JPH0881354A - Cleaning agent composition for body - Google Patents

Abstract

PURPOSE: To provide a body-cleaning agent composition containing a silicone derivative and a surfactant selected from among a 2-hydroxypropanediamine derivative, an amido compound and an amine derivative, having low stimulation and exhibiting excellent frothing property and cleaning performance. CONSTITUTION: This composition contains 1-90wt.% of a surfactant A and 0.01-5wt.% of a silicone derivative B. The weight ratio of A/B is preferably (1-100)/1. The component A is one or more compounds selected from among a compound of formula I (R<1> and R<2> are each a 3-36C alkenyl; X is a 1-6C alkylene, etc.; Y<1> is sulfonic acid residue, sulfuric acid residue, etc.; Y<2> is hydroxy, etc.; (n) is 0 or 1), its salt, its quaternarized product, a compound of formula II (R<3> and R<4> are each a 1-24C alkyl, etc.; Z is sulfoethyl or a group produced by removing one amino group from an amino acid, etc.) and a compound of formula III (A is a 1-6C alkylene; Y<3> is carboxyl, etc.) and the silicone derivative of the component B is a dimethylpolysiloxane, an amino-modified silicone, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has low irritation to hair, skin, etc., has excellent foaming properties and detergency, and when used,
The present invention relates to a cleansing composition for personal use which gives good feel to the fingers when rinsing and drying and gives a smooth and good feel.

[0002]

2. Description of the Related Art In recent years,
In addition to the fact that the cleaning agent main component of the body cleaning agent used for hair and skin is required to have excellent foaming and cleaning properties, it is also safe and has low irritation to the skin and eye mucous membranes. It is required to have excellent properties.

Anionic surfactants (soap, linear alkylbenzene sulfonate (LAS), alkyl sulfate ester salt (A) which are generally used as the main components of detergents.
S), polyoxyethylene alkyl ether sulfate ester salt (AES), α-olefin sulfonate (AO)
S) and the like) have good detergency and foamability, but on the other hand, they are irritating to eyes and skin. On the other hand, N-acetic acid salts such as monoalkyl phosphates, N-acylglutamates, N-acyl-N-alkyl-β-alanine salts, and N-acyl-N-alkylglycine salts that have been proposed as mild stimulants. Acyl amino acid salts have a drawback that they are inferior to the original performance of the cleaning agent, such as hard water resistance, foaming property and detergency, although they have low irritation.

[0004] Therefore, it contains a detergent main ingredient which is both mild to hair and skin and has excellent cleaning properties and foaming properties, and has a good feeling to hair and skin. There has been a long-felt need for a personal cleansing agent that can provide

[0005]

Under the above circumstances, the present inventors have made diligent studies and as a result, as a result, a 2-hydroxypropanediamine derivative represented by the following general formula (1), a salt thereof or a quaternary compound thereof, and a general description below. When a silicone derivative is used in combination with a surfactant selected from the amide compound represented by the formula (3) and the amine derivative represented by the general formula (4) described below, it is mild to hair and skin,
In order to complete the present invention, it was found that a cleaning agent having excellent foaming property and detergency, and having a good finger-passing property, good slipperiness during use, rinsing and drying, and a good smooth feel can be obtained. I arrived.

That is, the present invention provides the following components (A) and (B): (A) (a) the following general formula (1);

[0007]

[Chemical 5]

[Wherein R ¹ and R ² are the same or different and each represents a linear or branched alkyl or alkenyl group having 6 to 36 carbon atoms, and X is substituted with a hydroxyl group, a sulfonic acid group or a carboxyl group. Optionally represents an alkylene or alkenylene group having 1 to 6 carbon atoms, Y ¹ represents a sulfonic acid group, a sulfuric acid residue or a carboxyl group or a salt thereof, and Y ² represents a hydroxyl group, a sulfuric acid residue or a salt thereof or the following: Formula (2);

[0009]

[Chemical 6]

Represents a group represented by the formula, n is 0 or 1. ] The 2-hydroxy propane diamine derivative represented by these, its salt or its quaternary compound, (b) The following general formula (3);

[0011]

[Chemical 7]

[In the formula, X, Y ¹ and Y ² have the same meanings as described above, R ³ and R ⁴ are the same or different and each is a direct group having 1 to 24 carbon atoms which may be substituted with a hydroxyl group. A chain or branched alkyl or alkenyl group is shown, and Z is a sulfoethyl group or an amino acid or its salt with one amino group removed. ] An amide compound represented by
And (c) the following general formula (4);

[0013]

Embedded image

[In the formula, R ³ , R ⁴ and Z have the same meanings as described above, and A represents a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group. ,
Y ³ represents a carboxyl group or a sulfonic acid group. ] It is intended to provide a personal cleansing composition containing one or more surfactants selected from amine derivatives represented by the following formula (B) and one or more surfactants (B) silicone derivatives.

The component (A) used in the present invention is used as a cleaning active ingredient. Of the component (A), (a) the 2-hydroxypropanediamine derivative, its salt or its quaternary compound is represented by the above general formula (1), and is represented by R ¹ and R ² in the formula (1). Carbon number 6
As the linear or branched alkyl group of to 36, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group,
Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group, tricosyl group, straight chain alkyl group such as tetracosyl group and these Branched chain alkyl groups can be mentioned. Further, as the linear or branched alkenyl group having 6 to 36 carbon atoms, a hexenyl group,
Heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, undecenyl group, tridecenyl group,
Examples thereof include a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, an eicosenyl group, a heneicocenyl group, a docosenyl group, a tricocenyl group, a linear alkenyl group such as a tetracocenyl group, and these branched alkenyl groups. . Among them, R ¹ and R ² are an alkyl group or an alkenyl group having 6 to 24 carbon atoms, particularly an alkyl group having 6 to 24 carbon atoms, and further 6 to 18 carbon atoms.
Alkyl groups of are preferred.

Examples of the alkylene or alkenylene group having 1 to 6 carbon atoms represented by X in the formula (1) include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, methylethylene group. Group, ethylethylene group, ethenylene group, propenylene group, butenylene group, pentenylene group, hexenylene group and the like. Of these, those having 1 to 4 carbon atoms are preferable, those having 1 to 3 carbon atoms are more preferable, and methylene group,
Particularly preferred are ethylene group, trimethylene group and ethenylene group.

A hydroxyl group (-OH), a sulfonic acid group (-SO ₃ H) or a carboxyl group (-COOH) may be substituted on these alkylene or alkenylene groups (provided that X ¹ described later is a hydroxyl group or Carboxyl group may be substituted), but 1 to 4 of these substituents may be substituted singly or in combination of two or more.

The hydroxyl-substituted alkylene or alkenylene group includes 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,
Examples thereof include a 2,3,4-tetrahydroxytetramethylene group, and among these, a 1,2-dihydroxyethylene group, a 1-hydroxyethylene group, a 2-hydroxyethylene group, and a 2-hydroxytrimethylene group are particularly preferable.

The sulfonic acid group-substituted alkylene or alkenylene group includes 1-sulfoethylene group, 2-sulfoethylene group, 1-sulfotrimethylene group, 2-sulfotrimethylene group, 3-sulfotrimethylene group, 1-sulfo group. Tetramethylene group, 2-sulfotetramethylene group, 3-sulfotetramethylene group, 4-sulfotetramethylene group,
Examples thereof include a 1,3-disulfotetramethylene group, a 1,4-disulfotetramethylene group, a 2,3-disulfotetramethylene group and a 2,4-disulfotetramethylene group, and among them, 1- A sulfoethylene group and a 2-sulfoethylene group are particularly preferable.

The alkylene or alkenylene group substituted with a carboxyl group is a 1-carboxyethylene group,
Examples thereof include a 2-carboxyethylene group, a 1-carboxytrimethylene group, a 2-carboxytrimethylene group, a 3-carboxytrimethylene group and a 1-carboxytetramethylene group.

Examples of the alkylene or alkenylene group substituted with a hydroxyl group and a carboxyl group include 2-carboxy-1-hydroxytrimethylene group, 2-carboxy-1,3-dihydroxytrimethylene group and 2-carboxy-2-hydroxytrimethylene group. Examples thereof include a methylene group and a 3-carboxy-2,4-dihydroxytetramethylene group. Among these, 2-carboxy-2-hydroxytrimethylene group is preferable.

Examples of the alkylene or alkenylene group substituted with a hydroxyl group and a sulfonic acid group include 1-hydroxy-2-sulfoethylene group, 2-hydroxy-1-sulfoethylene group, 1-hydroxy-2-sulfotrimethylene group, 1-hydroxy-3-sulfotrimethylene group,
2-hydroxy-1-sulfotrimethylene group, 2-hydroxy-3-sulfotrimethylene group, 1,2-dihydroxy-3-sulfotrimethylene group, 1,3-dihydroxy-2-sulfotrimethylene group, 1- Hydroxy-2-
Examples thereof include a sulfotetramethylene group, a 1-hydroxy-4-sulfotetramethylene group, a 2-hydroxy-4-sulfotetramethylene group and a 3-hydroxy-4-sulfotetramethylene group.

The compound represented by the general formula (1) is
Sulfonic acid group (-SO ₃ H), can form salts between the various basic substances because it has a sulfuric acid residue (-OSO ₃ H) or carboxyl group (-COOH). Examples thereof include alkali metal salts, alkaline earth metal salts, amine salts, basic amino acid salts, ammonium salts and the like. Specifically, sodium, potassium, lithium, magnesium, calcium,
Examples thereof include salts with trimethylamine, triethylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, lysine, arginine, choline, ammonia and the like, and among these, alkali metal salts, particularly sodium salts are preferable. In addition,
Since the compound (1) has a tertiary amino group, the proton is coordinated on the nitrogen atom of the tertiary amino group, the tertiary amino group becomes an ammonium cation, and a sulfonic acid group, a sulfuric acid residue or The carboxyl group may have a quaternary salt structure in which a sulfonate anion, a sulfate anion or a carboxy anion is formed.

If necessary, the compound (1) can be made into a quaternized compound. Specifically, the compound (1f) in which two nitrogen atoms in the formula (1) are quaternized is used. Can be mentioned.

[0025]

[Chemical 9]

[Wherein R ¹ ′ and R ² ′ are sulfonic acid groups,
A carboxyl group or an alkyl or alkenyl group having 1 to 6 carbon atoms which may be substituted by a hydroxyl group, a benzyl group or-(R ⁵ O) _m H (wherein R ⁵ represents an alkylene group having 2 to 4 carbon atoms, m Indicates a number from 1 to 50)]

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, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a pentyl group. Group, hexyl group, hydroxyethyl group, 1,2-dihydroxypropyl group, carboxymethyl group, 2-hydroxy-3-
Examples thereof include a sulfopropyl group. Specific examples of the group represented by the group — (R ⁵ O) _m H include a polyoxyethylene group, a polyoxypropylene group, and the like, where m = 1 to 20.
Are preferred. The quaternary compound of the compound (1) can be present when n in the formula (1) is 0.

