JPH0597787A - Process for producing N-long-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactant, and detergent composition containing the surfactant - Google Patents

Abstract

(57) [Summary] [Structure] (a) Distilled fatty acid chloride obtained by distilling a crude fatty acid chloride obtained by reacting carbonyl chloride with a fatty acid having 8 to 24 carbon atoms,
(B) A method for producing an N-long-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactant by reacting aminocarboxylic acid or aminosulfonic acid in the presence of an alkaline substance, and A detergent composition containing an activator. [Effect] By this method, a surfactant having a good hue and high purity can be obtained. Further, the detergent containing this surfactant has little irritation to the skin and eyes and has an excellent detergency.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an N-long-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactant and a surfactant containing the same, which has a good hue and is suitable for skin. The present invention relates to a detergent composition that is mild and has excellent detergency.

[0002]

BACKGROUND OF THE INVENTION N-long-chain acylaminocarboxylic acid or aminosulfonic acid type surfactants such as N-long-chain acylglutamic acid, N-long-chain acyl-β-alanine, etc. Since it has a bactericidal action and is low in irritation, it has been widely used recently. Conventionally, these N-
The long-chain acylaminocarboxylic acid or aminosulfonic acid type surfactant is a Schotten-Baumann (Schott) which reacts an alkaline aqueous solution of an amino acid with a fatty acid chloride.
en-Baumann) method or a method of reacting an amino acid aqueous solution containing a hydrophilic solvent with a fatty acid chloride in the presence of an alkaline substance as described in JP-B-51-38681, which is an improved invention thereof. ing.

The methods for industrially obtaining the fatty acid chloride as the starting material are roughly classified into a method of reacting phosphorus trichloride with a fatty acid and a method of reacting carbonyl chloride with a fatty acid. When a fatty acid chloride is produced from this phosphorus trichloride as a raw material, phosphorous acid is by-produced, and the method of treating or discarding it is a problem.

On the other hand, when fatty acid chloride is produced from carbonyl chloride as a raw material, the by-products are carbon dioxide and hydrogen chloride, and the facility load required for the treatment or disposal of them is small relative to phosphorous acid. However, in the reaction using carbonyl chloride as a raw material, although lower fatty acids show high reactivity, higher fatty acids have low reactivity and require a high reaction temperature. Therefore, the hue of the resulting fatty acid chloride is There is a drawback that it becomes worse (JP-A 64-19038). As a method for producing an N-long-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactant using such a fatty acid chloride, there is a method described in JP-A-61-216724. As a result of additional tests conducted by the inventors, there was a problem that the hue of the obtained N-long-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactant was not good.

Therefore, a method for producing an N-long chain acylaminocarboxylic acid or N-long chain acylaminosulfonic acid type surfactant having a good hue using a fatty acid chloride produced from carbonyl chloride and a fatty acid is desired. Was there.

[0006]

Under these circumstances, the inventors of the present invention have conducted extensive studies and as a result, as a result of using fatty acid chloride obtained by reacting carbonyl chloride with a fatty acid and then distilling it, an N-length having a good hue is obtained. A high-purity N-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactant can be produced, and the amount of unreacted fatty acid in the fatty acid chloride can be reduced by distillation.
-A long-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactant can be produced, and
The present invention has been completed by finding that a detergent composition containing the surfactant is mild to the skin and has an excellent detergency.

That is, the present invention relates to (b) a distilled fatty acid chloride obtained by distilling a crude fatty acid chloride obtained by reacting carbonyl chloride with a fatty acid having 8 to 24 carbon atoms, and (b) an aminocarboxylic acid. N-long-chain acylaminocarboxylic acid or N characterized by reacting an acid or an aminosulfonic acid in the presence of an alkaline substance
-To provide a method for producing a long-chain acylaminosulfonic acid type surfactant. The present invention also provides a detergent composition containing the N-long-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactant obtained as described above.

