours at room temperature, 347 g (2.7 mol) of octylamine and 100 g of methanol were added, and the temperature was raised to 50 ° C. After reacting at 50 ° C. for 16 hours, water and methanol were distilled off under reduced pressure. After that, unreacted octylamine was distilled off at 100 ° C. and 0.5 mmHg, and 800 ml of chloroform and 800 ml of 5% sodium hydroxide aqueous solution were added to the residue, extracted and washed with water to separate the chloroform layer, and the solvent was distilled off 94 g of 11,15-dihydroxy-13-sulfoethyl-9,13,17-triazapentacosane was obtained (isolation yield 79%). The ¹ H-NMR data is shown below.

[0062]

[Chemical formula 22]

Example 6 In a reaction vessel, 20 g (0.04 mol) of 11,15-dihydroxy-13-sulfoethyl-9,13,17-triazapentacosane obtained in the same manner as in Example 5 and 35 g of ethanol were placed. The temperature was raised to 60 ° C. To this, 3-chloro-2-hydroxy-propanesulfonic acid sodium salt 2
A solution prepared by dissolving 9 g (0.15 mol) in 35 g of water was added dropwise over 1 hour and 30 minutes. During that time, the pH was adjusted to 8 to 10 with an aqueous sodium hydroxide solution. 3 at 60 ° C
After stirring for 3 hours, ethanol was distilled off under reduced pressure. After that, redissolve in 500 ml of water and desalinate by electrodialysis.
By freeze-drying the aqueous solution, 2, 6, 10, 14
-Tetrahydroxy-4,12-dioctyl-8-sulfoethyl-4,8,12-triazapentadecane-1,
24 g of 15-disulfonic acid was obtained as a white powder (isolated yield 78%). The ¹ H-NMR data is shown below.

[0064]

[Chemical formula 23]

Formulation Example 1 A shampoo having the following composition was produced using the compound of the present invention.

[0066]

[Table 1] (Composition) (wt%) Compound of Example 4 15.0 Lauroyldiethanolamide 3.0 Lauryldimethylamine oxide 0.5 Hydroxyethyl cellulose (manufactured by Daicel) 0.1 Sodium benzoate 0.3 Dye Suitable amount Perfume proper amount citric acid proper amount water balance 100.0

Formulation Example 2 A shampoo was prepared in the same manner as in Formulation Example 1, except that the compound of Example 6 was used instead of the compound of Example 4.

The shampoos of Formulation Examples 1 and 2 were both excellent in foaming property and detergency, and had good feelings when washing hair and rinsing.

Formulation Example 3 A body shampoo having the following composition was produced using the compound of the present invention.

[0070]

Table 2 (Composition) (wt%) Compound of Example 4 17.0 Polyoxyethylene (EO 3) lauryl glucoside 5.0 Lauryl dimethylamine oxide 3.0 Glycerin 4.0 Sucrose fatty acid ester 1.0 Methylparaben 0.3 Dye Appropriate amount Perfume Appropriate amount Citric acid Appropriate amount Water Balance 100.0

Formulation Example 4 A body shampoo was prepared in the same manner as in Formulation Example 3, except that the compound of Example 6 was used instead of the compound of Example 4.

The body shampoos of Prescription Examples 3 and 4 were excellent in foaming property and detergency, and had a moist and good feeling after washing.

Formulation Example 5 A powder detergent composition for clothes having the following composition was prepared. This detergent was excellent in detergency at low temperatures (5 ° C) and did not impair detergency even when the hardness of water used was high (4 to 8 ° DH).

[0074]

TABLE 3 (Composition) (wt%) Compound 5.0 Polyoxyethylene (EO4-18) of Example 4 or 6 C ₈ -C ₂₂ alkyl ether 3.0 C ₁₂ alkyl benzene sulfonate Na 20.0 C ₁₂ To C ₁₄ alkyl sulfate Na 5.0 C _{12 to} C ₁₈ fatty acid Na 6.0 zeolite (4A type) 30.0 sodium carbonate 20.0 enzyme (protease, cellulase) 2.0 polymer (acrylic acid-maleic acid copolymer) Combined, Mw = 50,000) 3.0 Fluorescent dye (DM type, Chinopearl CBS mixed system) 0.5 Perfume 0.2 Water Balance total 100.0

Formulation Example 6 A powdery detergent for clothes containing a nonionic surfactant having the following composition as a main component was prepared. This cleaning agent has improved the drawbacks of conventional cleaning agents containing a nonionic surfactant as the main component, which are less foaming during washing and poor rinseability.

[0076]

Table 4 (Composition) (wt%) Example 4 or Compounds 5.0 Polyoxyethylene of ₆ (EO4-18) C 6 ~C ₂₂ alkyl ether 22.0 C ₁₂ -C ₁₈ fatty acid Na 1.0 Zeolite (4A-type) 30.0 sodium 25.0 atypical aluminosilicate carbonate _{(Na 2 O · Al 2 O} 3 · 3SiO 2) 10.0 enzyme (protease, cellulase) 2.0 polymer (acrylic acid - maleic acid copolymerization Combined, Mw = 100,000) 3.0 Fluorescent dye (DM type, Chinopearl CBS mixed system) 0.5 Perfume 0.2 Water balance 100.0

Test Example 1 A dishwashing detergent having the composition shown below was prepared, and its foaming power,
The detergency, the skin irritation and the feeling of use (hand feel) were evaluated.

