JPH09227479A - New amideestercarboxylic acid or its salt, their production, and cleaning agent composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new amideestercarboxylic acid (salt) low in the irritation of the skins, ocular-mucous membranes, etc., excellent in foamability and touches to the skin, etc., and useful as a component for cleaning agents for skin, hair, etc. SOLUTION: A compound of formula I [R<1> , R<2> are each a 2-20C (branched) alkyl in which an oxygen atom may be inserted into the carbon atoms; A is 1-ethanyl-2-idene, 1-ethenyl-2-idene; M is H, an alkali(ne earth) metal, a trialkylamine, a trialkanolamine; X is H, a group of the formula: SO3 M]. For example, 1-[N-octyl-N-(3-carboxy-3-sulfopropionyl)] amino-2-(3-carboxy-3- sulfoproplonyl)oxy-3-hexyloxypropane tetrasodium salt. The compound of formula I is obtained by reacting a compound of formula II with succinic anhydride or maleic anhydride or with the maleic anhydride and subsequently with a sulfonating agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an amide ester carboxylic acid or a salt thereof useful as a surfactant for hair and skin, a method for producing them, and a detergent composition containing them.

[0002]

2. Description of the Related Art Conventionally, surfactants such as alkylsulfates, polyoxyethylenealkylsulfates, and alkylbenzenesulfonates have been used as detergents and emulsifiers.
However, most of them have a problem that the skin, the eye mucous membrane, etc. are slightly irritating during use. Due to such problems and increased awareness of skin irritation, in recent years, surfactants with weak skin irritation such as alkyl phosphates and acylated amino acid salts are used as bases and emulsifiers for hair and skin cosmetics, Alternatively, it is used as a cleansing agent for skin and hair.

However, while a higher level of low irritation to sensitive skin, atopy, ocular mucous membranes, etc. is desired, diversification of consumers' requirements and high-grade orientation are further advanced, and good foamability, At the same time, it is becoming an important factor to have properties such as good feel on the skin, and it is difficult to say that conventional surfactants sufficiently satisfy these requirements.

[0004]

Accordingly, the object of the present invention is to provide a base for hair and skin cosmetics which has extremely low irritation to the skin, ocular mucous membranes, etc., is excellent in foaming property, and is also excellent in touch to the skin. An object of the present invention is to provide a compound useful as an agent, an emulsifier, a cleanser for skin and hair, and a cleansing composition containing the same.

[0005]

Under the circumstances, the inventors of the present invention have conducted diligent research and as a result, the novel amide ester carboxylic acid represented by the following general formula (1) or a salt thereof has the above performance. The present invention has been completed by finding out that it is a thing.

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

[0007]

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[In the formula, R ¹ and R ² are the same or different and each represents a linear or branched alkyl group having 2 to 20 carbon atoms in which an oxygen atom may be inserted between carbon atoms, and A 1
Is a 1-ethanyl-2-ylidene group or 1-ethenyl-2
-Ylidene group is shown, two X are the same or different, and a hydrogen atom or -SO ₃ M is shown, and 2 to 4 M are the same or different, and a hydrogen atom, an alkali metal, an alkaline earth metal, Indicates a trialkylamine or a trialkanolamine. ] The amide ester carboxylic acid or its salt represented by these, its manufacturing method, and the detergent composition containing them are provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), a linear or branched alkyl group having 2 to 20 carbon atoms in which an oxygen atom may be inserted between the carbon atoms represented by R ¹ and R ^2. As, for example, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, 2-ethylhexyl group, isostearyl group, and other alkyl groups such as ethoxyethyl group, butoxyethyl group, hex Alkoxyalkyl groups such as siloxyethyl group and methoxyhexyl group,
Examples thereof include alkoxyalkoxyalkyl groups such as methoxyethoxymethyl group, methoxyethoxyethyl group and ethoxyethoxyethyl group. Of these, a linear or branched alkyl group having a total carbon number of 4 to 12 is preferable.

M is a hydrogen atom such as lithium,
Alkali metals such as sodium and potassium, for example, alkaline earth metals such as barium, calcium and magnesium,
Examples thereof include tri C _1-4 alkylamines such as trimethylamine, triethylamine, tripropylamine, tributylamine and ethyldimethylamine, and triC _1-4 alkanolamines such as trimethanolamine, triethanolamine and tripropanolamine. Of these, hydrogen atom, sodium, potassium and triethanolamine are preferable.

A is preferably a 1-ethanyl-2-ylidene group.