Examples of the fatty acid having 8 to 24 carbon atoms which is a raw material of the distilled fatty acid chloride used in the production method of the present invention include lauric acid, palmitic acid, stearic acid,
In addition to single-component fatty acids such as oleic acid, coconut oil fatty acids,
Examples include mixed fatty acids such as beef tallow fatty acid.

The reaction of these fatty acids with carbonyl chloride is preferably carried out, for example, in an amount equal to or more than the equivalent amount of carbonyl chloride in the absence of a catalyst or in the presence of a catalyst, at 60 to 160 ° C. for about 2 to 6 hours. Examples of the catalyst used here include dimethylformamide (Japanese Patent Publication No. 43-10613), quaternary ammonium salts, sulfonium salts (Japanese Patent Publication No. 44-273).
63), tetraalkylthiourea (Japanese Patent Publication No. 44-27)
762) and the like. Distillation of the obtained crude fatty acid chloride is 50 to 50 depending on the number of carbon atoms of the fatty acid used.
The conditions of normal pressure to 1 mmHg at 200 ° C. are preferable. Further, in the distillation, either a batch system or a continuous system may be adopted.

The condensation reaction of the thus-obtained distilled fatty acid chloride with aminocarboxylic acid or aminosulfonic acid is carried out, for example, with 1 to 2 equivalents of aminocarboxylic acid or aminosulfonic acid and 2 to 4 equivalents of alkaline substance with respect to the distilled fatty acid chloride. Distilled fatty acid chloride into the aqueous solution of
Add at ~ 50 ° C over 0.5-5 hours at the same temperature or 4
It is carried out by aging at 0 to 70 ° C. for 1 to 5 hours.
Examples of the aminocarboxylic acid or aminosulfonic acid used here include glycine, glutamic acid, aspartic acid, sarcosine, β-alanine, N-methyl-β-
Examples thereof include alanine, taurine, N-methyltaurine and the like. When glutamic acid or aspartic acid is used, it is preferable to add a hydrophilic solvent such as acetone and drop an aqueous alkali solution at the same time as described in JP-B-46-8085.

The alkaline substance is an inorganic base,
Of the organic bases, alkali metal hydroxides, carbonates, hydrogen carbonates or aqueous solutions thereof are particularly preferable. When an N-long-chain acylaminocarboxylic acid type surfactant containing no inorganic salt is desired, for example, as a post-treatment, the reaction solution is adjusted to pH 1 to 3 with an inorganic acid such as hydrochloric acid and precipitated N-
The long-chain acylaminocarboxylic acid type surfactant may be filtered out or extracted with a suitable solvent and dried, or may be neutralized with an inorganic base or an organic base.

The N-long chain acylaminocarboxylic acid or N-long chain acylaminosulfonic acid type surfactant of the present invention thus obtained is, for example, N-long chain acylglycine or N-long chain acylglutamic acid. , N-long chain acyl aspartic acid, N-long chain acyl sarcosine, N-long chain acyl-β-alanine, N-long chain acyl-N-methyl-
β-alanine, N-long-chain acyltaurine, N-long-chain acyl-N-methyltaurine and salts thereof can be mentioned, and as the salt, metal salts such as sodium salt and potassium salt,
Basic amino acid salts such as alkanolamine salts such as ammonium salts and triethanolamine salts and lysine salts are preferable.

The detergent composition of the present invention preferably contains 0.5 to 50% by weight of the N-long chain acylaminocarboxylic acid or N-long chain acylaminosulfonic acid type surfactant produced by the above method. If necessary, an auxiliary agent such as a dye, a fragrance, a solubilizing agent, a builder, etc. can be appropriately added.