The compound (1) is produced, for example, according to the following reactions a to d.

[0029]

[Chemical 10]

[In the formula, A ¹ and A ² represent a halogen atom, X ¹ represents an alkylene or alkenylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or a carboxyl group, and Y ⁴ represents a sulfone. An acid group or a carboxyl group, and R ¹ and R ² are the same as above]

That is, the amine derivative (8) obtained by the reaction of two amines ((5) and (6)) with epihalohydrin (7) is reacted with compound (9) or a salt thereof to give compound (1a). ) Is manufactured.

The reaction of two amines with epihalohydrin is described, for example, in US Pat. No. 3,017,258 or 365.
Follow No. 4158.

The reaction between the amine derivative (8) and the compound (9) or a salt thereof is carried out, for example, in the presence of an inert solvent at 20 to 15
The reaction is carried out at 0 ° C., preferably 40 to 100 ° C., by reacting the amine derivative (8) with 1 to 10 times mol, preferably 2 to 5 times mol of the compound (9) or a salt thereof. Here, examples of the halogen atom represented by A ² of the compound (9) include a chlorine atom, a bromine atom and an iodine atom, and among these, a chlorine atom is more preferable. Specific examples of the compound (9) or a salt thereof include sodium chloroacetate, sodium 3-chloro-2-hydroxypropanesulfonate, sodium 3-chloropropionate, and 4
-Chloro-n-butyric acid sodium etc. are mentioned, Of these, sodium chloroacetate and sodium 3-chloro-2-hydroxypropane sulfonate are more preferable. Examples of the inert solvent used herein include polar solvents such as water, methanol, ethanol, isopropanol, dimethylformamide, and dimethylsulfoxide, and these can be used alone or in combination of two or more. However, among them, water, a lower alcohol or a mixed solvent of water and a lower alcohol is preferable.

In this reaction, the amine derivative (8)
On the other hand, when the compound (9) is used in excess, the following quaternary compound (1f ') is produced.

[0035]

[Chemical 11]

[In the formula, R ¹ , R ² , X ¹ and Y ⁴ are the same as above]

After the completion of this reaction, in addition to the desired compound (1a), 1 mol of the compound (9) was added to the inorganic salt, unreacted amine derivative (8) and amine derivative (8) in the reaction mixture. The compound and unreacted compound (9) may be contained. In this case, the reaction mixture can be purified by the following method, unless the reaction mixture can be used as it is. As a purification method, for example, a conventional method such as a solvent fractionation method, an ion exchange chromatography method, a recrystallization method or an electrodialysis method can be adopted. 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.

[0038]

[Chemical 12]

[In the formula, R ⁶ and R ⁷ are the same or different and each represents an alkyl group or an alkenyl group which may be substituted with a hydrogen atom, a hydroxyl group or a carboxyl group,
Y ² ′ represents a hydroxyl group or a sulfuric acid residue, and R ¹ , R
² and X ¹ are the same as above]

That is, by reacting the amine derivative (8) with an epoxy compound (10), the resulting amino alcohol (11) with a sulfuric acid esterifying agent (12), and optionally neutralizing with a basic substance. , Compound (1
b) is produced.

The amine derivative (8) and the epoxy compound (1
The reaction with 0) is carried out, for example, in an inert solvent, preferably 10
It is preferably carried out at 0 to 200 ° C., particularly preferably at 130 to 180 ° C., by reacting the amine derivative (8) with the epoxy compound (10) in a molar amount of 2 to 5 times.
The inert solvent used in this reaction is not particularly limited as long as it is an aprotic solvent, but in view of price and solubility, lower hydrocarbons, aromatic hydrocarbons, ethers And halohydrocarbons are preferred.
Further, this reaction is preferably carried out in a pressure resistant vessel such as an autoclave in consideration of the boiling points of the epoxy compound (10) and the inert solvent used. Epoxy compound (1
As 0), ethylene oxide,
Propylene oxide and butylene oxide are preferable, and ethylene oxide is particularly preferable.

Then, the reaction of the amino alcohol (11) thus obtained with a sulfuric acid esterifying agent (12) such as ClSO ₃ H or SO ₃ is carried out in an inert solvent or without a solvent at -7.
It is preferably carried out in the temperature range of 5 ° C to 150 ° C. ClSO ₃ H
The amount of or SO ₃ used is preferably 1 to 3 times the mol of the amino alcohol (11). In addition, after the completion of this reaction, in a neutralization reaction performed as necessary, a desired amount of sodium hydroxide, potassium hydroxide, or the like depending on the desired degree of neutralization.
Basic substances such as lithium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, trimethylamine, triethylamine, tributylamine, alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.), lysine, arginine, choline, etc., preferably hydroxylated It can be carried out by reacting an alkali metal hydroxide such as sodium or potassium hydroxide.

In the reaction of the amine derivative (8) with the epoxy compound (10) during the above reaction, a small amount of the following formula;

[0044]

[Chemical 13]

In the reaction of the amino alcohol (11) with the sulfuric acid esterifying agent (12), a compound represented by the following formula is obtained:

[0046]

Embedded image

The compound represented by may be produced as a by-product. This reaction product can be used as it is for various uses, but when a higher purity one is required, an ordinary method such as recrystallization, column chromatography,
It can also be used after being purified by distillation or the like.

[0048]

[Chemical 15]

[In the formula, R ⁸ represents a hydrogen atom or an alkyl group which may have a substituent, and R ¹ , R ² , X ¹ and Y ² ′ are the same as the above]

That is, the amine derivative (8) is reacted with a lactone or an oxycarboxylic acid, the resulting amide alcohol (13) is reacted with a sulfuric acid esterifying agent (12), and, if desired, neutralized with a basic substance. To produce compound (1c).

The reaction of the amine derivative (8) with a lactone or an oxycarboxylic acid is carried out, for example, in an inert solvent or without a solvent, preferably 20 to 180 ° C., particularly preferably 4
It is preferable to carry out the reaction by reacting the amine derivative (8) with a lactone or oxycarboxylic acid in a molar amount of 2 to 5 times at 0 to 150 ° C. The inert solvent used in this reaction is not particularly limited as long as it is an aprotic solvent, but in view of price and solubility, lower hydrocarbons, aromatic hydrocarbons, ethers Kind,
Halohydrocarbons and the like are preferable. As the lactones and oxycarboxylic acids used in this reaction, γ-lactone, δ-lactone, glycolic acid, lactic acid, α-hydroxy acid and their methyl esters, ethyl esters and the like are preferable because they are inexpensive.

The amide alcohol (13) thus obtained and a sulfate esterifying agent (12) such as ClSO ₃ H or SO ₃
The reaction with is carried out in an inert solvent or without a solvent at -75 ° C to 1
It is preferably carried out in the temperature range of 50 ° C. The amount of ClSO ₃ H or SO ₃ used is preferably 1 to 3 times the molar amount of the amide alcohol (13). After the completion of this reaction, the neutralization reaction, which is carried out if necessary, can be carried out in the same manner as in the case of the reaction b.

In the reaction of the amine derivative (8) with a lactone or an oxycarboxylic acid during the above reaction, a small amount of the following formula;

[0054]

Embedded image

A compound represented by the following formula is formed as a by-product, and in the reaction between the amide alcohol (13) and the sulfuric acid esterifying agent, the following formula;

[0056]

[Chemical 17]

The compound represented by may be produced as a by-product. This reaction product can be used as it is for various uses, but when a higher purity one is required, an ordinary method such as recrystallization, column chromatography,
It can also be used after being purified by distillation or the like.

[0058]

[Chemical 18]

[In the formula, R ⁹ and R ¹⁰ represent a hydrogen atom, an alkyl group or an alkenyl group which may have a substituent, and X ² represents a sulfonic acid which may be substituted by a hydroxyl group or a carboxyl group. 1 to 6 carbon atoms substituted by a group
Represents an alkylene group of Y ² ″ is a hydroxyl group or the following formula (14);

[0060]

[Chemical 19]

And R ¹ , R ² , X and X ¹ are the same as defined above.

That is, by reacting the amine derivative (8) with an acid anhydride, a dicarboxylic acid or an ester thereof, the ester is further hydrolyzed and, if necessary, neutralized with a basic substance to give a compound. (1d) can be produced. Further, when -CH = CH- is present in X ^{1 of} the obtained compound (1d), it is reacted with a sulfonating agent such as SO ₃ , sodium sulfite, sodium hydrogen sulfite and the like, and if necessary, a base. Compound (1d) ′ is produced by neutralizing with a volatile substance.

The reaction between the amine derivative (8) and the acid anhydride is carried out, for example, in the presence of an anhydrous inert solvent at 20 to 150 ° C.
It is preferably carried out at 40 to 100 ° C. by reacting the amine derivative (8) with 1.0 to 5.0 times mol of an acid anhydride. Examples of the anhydrous inert solvent used here include ether, tetrahydrofuran, benzene, pyridine and the like. In this reaction, the hydroxyl group of the amine derivative (8) reacts with the acid anhydride to obtain a compound in which Y ² ″ is a group represented by the above formula (14) in the formula (1d).

The reaction of the amine derivative (8) with the dicarboxylic acid or its ester can be carried out, for example, in an inert solvent,
It is preferably carried out at 40 to 180 ° C., preferably 80 to 150 ° C., by reacting the amine derivative (8) with a dicarboxylic acid or ester thereof in a molar amount of preferably 2.0 to 5.0 times. This reaction is preferably carried out while removing the produced alcohol or water. As the inert solvent used in this reaction, hexane, benzene,
Examples thereof include toluene and xylene.

In the dicarboxylic acid ester, examples of the alkyl group or alkenyl group represented by R ⁹ and R ¹⁰ in the formula include those having 1 to 5 carbon atoms, and among these, a methyl group is preferable. , And an ethyl group is preferable.

When the dicarboxylic acid ester is used here, a production intermediate represented by the general formula (16) is obtained, which is then hydrolyzed, for example, in a hydrous alcohol under an acid or base catalyst. It is necessary to disassemble.

[0067]

Embedded image

[In the formula, R ¹¹ and R ¹² represent an alkyl or alkenyl group corresponding to R ⁹ or R ¹⁰ , and R ¹ , R ² and X ¹ are the same as the above]

Next, the reaction of the compound (1d) having —CH═CH— in X ¹ with a sulfonating agent such as SO ₃ , sodium sulfite or sodium hydrogen sulfite is carried out, for example, in water at 30 to 100 ° C. , Preferably 40 to 80 ° C., 1.0 to 6.0 times mol, preferably 2.0 to 5.0 times mol of SO ₃ , sodium sulfite or sodium bisulfite with respect to the compound (1d) at pH 4; It is preferable to carry out the reaction at a rate of 0 to 11.0, preferably 5.0 to 8.0.