The amide ester carboxylic acid or its salt (1) of the present invention has an optical isomer because it has an asymmetric carbon atom, and when A is a 1-ethenyl-2-ylidene group, it has an optical isomer. It has the base E, Z isomer. The present invention includes any of these stereoisomers as well as solvates such as hydrates, if any.

Specific examples of the amide ester carboxylic acid or its salt (1) of the present invention include the following compounds (1a) to
(1f) is mentioned.

[0014]

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[0015]

[Chemical 6]

The amide ester carboxylic acid or its salt (1) of the present invention can be produced, for example, according to the following reaction formula.

[0017]

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[In the formula, R ¹ , R ² and M have the same meanings as described above, and Y represents a halogen atom. ]

That is, an amino alcohol (2) is obtained by reacting an amine (6) with an alkyl glycidyl ether (5) obtained by reacting an alcohol (3) with an epihalohydrin (4). Then, this is reacted with succinic anhydride and neutralized as necessary, so that in the general formula (1), A is a 1-ethanyl-2-ylidene group and X
A compound of the present invention (1A) in which is a hydrogen atom is obtained. Further, the compound of the present invention in which A is 1-ethenyl-2-ylidene group and X is a hydrogen atom in the general formula (1) by reacting amino alcohol (2) with maleic anhydride and neutralizing as necessary ( 1B) is obtained, and this is reacted with a sulfonating agent to neutralize it, whereby A is 1-ethanyl-2-ylidene group in the general formula (1).
A compound of the present invention (1C) in which is —SO ₃ M is obtained.

The reaction for synthesizing the glycidyl ether (5) from the alcohol (3) and the epihalohydrin (4) is mainly known in two ways. The glycidyl ether is synthesized in one step using a base such as NaOH. If you want to
Epihalohydrin is used in an amount of 1 to 10 molar times, preferably 3 to 5 molar times, relative to the alcohol, and the reaction temperature is 0 to 10
It may be performed at 0 ° C, preferably 10 to 80 ° C. On the other hand, when the corresponding halohydrin is formed using an acid catalyst such as BF ₃ or SnCl ₄ , and then the ring is opened using a base such as NaOH to synthesize a glycidyl ether, the alcohol is used in an amount of 1 to 10 mols based on the epihalohydrin. Double the amount, preferably 1 to 5 molar amount, and the reaction temperature is 0 to 150 ° C., preferably 10 to
It may be carried out at 100 ° C. In addition, epichlorohydrin is preferable as the epihalohydrin.

Glycidyl ether (5) and amine (6)
In the reaction with, the nitrogen (6) is introduced into the glycidyl ether (5) in an amount of 1 to 10 mol times, preferably 3 to 10 times, the amine (6).
The reaction temperature is 0 to 100 ° C., preferably 5
It may be carried out at 0 to 80 ° C.

The reaction of amino alcohol (2) with succinic anhydride or maleic anhydride is carried out by reacting amino alcohol (2)
To succinic anhydride or maleic anhydride in an amount of 2 to 10 mole times, preferably 2 to 3 mole times, at a reaction temperature of 0 to
It may be performed at 150 ° C., preferably 20 to 100 ° C.

Further, the sulfonation reaction of the maleic acid ester (1B) obtained by the reaction of the amino alcohol (2) and maleic anhydride is carried out by the obtained maleic acid ester (1
In B), a suitable sulfonating agent, preferably sodium sulfite, sodium hydrogen sulfite, or the like, is added in water or a water / ethanol mixed solvent in an amount of 1.9 to 2.1 molar times, preferably 2.0 to 2.05. Use a molar amount, reaction temperature 0-100
C., preferably 40 to 70.degree. C. In this reaction, the following two kinds of structures (a) and (b) were obtained, and the analysis result showed that the structure (a) was the main component. These can be separated and purified using high performance HPLC or the like, if necessary.

[0024]

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The compound (1) of the present invention produced in each of the above-mentioned reactions can be converted into an acid form by extracting with acid, and an alkali metal hydroxide, an alkaline earth metal hydroxide or a trialkylamine can be obtained. Alternatively, a desired salt can be obtained by neutralizing or salt exchange with trialkanolamine.

The amide ester carboxylic acid or its salt (1) of the present invention has extremely low irritation to the skin, eye mucous membrane and the like, is excellent in foaming power and detergency, and has a refreshing and pleasant feel when used. Therefore, it can be suitably used for applications utilizing this property, for example, for skin and hair cleansing agents, conditioning agents, cosmetics bases, emulsifiers and the like. In particular, the amide ester carboxylic acid of the present invention or a salt thereof (1) is preferably blended in a detergent due to its properties, for example, a hair detergent such as shampoo or a skin detergent such as body soap or facial cleanser, and tableware. It is suitable to be applied to hard surface cleaning agents such as, and textile cleaning agents such as clothing detergents.