For the purpose of adjusting the cleaning power and foaming,
Other anionic surfactants, amphoteric surfactants, nonionic surfactants, and the like can also be blended, and such surfactants are not particularly limited as long as they are used in ordinary detergent compositions. , For example, fatty acid soap, higher alcohol sulfate ester salt, polyoxyethylene higher alcohol phosphate ester and salts thereof, sulfonated higher fatty acid alcohol sulfate ester salt, α-sulfo higher alcohol acetate ester salt, dialkyldimethylammonium salt, fatty acid alkanolamide and The ethylene oxide condensate, polyoxyethylene higher fatty acid monoethanolamide phosphate, N-acyl peptide salt, alkyliminodiacetic acid salt, higher alkylamine oxide, higher alkylamidoamine oxide, higher alkyldimethylbetaine, higher alkyl Kill azide betaine, and the like. The detergent composition of the present invention can be produced according to a usual method, and can be applied to a wide range of applications such as shampoo, body shampoo, liquid soap, kitchen detergent and the like.

[0015]

INDUSTRIAL APPLICABILITY According to the present invention, by using a distilled fatty acid chloride obtained by reacting carbonyl chloride with a fatty acid and then distilling it, N-
Long-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactants can be produced. In addition, the N-long-chain acylaminocarboxylic acid or N-of the present invention
A detergent composition containing a long-chain acylaminosulfonic acid type surfactant has little irritation to the skin and eyes and has excellent detergency.

[0016]

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

Example 1 Preparation of N-lauroyl-glycine sodium salt 1000 g (5 mol) of lauric acid was dissolved to give 100-1
While maintaining the temperature at 10 ° C, carbonyl chloride was blown at a rate of 200 g / hour to carry out a reaction for 4 hours. After the reaction, nitrogen gas was passed under the reduced pressure at the same temperature at a rate of 20 l / hour for about 1 hour,
Excess carbonyl chloride was removed. The hue of this product is Gardner (hereinafter G) 10, and the free fatty acid is 1.5
%, And the purity was 98.0%. This crude product was distilled under reduced pressure with a glass distillation apparatus to obtain 1060 g of distilled lauric acid chloride. This product had a hue of APHA20, a free fatty acid of 0.15% and a purity of 99.8%. Glycine 83g
Was dissolved in 404 ml of water, and 92 g of a 48% sodium hydroxide aqueous solution was added thereto to obtain a glycine sodium salt aqueous solution. Then, while maintaining this at 15 to 20 ° C., 219 g of distilled lauric acid chloride was adjusted to pH 11.5 using 133 g of a 30% aqueous sodium hydroxide solution,
Added over about 1.5 hours. After the addition was completed, the mixture was further stirred at the same temperature for 1 hour to obtain 868 g of an aqueous solution containing 28.5% of N-lauroyl-glycine sodium salt. This product had a hue of G1 or less, and contained 1.1% of lauric acid.

Comparative Example 1 Production of N-lauroyl-glycine sodium salt A reaction was carried out in the same manner as in Example 1 using the undistilled lauric acid chloride obtained in Example 1. The obtained aqueous solution contained 27% N-lauroyl-glycine sodium salt and 2.1% lauric acid, and had a hue of G3.

Example 2 Production of N-lauroyl-glycine 35% hydrochloric acid was added to 868 g of an aqueous solution containing 28.5% of N-lauroyl-glycine sodium salt obtained in Example 1.
The pH was adjusted to 1, and the precipitated crude crystals of N-lauroylglycine were filtered off and dried. The yield of crude crystals was 253 g. This product has a whiteness of 98%, lauric acid of 3% and a purity of 9
It was 6%. Here, the whiteness is a color difference from a standard white plate and was measured using SZ-Σ80 manufactured by Nippon Denshoku Industries Co., Ltd.

Comparative Example 2 Production of N-lauroyl-glycine Using the aqueous solution containing 27% of N-lauroyl-glycine sodium salt obtained in Comparative Example 1, the same procedure as in Example 2 was carried out to obtain 252 g of crude crystals. It was This product has a whiteness of 92
%, Lauric acid 8%, and purity 91%.

