JPH11322688A - N-acylamino acids, anionic surfactant, detergent composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel N-acyl amino acid that has low stimulation to human body, excellent resistance to hard water, good foaming properties and foam feeling and is useful as an anionic surfactant and a variety of detergent composition. SOLUTION: This compound is represented by formula I (R<1> is a 7-21C alkyl, an alkenyl, a hydroxyalkyl; M is H, a salt-forming cationic ion; n is 1-3), typically N-lauroyl-N-(2,3-dihydroxypropyl)glycine. The compound of formula I is prepared by reaction of an amino acid derivative of formula II, for example, N-(2,3-dihydroxypropyl)glycine sodium or the like with a fatty acid halide of the formula: R<1> COX (X is a halogen), as lauroyl chloride, preferably in an amount of 0.8-1.2 equivalent in a solvent such as water or the like at 10-60 deg.C, as the liberating hydrogen halide is neutralized with an alkali, for example, caustic soda.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel N-acylamino acid compound which has low irritation to the skin, has foaming properties even in hard water, and has excellent surfactant properties, and an anionic surfactant comprising the same. The present invention relates to a cleaning composition comprising:

[0002]

2. Description of the Related Art Surfactants used as detergent raw materials such as dishwashing vegetable detergents, shampoos, and fashionable detergents not only have various performances such as detergency and foaming, but also are biodegradable and environmentally safe. It is necessary to have excellent properties and stability to the human body such as hand skin, hair and eyes. Acyl amino acid salts, alkyl glucosides, (amide) ether carboxylate salts, acyl imino dibasic salts, and the like have been used to satisfy these demands. It is not sufficient in solubility and foaming.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to provide a surface active compound which is less irritating to the human body, hard water resistant, foams, and has an excellent foam feel, and a detergent composition containing the same. The subject.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies on surfactants such as N-acylamino acids which are mild to the skin, have excellent hard water resistance, foam, and have a good foam feel. It has been found that an N-acylamino acid type surfactant having a 2,3-dihydroxypropyl group therein is effective, and the present invention has been completed. That is, according to the present invention, N- represented by the following general formula (1)
An acylamino acid compound, an anionic surfactant comprising the same, and a detergent composition containing the same are provided.

Embedded image [R ¹ : an alkyl group, alkenyl group or hydroxyalkyl group having 7 to 21 carbon atoms; M: a hydrogen atom or a salt-forming cation; n;

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (1), R ¹
Represents an alkyl group, an alkenyl group or a hydroxyalkyl group, and each of those groups has 7 to 21 carbon atoms.
Preferably it is 9-17. Each of those groups can be linear or branched. Specific examples of R ¹ include n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-pentadecyl group, and n. -A heptadecyl group, a heptadecenyl group, an ethylpentyl group, a methylhexadecyl group and the like. Among them, an alkyl group and an alkenyl group having 9 to 17 carbon atoms are particularly preferable.

M represents a hydrogen atom or a salt-forming cation. Salt-forming cations include alkali metal ions, alkaline earth metal ions and ammonium ions. Examples of the alkali metal ion include Na ion, K ion and Li ion, and examples of the alkaline earth metal ion include Ca ion and Mg ion.
Ammonium ions include NH ₄ ions and organic ammonium ions. Examples of the organic ammonium ion include those derived from alkanolamines such as monoethanolammonium ion, diethanolammonium ion, and triethanolammonium ion, and various organic amines, for example, those derived from ethylenediamine, propylenediamine, and the like. .
Examples of the cation M include hydrogen, Na, K, and M.
g, ammonium, triethanolammonium, ammonium from ethylenediamine and ammonium from propylenediamine are preferred.

