JPH04321656A - Production of n-long-chain acylaminocarboxylic acid or aminosulfonic acid type surfactant and cleaner composition containing the same surfactant - Google Patents

Abstract

PURPOSE:To extremely efficiently obtain the title surfactant having mildness to skin and excellent cleaning power, preventing thickening during acylation reaction without using specific facilities by using fatty acid chloride purified by a specific method as a raw material. CONSTITUTION:A fatty acid chloride obtained by reacting phosphorus trichloride with a fatty acid and partially or wholly distilling under <=200mmHg, especially 0.1-100mmHg reduced pressure at normal temperature or under heating at about 30-100 deg.C by a batch process while introducing an inert gas such as N2 into the reaction mixture to purify the fatty acid chloride is used as a fatty acid chloride in the reaction and reacted with an aminocarboxylic acid or aminosulfonic acid in the presence of an alkali substance to give an N-long-chain acylaminocarboxylic acid or aminosulfonic acid type surfactant. A cleaner composition containing the surfactant has little irritation to skin and an eye and excellent cleaning power.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a method for producing an N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactant, which contains the surfactant, is mild to the skin, and has excellent detergency. The present invention relates to a cleaning composition having the following.

0002

[Prior Art and Problems to be Solved by the Invention] N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactants such as N-long chain acylglutamic acid and N-long chain acyl-β-alanine are It has been widely used recently because it has a bactericidal effect and is less irritating. Conventionally, these N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactants have been produced using the Schotten-Baumann method, in which a fatty acid chloride is reacted with an alkaline aqueous solution of an amino acid, and the method disclosed in Japanese Patent Publication No. 8685/1985, which is an improved invention thereof. It is produced by the method described in Japanese Patent Publication No. 51-38681, in which an aqueous amino acid solution containing a hydrophilic solvent is reacted with a fatty acid chloride in the presence of an alkaline substance. The fatty acid chloride used as the raw material is currently manufactured industrially from phosphorus trichloride and fatty acids, which are inexpensive and easy to produce.

[0003] When carrying out acylation using the fatty acid chloride produced using phosphorus trichloride as a raw material,
Since fatty acid chloride contains trace amounts of inorganic or organic phosphorus compounds, an excess of alkaline material is required for the reaction to maintain reactivity. There are also problems in that the reaction system becomes thicker due to the salt produced by neutralizing this, and the load in the desalting step after the reaction increases. In addition, when performing acylation using fatty acid chloride purified by distillation (Japanese Patent Application Laid-open No. 63-2962),
Since the amount of phosphorus compounds in fatty acid chloride can be reduced, highly pure N-long chain acylamino surfactants can be produced. There was a problem that chloride thermally decomposed.

On the other hand, methods for purifying fatty acid chloride include membrane treatment (Japanese Unexamined Patent Application Publication No. 64-19038), adsorption treatment (Japanese Unexamined Patent Publication No. 64-50839, Unexamined Japanese Patent Publication No. 1-2115).
47) and the removal of volatile substances by thin film distillation (Japanese Patent Application Laid-Open No. 64-50839), however, post-treatment is difficult with adsorption treatment, and thin film distillation requires a heavy equipment load. There were problems such as being large.

[0005] Therefore, there is a need for a method for efficiently producing N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactants without increasing the viscosity during the acylation reaction and reducing the load on equipment. was.

[0006]

[Means for Solving the Problems] Under these circumstances, the present inventors have conducted intensive research and found that if fatty acid chloride purified by a specific method is used, it will not thicken during the acylation reaction and will require less equipment. N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactants can be produced with low load and extremely efficiently, and furthermore, cleaning compositions containing the surfactants are mild to the skin;
Moreover, they discovered that it has excellent detergency, and completed the present invention.