Example 3 Preparation of N-lauroyl-β-alanine potassium salt 98 g of β-alanine was dissolved in 399 ml of water, and 4 g of this was dissolved.
129 g of 8% potassium hydroxide aqueous solution was added to obtain a β-alanine potassium salt aqueous solution. Then, from 20 ° C., 219 g of distilled lauric acid chloride obtained in Example 1 was added to 30%.
While adjusting the pH to 11.5 using 187 g of an aqueous potassium hydroxide solution, the solution was added over about 1.5 hours. At that time, the temperature of the reaction product was 48 ° C. Further, the mixture was stirred at 50 ° C. for 1 hour, and N-lauroyl-β-alanine potassium salt was added to 2
1032 g of an aqueous solution containing 8.5% was obtained. This product had a hue of G1 or less and contained 0.8% of lauric acid.

Comparative Example 3 Production of N-lauroyl-β-alanine potassium salt A reaction was carried out in the same manner as in Example 3 except that the undistilled lauric acid chloride obtained in Example 1 was used. The obtained aqueous solution contained 27% N-lauroyl-β-alanine potassium salt and 1.9% lauric acid, and had a hue of G3.

Example 4 Production of N-lauroyl-β-alanine 35% hydrochloric acid was added to 1032 g of an aqueous solution containing 27% of N-lauroyl-β-alanine potassium salt obtained in Example 3.
The pH was adjusted to 1, and the precipitated crude crystals of N-lauroyl-β-alanine were filtered off and dried. Yield of crude crystals is 267g
Met. This product has a whiteness of 98%, lauric acid of 3%,
The purity was 96%.

Comparative Example 4 Preparation of N-lauroyl-β-alanine 35% hydrochloric acid was added to 1032 g of an aqueous solution containing 27% of N-lauroyl-β-alanine potassium salt obtained in Comparative Example 3.
The pH was adjusted to 1, and the precipitated crude crystals of N-lauroyl-β-alanine were filtered off and dried. The yield of crude crystals is 263g
Met. This product has a whiteness of 92%, lauric acid 7%,
The purity was 92%.

Example 5 Preparation of N-cocoyl-N-methyl-taurine sodium salt
While maintaining dissolved granulated coconut oil fatty acid 1000g and (4.3 mole) of a mixture of dimethylformamide 20g to 80-90 ° C., blown carbonyl chloride at a rate of time 200 g /, the reaction was carried out for 4 hours. After the reaction, nitrogen gas was passed at a rate of 20 l / hour for about 1 hour under reduced pressure at the same temperature to remove excess carbonyl chloride. The hue of this product was G12, the free fatty acid was 1.7%, and the purity was 96.0%. This crude product was distilled under reduced pressure with a glass distillation apparatus to obtain 105
0 g of distilled lauric acid chloride was obtained. This product has a hue of APHA20, free fatty acids of 0.17% and purity of 99.7.
%Met. 153 g of N-methyl-taurine was added to 886 of water.
Dissolve it in ml and add 48% sodium hydroxide solution 9 to it.
2 g was added to obtain N-methyl-taurine sodium salt aqueous solution. Next, 255 g of distilled coconut oil fatty acid chloride was added while maintaining the temperature at 15 to 20 ° C., while adjusting the pH to 9.5 using 133 g of a 30% aqueous sodium hydroxide solution, and added over about 1.5 hours. After the addition was completed, the mixture was further stirred at the same temperature for 1 hour, and 1519 g of an aqueous solution containing 23.8% of N-cocoyl-N-methyl-taurine sodium salt.
Got This product had a hue of G1 or less and contained coconut oil fatty acid in an amount of 0.6%.

Comparative Example 5 Preparation of N-cocoyl-N-methyl-taurine sodium salt
Using the undistilled coconut oil fatty acid chloride obtained in Preparation Example 5,
The reaction was carried out in the same manner as in Example 5. The obtained aqueous solution is N-
Cocoyl-N-methyl-taurine sodium salt was added to 22.
It contains 5% and 1.6% coconut oil fatty acid, and the hue is G4.
Met.