The amount of the amide ester carboxylic acid of the present invention or its salt (1) to be added to the detergent composition of the present invention is 0.1.
-50% by weight, especially 1-40% by weight is preferred.

The cleaning composition of the present invention may contain components conventionally used in hair cleaning agents, body cleaning agents, hard surface cleaning agents, etc. within a range that does not impair the effects of the present invention. . Such components include anionic surfactants such as alkyl sulphates, alkyl ether sulphates, alkyl sulphonates and sulphosuccinates; nonionic surfactants such as oxyalkylene alkyl ethers, alkyl glycosides and monoglycerides; long chain alkyls. Amphoteric surfactants such as dimethylcarboxyl betaine; cationic surfactants such as long-chain alkyldimethylammonium; moisturizers such as glycerin, propylene glycol, ethylene glycol; other silicone derivatives, water-soluble cationic polymers, germicides, emulsifiers, fragrances, etc. Is mentioned.

The detergent composition of the present invention can be produced according to a conventional method, and its dosage form may be any of liquid, paste, solid, powder, etc., but particularly liquid or paste. Is preferred.

[0030]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 Synthesis of Compound (1a) 50 g (0.47 mol) of 1-hexanol, 132 g (1.43 mol) of epichlorohydrin and 22 g (0.55 mol) of sodium hydroxide were placed in a 500 ml four-necked flask. After stirring for 2.5 hours at a reaction temperature of 60 ° C. or lower under introduction of nitrogen, 500 ml of toluene was added. After washing with water, the solvent was distilled off, and unreacted 1-hexanol and epichlorohydrin were distilled off under reduced pressure to obtain 81 g of hexyl glycidyl ether as a colorless transparent oil. According to GLC, the purity was 99% or higher.

Hexyl glycidyl ether 50 g (0.
32 mol) and 163 g (1.27 mol) of octylamine
Was placed in a 500 ml four-necked flask, and the mixture was stirred under a nitrogen atmosphere at a reaction temperature of 50 to 70 ° C. for 5 hours, unreacted octylamine was distilled off under reduced pressure, and the residue was washed with 100 ml of hexane to give 50 g of amino acid. The alcohol was obtained as white crystals. 200 MHz ¹ H-NMR (solvent CDCl ₃ , TM
S standard), methyl at δ = 0.9, δ = 1.2-1.6
Proton signals of methine and methylene were observed at 5, 2.5, 2.6-2.75 and 3.4, and NH at δ = 3.85, respectively, to identify the product. From HPLC, the purity was 98%.

7.24 g of amino alcohol (0.025
mol) into a 100 ml four-necked flask, maleic anhydride 5.44 g (0.056 mol) and chloroform 50 m
l was added and refluxed for 8 hours. After completion of the reaction, the reaction product was washed with water and the solvent was distilled off to obtain 12.4 g of amide ester carboxylic acid, and 200 MHz ¹ H-NMR (solvent CDCl ₃ , TM
S standard), the disappearance of the NH proton signal at δ = 3.85, methyl at δ = 0.9, δ = 1.25-1.6,
Methine and methylene at 3.4-3.75, δ = 6.15
At -6.75, a proton signal of each olefin was observed, and the product was identified.

12.4 g of amido ester carboxylic acid was dissolved in ethanol / water solution and sodium sulphite 6.8
8 g (0.055 mol) was added, and the mixture was stirred at 50 ° C. for 3 hours. After distilling off the solvent, reverse phase column chromatography (DM1020T manufactured by Fuji Silysia Ltd., developed methanol / water)
And then desalted by electrodialysis and lyophilized to obtain the compound of the present invention (1a) as white crystals (9.5 g). 200M
From Hz ¹ H-NMR (solvent D ₂ O, TMS standard) δ =
Disappearance of olefin proton signal at 6.15-6.75, methyl at δ = 0.9, δ = 1.35-1.75,
Proton signals of methine and methylene were observed at 2.85-3.25, 3.35-3.75 and 4.0,
The product was identified. The purity was 95% by HPLC.

Example 2 Synthesis of Compound (1b) 6.11 g of the amino alcohol obtained in Example 1 (0.
(021 mol) was placed in a 100 ml four-necked flask, dissolved in 50 ml of chloroform, and 4.68 g (0.6% of succinic anhydride) was added.
(047 mol) was added and the mixture was refluxed for 12 hours. After washing with water, the solvent was distilled off and the solution was neutralized with 2N aqueous sodium hydroxide solution (pH
7.06). After the solvent was distilled off, the residue was purified by reversed phase column chromatography (Fuji Silysia DM1020T, developed methanol / water), desalted by electrodialysis, and lyophilized to give 10 g of the present compound (1b) as white crystals. Get 20
0 MHz ¹ H-NMR (solvent CDCl ₃ , TMS standard)
From δ = 0.85, methyl, δ = 1.2-1.7, 2.
Proton signals of methine and methylene were observed at 6, 3.35-3.6 to identify the product. The purity was 98% by HPLC.

Test Example 1 The foaming ability of the compounds (1a) and (1b) of the present invention obtained in Examples 1 and 2 was compared with that of sodium lauric acid salt by the method described below, and as a result, the compounds of the present invention were found to be sufficient. It was found to have a foaming power.

(Test Method) First, 100 ml of a 0.1% by weight aqueous solution of each compound was placed in a measuring cylinder of about 800 ml, and inverted stirring was carried out at 40 ° C. for 5 minutes. Then leave it still,
The foaming amount (ml) was measured after 30 seconds and 5 minutes. The results are shown in Table 1.

[0038]

[Table 1]

Example 3 Shampoo

[Table 2] Composition Compounding amount (wt%) Compound of the present invention (1a) or (1b) 15.0 Lauroyldiethanolamide 3.0 Lauryldimethylamine oxide 0.5 Sodium benzoate 0.3 Hydroxyethylcellulose 0.1 Dye Suitable amount Perfume proper amount citric acid proper amount water balance meter 100

Using the compound (1a) or (1b) of the present invention, a shampoo was prepared according to the above formulation. All of these shampoos were excellent in foamability and detergency, and also had good feel when washing hair and rinsing.

Example 4 Body shampoo

[Table 3] Composition blending amount (% by weight) (1) Inventive compound (1a) or (1b) 15 (2) Lauroylamidopropyl dimethylcarboxybetaine 3 (3) Lauryl dimethylhydroxysulfobetaine 1 (4) Coconut oil fatty acid 4 (5) Triethanolamine 4 (6) Dibutylhydroxytoluene 0.1 (7) Ethanol 2 (8) Perfume 0.5 (9) Water balance meter 100

According to the above composition, components (1) to (6) were dissolved in heated water (9), and after cooling, components (7) and (8) were added to prepare a transparent body shampoo. When the skin was washed with the obtained body shampoo, it had low irritation, good foaming, and excellent feeling in use.

[0043]

INDUSTRIAL APPLICABILITY The amide ester carboxylic acid or its salt (1) of the present invention has extremely low irritation to the skin, ocular mucous membrane and the like, is excellent in foaming property and is also excellent in touch to the skin and the like. It is useful as a component of detergents and the like.

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Claims (6)

[Claims] 1. The following general formula (1): [In the formula, R ¹ and R ² are the same or different and each represents a linear or branched alkyl group having 2 to 20 carbon atoms in which an oxygen atom may be inserted between carbon atoms, and A represents 1- Ethaneyl-2-ylidene group or 1-ethenyl-2-ylidene group is shown, and two Xs are the same or different and are hydrogen atom or -SO ₃
2 to 4 M are the same or different and represent a hydrogen atom, an alkali metal, an alkaline earth metal, a trialkylamine or a trialkanolamine. ] The amide ester carboxylic acid or its salt represented by these. 2. The amide ester carboxylic acid or a salt thereof according to claim 1, wherein two X's in the general formula (1) are both hydrogen atoms. 3. In the general formula (1), A is 1-ethanyl-2.
An amide ester carboxylic acid or a salt thereof according to claim 1, which is an -ylidene group, and two X's are both -SO ₃ M. 4. The following general formula (2): [In the formula, R ¹ and R ² are the same or different and each represents a linear or branched alkyl group having 2 to 20 carbon atoms in which an oxygen atom may be inserted between the carbon atoms. ] The amide ester carboxylic acid of Claim 2 or its salt is made to react with the amino alcohol represented by these, and succinic anhydride or maleic anhydride. 5. The following general formula (2): [In the formula, R ¹ and R ² are the same or different and each represents a linear or branched alkyl group having 2 to 20 carbon atoms in which an oxygen atom may be inserted between the carbon atoms. ] The method for producing an amide ester carboxylic acid or a salt thereof according to claim 3, which comprises reacting an amino alcohol represented by the following formula with maleic anhydride to form a maleic acid ester and then reacting with a sulfonating agent. 6. A detergent composition comprising the amide ester carboxylic acid according to claim 1.