The neutralization reaction of the obtained compounds (1d) and (1d) 'can be carried out in the same manner as in the reaction b.
In addition, in these reactions, the above reaction b and reaction c
Similarly, a compound in which only one amino group is amidated is produced as a by-product, but the reaction product can be used as it is for various purposes. However, when a higher-purity product is required, it can be purified by a conventional method, for example, recrystallization, column chromatography, electrodialysis, etc., and then used.

In the general formula (1), when n = 0, a quaternizing agent is reacted with this to give a compound (2) in which two nitrogen atoms in the compound (1) are quaternized. 1
f) is obtained. As the quaternizing agent, an alkyl (alkenyl) halide having 1 to 6 carbon atoms, which may be substituted with a sulfonic acid group, a carboxyl group or a hydroxyl group,
Examples thereof include benzyl halide, alkylene oxide or salts thereof. Of these, alkyl halides are more preferable. Here, as the alkyl group, a methyl group, an ethyl group,
Examples thereof include n-propyl group, n-butyl group and isopropyl group, and examples of halogen include chlorine, bromine and iodine. Of these, methyl chloride is particularly preferable.

Specific examples of the compound (1) thus produced include the following.

[0073]

[Chemical 21]

[0074]

[Chemical formula 22]

[0075]

[Chemical formula 23]

Of the component (A), the amide compound (b) as an anionic surfactant is represented by the above general formula (3), wherein X, Y ¹ and Y ² are represented by the formula (1). Has the same meaning as. Specific examples of the linear or branched alkyl group and alkenyl group having 1 to 24 carbon atoms which may be substituted with the hydroxyl group represented by R ³ and R ⁴ include:
The following can be mentioned.

Examples of the straight chain alkyl group include methyl,
Groups such as ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl and the like. Examples of the branched chain alkyl group include methylhexyl, ethylhexyl, methylheptyl, ethylheptyl, methylnonyl,
Examples thereof include groups such as methylundecyl, methylheptadecyl, hexyldecyl and octyldecyl.

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, eicosenyl, heneicosenyl, docosenyl, tricosenyl, and tetracosenyl, and examples of the branched chain alkenyl group include methylhexenyl, ethylhexenyl, methylheptenyl, ethylheptenyl, methylnonenyl, and
Mention may be made of groups such as methylundecenyl, 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, hydroxyeicosyl, hydroxyheneicosyl, 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, hydroxyeicosenyl, hydroxyheneicosenyl, hydroxydocosenyl, hydroxytricosenyl, hydroxytetracosenyl, hydr Groups such as xymethylhexenyl, hydroxyethylhexenyl, hydroxymethylheptenyl, hydroxyethylheptenyl, hydroxymethylnonenyl, hydroxymethylundecenyl, hydroxymethylheptadecenyl, hydroxyhexyldecenyl, hydroxyoctyldecenyl Can be mentioned.

Of these, R ³ and R ⁴ are preferably linear or branched alkyl groups having 6 to 24 carbon atoms or alkenyl groups, and particularly preferably alkyl groups having 6 to 12 carbon atoms.

Among the groups represented by Z, in the group obtained by removing one amino group from an amino acid or a salt thereof, specific examples of the amino acid include, for example, 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, taurine, α-aminobutyric acid, isoserine, ornithine, glutathione, glycylglycine, γ-aminobutyric acid, ε-aminocaproic acid. ,
Ratrulline and the like can be mentioned.

Z is preferably a protein-containing amino acid, β-alanine or taurine, and particularly preferably taurine.

The amide compound of the formula (3) can be produced, for example, according to the following reactions e to reaction g.

[0085]

[Chemical formula 24]

[0086] wherein, R ^3, R ⁴ and Z are as defined above, R ³ 'represents a linear or branched alkyl group having 1 to 4 carbon hydrogen atom or a C, X ^1' is Shows a linear or branched alkylene group having 1 to 6 carbon atoms or an alkenylene group which may be substituted with a hydroxyl group,
Y ² 'represents a hydroxyl group or a sulfuric acid residue. ]

That is, the amine derivative (18) is reacted with a lactone (19) or an oxycarboxylic acid (20), and the resulting amide alcohol (17) is reacted with a sulfuric acid esterifying agent. Compound (3e) or a salt thereof can be produced by the addition.

The amine derivative (18) and the lactone (1
The reaction with 9) or the oxycarboxylic acid (20) is carried out, for example, in an inert solvent or without a solvent, preferably 20 to 180.
It is preferable to carry out the reaction by reacting the amine derivative (18) with the lactone (19) or the oxycarboxylic acid (20) in a molar amount of 2 to 5 times at 40 ° C., particularly preferably 40 to 150 ° C. The inert solvent used in this reaction is not particularly limited as long as it is an aprotic solvent, but in view of price and solubility, lower hydrocarbons, aromatic hydrocarbons, ethers And halohydrocarbons are preferred. Lactones (1
Since 9) and oxycarboxylic acids (20) are inexpensive, lactones (19) include γ-lactone and δ-lactone, and oxycarboxylic acids (20) include glycolic acid, lactic acid, and α-hydroxy. Acids and their methyl and ethyl esters are preferred.

The reaction of the amide alcohol (17) thus obtained with the sulfuric acid esterifying agent is preferably carried out in an inert solvent or without a solvent in the temperature range of -75 to 150 ° C. As the sulfuric acid esterifying agent, ClSO ₃ H, SO _{3 and the} like are used, and the amount thereof is preferably 1 to 10 times mol, particularly preferably 2 to 5 times mol, of the amide alcohol (17). In addition, after the completion of this reaction, in a neutralization reaction carried out as necessary, a desired amount of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia depending on the desired degree of neutralization. , Trimethylamine, triethylamine, tributylamine, alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.), lysine, arginine, choline and other basic substances, preferably sodium hydroxide, potassium hydroxide and other alkali metal hydroxides. Can be carried out by reacting.

During the above reaction, the amine derivative (18)
And lactones (19) or oxycarboxylic acids (20)
In the reaction with, a small amount of the following formula;

[0091]

[Chemical 25]

A compound represented by the following formula is formed as a by-product, and in the reaction between the amide alcohol (17) and the sulfuric acid esterifying agent, the following formula;

[0093]

[Chemical formula 26]

The compound represented by may be produced as a by-product.
This reaction product can be used as it is for various purposes, but if a higher purity is required, it can be used after purification by a conventional method, for example, recrystallization, column chromatography, distillation or the like. it can.

[0095]

[Chemical 27]

[Wherein R ³ , R ⁴ , Z and M have the same meanings as described above, and X ² ′ is an alkylene group having 2 to 4 carbon atoms which may be substituted with a hydroxyl group or a carboxyl group, or an alkenylene. R ¹³ and R ¹⁴ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, and Y ² ″
Represents a hydroxyl group or a group —OCO—X ² ′ -COOH, and M represents a hydrogen atom or a cation atom. ]

[0097]

[Chemical 28]

[Wherein R ³ , R ⁴ , Z and M have the same meanings as described above, X ³ represents an alkenylene group having 2 to 4 carbon atoms which may be substituted by a hydroxyl group, and X ⁴ represents It may be substituted with a hydroxyl group and represents an alkylene group having 2 to 4 carbon atoms, which is substituted with a sulfonic acid group,
Y ² ″ ″ represents a hydroxyl group or a group —OCO—X ³ —COOH, and Y ² ″ ″ ″ represents a hydroxyl group or a group —OCO-X ⁴ —COOH.
Indicates. ]

That is, an amine derivative (18) is added to an acid anhydride (21) or a dicarboxylic acid or its ester (2).
2) is reacted and is hydrolyzed when an ester is used,
The amide carboxylic acid (3f) or a salt thereof can be produced by neutralizing with a basic substance if necessary.

Of the amidocarboxylic acid (3f),
X ² ′ has 2 carbon atoms which may be substituted with a hydroxyl group
To the amide carboxylic acid (3 g) of the present invention, which is an alkenylene group (X ³ ) of 4 to 4, is reacted with a sulfonating agent and, if necessary, neutralized with a basic substance. Alternatively, a salt thereof can be produced.

Amine derivative (18) and acid anhydride (21)
Alternatively, the reaction with (21 ′) is carried out, for example, in the presence of an anhydrous inert solvent at 20 to 150 ° C., preferably 40 to 100 ° C.
With respect to the amine derivative (18), preferably 1.0 to
It is preferably carried out by reacting 5.0 times mol of acid anhydride (21) or (21 ′). Examples of the anhydrous inert solvent used here include ether, tetrahydrofuran, benzene, pyridine and the like. In this reaction, a compound in which the hydroxyl group of the amine derivative (18) and the acid anhydride have reacted is also produced.

The reaction of the amine derivative (18) with the dicarboxylic acid or its ester (22) is carried out, for example, in an inert solvent at 40 to 180 ° C, preferably 80 to 150 ° C.
And preferably 2.0 with respect to the amine derivative (18).
~ 5.0 times mol of dicarboxylic acid or its ester (2
It is preferably carried out by reacting 2). This reaction is preferably carried out while removing the produced alcohol or water. Examples of the inert solvent used in this reaction include hexane, benzene, toluene, xylene and the like.

In the dicarboxylic acid ester, the alkyl group or alkenyl group represented by R ¹³ and R ¹⁴ in the formula (22) is preferably a methyl group or an ethyl group.

When the dicarboxylic acid ester is used here, a production intermediate represented by the general formula (23) is obtained, which is then treated, for example, in a hydrous alcohol under an acid or base catalyst. Hydrolysis is required.

[0105]

[Chemical 29]

[In the formula, R ³ , R ⁴ , X ² ′ and Z have the same meaning as described above, and R ¹³ ′ and R ¹⁴ ′ each represent an alkyl group or an alkenyl group corresponding to R ¹³ and R ^14. . ]

Next, the reaction of the amidocarboxylic acid (3 g) having an alkenylene group X ³ with an esterifying agent is carried out, for example, in water at 30 to 100 ° C., preferably 40 to 40 ° C.
At 80 ° C., the sulfonating agent is added in an amount of 1.0 to 6.0 times, preferably 2.0 to 5.0 times, the molar amount of the compound (3 g) at a pH of 4.0 to 11.0, preferably 5. It is preferable to carry out the reaction at 0 to 8.0. As the sulfonating agent, SO ₃ , sodium sulfite, sodium hydrogen sulfite and the like are used.

The neutralization reaction of the obtained compounds (3f), (3g) and (3g) 'can be carried out in the same manner as in the reaction e. Further, in these reactions, a compound in which only one amino group is amidated is produced as a by-product as in the reactions f and g, but the reaction product can be used as it is for various purposes. However, when a higher-purity product is required, it can be purified by a conventional method, for example, recrystallization, column chromatography, electrodialysis, etc., and then used.

Specific examples of the compound (3) thus produced include the following.