That is, the present invention produces an N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactant by reacting a fatty acid chloride with an aminocarboxylic acid or an aminosulfonic acid in the presence of an alkaline substance. In this method, after reacting phosphorus trichloride with a fatty acid, one of the low-boiling substances is added under reduced pressure of 200 mmHg or less and at room temperature to elevated temperature while blowing an inert gas into the reaction mixture and/or stirring. A method for producing an N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactant, characterized by using purified fatty acid chloride obtained by distilling part or all of it in a batch operation, and containing the surfactant. The present invention provides a cleaning composition that cleanses the skin.

The fatty acid chloride used in the present invention is preferably a linear or branched saturated or unsaturated fatty acid chloride having 8 to 24 carbon atoms, such as lauroyl chloride, palmitoyl chloride, stearoyl chloride, oleoyl chloride, etc. In addition to fatty acid chloride having a single composition, mixed fatty acid chlorides such as coconut oil fatty acid chloride and beef tallow fatty acid chloride can also be used.

In the present invention, the fatty acid chloride is prepared by adding 1 to 2 times the equivalent of phosphorus trichloride to the fatty acid at 50 to 70°C.
It is added over a period of 0.5 to 2 hours, aged for 1 to 5 hours, and left to stand for about 1 to 24 hours to remove the phosphorous acid in the lower layer.
The product used is one produced by distilling off part or all of the low-boiling point substances in a batch operation under reduced pressure of 200 mmHg or less and at room temperature or elevated temperature while blowing inert gas and/or stirring. Examples of the inert gas used here include nitrogen, helium, neon, argon, etc., with nitrogen being particularly preferred. Distillation of low-boiling substances is carried out under reduced pressure of 200 mmHg or less, but in particular
It is preferable to carry out under reduced pressure of 0.1 to 100 mmHg. Also, the temperature at this time is 30 to 100°C, especially 30°C.
~70°C is preferred, 0.5 to 50 hours, especially 0.5
It is preferable to carry out the distillation treatment for ~10 hours. Note that the low-boiling substances distilled off by this treatment include phosphorus trichloride, hydrogen chloride, and the like.

In the present invention, the condensation reaction of fatty acid chloride and aminocarboxylic acid or aminosulfonic acid is carried out using, for example, 1 to 2 equivalents of aminocarboxylic acid or aminosulfonic acid and 2 to 4 equivalents of an alkali substance relative to the fatty acid chloride. Adding the fatty acid chloride obtained as described above to the aqueous solution at -5 to 30°C over 0.5 to 5 hours,
This is done by aging for 1 to 5 hours at the same temperature or 40 to 70°C. Examples of the aminocarboxylic acid or aminosulfonic acid used here include glycine, glutamic acid, aspartic acid, sarcosine, β-alanine, N-
Examples include methyl-β-alanine and taurine. Note that both optically active forms and racemic forms of glutamic acid and aspartic acid can be used. When glutamic acid or aspartic acid is used, it is preferable to add a hydrophilic solvent such as acetone and dropwise add an alkaline aqueous solution at the same time, as described in Japanese Patent Publication No. 46-8085. In addition, as an alkaline substance,
Among inorganic bases and organic bases, alkali metal hydroxides, carbonates, hydrogen carbonates, and aqueous solutions thereof are particularly preferred. In addition, if an N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactant that does not contain an 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 then precipitated. The resulting N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactant may be separated by filtration or extracted with a suitable solvent, and then dried or neutralized with an inorganic or organic base.

The N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactants of the present invention thus obtained include, for example, N-long chain acylglycine, N-long chain acylglutamic acid, N-long chain acylglutamic acid, Acyl aspartic acid, N-long chain acyl sarcosine, N-long chain acyl-β-alanine, N-long chain acyl-N-methyl-β-alanine,
Examples include N-long chain acyltaurine and salts thereof, and salts include, in particular, alkali metal salts such as sodium salts and potassium salts, alkanolamine salts such as ammonium salts and triethanolamine salts, and basic amino acid salts such as lysine salts. Salt is preferred.