[0078]

Table 5 (Composition) (wt%) Compound of Example 4 or 6 5.0 Polyoxyethylene (average number of moles added: 3) Sodium lauryl ether sulfate 12.0 Lauryl dimethylamine oxide 3.0 Palm fatty acid monoethanolamide 5.0 Ethanol 2.5 Sodium meta-xylene sulfonate 2.0 Sodium benzoate 1.0 Dye Perfume Percentage Water Balance Total 100.0

<Test Method> 2.5 g of beef tallow containing 0.1% by weight of Sudan III (red pigment) as an indicator is applied to a porcelain dish (25 cm in diameter). This was scrubbed at 40 ° C. with a sponge soaked with 3 g of detergent and 27 g of water (hardness 3.5 ° DH). This was performed on 10 panelists, and the detergency, feeling of use and the like were evaluated.

<Results> As a result, the dishwashing agent containing the compound of the present invention had a good foaming power and an excellent cleaning power, and was not irritating to the hands, and had a good feeling in use.

[0081]

EFFECTS OF THE INVENTION The amine compound (1), a salt thereof or a quaternary compound thereof, which is a novel compound of the present invention, has excellent foaming properties, less irritation to the skin and the like, and gives a favorable feel to the skin and hair. You can Therefore, the compound of the present invention is useful as a base for hair and skin cosmetics, a detergent, an emulsifier, a humectant, a conditioning agent, a modifier and the like.

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-3-66660 (JP, A) JP-A-60-215656 (JP, A) JP-B-49-7574 (JP, B1) (58) Field (Int.Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (8)

(57) [Claims] 1. The following general formula (1): [In the formula, R ¹ and R ² are the same or different and are linear or branched carbon atoms 1 which may be substituted with a hydroxyl group.
To 24 alkyl groups or alkenyl groups, A represents a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, Y represents a carboxyl group or a sulfonic acid group, Z represents a sulfoalkyl group or a group obtained by removing one amino group from an amino acid or a salt thereof. ] The amine compound represented by these, its salt, or its quaternary compound. 2. In the general formula (1), R ¹ and R ² are linear or branched alkyl groups having 6 to 24 carbon atoms,
The compound according to claim 1, wherein Z is a sulfoalkyl group or an amino acid constituting a protein, β-alanine or a salt thereof from which one amino group has been removed. 3. The compound according to claim 1, which is in the form of a free base or a salt thereof. 4. The following general formula (2): [In the formula, R ¹ and R ² are the same or different and are linear or branched carbon atoms 1 which may be substituted with a hydroxyl group.
To 24 alkyl groups or alkenyl groups, R ³ is the same or different and is a hydrogen atom or a linear or branched C 1-24 alkyl group or alkenyl group which may be substituted with a hydroxyl group, Z represents a sulfoalkyl group or a group obtained by removing one amino group from an amino acid or a salt thereof. ] The amine compound represented by these. 5. In the general formula (2), R ³ is a hydrogen atom, and Z is a sulfoalkyl group or an amino acid constituting a protein, β-alanine or a salt thereof from which one amino group has been removed. Item 4. The amine compound according to item 4. 6. The following general formula (3) or (4) ## STR3 ## [In the formula, X ¹ represents a halogen atom, and Z is sulfoalkyl.
Group or one amino group from an amino acid or its salt
The removed groups are shown. ] The amine compound represented by
General formula (7) and (7) '[of 4] [Wherein R ¹ and R ² are the same or different and
1 straight or branched chain carbon number which may be substituted by a group
To 24 alkyl groups or alkenyl groups, and R ³ is the same.
One or differently replaced by a hydrogen atom or a hydroxyl group
May be straight or branched chain C1-C24 al.
A kill group or an alkenyl group is shown. ] Ami
The following general formula characterized by reacting
(2) [Chemical formula 5] [Wherein R ¹ , R ² , R ³ and Z have the same meanings as described above.
You ] The manufacturing method of the amine compound represented by these. 7. following general formula (2) 'embedded image [Wherein R ¹ and R ² are the same or different and
1 straight or branched chain carbon number which may be substituted by a group
~ 24 alkyl groups or alkenyl groups, Z is
One alkyl group or amino acid or salt thereof
A group excluding a mino group is shown. ] Amine compound represented by
And the following general formula (8) X ² -AY (8) [in the formula, A is a straight chain which may be substituted with a hydroxyl group.
Or a branched alkylene group having 1 to 6 carbon atoms, X ²
Represents a halogen atom, Y represents a carboxyl group or sulfo group.
Indicates an acid group. ] Reacted with a compound represented by
Following general formula, characterized in that to (1) embedded image [Wherein R ¹ , R ² , A, Y and Z have the same meanings as described above.
Show. ] The amine compound, its salt, or its quaternary represented by
Method for producing compound. 8. The compound according to claim 1.
A detergent composition containing: