JPS632962A - Production of n-long-chain acylamino acid type surface active agent and liquid detergent composition containing said active agent - Google Patents

Abstract

PURPOSE:To obtain the titled compound neither producing turbidity nor precipitate even by blending with a liquid detergent and yet no fading dyestuff of the detergent, by reacting a fatty acid chloride obtained by distillation as a raw material with an amine acid in the presence of an alkali. CONSTITUTION:A distilled fatty acid chloride which is obtained by reacting phosphorus trichloride with a fatty acid and distillation is dripped for 0.5-5hr at -5-30 deg.C to an aqueous solution containing 0.1-1.5 equivalent amine acid and 2.2-3.3 equivalent alkali and aged at the same temperature or 40-60 deg.C to give the aimed compound. Glutamic acid, aspartic acid, sarcosine, beta-alanine and N-methyl-beta-alanine are used as the amino acid. 0.5-50wt% of the surface active agent is added to a liquid detergent composition, which is useful as a shampoo, body shampoo, liquid soap, detergent for kitchen, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Advantages The present invention relates to a method for producing an N-long chain acylamino acid type surfactant. To elaborate further,
The present invention relates to a method for producing an N-long chain acylamino acid type surfactant, which is characterized by reacting a fatty acid chloride obtained by distillation with an amino acid, and a liquid detergent composition containing the surfactant.

Obedience! l Branch- N-long chain acyl glutamate and N-long chain acyl-β-
N-long chain acylamino acid type surfactants such as alanine salts are hypoallergenic and have bacteriostatic action, and have recently been widely used. Cleaning agents containing these are known to have a mild effect on the skin and excellent cleaning power.

Methods for producing N-long chain acylamino acid type surfactants include the Schotten-Baumann method in which fatty acid chloride is reacted with an alkaline aqueous solution of amino acids, and improved inventions thereof, such as Japanese Patent Publication No. 46-8685 and Japanese Patent Publication No. 51-3868.
A method is known in which a fatty acid chloride is reacted with an aqueous amino acid solution containing a hydrophilic solvent in the presence of an alkali, as described in Japanese Patent No. 1.

At present, fatty acid chloride, which is a raw material for N-long chain acylamino acid type surfactants, is mostly industrially produced from phosphorus trichloride and fatty acids, which are inexpensive and easy to produce. N-long chain acylamino acid type surfactants that are manufactured using fatty acid chloride made from phosphorus trichloride as a raw material contain trace amounts of inorganic or organic phosphorus compounds. When such an N-long chain acylamino acid type surfactant is made into an aqueous solution, the quality deteriorates significantly due to phenomena such as deterioration of hue over time, turbidity, and precipitation, which are thought to be caused by phosphorus compounds, and liquids containing these. Detergent compositions also have the disadvantage of causing turbidity and precipitation, and furthermore, discoloring the pigments of the liquid detergent.

The present invention is based on N-- which does not cause turbidity or precipitation even when added to a liquid detergent, and does not discolor the pigment of the liquid detergent.
The object of the present invention is to provide a method for producing long-chain acylamino acid surfactants and a liquid detergent composition containing them.

The above-mentioned problems can be solved by using the distilled fatty acid chloride of the present invention obtained by reacting phosphorus trichloride with a fatty acid and then distilling the reaction.

That is, the present invention relates to a method for producing an N-long chain acylamino acid type surfactant by reacting a fatty acid chloride and an amino acid in the presence of an alkali. This invention relates to a method for producing an N-long chain acylamino acid type surfactant, which is characterized by condensing a distilled fatty acid chloride and an amino acid in the presence of an alkali, and to a liquid detergent composition containing the same.

In the method of the present invention, the fatty acid chloride is
/3 to 1/2 equivalent of phosphorus trichloride at 50 to 60℃
The mixture is added dropwise over 0 minutes, aged for 3 hours, left to stand for about 4 to 8 hours, and the phosphorous acid in the lower layer is removed, followed by distillation. For distillation, either a batch method or a continuous method may be used.