The compound of the general formula (1) is obtained by reacting a fatty acid halide (R ¹ COX, X: halogen) with an amino acid derivative (2) represented by the following general formula (2) as a raw material. It is manufactured by

Embedded image The reaction between the compound (2) and the fatty acid halide occurs at 0.8 to 1.2 equivalents of the fatty acid halide with respect to the amine in a solvent such as water, methanol, ethanol, isopropanol, or acetone at 10 to 60 ° C. The reaction is carried out while neutralizing the hydrogen halide with an alkali. As the halide, a corresponding cloth or bromide is preferable.

As a method for producing the amino acid derivative (2) represented by the general formula (2), for example, the following method can be shown. A method of adding equimolar glycidol to amino acids such as glycine, β-alanine, α-alanine, and γ-aminobutanoic acid. The reaction in this case is represented by the following formula.

Embedded image A method in which 2,3-dihydroxypropylamine is reacted with an equimolar haloalkanoate such as monochloroacetate, α-chloropropionate, β-chloropropionate, and γ-chlorobutanoate. The reaction in this case is represented by the following formula.

Embedded image A method in which an equimolar amount of acrylonitrile is added to 2,3-dihydroxypropylamine and hydrolyzed with an alkali or an acid. The reaction in this case is represented by the following formula.

Embedded image A method of reacting 2,3-dihydroxypropylamine with an equimolar lactone.

The surfactant represented by the general formula (1) according to the present invention is less irritating to skin, hair and the like,
Bubbling and good detergency. Detergent compositions containing these include clothing detergents, dish and vegetable detergents, residential detergents, shampoos, body shampoos, hand soaps,
It is effective as a foaming agent for toothpaste and a cleaning agent for precision parts such as electronic parts.

The surfactant of the present invention represented by the general formula (1) can form a stable composition not only by itself but also by mixing with other surfactants. As surfactants that can be used in combination, all anionic surfactants,
There are nonionic surfactants, amphoteric surfactants, and cationic surfactants, but since they are mild surfactants for the human body such as skin and hair, they are preferably used in combination with mild surfactants. Specific examples are shown below.

(Anionic surfactant) Alkyl sulfate, polyoxyethylene alkyl sulfate,
Fatty acid salts, alkylbenzene sulfonates, alkyl sulfonates, α-olefin sulfonates, α-sulfofatty acid ester salts, alkyl or hydroxyalkyl ether carboxylates, N-acylated taurides, N-acylated methyl taurides, N-acyl-N-methyl tauride, N-acylated glycine, N-acylated aspartic acid, N-acylated sarcosine, N-acylated glutamic acid, monoalkyl phosphate ester salt, acyl amino acid, alkyl amide ether sulfate Fatty acid monoglyceride sulfate, alkyl iminodicarboxylate, secondary amide type N-acyl amino acid salt, tartaric acid alkylamide, malic acid alkylamide, citric acid alkylamide and the like.

(Nonionic surfactant) Alkyl polyhydric alcohol ether, hydroxyalkyl polyhydric alcohol ether, higher alcohol ethoxylate, higher alcohol ethoxypropoxylate, nonylphenol ethoxylate, fatty acid alkanolamide, sucrose fatty acid ester, alkyl (poly) Glycoside, polyglycerin fatty acid ester, fatty acid 2,3-dihydroxypropylamide, fatty acid polyoxyethylene amide, alkylamine oxide, alkylamidoamine oxide, polyoxyethylene fatty acid ester, methyl or ethyl glycoside fatty acid ester, acyl glucamide and the like.

(Amphoteric surfactant) Amido-amino acid type amphoteric surfactant, carboxybetaine, phosphobetaine, sulfobetaine, imidazolium betaine, glycine type,
Alanine type amino acid type amphoteric surfactants and the like.

(Cationic surfactant) Mono- or di-alkyl quaternary ammonium salts, mono- or di-alkyl quaternary ammonium salts having an amide group and / or an ester group, or their hydrochlorides, sulfates, organic acid salts and the like.

In the present invention, it is particularly preferable to use an amide type nonionic surfactant represented by the following general formulas (3) and (4) in combination, and this combination has a synergistic effect in terms of foaming. Is expressed.