[0110]

[Chemical 30]

Among the components (A), the amine derivative (c) is represented by the above general formula (4).
R ³ , R ⁴ and Z have the same meanings as in formula (3). The number of carbon atoms that may be substituted by the hydroxyl group represented by A is 1
Examples of the linear or branched alkylene group of to 6 include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, methylethylene group, ethylethylene group and the like. 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 and trimethylene group are particularly preferable.

The amine derivative of the formula (4) can be produced, for example, according to the following reaction h.

[0113]

[Chemical 31]

[In the formula, R ³ , R ⁴ and Z have the same meanings as described above, and X ⁵ represents a halogen atom. ]

Specifically, a halohydrin compound (26) obtained by reacting an aminoalkylsulfonic acid or amino acid or a salt thereof (24) with epihalohydrin (25), or an epoxy compound obtained by reacting this with a basic compound. (27) and a primary amine compound (2
By reacting with 8), an amine compound (29) is obtained. Further, the target compound (4h) can be produced by reacting the compound (30).

Examples of the halogen atom of the epihalohydrin (25) used in the synthesis of the halohydrin compound (26), that is, X ⁵ in the formula (25) include chlorine, bromine and iodine, and preferably chlorine. The reaction of aminoalkylsulfonic acid or amino acid or a salt thereof (24) with epihalohydrin (25) is carried out 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, it can be carried out at 0 to 60 ° C. The amount ratio of the compound (24) to the epihalohydroline (25) used can be appropriately set, but it is preferable to use the epihalohydrin (25) in an amount of 2 to 5 times the molar amount of the compound (24).

The obtained halohydrin compound (26) is
An epoxy compound (27) can be obtained by acting a basic compound, and as the basic compound, for example, alkali metal hydroxides, alkali metal carbonates, amines and the like are preferable, and sodium hydroxide,
Potassium hydroxide is preferred. Halohydrin compound (2
The reaction of 6) with a basic compound is carried out in a solvent inert to the reaction such as water or a lower alcohol or a mixture thereof, preferably 0 to 80 ° C., particularly preferably 20 to 60.
It can be performed at ° C. The amount ratio of the halohydrin compound (26) to the basic compound used can be set appropriately, but it is preferable to use the basic compound in an amount of 2 to 5 times the molar amount of the halohydrin compound (26).

Then, the obtained halohydrin compound (2
6) or an epoxy compound (27) and an amine compound (2
The reaction with 8) is carried out in a solvent inert to the reaction, such as water, lower alcohol, ether or aromatic hydrocarbon or a mixture thereof, preferably at 40 to 150 ° C, particularly preferably at 70 to 120 ° C. You can The amount ratio of each compound used can be appropriately set, but in general, the amine compound (28) is replaced with the halohydrin compound (2
It is preferable to use 2 to 20 times mol, especially 2 to 10 times mol for 6) or the epoxy compound (27).

The reaction of the amine compound (29) thus obtained with the compound (30) is carried out in a solvent inert to the reaction, such as water or a lower alcohol, preferably 40
It can be carried out at ˜150 ° C., particularly preferably 70˜100 ° C. The amount ratio of the compound used in the reaction can be appropriately set, but in general, it is 2 with respect to the amine compound.
It is preferably used in an amount of about 20 to 20 times, especially 2 to 10 times.

By such a reaction, the compound (4h) used in the present invention can be obtained. In addition to this, depending on the reaction conditions and the like, salts of amine and acid, inorganic salts, unreacted compounds and salts thereof can also be obtained. Also, by-products represented by the following formula (31) in which only one of the two reaction points reacts in each reaction are by-products,
May remain.

[0121]

[Chemical 32]

In the present invention, the reaction product can be used as it is, but if necessary, solvent fractionation method, dialysis method, recrystallization method, distillation method, partition chromatography method, gel filtration method, etc. It is also possible to use a product further purified by a known method.

Specific examples of the compound (4) thus produced include the following.

[0124]

[Chemical 33]

As the surfactant as the component (A), one or more selected from these (a), (b) and (c) can be used, and in the detergent composition of the present invention. 1 to
It is preferable to add 90% by weight, and particularly preferably 1 to 80% by weight, and more preferably 1 to 50% by weight because foaming property and cleaning property are improved.

Examples of the silicone derivative of the component (B) used in the present invention include those shown in 1) to 9) below.

1) Dimethyl polysiloxane

Embedded image (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m Si (CH ₃ ) ₃ (m = 30,000 to 20,000)

2) Methylphenyl polysiloxane

[0129]

Embedded image

3) Polyether-modified silicone

[0131]

Embedded image

4) Epoxy-modified silicone

[0133]

Embedded image

5) Fluorine-modified silicone

[0135]

[Chemical 38]

6) Alcohol-modified silicone

[0137]

[Chemical Formula 39]

7) Alkyl-modified silicone

[0139]

[Chemical 40]

8) Alkoxy-modified silicone

[0141]

Embedded image

9) Amino-modified silicone

[0143]

Embedded image

Of these, particularly preferred amino-modified silicones are represented by the following general formula.

[0145]

[Chemical 43]

A typical amino-modified silicone is represented by the following general formula and has an average molecular weight of about 3,0.
00 to 100,000, which is CT under the name of Amodimethicone
FA dictionary (Cosmetic Ingredie, USA)
nt Dictionary) 3rd edition.

[0147]

[Chemical 44]

The above amino-modified silicone is preferably used as an aqueous emulsion, and the aqueous emulsion is combined with a cyclic diorganopolysiloxane according to the method described in JP-B-56-38609. Aminoalkyl group and hydroxy group, hydroxyalkyl group,
It is obtained by emulsion polymerization of an organodialkoxysilane having an oxyalkylene group or a polyoxyarlene group in the presence of a quaternary ammonium salt surfactant and water.

When the above amino-modified silicone is used as an aqueous emulsion, the amount of amino-modified silicone contained in the aqueous emulsion is usually 20 to 60% by weight, preferably 30 to 50% by weight. .

Examples of commercially available amino modified silicone aqueous emulsions include SM 8702C (manufactured by Toray Dow Corning Silicone) and DC 929 (manufactured by Dow Corning).

The above silicone derivatives 1) to 9) are used individually in the form as they are, when they are used by mixing at least two kinds in advance, or when they are usually used as surfactants such as emulsifiers such as nonionic active agents. State in which a silicone derivative is micro-dispersed in an aqueous medium by combining one or two or more agents, anionic activators, cationic activators and amphoteric activators (silicone emulsion)
May be used in.

The silicone emulsion can be obtained by a method of stirring and mixing, a method of emulsion polymerization, or the like. As such a silicone emulsion, for example, KM8
80, KM883, KM884, KM885, KM88
6, KM887 (made by Shin-Etsu Chemical Co., Ltd.) and TEX10
0, TSW831, TEX150, TEX154, TE
X170, TEX152, TEX172, XS65-A
2773, TSC930 (made by Toshiba Silicone Co., Ltd.), B
Y22-007, BY22-029, BY22-01
9, BY22-034, BY22-020, BY22-
009, BY22-008, BY22-835, SM5
571, SM8705 (manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like are commercially available.

Of these silicone derivatives, dimethylpolysiloxane, polyether-modified silicone and amino-modified silicone are particularly preferable.

The silicone derivative of the component (B) is preferably added to the personal cleansing composition of the present invention in an amount of 0.01 to 5% by weight, and particularly 0.1 to 3% by weight makes it easy for fingers to pass and slide. Is more preferable, which is preferable. The weight ratio of component (A) and component (B) is preferably 1/1 to 100/1.

In addition to the above-mentioned essential components, the personal cleansing composition of the present invention is used in conventional cleansing agents such as shampoos and personal cleansing agents within a range that does not impair the effects of the present invention. The components can be used together if necessary. Examples of such concomitant components include pearling agents, emulsifiers, fragrances, dyes, preservatives, antioxidants, thickeners and anti-dandruff agents, bactericides, antiphlogistics, vitamins, UV absorbers, etc. Yes, other "Encyclopedia o
f Shampoo Ingredients (Mic
elle press, 1985) ”, and the like.

The personal cleansing composition of the present invention can be produced by a conventional method, for example, shampoo,
It can be widely applied to rinse-in shampoo, body shampoo, facial cleanser, hand wash, toothpaste and other hair, skin and oral cleaners.

[0157]

The cleansing composition for personal use according to the present invention contains
It has low irritation to the skin, etc., and has high foaming property and high cleansing property, and it has good finger feel during use, rinsing and drying, and has a good dry feel.

[0158]

The present invention will be further described with reference to examples, but the present invention is not limited to these examples.
Prior to the description of the examples, the component (A) used in each example
A synthesis example of will be described. Synthetic Examples 1 to 22 are synthetic examples of a 2-hydroxypropanediamine derivative represented by Formula (1), a salt thereof or a quaternary compound thereof, and Synthetic Example 23.
To 27 are synthesis examples of the anionic surfactant represented by the formula (3), and Synthesis examples 28 to 32 are synthesis examples of the amphoteric surfactant represented by the formula (4).

Synthesis Example 1 Bis- (1,3-decylamino) propane-in a reaction vessel
2-Ol 40.2g (0.108mol), ethanol 260g, and water 100g were put, and it heated up at 50 degreeC. To this, 50.3 g of sodium monochloroacetate (0.432
Was added to a solution of 100 g of ethanol in 70 g of water, and the mixture was reacted under reflux for 20 hours while maintaining the pH at 8 to 10 with an aqueous sodium hydroxide solution. After completion of the reaction, the solvent was distilled off and the residue was dissolved in chloroform to remove insoluble unreacted sodium monochloroacetate and by-produced salts such as sodium chloride. This was followed by silica gel column chromatography purification by thin layer chromatography to give a single spot, 2,6-didecyl-4-hydroxy-2,6-diaza-1,7-heptanedicarboxylic acid 2
3 g was obtained as a white powder (isolated yield 44%).

This product was analyzed by HPLC (column: RP-1
8 (manufactured by Merck), eluent methanol / H ₂ O = 80 /
A single peak was given in 20 measurements. Below ¹ H-
The NMR data is shown.

[0161]

[Chemical formula 45]

Synthesis Example 2 40 g (0.13 mol) of bis- (1,3-octylamino) propan-2-ol and 15 ethanol in a reaction vessel.
0 g and 70 g of water were added and the temperature was raised to 50 ° C. Add 52 g (0.44 mol) of sodium monochloroacetate to 100 g.
Of ethanol and 70 g of water dissolved in water,
The reaction was carried out for 26 hours under reflux while maintaining the pH at 8 to 10 with an aqueous sodium hydroxide solution. After completion of the reaction, the solvent was distilled off,
It was dissolved in chloroform and insoluble unreacted sodium monochloroacetate and by-produced salts such as sodium chloride were removed. This was followed by silica gel column chromatography purification by thin layer chromatography to give a single spot, 2,6-dioctyl-4-hydroxy-
19 g of 2,6-diaza-1,7-heptanedicarboxylic acid
(Isolated yield 34%) was obtained as a white powder.