The cleaning composition of the present invention contains the N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactant produced by the above method, preferably in an amount of 0.5 to 50%.
% by weight, and auxiliary agents such as pigments, fragrances, solubilizers, builders, etc. can be blended as necessary. In addition, for the purpose of adjusting detergency and foaming, other anionic surfactants, amphoteric surfactants, nonionic surfactants, etc. can be blended, and such surfactants include ordinary detergent compositions. For example, fatty acid soaps, higher alcohol sulfate ester salts, polyoxyethylene higher alcohol phosphate esters and their salts, sulfonated higher fatty acid alcohol sulfate ester salts, and higher alcohol sulfosuccinate ester salts. , isethionic acid higher fatty acid ester salt, α-sulfohate alcohol acetate ester salt, dialkyl dimethyl ammonium salt, fatty acid alkanolamide and its ethylene oxide condensate, polyoxyethylene higher fatty acid monoethanolamide phosphate ester, N-acyl peptide salt, Alkyliminodiacetates, higher alkylamine oxides, higher alkylamidoamine oxides,
Examples include higher alkyl dimethyl betaine and higher alkyl azide betaine.

The cleaning composition of the present invention can be manufactured according to a conventional method and can be applied to a wide range of uses such as shampoo, body shampoo, liquid soap, and kitchen detergent.

[0014]

According to the present invention, by using fatty acid chloride from which low-boiling substances have been distilled off in batch-type reaction equipment without using heavy equipment, N - Long chain acylaminocarboxylic acid or aminosulfonic acid type surfactants can be produced. Further, the cleaning composition containing the N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactant of the present invention is less irritating to the skin and eyes and has excellent cleaning power.

[0015]

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 Production of N-lauroyl-β-alanine: Lauric acid 30
00g (15 mol) was dissolved at 50°C, and phosphorus trichloride 1
After adding 030 g (7.5 mol) over about 2 hours, the mixture was stirred at 50 to 60°C for about 1 hour. After the reaction, the mixture was allowed to stand at 50° C. for 24 hours, and then the phosphorous acid in the lower layer was removed to obtain 3331 g of crude lauric acid chloride. This product has a free fatty acid content of 1.6%, a phosphorus content of 1.1%, and a purity of 93.5%.
Met. From 1500 g of this crude lauric acid chloride, low-boiling components were distilled off at 1 mmHg and 50° C. for 1 hour while blowing nitrogen, to obtain 1410 g of purified lauric acid chloride. This stuff contains 1.6% free fatty acids,
The phosphorus content was 0.09% and the purity was 98.0%. 90.1 g (1.0 mol) of β-alanine was dissolved in 377 ml of water, and 107 g of 48% potassium hydroxide aqueous solution was added to this.
was added to obtain a β-alanine potassium salt aqueous solution. While maintaining this at 15-20°C, 200g of purified lauric acid chloride was added to 171g of 30% potassium hydroxide aqueous solution.
The mixture was added over a period of 1.5 hours while adjusting the pH to 11.5. The viscosity after the addition was completed was 2500 cP. After the addition was completed, the mixture was further stirred at the same temperature for 1 hour,
The pH was adjusted to 2 by adding 36% hydrochloric acid, and the precipitated crude crystals of N-lauroyl-β-alanine were filtered and dried. The yield of crude crystals was 245 g. The phosphorus content of this product was 0.014%.

Comparative Example 1 Production of N-lauroyl-β-alanine: Using the unpurified lauric acid chloride obtained in Example 1, a reaction was carried out in the same manner as in Example 1. The viscosity at the end of the reaction is 20000c
This was treated with P in the same manner as in Example 1 to obtain 230 g of crude crystals of N-lauroyl-β-alanine. The phosphorus content of this product was 0.022%.