The fatty acid chloride in the present invention has 8 to 2 carbon atoms.
0 saturated or unsaturated fatty acid chlorides, such as single composition fatty acid chlorides such as lauroyl chloride, balmitoyl chloride, stearoyl chloride, and oleoyl chloride, as well as mixed fatty acid chlorides such as coconut oil fatty acid chloride and beef tallow fatty acid chloride. can be used as well.

The condensation reaction of distilled fatty acid chloride and amino acid in the method of the present invention is carried out by distillation at -5 to 30°C in an aqueous solution of 1.0 to 1.5 equivalents of amino acid and 2.2 to 3.3 equivalents of alkali based on distilled fatty acid chloride. Fatty acid chloride is cleaved at 0.5 to 5 hours and added dropwise, and aging is carried out at the same temperature or 40 to 70°C for 1 to 3 hours.

Amino acids used in the present invention include glutamic acid, aspartic acid, sarcosine, β-alanine and N-methyl-β
- At least one selected from alanine. Note that glutamic acid and aspartic acid may be either optically active forms or racemic forms. In addition, if the amino acid used as the raw material is glutamic acid or aspartic acid,
It is more advantageous to add a hydrophilic solvent such as acetone as described in Japanese Patent Publication No. 6-8085 and drop an alkaline aqueous solution at the same time.

If an N-long chain acylamino acid type surfactant that does not contain an inorganic salt is desired, the reaction solution is adjusted to pH 1 to 2 with an inorganic acid such as hydrochloric acid as a post-treatment to precipitate free N-long chain acylamino acid. The type surfactant may be filtered off or extracted with a suitable solvent, and then dried or neutralized with an inorganic or organic base.

Among inorganic bases and organic bases, sodium hydroxide and potassium hydroxide are particularly preferred as they are practical as the alkali used in the present invention.

The N-long chain acylamino acid type surfactants thus obtained include 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-alanine and salts thereof, and the salts are preferably basic amino acid salts such as sodium salt, potassium salt, ammonium salt, triethanolamine salt and lysine salt.

The liquid detergent composition, which is the other invention of the present invention, contains 0.5 to 50% by weight of the N-long chain acylamino acid type surfactant produced by the method of the present invention, and if necessary, , dyes, fragrances, solubilizers, builders, and other auxiliary agents can be added as appropriate. Furthermore, other anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. can be added for the purpose of adjusting detergency and foaming. These include, for example, fatty acid esters, higher alcohol sulfate ester salts, polyoxyethylene higher alcohol phosphate esters and their salts, sulfonated higher fatty acid alcohol sulfate ester salts, higher alcohol sulfosuccinate ester salts, and isethionic acid higher fatty acid esters. salt, α-sulfohigher alcohol acetate salt, dialkyldimethylammonium salt, fatty acid alkanolamide and its ethylene oxide condensate, polyoxyethylene higher fatty acid monoethanolamide phosphate, N-acyl peptide salt, alkyliminodiacetate, Examples include, but are not limited to, higher alkyl amine oxides, higher alkyl amide amine oxides, higher alkyl dimethyl betaines, and higher alkyl amide betaines.

Since the liquid detergent of the present invention causes little irritation to the skin and eyes, it can be applied to a wide range of uses such as shampoos, body shampoos, liquid soaps, and kitchen detergents.

Since the N-long chain acylamino acid type surfactant produced by the method of the present invention is made from fatty acid chloride obtained by distillation, it does not contain any inorganic or organic phosphorus compounds. It is thought that it will not cause turbidity or precipitation even if it is blended into liquid detergents.

After dissolving 200 g (1 mol) of lauric acid at 50°C, 69 g (0.5 mol) of phosphorus trichloride is added dropwise over about 30 minutes, followed by stirring at 50-60°C for 3 hours. After the reaction was left for 8 hours, the lower layer of phosphorous acid was removed to obtain 228 g of crude lauric acid chloride. This one has 1.2 free fatty acids
%, phosphorus content was 0.9%, and purity was 95%.

This crude lauric acid chloride was distilled using a glass distillation apparatus to obtain 212 g of distilled lauric acid chloride. This product has free fatty acids of 0.20%, phosphorus content of 0.04%, and purity of 9.
It was 9.5%.