This product was analyzed by HPLC (column: RP-1
8 (manufactured by Merck), eluent methanol / H ₂ O = 80 /
A single peak was given in 20 measurements. Below ¹ H-
The NMR data is shown.

[0164]

[Chemical formula 46]

Synthesis Example 3 Bis- (1,3-decylamino) propane-in a reaction vessel
2-Ol 31.8g (0.086mol), ethanol 244g, and water 51g were put, and it heated up at 75 degreeC. To this, a solution of 76.7 g (0.390 mol) of sodium 3-chloro-2-hydroxypropane-1-sulfonate dissolved in 361 g of water was added, and a sodium hydroxide aqueous solution was added.
The temperature was maintained at 75 ° C for 20 hours while maintaining the pH at 8-10. After completion of the reaction, the solvent was distilled off under reduced pressure, crystallized from water-ethanol, washed with acetone, desalted by electrodialysis, and freeze-dried to give 4,8-didecyl-.
2,6,10-trihydroxy-4,8-diaza-1,
37.3 g of 11-undecanedisulfonic acid (0.057
Mol) was obtained as a white powder.

This product was analyzed by HPLC (column: RP-1
8 (manufactured by Merck); eluent; methanol / water = 80 /
A single peak was given in 20 measurements. ¹ H below
-NMR data (where a-i represents the site in the following chemical formula that gives each signal).

[0167]

[Chemical 47]

Synthesis Example 4 Preparation of 3,7-didodecyl-3,7-diaza-1,5,9-nonanetriol: In an autoclave having a volume of 1 liter, 50.2 g (0) of 15-hydroxy-13,17-diazanonacosane (0.12 mol) and 500 ml of xylene were added and the temperature was raised to 155 ° C. Ethylene oxide 2
2 g (0.5 mol) was injected and the mixture was kept at 155 ° C. for 6 hours for reaction. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 60 g (yield 99%) of the title compound as a viscous liquid.

Mass spectrometry (FAB ionization method) m / z = 515 (M + H) + (M = C ₃₁ H ₆₆ O
₃ N ₂ ), ¹ H-NMR (CDCl ₃ ): δ (ppm), 0.85 (triplet line, 6H, a), 1.21 (wide singlet line, 36H, b), 1.45 (pentuplet) Line, 4H, c), 2.41-2.70 (complex multiline, 12H, de.
g), 3.57 (triplet line, 4H, h), 3.75 (quintet line, 1H, f),

[0170]

[Chemical 48]

Synthesis Example 5 Preparation of 3,7-didodecyl-5-hydroxy-3,7-diaza-1,9-nonanedisulfate: 3,7-didodecyl-3,7 obtained in Synthesis Example 4 in a reaction vessel. -Diaza-
18 g (0.035 mol) of 1,5,9-nonanetriol and 135 ml of dichloromethane were added, and under a nitrogen stream,
While cooling with ice, 5.1 ml (0.077 mol) of chlorosulfonic acid was added dropwise. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated using nitrogen were removed. N-Butanol was added to the residue to dissolve it, washed with water, and then the solvent was distilled off under reduced pressure to obtain 24.8 g of a solid. Next, this solid is dissolved in water and 1N sodium hydroxide aqueous solution is used.
The pH was adjusted to 7. After that, desalting was carried out by a desalting apparatus (Micro Acylyzer G3, manufactured by Asahi Kasei Co., Ltd.), and further dried by a freeze dryer to obtain 17.2 g (yield 85
%) As a white powder.

It was confirmed by thin layer chromatography (developing solvent: chloroform / methanol = 3/1) that this compound had a single spot (Rf = 0.5). A ¹ H-NMR (solvent: CDCl ₃ ) chart of this compound is shown in FIG. Furthermore, the IR spectrum of this compound was as follows.

IR (KBr tablet method, cm ^-1 ): 3600-
3200 (ν _OH ), 1390, 1192 (ν _{S = O} ).

Synthesis Example 6 Sodium 3,7-didodecyl-3,7-diaza-1,
Preparation of 5,9-nonanetrisulfate: 3,7-didodecyl-3,7-diaza-obtained in Synthesis Example 4 was placed in a reaction vessel.
18 g (0.035 mol) of 1,5,9-nonanetriol and 150 ml of dichloromethane were added, and under a nitrogen stream.
While cooling with ice, 7.7 ml (0.115 mol) of chlorosulfonic acid was added dropwise. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated using nitrogen were removed. Water was added to the residue to dissolve it, and the pH was adjusted to 7 with a 1N aqueous sodium hydroxide solution. After that, desalting was performed using a desalting device (Micro Acylyzer G3, manufactured by Asahi Kasei Co., Ltd.), and the desalting was further dried using a freeze dryer to obtain 26.7 g of the title compound
(Yield 97%) was obtained as a white powder.

As a result of measurement by thin layer chromatography (developing solvent: chloroform / methanol = 1/1), this compound was confirmed to be a single spot (Rf = 0.3). In addition, ¹ H-NMR of this compound (solvent: D ₂
O) chart is shown in FIG. Furthermore, the IR spectrum of this compound was as follows.

IR (KBr tablet method, cm ^-1 ): 1390,
1186 (ν _{S = O} )

Synthesis Example 7 Preparation of 5,9-didodecyl-4,10-dioxo-5,9-diaza-1,7,13-tridecanetriol: 15-hydroxy-13,17-diazanonacosane 9 was placed in a reaction vessel. 0.5 g (0.02 mol) and γ-butyrolactone 11.7 g (0.13 mol) were added, the temperature was raised to 160 ° C., and the temperature was maintained for 5 hours for reaction. After completion of the reaction, column chromatography (silica gel 500 g,
Purification with a developing solvent: chloroform / methanol = 97/3) gave 6 g (yield 45%) of the title compound as a viscous liquid.

Mass spectrometry (FAB ionization method) m / z = 600 (M + H) + (M = C ₃₅ H ₇₀ O ₅ N ₂ ) ¹ H-NMR (CDCl ₃ ): δ (ppm) 0.87 (triplet line) , 6H, a), 1.23 (wide singlet, 36H, b), 1.53 (quintet, 4H, c), 1.85 (quintet, 4H, h), 2.40-2. .52 (wide line, 4H, g), 3.28 to 3.40 (wide line, 8H, de), 3.65 (triple line, 4H, i), 4.03 (wide line) , 1H, f)

[0179]

[Chemical 49]

Synthesis Example 8 Disodium 5,9-didodecyl-7-hydroxy-
Production of 4,10-dioxo-5,9-diaza-1,13-tridecanedisulfate: 5,9-didodecyl-4,10-dioxo-5,9-obtained in Synthesis Example 7 in a reaction vessel
Diaza-1,7,13-tridecanetriol 6g
(0.01 mol), pyridine 4.5 g (0.06 mol)
And 50 ml of dichloromethane were added thereto, and 3 ml (0.02 mol) of chlorosulfonic acid was added dropwise while cooling with ice under a nitrogen stream. Then, 0-5 degreeC was maintained and stirring was continued for 4 hours.
After completion of the reaction, it was treated with 11 g (0.06 mol) of sodium methylate (28% methanol solution). next,
The solvent was distilled off under reduced pressure, the residue was dissolved in water, and desalted by electrodialysis. By freeze-drying this aqueous solution, 3.3 g (41% yield) of the title compound was obtained as a white powder.

As a result of measurement by thin layer chromatography (developing solvent: chloroform / methanol = 2/1), this compound was confirmed to be a single spot (Rf = 0.3). In addition, ¹ H-NMR of this compound (solvent: C
The DCl ₃ ) chart is shown in FIG. Furthermore, the IR spectrum of this compound was as follows.

IR (KBr tablet method, cm ^-1 ): 3620
~ 3300 (ν _OH ), 1690, (ν _{C = O} ), 139
2,1188 (ν _{S = O} )

Synthesis Example 9 Preparation of 3,7-didodecyl-2,8-dioxo-3,7-diaza-1,5,9-nonanetriol: 15-hydroxy-13,17-diazanononacosane 1 in a reaction vessel
Add 0.7 g (0.03 mol), 50 ml of toluene and 7.1 ml (0.07 mol) of ethyl glycolate, and add 100
The temperature was raised to 0 ° C., and stirring was continued for 7.5 hours while driving out the ethanol produced by the nitrogen stream. After the reaction was completed, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel 200 g, developing solvent: chloroform / methanol = 100/1) to give 13 g of the title compound.
(96% yield) was obtained as a viscous liquid.

Mass spectrometry (FAB ionization method) m / z = 543 (M + H) + (M = C ₃₁ H ₆₂ O ₅ N ₂ ) ¹ H-NMR (CDCl ₃ ): δ (ppm) 0.82 (triplet line) , 6H, a), 1.28 (wide singlet, 36H, b), 1.49 to 1.60 (wide multiplet, 4H, c), 3.18 (triple line, 4H, d), 3. 48 (multiple lines, 4H, e), 4.05 (wide multiple lines, 1H, f), 4.20 (single line, 4H, g)

[0185]

Embedded image

Synthesis Example 10 Disodium 3,7-didodecyl-5-hydroxy-
Preparation of 2,8-dioxo-3,7-diaza-1,9-nonanedisulfate: 3,7 obtained in Synthesis Example 9 in a reaction vessel
-Didodecyl-2,8-dioxo-3,7-diaza-
10.8 g (0.02 mol) of 1,5,9-nonanetriol and 50 ml of dichloromethane were added, and 2 ml of 3 ml (0.04 mol) of chlorosulfonic acid was added while cooling with ice under a nitrogen stream.
It was added dropwise over 0 minutes. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated by a nitrogen stream were removed. Water was added to the residue to dissolve it, and the pH was adjusted to 7 with a 1N aqueous sodium hydroxide solution. The aqueous solution was desalted by electrodialysis and then freeze-dried to obtain 11.8 g (yield 79%) of the title compound as a white powder.

As a result of measurement by thin layer chromatography (developing solvent: chloroform / methanol = 3/1), this compound was confirmed to be a single spot (Rf = 0.2). In addition, ¹ H-NMR of this compound (solvent: D ₂
O) chart is shown in FIG. Furthermore, the IR spectrum of this compound was as follows.

IR (KBr tablet method, cm ^-1 ): 3600
~ 3200 (ν _OH ), 1658 (ν _{C = O} ), 138
5, 1195 (ν _{S = O} )

Synthesis Example 11 Preparation of trisodium 3,7-didodecyl-2,8-dioxo-3,7-diaza-1,5,9-nonanetrisulfate: 3,7 obtained in Synthesis Example 9 in a reaction vessel -Didodecyl-2,8-dioxo-3,7-diaza-1,5,9-
28 g (0.05 mol) of nonanetriol and 100 ml of dichloromethane were added, and 11 ml (0.16 mol) of chlorosulfonic acid was added dropwise while cooling with ice under a nitrogen stream. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated by a nitrogen stream were removed. Water was added to the residue to dissolve it, and the pH was adjusted to 7 with a 1N aqueous sodium hydroxide solution. This aqueous solution was desalted by electrodialysis and then freeze-dried to give 28 g of the title compound (yield: 66
%) As a white powder.