Example 2 Production of N-stearoyl-β-alanine: Using 284 g of stearic acid, 305 g of crude stearic acid chloride was obtained in the same manner as in Example 1. This product had a free fatty acid content of 2.0%, a phosphorus content of 1.1%, and a purity of 93.1%. From 150 g of this crude stearic acid chloride, nitrogen was blown into the mixture at 30 mmHg and 70°C while stirring.
The low boiling point components were distilled off over 5 hours to obtain 140 g of purified stearic acid chloride. This product had a free fatty acid content of 2.1%, a phosphorus content of 0.1%, and a purity of 97.5%. Dissolve 42.6 g (0.48 mol) of β-alanine and 26.7 g of potassium hydroxide in 550 ml of water, and
While maintaining at 30℃, purified stearic acid chloride 1
20 g was added over about 2 hours simultaneously with 46.3 g of a 48% aqueous potassium hydroxide solution at a pH in the range of 11 to 13. The viscosity after the addition was completed was 2700 cP. After the addition was completed, the mixture was further stirred at the same temperature for 1.5 hours.
The pH was adjusted to 1 by adding 6N hydrochloric acid, and the precipitated crude crystals of N-stearoyl-β-alanine were filtered and dried. The yield of crude crystals was 135 g. The phosphorus content of this product is
It was 0.010%.

Comparative Example 2 Production of N-stearoyl-β-alanine: Using the unpurified stearic acid chloride obtained in Example 2,
The reaction was carried out in the same manner. The viscosity at the end of the reaction is 1500
At 0 cP, this was treated in the same manner as in Example 2 to obtain 132 g of crude crystals of N-stearoyl-β-alanine. The phosphorus content of this product was 0.018%.

Example 3 Production of N-cocoylglycine: 501 g of coconut oil fatty acid
545 g of crude coconut oil fatty acid chloride was obtained in the same manner as in Example 1. This is free fatty acid 1.
8%, phosphorus content 1.0%, and purity 93.8%. From 240 g of this crude coconut oil fatty acid chloride, low boiling point components were distilled off over 6 hours at 200 mmHg and 50° C. while blowing nitrogen, to obtain 216 g of purified coconut oil fatty acid chloride. This product had a free fatty acid content of 1.8%, a phosphorus content of 0.1%, and a purity of 97.8%. Glycine 1
03 g (1.40 mol) and 55 g of sodium hydroxide were dissolved in 1110 ml of water, and while maintaining the temperature at 20 to 30°C, 200 g of purified coconut oil fatty acid chloride was adjusted to pH 11.5 using 75 g of a 48% aqueous sodium hydroxide solution. The mixture was added over a period of approximately 1.5 hours while being adjusted. The viscosity at the end of the addition was 2000 cP. After the addition was completed, the mixture was further stirred at the same temperature for 2 hours, and then the pH was adjusted to 1 by adding 36% hydrochloric acid, and the precipitated crude crystals of N-cocoylglycine were separated by filtration and dried. The yield of crude crystals was 250 g. The phosphorus content of this product was 0.012%.

Comparative Example 3 Production of N-cocoylglycine: Using the unrefined coconut oil fatty acid chloride obtained in Example 3, a reaction was carried out in the same manner as in Example 3. The viscosity at the end of the reaction is 10,000 cP,
This was treated in the same manner as in Example 3 to obtain 245 g of crude crystals of N-cocoylglycine. The phosphorus content of this product is 0.
It was 0.032%.

Example 4 Production of N-oleoylglycine: 500 g of oleic acid
The reaction and treatment were carried out in the same manner as in Example 1, to obtain 528 g of purified oleic acid chloride. This product had a free fatty acid content of 3.1%, a phosphorus content of 0.22%, and a purity of 95.9%. 89.9 g (1.20 mol) of glycine and 60 mol of water
Dissolve in a mixed solvent of 0 ml and 200 ml of acetone, 48
% aqueous sodium hydroxide solution was added. While maintaining this aqueous solution at 20 to 30°C, 200 g of purified oleic acid chloride was adjusted to pH 11.5 using 56 g of 48% sodium hydroxide aqueous solution, and the pH was adjusted to about 1.
It was added over a period of 5 hours. Viscosity at the end of addition is 2600c
It was P. After the addition was completed, the mixture was further stirred at the same temperature for 2 hours, and then 36% hydrochloric acid was added to adjust the pH to 2, and the precipitated N
- Crude crystals of oleoylglycine were filtered and dried. The yield of crude crystals was 218 g. The phosphorus content of this product was 0.010%.