Embedded image

Embedded image Here, R ² and R ⁵ represent a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, and R ³ represents a hydrogen atom, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, or 2,3- Indicates a dihydroxypropyl group. R ⁴
Represents a hydroxyalkyl group having 1 to 4 carbon atoms or a 2,3-dihydroxypropyl group.

When the surfactant (A) of the general formula (1) of the present invention is mixed with another surfactant (B), the mixing ratio (A) / (B) is expressed by weight. 99 /
It is 1/20/80, preferably 95/5 to 40/60. If the mixing ratio is lower than the above, the characteristics of the surfactant of the present invention cannot be sufficiently exhibited. The amount of the surfactant of the present invention in the detergent composition varies depending on the dosage form of the detergent, but is 0.5 to 50% by weight of the composition in a liquid state, and 1 to 50% by weight in a paste form. 70% by weight, 1 to 80 in case of solid
% By weight is preferred. PH when detergent is dissolved in water
Although it varies depending on the type and use of the active agent to be blended, the preferable range is pH 4 to 8 for shampoo, body shampoo and kitchen detergent, and 6 to 11 for clothing detergent. If the pH is out of the above range, it is not preferable in terms of irritation to the skin and damage to the object to be washed.

The cleaning composition of the present invention may contain, if necessary, known auxiliary components to be added to the cleaning composition. Such auxiliary ingredients include builders, humectants,
Viscosity regulators, preservatives, anti-inflammatory agents, antioxidants, ultraviolet absorbers, sequestering agents, anti-migration agents, antibacterial agents, water-soluble polymer compounds, water-soluble inorganic salts, organic and Inorganic compounds, pearlescent agents, pigments, fragrances, enzymes,
Bleaching agents and the like.

[0018]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Production Example 1 (N-2,3-dihydroxypropyl) -glycine Na
Preparation of 2,3-dihydroxypropylamine 64 g, ethanol 250 g, and water 100 g were mixed and heated to 50 ° C.
70 g of sodium monochloroacetate was added as a solution in an aqueous ethanol solution, and the pH was adjusted with sodium hydroxide.
The reaction was carried out for 6 hours while maintaining the pH at 8 or more. The solvent was distilled off and dissolved in chloroform to remove insolubles.
68.5 g of sodium (2,3-dihydroxypropyl) -glycine were obtained. (Yield 77%)

Production Example 2 Production of sodium N- (2,3-dihydroxypropyl) -β-aminopropionate 250 g of 2,3-dihydroxypropylamine was added at 60 ° C.
Then, 106 g of acrylonitrile is gradually added dropwise with a dropping funnel while stirring. After completion of the dropwise addition, the mixture was further stirred at 60 ° C. for 2 hours to obtain N- (2,3-dihydroxypropyl) -β-aminopropionitrile. 88 g of sodium hydroxide is dissolved in 1500 g of purified water, and this sodium hydroxide solution is added dropwise to the obtained N- (2,3-dihydroxypropyl) -β-aminopropionitrile while refluxing the solution, thereby hydrolyzing. did. After neutralization, water and unreacted amine are topped and desalted to give N-
314 g of sodium (2,3-dihydroxypropyl) -β-aminopropionate was obtained. (Yield 85%)

Production Example 3 Production of sodium N- (2,3-dihydroxypropyl) -γ-aminobutanoate In the same manner as in Production Example 1, N- (2,3-dihydroxypropyl) -sodium γ-chlorobutanoate
Sodium (2,3-dihydroxypropyl) -γ-aminobutanoate was obtained. (Yield 72%)

Production Example 4 Production of N-lauroyl-N- (2,3-dihydroxypropyl) -glycine N- (2,3-dihydroxypropyl) obtained in Production Example 1
92.5 g of sodium glycine and 400 g of purified water
And the pH is adjusted to 10 to 11 with caustic soda at 20 ° C.
While maintaining the pH at 109 g, lauric chloride 109 g was gradually added dropwise. After completion of the dropwise addition, stirring was continued for another 2 hours. After the completion of the reaction, the pH was adjusted to about 2 with hydrochloric acid, extracted with ether, washed with water, dehydrated, and the ether was distilled off to give N-lauroyl-
N- (2,3-dihydroxypropyl) -glycine 13
4 g were obtained (81% yield). 1720 cm ^-1 in IR, 1
There was an absorption at 625 cm ^-1 .