As a result of measurement by thin layer chromatography (developing solvent: chloroform / methanol = 1/1), this compound was confirmed to be a single spot (Rf = 0.3). In addition, ¹ H-NMR of this compound (solvent: D ₂
O) chart is shown in FIG. Furthermore, the IR spectrum of this compound was as follows.

IR (KBr tablet method, cm ^-1 ): 139
0, 1185 (ν _{S = O} ), 1660 (ν _{C = O} ).

Synthesis Example 12 Bis- (1,3-decylamino) propan-2-ol 22.2 g (0.06 mol), succinic anhydride 13.2 g (0.12 mol) and anhydrous ether 300 were placed in a reaction vessel.
ml was added and refluxed for 5 hours. After completion of the reaction, ether was distilled off under reduced pressure to give 4,8-didecyl-3,9-
Dioxo-6-hydroxy-4,8-diaza-1,11
34 g (0.06 mol) of undecanedicarboxylic acid were obtained as a glassy solid.

The compound was adjusted to pH 10 with sodium hydroxide.
The ones adjusted to (column: R
P-18 (Merck), eluent methanol / water = 8
A single peak was given in the 0/20 measurement. Below, ¹
1H-NMR data are shown.

¹ H-NMR (CDCl ₃ ): δ (ppm)
TMS standard 0.88 (triple line, 6H, a), 1.26 (wide singlet, 28H, b), 1.47 (wide singlet, 4H, c), 2.64 (complex multiplex, 8H) , Gh), 3.3-3.9 (complex multiline, 9H, df).

[0195]

[Chemical 51]

Synthesis Example 13 In a reaction vessel, 17.04 g (0.04 mol) of bis- (1,3-decylamino) propan-2-ol, 7.8 g (0.08 mol) of maleic anhydride and anhydrous ether 20 were added.
0 ml was added and the mixture was refluxed for 3 hours. After completion of the reaction, ether was distilled off under reduced pressure to obtain 25 g (0,0) of 4,8-didodecyl-3,9-dioxo-6-hydroxy-4,8-diaza-1,10-undecene-1,11-dicarboxylic acid. 0.04 mol) was obtained as a glassy solid.

The compound of the present invention adjusted to pH 7 with sodium hydroxide was tested by HPLC (column: RP
-18 (Merck), eluent methanol / water = 75
A single peak was given in the / 25 measurement. Below, ¹ H
-Indicates NMR data.

¹ H-NMR (CDCl ₃ ): δ (ppm)
TMS standard 0.89 (triple line, 6H, a), 1.27 (wide singlet, 36H, b), 1.56 (wide singlet, 4H, c), 3.25 to 3.58 (complex) Multiplex line, 8H, de), 3.8 to 3.95 (complex multiplex line, 1H, f), 6.1 to 6.65 (complex multiplex line, 4H, gh)

[0199]

[Chemical 52]

Synthesis Example 14 Bis- (1,3-dodecylamino) propan-2-ol 10.65 g (0.025 mol), toluene 100 ml and diethyl tartrate 17.1 ml (0.1 mol) were placed in a reaction vessel. The reaction was carried out at 80 ° C. for 20 hours while removing generated ethanol. After completion of the reaction, excess diethyl tartrate was removed by washing with water, and the toluene layer was dried over anhydrous sodium sulfate. Then, by drying under reduced pressure, 4,8-didodecyl-3,9-dioxo-1,2,6,10,11-pentahydroxy-4,8
-Ethyl diaza-1,11-undecane dicarboxylate 1
8 g (0.024 mol) (97%) were obtained as a viscous liquid. The ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ ): δ (ppm)
TMS standard 0.89 (triple line, 6H, a), 1.2-1.3 (complex multiplex line, 42H, bj), 1.63 (wide singlet, 4H, c), 3.52 (Wide singlet, 8H, de), 3.7-4.1 (complex multiline, 5H, if), 4.6-4.85 (complex multiline, 4H, gh) )

[0202]

Embedded image

Synthesis Example 15 4,8-Didodecyl-3,9-dioxo-1,2,6,10,11-pentahydroxy-4, obtained in Synthesis Example 14
Ethyl 8-diaza-1,11-undecanedicarboxylate was dissolved in 50 ml of water-ethanol (1: 1), 2 g (0.05 mol) of sodium hydroxide was added, and the mixture was added at 10 ° C at 10 ° C.
Stir for hours. After completion of the reaction, ethanol in the mixed solution was distilled off under reduced pressure, and the aqueous solution was freeze-dried to give 4,8
-Didodecyl-3,9-dioxo-1,2,6,10,
11-pentahydroxy-4,8-diaza-1,11-
Sodium undecanedicarboxylate (quantitative) was obtained as a white powder.

This compound had an IR spectrum (KBr tablet method) of 3000-3700 cm ⁻¹ (ν _OH ), 1
Absorption was observed at 500-1800 cm ^-1 (ν _{C = O} ).

Synthesis Example 16 12.78 g (0.03 mol) of bis- (1,3-dodecylamino) propan-2-ol, 100 ml of toluene and 30 ml (0.12 mol) of triethyl citrate were placed in a reaction vessel, The reaction was carried out at 100 ° C. for 25 hours while removing generated ethanol. After completion of the reaction, toluene was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and 5,9-didodecyl-4,10-
25 g (0.028 mol) of ethyl dioxo-2,7,12-trihydroxy-5,9-diaza-1,2,12,13-tridecanetetracarboxylate was obtained as a white powder. The ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ ): δ (pp
m) TMS criteria 0.9 (triple line, 6H, a), 1.3 (complex multiplet line, 48H, bj), 1.65 (wide singlet, 4H, c), 2.7-2. .9 (complex multiline, 8H, gh), 3.45 (wide singlet, 8H, de), 3.85-4.3 (complex multiline, 9H, if)

[0207]

[Chemical 54]

Synthesis Example 17 5,9-Didodecyl-4,10-dioxo-2,7,12-trihydroxy-5,9-diaza-1,2,12,13-tridecanetetra obtained in Synthesis Example 16 22 g (0.025 mol) of ethyl carboxylate was added to water-ethanol (1:
1) Dissolve in 50 ml and 2 g of sodium hydroxide (0.05
Mol) was added and the mixture was stirred at 60 ° C. for 5 hours. After completion of the reaction, ethanol in the mixed solution was distilled off under reduced pressure, 2 g of sodium hydroxide was further added to the aqueous solution, and freeze-dried to give 5,9-didodecyl-4,10-dioxo-2,
7,12-trihydroxy-5,9-diaza-1,2,
Sodium 12,13-tridecanetetracarboxylate (quantitative) was obtained as a white powder.

This compound had an IR spectrum (KBr tablet method) of 3000-3700 cm ^-1 (ν _OH ), 1
Absorption was observed at 500-1800 cm ^-1 (ν _{C = O} ).

Synthesis Example 18 4,8-didodecyl-obtained in Synthesis Example 13 was placed in a reaction vessel.
3,9-dioxo-6-hydroxy-4,8-diaza-
1,10-undecene-1,11-dicarboxylic acid 21.
8 g (0.035 mol) and sodium sulfite 9.7 g
70 ml of an aqueous solution of (0.077 mol) was added, the pH of the reaction mixture was maintained at 5 to 6, and the mixture was stirred at 60 ° C. for 2 hours. After completion of the reaction, the reaction solution was adjusted to pH 7 with a 1N aqueous sodium hydroxide solution, and excess sodium sulfite was removed by electrodialysis. Then, it is freeze-dried and 4,8-didodecyl-
30 g of sodium 3,9-dioxo-6-hydroxy-1,11-dicarboxy-4,8-diaza-1,11-undecanedisulfonate was obtained as a white powder. The following formula obtained by treating this compound with 1N hydrochloric acid

[0211]

[Chemical 55]

4,8-didodecyl-3,9-represented by
Dioxo-6-hydroxy-1,11-dicarboxy-
4,8-diaza-1,11-undecanedisulfonic acid showed m / z = 7 as a result of mass spectrometry (FAB ionization method).
A peak of 83 (M + H) was shown. Also, ¹ H-N
The results of MR are as follows.

¹ H-NMR (CDCl ₃ ): δ (pp
m) TMS standard 0.88 (triple line, 6H, a), 1.26 (wide singlet, 36H, b), 1.54 (wide singlet, 4H, c), 2.74 (complex multiplex) , 2H, g), 3.25-3.9 (complex multiline, 11H, de.
f. h)

Synthesis Example 19 20 g (0.058 mol) of 9-hydroxy-7,11-diaza-tricosane and 13 g of succinic anhydride were placed in a reaction vessel.
(0.130 mol) and 300 ml of anhydrous ether,
Refluxed for 5 hours. After completion of the reaction, insoluble excess succinic anhydride was removed by filtration, and the ether layer was washed with water. The ether was distilled off under reduced pressure to give a viscous transparent liquid of 4-dodecyl-8-hexyl-3,9-dioxo-6-hydroxy-4,8-diaza-1,11-undecanedicarboxylic acid 30 g ( 0.055 mol) was obtained.

The compound was adjusted to pH 10 with sodium hydroxide.
The ones adjusted to (column: R
P-18 (manufactured by Merck), eluent methanol / water = 8
A single peak was given in the 0/20 measurement. ¹ H below
-Indicates NMR data.

¹ H-NMR (CDCl ₃ ): δ (pp
m) TMS standard 0.89 (triple line, 6H, a), 1.26 (wide singlet, 24H, b), 1.43 (wide singlet, 4H, c), 2.60 (complex multiplex) , 8H, gh), 3.29-3.87 (complex multiline, 9H, de.
f)

[0219]

[Chemical 56]

Synthesis Example 20 Bis- (1,3-dodecylamino) propan-2-ol 21.3 g (0.05 mol), succinic anhydride 16.5 g (0.15 mol) and anhydrous ether 300 were placed in a reaction vessel.
ml was added and refluxed for 5 hours. After the reaction was completed, ether was distilled off under reduced pressure to give 6- (3-carbohydroxy-propanoxy) -4,8-didodecyl-3,9-dioxo-4,8-diaza-1,11-undecanedicarboxylic acid. 37.8 g (quantitative) was obtained.

This compound was subjected to HPLC measurement (column: RP-
18 (manufactured by Merck), eluent methanol / water = 90 /
A single peak was given in the 10,50 mM ammonium acetate assay.