Comparative Example 4 Production of N-oleoylglycine: Using the unpurified oleic acid chloride obtained in Example 4, a reaction was carried out in the same manner as in Example 4. The viscosity at the end of the reaction was 11,000 cP,
This was treated in the same manner as in Example 4 to obtain 220 g of crude crystals of N-oleoylglycine. The phosphorus content of this product is 0.
It was 0.035%.

Example 5 Production of N-lauroylglycine: 75 g of glycine (1.
00 mol) was dissolved in 340 ml of water, and 117 g of a 48% sodium hydroxide aqueous solution was added thereto to obtain a glycine potassium salt aqueous solution. Next, while maintaining this at 15 to 20°C, 200 g of the purified lauric acid chloride obtained in Example 1 was added to 172 g of a 30% aqueous potassium hydroxide solution.
The mixture was added over a period of about 1.5 hours while adjusting the pH to 11.5 using g. The viscosity at the end of the addition was 1800 cP. After the addition was completed, the mixture was further stirred at the same temperature for 1 hour, and then the pH was adjusted to 1 by adding 36% hydrochloric acid, and the precipitated crude crystals of N-lauroylglycine were filtered out and dried. The yield of crude crystals was 230 g. The phosphorus content of this product is 0
．． It was 0.018%.

Comparative Example 5 Production of N-lauroylglycine: Using the unpurified lauric acid chloride obtained in Example 1, a reaction was carried out in the same manner as in Example 5. The viscosity at the end of the reaction was 18,000 cP,
This was treated in the same manner as in Example 5 to obtain 232 g of crude crystals of N-lauroylglycine. The phosphorus content of this product is 0.
It was 0.40%.

Comparative Example 6 Production of N-lauroylglycine: From 500 g of the unpurified lauric acid chloride obtained in Example 1, low boiling point components were distilled off at 500 mmHg and 50° C. for 6 hours while blowing nitrogen, and 496 g was obtained. Purified lauric acid chloride was obtained. This product had a free fatty acid content of 1.6%, a phosphorus content of 0.77%, and a purity of 95.0%. A reaction was carried out in the same manner as in Example 5 using the obtained purified lauric acid chloride. The viscosity at the end of the reaction was 16,000 cP, and this was treated in the same manner as in Example 5 to obtain 228 g of crude crystals of N-lauroylglycine. The phosphorus content of this product is 0.04
It was 1%.

As is clear from the results of Examples 1 to 5 and Comparative Examples 1 to 6, according to the present invention, by using fatty acid chloride from which part or all of the low boiling point substances have been distilled off, the acylation reaction can be carried out. It was possible to efficiently produce an N-long chain acylaminocarboxylic acid or sulfonic acid type surfactant without increasing the viscosity, and it was also possible to reduce the phosphorus content in the obtained surfactant.

Test Example 1 A liquid detergent composition prepared by a conventional method using N-lauroyl-β-alanine was examined for solubility, foaming, and amount of residual phosphorus. The results are shown in Table 1. (Ingredients) N-lauroyl-β-alanine
25 (wt%) Purified water
balance(
Evaluation method) Solubility: Appearance at 10°C was determined and evaluated visually according to the following criteria. ○; Transparent △; Slightly cloudy ×; Crystals precipitated, opaque or with sediment Foaming: 10
Prepare a twice diluted aqueous solution and add 100ml of this solution (liquid temperature: 4
0°C and 20°C) into a graduated cylinder. Next, a stirring blade is placed in the above solution, and the volume (ml) of foam generated 30 seconds after the start of stirring is measured, and this is defined as the amount of foaming, and 200 ml or more is considered good (○).
, Less than 200 ml was determined to be insufficient (×). Note that the rotation speed of the stirring blade was 1000 rpm, and the rotation speed was reversed every 5 seconds.