Preparation Example 5 Sodium N-lauroyl-N- (2,3-dihydroxypropyl) -β-aminopropionate N- (2,3-dihydroxypropyl) obtained in Preparation Example 2
-Sodium β-aminopropionate (37.0 g) and purified water (200 g) were charged at 20 ° C. with caustic soda.
Lauric chloride 4 while maintaining H at 10-11
3.5 g was gradually added dropwise. After dropping, add 3 more
Stirring continued for hours. After completion of the reaction, the pH was adjusted to about 2 with hydrochloric acid, extracted with ether, washed with water, dehydrated, and the ether was distilled off. 61 g of N-lauroyl-N- (2,3-dihydroxypropyl) -γ-aminobutanoic acid was added. Was obtained (85% yield). 1720cm ^-1 in the IR, there has been absorbed into the 1625cm ^-1.

Production Example 6 Production of sodium N-lauroyl-N- (2,3-dihydroxypropyl) -γ-aminobutanoate N- (2,3-dihydroxypropyl) obtained in Production Example 3
-39.8 g of sodium γ-aminobutanoate and 150 g of purified water were charged, and the pH was adjusted to 1 with sodium hydroxide at 20 ° C.
43.5 g of lauric chloride while keeping at 0-11
Was gradually added dropwise. After completion of the dropping, stirring was continued for another 2 hours. After completion of the reaction, the pH was adjusted to about 2 with hydrochloric acid, extracted with ether, washed with water, dehydrated, and the ether was distilled off.
Lauroyl-N- (2,3-dihydroxypropyl)-
61 g of γ-aminobutanoic acid was obtained (yield 85%). IR
In 1720cm ^-1, there has been absorbed into the 1625cm ^-1.

Examples 1 to 5 and Comparative Examples 1 to 4 The N-acyl-amino acid compounds of the present invention were measured for solubility in hard water, foaming, and feel of foams by the following methods. Table 1 shows the results. 1) Hardening resistance Using artificial hard water adjusted to calcium chloride 5 ° DH,
A 0.5 wt% surfactant concentration aqueous solution was prepared, and the appearance of each sample solution was visually determined at room temperature. ；: Uniform and transparent and no precipitate was observed. Δ: Uniform translucent and slightly turbid. X: Separation, precipitation, and aggregation were observed in a non-uniform manner. 2) Foaming test Using artificial hard water adjusted to 10 ° DH with calcium chloride, a surfactant concentration of 0.5 wt% aqueous solution was prepared, and 0.4 wt% of liquid paraffin was added as a dirt component to the test solution, and 20 ml of test liquid was added. This was shaken 20 times at 40 ° C. using a 100 ml Epton tube, and the foam volume (ml) after 1 minute was measured. 3) Feeling of foam The hands were washed with a 0.5 wt% surfactant solution adjusted to pH 7, and the feeling of foam during washing was sensory evaluated. 4 points; fine bubbles and very creamy. 3 points; foam is creamy. 2 points; foam is slightly coarse. 1 point; foam is coarse.

[0026]

[Table 1]

The specific contents of the reference numerals shown in Table 1 are as follows. (Surfactant A) Compound represented by the following formula (5)

Embedded image (Surfactant B) a compound represented by the following formula (6)

Embedded image (Surfactant C) a compound represented by the following formula (7)

Embedded image (Surfactant D) a compound represented by the following formula (8)

Embedded image (Surfactant E) a compound represented by the following formula (9)

Embedded image (Surfactant F) Compound represented by the following formula (10)

Embedded image

Examples 6 to 10 Experiments were carried out in the same manner as in Example 1, except that a mixed surfactant was used as the surfactant. Table 2 shows the results. The surfactants A to E indicated by symbols in Table 2 have the same meaning as described above, and the specific contents of the surfactants [I] to [III] are as follows. (Surfactant [I]) a compound represented by the following formula (11)

Embedded image (Surfactant [II]) Compound represented by the following formula (12)

Embedded image (Surfactant [III]) Compound represented by the following formula (13)

Embedded image

[0029]

[Table 2]

Examples of the formulation of the cleaning composition of the present invention are shown below.

Formulation Example 1 A shampoo having the following composition was prepared (pH 5.0).
This shampoo was excellent in foaming and detergency, and had a good foam feel during use. Surfactant A 15 (% by weight) Polyoxyethylene (3) lauryl ether sulfate Na 5 lauroyl diethanolamide 2 lauryl amide propyl acetate betaine 1 cationized cellulose 0.1 sodium benzoate qs dyes, fragrance qs citric acid qs Purified water balance

Formulation Example 2 A shampoo having the following composition was prepared (pH 5.5).
This shampoo was excellent in foaming and detergency, and had a good foam feel during use. Surfactant B 10 (wt%) polyoxyethylene (4) sodium lauric amide ether sulfate 3 polyoxyethylene (3) dodecyl glucoside 3 2,3-dihydroxypropyl-lauric amide 3 hydroxyethyl cellulose 0.1 sodium benzoate Appropriate amount Dyes, flavors Appropriate amount Citric acid Appropriate amount Purified water Balance

Formulation Example 3 A dishwashing vegetable detergent having the following composition was prepared (pH 7.
0). This detergent had low irritation to the skin, foamed, and was excellent in detergency. Surfactant D 10 (% by weight) Polyoxyethylene (5) sodium laurine ether acetate 5 N-lauryl glyceramide 3 lauryl dimethylamine oxide 2 diglycerin lauryl ether 1 magnesium chloride 0.2 sodium paratoluenesulfonate 4 denatured ethanol 5 Sodium benzoate appropriate amount dye, flavor appropriate amount citric acid appropriate amount tap water balance

Formulation Example 4 A body shampoo having the following composition was prepared (pH 6.
0). This body shampoo was hypoallergenic to the skin, had excellent lathering, and had a good moist feeling after use. Surfactant A 8 (% by weight) Potassium monolauryl phosphate 6 Potassium laurate 2 Potassium myristate 2 Sucrose fatty acid ester 1 Stearic acid 3 Propylene glycol 6 Dyes and flavors Appropriate amount Citric acid Appropriate amount Triethanolamine Appropriate amount Purified water balance

Formulation Example 5 A body shampoo having the following composition was prepared (pH 6.
5). This body shampoo was hypoallergenic to skin, had excellent lathering, and had a good feel upon rinsing. Surfactant B 10 (wt%) Sodium N-lauryl malate monoamide 3 Polyoxyethylene (5) Sodium lauryl ether sulfosuccinate 2 Amidopropyl betaine laurate 3 Propylene glycol 3 Dye, perfume Appropriate amount Citric acid Appropriate amount Triethanolamine Appropriate amount Purification Water balance

[0036]

The N-acylamino acid compound of the present invention is
It is hypoallergenic to the human body and has excellent foaming properties, and is advantageously used as a surfactant and a detergent component in various detergent compositions.

Claims (3)

[Claims] 1. An N-acyl amino acid compound represented by the following general formula (1). Embedded image [R ¹ : an alkyl group, alkenyl group or hydroxyalkyl group having 7 to 21 carbon atoms; M: a hydrogen atom or a salt-forming cation; n; 2. An anionic surfactant comprising the N-acylamino acid compound of claim 1. 3. A cleaning composition comprising the anionic surfactant according to claim 2.