¹ H-NMR (CDCl ₃ ): δ (pp
m) TMS standard 0.89 (triple line, 6H, a), 1.28 (wide singlet, 24H, b), 1.55 (wide singlet, 4H, c), 2.24-2.82 ( Complex multiline, 12H, g.
h), 2.90-3.83 (complex multiline, 9H, de.
f)

[0221]

[Chemical 57]

IR (KBr): 3560, 2940, 2
860, 1730, 1630, 1560 cm ^-1

Synthesis Example 21 Bis- (1,3-decylamino) propane-in a reaction vessel
2-Ol 40.2g (0.108mol), ethanol 260g, and water 100g were put, and it heated up at 50 degreeC. To this, sodium monochloroacetate 62.9 g (0.540
Was added to a solution of 150 g of isopropanol dissolved in 150 g of isopropanol and 100 g of water, and the mixture was reacted under reflux for 30 hours while keeping the pH at 8 to 10. After completion of the reaction, the solvent was distilled off and the residue was dissolved in chloroform to remove insoluble unreacted sodium monochloroacetate and by-produced salts such as sodium chloride. After that, it was purified by silica gel column chromatography until a single spot was obtained by thin layer chromatography, and 2,6-didecyl-4-hydroxy-2,6-diaza-1,1,7,7-heptanetetra was obtained. 20 g of carboxylic acid
Was obtained as a white powder (isolated yield 31%). This product was analyzed by HPLC (column: RP-18 (manufactured by Merck)),
Eluent methanol / water = gave a single peak in the 80/20 measurement. The ¹ H-NMR data is shown below.

¹ H-NMR (D ₂ O): δ (ppm) D ₂
O standard (4.75) 0.82 (triple line, 6H, a), 1.24 (wide singlet, 28H, b), 1.57 (wide singlet, 4H, c), 2.99-3. .32 (complex multiplex, 8H, d), 3.58 (wide singlet, 8H, f), 4.02 (wide singlet, 1H, e)

[0225]

[Chemical 58]

Synthesis Example 22 10 g (0.023 mol) of 2,6-dioctyl-4-hydroxy-2,6-diaza-1,7-heptanedicarboxylic acid obtained in Synthesis Example 2 and 20 g of methanol were placed in a reaction vessel. The temperature was raised to 50 ° C. 8.4g of methyl iodide
(0.06 mol) was added, and the mixture was reacted at 60 ° C for 14 hours. After completion of the reaction, the solvent was distilled off and desalted by electrodialysis,
By freeze-drying, 2,6-dimethyl-2,6-
Dioctyl-4-hydroxy-2,6-diaza-1,7
-9.5 g of heptane dicarboxylic acid (isolated yield 90%)
Obtained as a white powder. The ¹ H-NMR data is shown below.

¹ H-NMR (D ₂ O): δ (ppm) D ₂
O standard (4.75) 0.82 (triple line, 6H, a), 1.22 (wide singlet, 20H, b), 1.59 (wide singlet, 4H, c), 3.02 (single) Line, 6H, e), 3.05 to 3.30 (complex multiplex, 8H, d), 3.94 (single line, 4H, f), 4.11 (wide singlet, 1H, g),

[0228]

Embedded image

Synthesis Example 23 27 g of 11,15-dihydroxy-13-sulfoethyl-9,13,17-triazapentacosane was placed in a reaction vessel.
(0.05 mol) and xylene (100 g) were added, and then succinic anhydride (12 g, 0.12 mol) was added with stirring, and the mixture was reacted at 50 ° C. for 6 hours. After xylene was distilled off under reduced pressure, 300 ml of water was added, and 10% sodium hydroxide was further added to adjust the pH to 7. After that, perform electrodialysis,
Lyophilized to give 6,10-dihydroxy-4,12-dioctyl-3,13-dioxo-8-sulfoethyl-
28 g (isolated yield 76%) of 4,8,12-triaza-1,15-pentadecanedicarboxylic acid was obtained as white crystals. The ¹ H-NMR data is shown below.

[0230]

Embedded image

Further, the above compound was dispersed in water, the same equivalent of sodium hydroxide aqueous solution was added thereto, and the corresponding sodium salt was obtained by freeze-drying.

Synthesis Example 24 20 g of 11,15-dihydroxy-13-sulfoethyl-9,13,17-triazapentacosane was placed in a reaction vessel.
(0.04 mol) and xylene (100 g) were added, maleic anhydride (10 g, 0.1 mol) was added with stirring, and the mixture was reacted at 50 ° C. for 6 hours. After xylene was distilled off under reduced pressure, 300 ml of water was added, and 10% sodium hydroxide was further added to adjust the pH to 7. Then, electrodialysis is performed and lyophilization is performed to obtain 6,10-dihydroxy-4,12-dioctyl-3,13-dioxo-8-sulfoethyl-4,
8,12-Triaza-1,14-pentadecadiene-
22 g of 1,15-dicarboxylic acid (80% isolated yield) was obtained as a white powder. The ¹ H-NMR data is shown below.

[0233]

[Chemical formula 61]

Further, the above compound was dispersed in water, the same equivalent of sodium hydroxide aqueous solution was added thereto, and the corresponding sodium salt was obtained by freeze-drying.

Synthesis Example 25 6,10-dihydroxy-obtained in Example 2 was placed in a reaction vessel.
20 g (0.02) of 4,12-dioctyl-3,13-dioxo-8-sulfoethyl-4,8,12-triaza-1,14-pentadecadiene-1,15-dicarboxylic acid
(9 mol) and 70 g of an aqueous solution of 8 g (0.064 mol) of sodium sulfite were added, the pH in the reaction mixture was maintained at 5 to 6, and the mixture was stirred at 60 ° C. for 3 hours. After the reaction is complete, add 1
The pH was adjusted to 7 with an aqueous sodium hydroxide solution, and excess sodium sulfite was removed by electrodialysis. Then, it is lyophilized to give 1,15-dicarboxy-6,10-dihydroxy-4,12-dioctyl-3,13-dioxo-8.
21 g of sodium sulfoethyl-4,8,12-triazapentadecane-1,15-disulfonate (isolated yield 86%) was obtained as a white powder. The ¹ H-NMR data is shown below.

[0236]

Embedded image

Also, the above compound was dispersed in water, an equivalent amount of an aqueous sodium hydroxide solution was added thereto, and the corresponding sodium salt was obtained by freeze-drying.

Synthesis Example 26 In a reaction vessel, 10 g of 11,15-dihydroxy-13-sulfoethyl-9,13,17-triazapentacosane was used.
(0.02 mol), 50 ml of toluene and 5.1 ml (0.05 mol) of ethyl glycolate were added, the temperature was raised to 100 ° C., and stirring was continued for 7.5 hours while expelling ethanol generated by a nitrogen stream. After the reaction was completed, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography (silica gel 200 g, developing solvent: chloroform / methanol = 1.
00/1 → 20/1) to give 3,11-dioctyl-2,12-dioxo-7-sulfoethyl-3,
10.6 g (isolation yield 91%) of 7,11-triaza-1,5,9,13-tridecanetetraol was obtained. The ¹ H-NMR data is shown below.

[0239]

[Chemical formula 63]

Synthesis Example 27 3,11-Dioctyl-2 obtained in Synthesis Example 4 was placed in a reaction vessel.
12-dioxo-7-sulfoethyl-3,7,11-triaza-1,5,9,13-tridecanetetraol 1
0 g (0.016 mol) and 100 ml of dichloromethane were added, and chlorosulfonic acid under a nitrogen stream was cooled with ice.
2 ml (0.032 mol) was added dropwise. After that, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated by a nitrogen stream were removed. Water was added to the residue to dissolve it, and the pH was adjusted to 7 with a 1N aqueous sodium hydroxide solution. The aqueous solution was desalted by electrodialysis and then lyophilized to give disodium 5,9-dihydroxy-7-sulfoethyl-2,12-dioxo-3,11-dioctyl-.
9.2 g of 3,7,11-triaza-1,13-tridecane disulfate was obtained (isolation yield 75%). IR (K
Br tablet method cm ⁻¹ ): 1388, 1184 (ν _{s = o} ), 1
660 (ν _{C = O} )

Synthesis Example 28 50 g of glycine (0.67 mol), 70 g of water,
Add 27g (0.67mol) of sodium hydroxide, 5 ℃
Cooled to. Thereafter, 124 g of epichlorohydrin (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 removed 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.

¹ H-NMR (D ₂ O): δ (ppm) D ₂
O standard (4.75) 2.58 to 2.85 (complex multiline, 4H, a), 3.27 (single line, 2H, b), 3.44 to 3.76 (complex multiline, 4H, c), 3.88-4.09 (complex multiline, 2H, d)

[0243]

[Chemical 64]

Synthesis Example 29 N, N-bis-obtained in the same manner as in Synthesis Example 28 in a reactor.
(3-chloro-2-hydroxypropyl) -glycine sodium salt 40 g (0.14 mol), methanol 100
g and 181 g of octylamine (1.4 mol) were added,
The temperature was raised to 90 ° 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. A mixture of 700 ml of xylene and 700 ml of water was added to the residue, and the mixture was extracted and washed. The xylene layer was collected and concentrated to give 13-carboxymethyl-11,
47 g of 15-dihydroxy-9,13,17-triazapentacosane was obtained (isolated yield 79%). Below ¹ H-
The NMR data is shown.

¹ H-NMR: δ (ppm) CDCl ₃ 0.88 (triplet, 6H, a), 1.25 (wide singlet, 20H, b), 1.45 (wide singlet, 4H, c). ), 2.31-2.70 (complex multiplex, 12H, d), 3.20 (single line, 2H, e), 3.75 (wide singlet, 2H, f).

[0246]

[Chemical 65]

Synthesis Example 30 13-Carboxymethyl-11,15-dihydroxy-9,13,17-obtained in the same manner as in Synthesis Example 29 in a reactor.
26.5 g (0.06 mol) of triazapentacosane and 40 g of ethanol were added and the temperature was raised to 50 ° C. Add 40 g (0.34 mol) of sodium monochloroacetate to 80 parts of water.
g, a solution dissolved in 20 g of ethanol was added, and the mixture was reacted for 30 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 or unreacted sodium chloroacetate was removed by electrodialysis, and the aqueous solution was lyophilized to give 11,15- 22 g of dihydroxy-9,13,17-triaza-9,13,17-tricarboxymethylpentacosane was obtained as a white powder (isolated yield 65%).

¹ H-NMR: δ (ppm) D ₂ O 0.86 (triplet, 6H, a), 1.22 (wide singlet, 20H, b), 1.41 (wide singlet, 4H, c), 2.40 to 2.83 (complex multiplex, 12H, d), 3.20 (wide singlet, 6H, e), 3.72 (wide singlet, 2H, f)

[0249]

[Chemical formula 66]

Synthesis Example 31 Taurine 30 g (0.24 mol) and water 30 g 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, 100 ℃, 0.5mmHg
Then, unreacted octylamine was distilled off, and 800 ml of chloroform and 800 ml of 5% sodium hydroxide aqueous solution were added to the residue, which was then extracted and washed with water. The chloroform layer was separated and the solvent was distilled off to give 11,15-dihydroxy. 94 g of -13-sulfoethyl-9,13,17-triazapentacosane was obtained (isolation yield 79%). The ¹ H-NMR data is shown below.