Example 6 Preparation of N-stearoyl-β-alanine potassium salt 1000 g (3.5 mol) of stearic acid was dissolved to obtain 10
Carbonyl chloride 200g /
It was blown in at the speed of time and reacted for 4 hours. After the reaction, nitrogen gas was passed at a rate of 20 l / hour for about 1 hour under reduced pressure at the same temperature to remove excess carbonyl chloride. The hue of this product is G10, and the free fatty acid is 1.9% and the purity is 9
It was 8.0%. This crude product was distilled under reduced pressure using a glass distillation apparatus to obtain 1016 g of distilled stearic acid chloride. This product has a hue of APHA40 and free fatty acid of 0.19.
%, And the purity was 99.4%. 98 g of β-alanine was dissolved in 1137 ml of water, and 129 g of 48% potassium hydroxide aqueous solution was added thereto to obtain an aqueous β-alanine potassium salt solution. Then, at 20 ° C., 303 g of distilled stearyl chloride was added to 219 g of a 30% potassium hydroxide aqueous solution 219.
It was added over about 1.5 hours while adjusting the pH to 11.5 using g. The reaction temperature at that time was 51 ° C. The mixture was further stirred at 50 ° C. for 1 hour to obtain 1886 g of an aqueous solution containing 19.0% N-stearoyl-β-alanine potassium salt. It had a hue of G1 or less and contained 0.6% of stearic acid.

Comparative Example 6 Preparation of N-stearoyl-β-alanine potassium salt Using the undistilled stearic acid chloride obtained in Example 6,
The reaction was carried out in the same manner as in Example 6. The obtained aqueous solution is N-
18.0% of stearoyl-β-alanine potassium salt,
It contained 1.5% stearic acid and had a hue of G3. As is clear from the results of Examples 1 to 6 and Comparative Examples 1 to 6, according to the present invention, by using a distilled fatty acid chloride obtained by reacting carbonyl chloride with a fatty acid and then distilling it, A good N-long-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactant can be produced, and the amount of fatty acid in the fatty acid chloride can be reduced by distilling the fatty acid chloride, so that the purity can be improved. A high N-long chain acylaminocarboxylic acid or N-long chain acylaminosulfonic acid type surfactant could be produced.

Example 7 (Components) (1) N-lauroylglycine 17 (% by weight) (2) Triethanolamine 8 (3) Cocoyl isethionate 5 (4) Perfume 0.5 (5) Ethanol 3 (6) ) Water balance Components (1) to (3) were dissolved in heated water, and after cooling, components (4) and (5) were added to produce a liquid detergent composition. When the skin and hair were washed with the obtained cleaning composition, it was confirmed that the cleaning agent had less irritation and good foaming and defoaming, and had excellent performance.

Example 8 (1) 28.5% N-lauroyl-β-alanine 60 (wt%) potassium salt aqueous solution (2) lauroyl glycoside (sugar condensation degree 1.4) 5 (3) lauric acid diethanolamide 2 (4) Fragrance 0.5 (5) Ethanol 3 (6) Water balance Components (1) to (3) are dissolved in heated water, and after cooling, components (4) and (5) are added to wash the liquid. An agent composition was produced. When the skin and hair were washed with the obtained cleaning composition, it was confirmed that the cleaning agent had less irritation and good foaming and defoaming, and had excellent performance.

Claims (4)

[Claims] 1. (a) Carbonyl chloride and 8 to 24 carbon atoms
Distilled fatty acid chloride obtained by distilling the crude fatty acid chloride obtained by reacting with the fatty acid of
(B) N-characterized by reacting aminocarboxylic acid or aminosulfonic acid in the presence of an alkaline substance
A method for producing a long-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactant. 2. The aminocarboxylic acid or aminosulfonic acid is selected from glycine, glutamic acid, aspartic acid, sarcosine, β-alanine, N-methyl-β-alanine, taurine and N-methyltaurine. The manufacturing method described. 3. A detergent composition containing the N-long-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactant obtained by the production method according to claim 1. 4. A detergent composition containing an N-long-chain acylaminocarboxylic acid or N-long-chain acylaminosulfonic acid type surfactant obtained by the production method according to claim 2.