[0028]

[Table 1]

As is clear from the results in Table 1, when N-lauroyl-β-alanine produced by the method of the present invention is used, the amount of residual phosphorus is reduced compared to that produced using untreated acid chloride. Furthermore, it is possible to obtain a cleaning agent with performance equivalent to that produced using distilled acid chloride.

Example 6 (Components) (1) N-lauroylglycine triethanolamine salt 25 (wt%) (2) Cocoyl isethionic acid
5 (3) Flavorings

0.5
(4) Ethanol

3 (5) Water

Balance Ingredients (1) in heated water
After dissolving and cooling components (3) and (4), a liquid cleaning composition was produced. When the skin and hair were washed with the obtained detergent composition, it was confirmed that it was a detergent with excellent performance, with little irritation and good foaming and foam removal.

Example 7 (Components) (1) N-lauroyl-β-alanine triethanolamine salt 25 (wt%) (2) Lauryl glycoside (degree of sugar condensation 1.4)
5 (3) Lauric acid diethanolamide
2 (4) Fragrance


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 cleaning composition. When the skin and hair were washed with the obtained detergent composition, it was confirmed that it was a detergent with excellent performance, with little irritation and good foaming and foam removal.

Claims (12)

[Claims] Claim 1. A method for producing an N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactant by reacting a fatty acid chloride with an aminocarboxylic acid or an aminosulfonic acid in the presence of an alkaline substance, comprising: After reacting phosphorus chloride and fatty acid, while blowing an inert gas into the reaction mixture and/or stirring, 2.
N-long chain acylaminocarboxylic acid or A method for producing an aminosulfonic acid type surfactant. 2. The production method according to claim 1, wherein the low boiling point substance contains phosphorus trichloride and/or hydrogen chloride. 3. The manufacturing method according to claim 1 or 2, wherein the low boiling point substance is distilled off at 30 to 100°C. 4. The production method according to claim 1, wherein the low boiling point substance is distilled off for 0.5 to 50 hours. [Claim 5] The total number of carbon atoms in the fatty acid chloride is 8 to 2.
5. The manufacturing method according to any one of claims 1 to 4. 6. The aminocarboxylic acid or aminosulfonic acid is at least one selected from glycine, glutamic acid, aspartic acid, sarcosine, β-alanine, N-methyl-β-alanine, and taurine.
5. The manufacturing method described in any of the items. 7. The production method according to claim 1, wherein the alkaline substance is an alkali metal hydroxide, carbonate, or hydrogen carbonate, or an aqueous solution containing these. 8. The manufacturing method according to claim 1, wherein the inert gas is nitrogen, helium, neon or argon. 9. The N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactant is an N-long chain acylamino acid, an N-long chain acylamino acid alkali metal salt, an N-long chain acylamino acid alkanolamine salt, The method according to claim 1, which is an N-long chain acylamino acid ammonium salt or an N-long chain acylamino acid basic amino acid salt. 10. After reacting phosphorus trichloride with a fatty acid, a low boiling point substance is reacted with the reaction mixture under reduced pressure of 200 mmHg or less and at room temperature or elevated temperature while blowing an inert gas into the reaction mixture and/or while stirring. An N-long chain acylaminocarboxylic acid obtained by reacting a purified fatty acid chloride obtained by distilling off part or all of it in a batch operation with an aminocarboxylic acid or an aminosulfonic acid in the presence of an alkaline substance. Or a cleaning composition characterized by containing an aminosulfonic acid type surfactant. 11. The cleaning composition according to claim 10, wherein the long chain acyl groups of the N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactant have a total carbon number of 8 to 24. 12. The N-long chain acylaminocarboxylic acid or aminosulfonic acid type surfactant is N-long chain acylglycine, N-long chain acylglutamic acid, N-long chain acylaspartic acid, N-long chain acyl sarcosine. , N-long chain acyl-β-alanine, N-long chain acyl-N-methyl-β
The cleaning composition according to claim 10 or 11, which is at least one selected from -alanine, N-long chain acyltaurine, and alkali metal salts, ammonium salts, alkanolamine salts, and basic amino acid salts thereof.