¹ H-NMR: δ (ppm) CDCl ₃ 0.84 (triplet, 6H, a), 1.26 (wide singlet, 20H, b), 1.44 (wide singlet, 4H, c) ), 2.15 to 2.50 (complex multiplex, 2H, e), 2.61 to 2.87 (complex multiplex, 14H, d), 3.44 to 3.63 (complex multiplex) , 2H, f)

[0252]

Embedded image

Synthesis Example 32 11,15-Dihydroxy-13-sulfoethyl-9,13,17-triazapentacosane (20 g, 0.04 mol) and ethanol (35 g) obtained in the same manner as in Synthesis Example 31 were placed in a reaction vessel. The temperature was raised to 60 ° C. To this, 29 g of 3-chloro-2-hydroxy-propanesulfonic acid (0.1 g
5 mol) was dissolved in 35 g of water, and the solution was added dropwise over 1 hour and 30 minutes. After stirring at 60 ° C. for 33 hours, under reduced pressure,
The ethanol was distilled off. Then, it is redissolved in 500 ml of water, desalted by electrodialysis, and then freeze-dried to give 2,6,10,14-tetrahydroxy-4,12-dioctyl-8-sulfoethyl-4,
24 g of 8,12-triaza-1,15-pentadecanedisulfonic acid was obtained as a white powder (isolated yield 78%).
The ¹ H-NMR data is shown below.

¹ H-NMR: δ (ppm) D ₂ O 0.81 (triplet, 6H, a), 1.25 (wide singlet, 20H, b), 1.47 (wide singlet, 4H, 4H, c), 2.11 to 2.56 (complex multiplex line, 6H, f), 2.73 to 2.94 (complex multiplex line, 18H, d), 3.70 to 3.85 (complex multiplex) Line, 2H, e), 3.98 (wide singlet, 2H, g)

[0255]

[Chemical 68]

Example 1 A cleaning composition having the composition shown in Table 1 was prepared, and its skin irritation, foaming property and feel of hair were evaluated by the following methods.

(Skin irritation) Two patch test plasters impregnated with 0.1 ml of a 1% aqueous solution of a sample detergent composition were used.
It was applied to 0 subjects for 24 hours, and 24 hours after the removal of the application, irritation was determined and evaluated according to the following criteria.

◯: Out of 20 persons, 2 or less showed erythema. (Triangle | delta): 3 people or more and 10 people or less showed the erythema in 20 people. X: Eleven or more of the 20 people showed erythema.

(Foaming property) A moisturizer consisting of human hair having a length of 20 cm and a weight of 20 g was moistened with warm water at 40 ° C., and then 1 g of the sample detergent composition was evenly applied and then foamed for 1 minute. The degree of foaming was evaluated according to the following criteria.

A: Excellent. ○: Normal. Δ: Somewhat insufficient. X: Very insufficient.

(Finger passage when rinsing hair) Length 20 cm,
A moisturizer consisting of 20 g of human hair was mixed with warm water of 40 ° C., 1 g of the sample cleaning composition was evenly applied, and after lathering for 1 minute, the hair was rinsed with water, and the fingers passed through it. The following criteria were evaluated by a professional panelist.

⊚: Very good. ○: Normal. Δ: Somewhat bad. X: Very bad.

(Smoothness after drying hair) Length 20 cm,
We specialize about hair which weighed 20 g of human hair and added 40 g of warm water at 40 ° C., evenly applied 1 g of sample detergent composition, then lathered for 1 minute, rinsed with water and dried with a dryer. The following criteria were evaluated by the panelists.

⊚: Very dry. ○: Normal. Δ: A little sticky. X: Very sticky.

[0265]

[Table 1]

As is clear from Table 1, the product of the present invention is hypoallergenic to the skin, has a high foaming property, has a good finger feel at the time of rinsing and drying, and has a good dry feeling. It was confirmed to be obtained.

Example 2 A shampoo having the following composition was prepared. The obtained shampoo was excellent in foamability and detergency, and had a smooth and good feel even after washing.

[0268]

(Composition) (wt%) Compound of Synthesis Example 3 20 Dimethyl polysiloxane (KF-96, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 Hydroxyethyl cellulose 0.05 Sodium benzoate 0.3 Dye proper amount Perfume proper amount Quen Acid Proper amount Purified water Balance meter 100.0

Example 3 A shampoo having the following composition was prepared. The obtained shampoo had excellent foamability and washability, and had a smooth and good feel even after washing.

[0270]

Table 3 (Composition) (wt%) Compound of Synthesis Example 5 15 Compound of Synthesis Example 30 5 Dimethylpolysiloxane 0.3 Hydroxyethyl cellulose 0.05 Sodium benzoate 0.3 Dye proper amount Perfume proper amount Citric acid proper amount Purified water balance 100.0 in total

Example 4 A body shampoo having the following composition was prepared. The obtained body shampoo was excellent in foamability and detergency, and had a smooth and good feel even after washing.

[0272]

[Table 4] (Composition) (wt%) Compound of Synthesis Example 10 18 Lauryl dimethylamine oxide 2 Amino-modified silicone (JR-400, manufactured by Union Carbide) 0.2 Glycerin 4 Sucrose fatty acid ester 1 Methylparaben 0.3 Dye Suitable amount Perfume Suitable amount Citric acid Suitable amount Purified water Balance meter 100.0

Example 5 A face wash having the following composition was prepared. The obtained face wash,
It was excellent in foamability and detergency, and had a smooth and good feel even after washing.

[0274]

[Table 5] (Composition) (wt%) Compound of Synthesis Example 23 15 Potassium laurate 3 Potassium myristate 2 Glycerin 10 Polyether-modified silicone (KF-6005, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 Cationized cellulose 1 Dye Appropriate amount Perfume Appropriate amount Purified water Balance meter 100.0

Example 6 A hand wash having the composition shown below was prepared. The obtained hand wash was excellent in foaming property and detergency, and had a smooth and good feel even after washing.

[0276]

(Table 6) (Composition) (wt%) Compound of Synthesis Example 32 10 Polyoxyethylene (20) sorbitan monolaurate 10 Triethanolamine oleate 5 Propylene glycol 5 Paraffin oil 2 Aluminum silicate 5 Amino-modified silicone (JR- 400, Union Carbide Co., Ltd.) 0.2 Colorant, proper amount Perfume, proper amount Purified water Balance meter 100.0

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR chart of the compound obtained in Synthesis Example 5.

FIG. 2 is a ¹ H-NMR chart of the compound obtained in Synthesis Example 6.

FIG. 3 is a ¹ H-NMR chart of the compound obtained in Synthesis Example 8.

FIG. 4 is a ¹ H-NMR chart of the compound obtained in Synthesis Example 10.

FIG. 5 is a ¹ H-NMR chart of the compound obtained in Synthesis Example 11.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junko Ouchi 2606-6 Akabane Kai, Haga-gun, Tochigi Prefecture Kao City 3-206 Kaisha House (206) Inventor Tomohito Kitsuki 1450 Nishihama, Wakayama City, Wakayama Kao Suisen Company housing No. 222

Claims (8)

[Claims] 1. The following components (A) and (B): (A) (a) The following general formula (1); [In the formula, R ¹ and R ² are the same or different and have 6 to 3 carbon atoms.
6 represents a linear or branched alkyl or alkenyl group, X represents an alkylene or alkenylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, a sulfonic acid group or a carboxyl group, and Y ¹ represents a sulfone. Represents an acid group, a sulfuric acid residue or a carboxyl group or a salt thereof, and Y ² represents a hydroxyl group, a sulfuric acid residue or a salt thereof or the following formula (2); Represents a group represented by and n represents 0 or 1. ] A 2-hydroxypropanediamine derivative represented by the following, a salt thereof or a quaternary compound thereof, (b) the following general formula (3); [Wherein, X, Y ¹ and Y ² have the same meanings as described above,
R ³ and R ⁴ are the same or different and each represents a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms which may be substituted with a hydroxyl group, and Z is 1 from a sulfoethyl group or an amino acid or a salt thereof. A group excluding two amino groups is shown. ] An amide compound represented by the following formula, and (c) the following general formula (4); [Wherein R ³ , R ⁴ and Z have the same meanings as described above,
A has 1 to 6 carbon atoms which may be substituted with a hydroxyl group.
Represents a linear or branched alkylene group, and Y ³ represents a carboxyl group or a sulfonic acid group. ] A personal cleansing composition containing one or more surfactants selected from amine derivatives represented by the following formula (B) and one or more surfactants (B). 2. The personal cleansing composition according to claim 1, wherein in the general formula (1), Y ¹ is a sulfonic acid group or a sulfuric acid residue, and Y ² is a hydroxyl group or a sulfuric acid residue. 3. In the general formula (1), Y ¹ is a carboxyl group, Y ² is a hydroxyl group or the above formula (2).
The personal cleansing composition according to claim 1, which is a group represented by: 4. In the general formula (1), R ¹ and R
^2. The personal cleansing composition according to any one of claims 1 to 3, wherein ² is a linear or branched alkyl or alkenyl group having 6 to 24 carbon atoms. 5. The personal cleansing agent according to any one of claims 1 to 4, wherein the 2-hydroxypropanediamine derivative represented by the general formula (1), a salt thereof or a quaternary compound thereof is in the form of a free base or a salt. Composition. 6. In the general formula (3), R ³ and R ⁴ are linear or branched alkyl groups having 6 to 24 carbon atoms,
Y ¹ is a sulfonic acid group or a carboxyl group or a salt thereof, Y ² is a hydroxyl group, and Z is a group in which one amino group is removed from amino acids, β-alanine, taurine or a salt constituting a protein. The personal cleansing composition according to any one of claims 1 to 5. 7. In the general formula (3), R ³ and R ⁴ are alkyl groups having 6 to 24 carbon atoms, and X is a straight chain or branched chain having 1 to 6 carbon atoms which may be substituted with a hydroxyl group. A chain alkylene or alkenylene group, Y ¹ is a sulfuric acid residue, Y ² is a hydroxyl group or a sulfuric acid residue or a salt thereof, Z is an amino acid constituting a protein,
The personal cleansing composition according to any one of claims 1 to 5, which is a group obtained by removing one amino group from β-alanine, taurine or a salt thereof. 8. In the general formula (4), R ³ and R ⁴ are alkyl groups having 6 to 24 carbon atoms, and Z is one amino group selected from amino acids, β-alanine, taurine or salts thereof which constitute a protein. The personal cleansing composition according to any one of claims 1 to 7, which is a group removed.