Chestnut 11" - 14.7 g (0.1 mol) of DL-glutamic acid was suspended in a mixed solution of 301 parts of acetone and 70 parts of water, and 8.0 g of DL-glutamic acid was suspended in a mixed solution of 301 parts of acetone and 70 parts of water.
g (0.2 mol) of sodium hydroxide was added to obtain a DL-glutamic acid disodium salt solution. Then 10-1
While maintaining the temperature at 5°C, 22.0 g (0.1 mol) of distilled lauric acid chloride obtained in Production Example 1 and 20% w/
30 g (0.15 mol) of an aqueous sodium hydroxide solution was simultaneously added dropwise over a period of about 1 hour. After the dropwise addition, 4,001 liters of 6-reaction water was stirred at the same temperature for 1 hour, and the solution was purified with 6N hydrochloric acid.
The crude crystals of N-lauroyl-DL-glutamic acid that did not precipitate were separated by filtration and dried.

The yield of crude crystals was 31.5 g.

Example 2 15.5 g (0.15 mol) of N-methyl-β-alanine in 60 g of 20% w/w 1-helium hydroxide aqueous solution
(0,3 mol), dissolved in water 1201, 10-15 °C
Distilled lauric acid chloride 22 of Production Example 1 while maintaining
．． 0 g (0.1 mol) was added dropwise over about 2 hours. After the dropwise addition, the mixture was further stirred at the same temperature for 2 hours. After the reaction, the pH was adjusted to 1 with 6N hydrochloric acid to obtain 28.0 g of crude crystals of N-lauroyl-N-methyl-β-alanine.

Example 3 13.3 g (0.1 mol) of L-aspartic acid of ``Nilauroyl-Asparan'' was suspended in a mixed solvent of 701 parts acetone and 701 parts water, and 8.0 g (0.1 mol) of L-aspartic acid was suspended in a mixed solvent of 701 parts acetone and 70 parts water.
2 mol) of sodium hydroxide was added to obtain an L-aspartic acid disodium salt solution. 22.0 g of distilled lauric acid chloride of Production Example 1 while maintaining the temperature at 10 to 15°C (
0.1 mol) and 30 g (0.15 mol) of a 20% W/W aqueous sodium hydroxide solution were simultaneously cleaved for about 1 hour and added dropwise. After the dropwise addition, the mixture was further stirred at the same temperature for 4 hours. 4,001 ml of reaction water was added and the pH was adjusted to 1 with 6N hydrochloric acid, and the crude crystals of N-lauroyl-L-aspartic acid that did not precipitate were separated by filtration and dried. The yield of crude crystals was 31.0 g.

Example 4 13.4 g (0.15 mol) of sarcosine at 20% w/
w Sodium hydroxide 60g (0.3 mol), water 120
22.2 g (0.1 mol) of distilled lauric acid chloride from Production Example 1 was added dropwise to the solution over a period of about 2 hours while maintaining the solution at 15 to 20°C. After the dropwise addition, the mixture was further stirred at the same temperature for 1 hour, and then at 60°C for 1 hour. After reaction, adjust pH to 1 with 6N hydrochloric acid.
After cooling to 5° C., the precipitate was filtered and dried to obtain 26.5 g of crude crystals of N-lauroyl-sarcosine. Add 13.5 g of this N-lauroyl-sarcosine to 2 ml of water.
51 plus 20% w/w sodium hydroxide 10
．． The solution was neutralized with 0 g to obtain a 30% clear aqueous solution of sodium N-lauroyl-sarcosinate.

Example 5 Preparation of N-lauroyl-β-alanine nβ-alanine 1
0.7 g (0.12 mol) of 20% w/w sodium hydroxide aqueous solution 24 g (0° 12 mol) and water 701,
It was dissolved in tetrahydrofuran 351 to obtain a β-alanine sodium salt aqueous solution. Then, while maintaining the temperature at 10 to 15°C, 22.0 g (0
. The yield of crude crystals is 26.5
It was g.

Example 6 21.0 g of coconut oil fatty acid of N-cocoyl-DL-glutamine was reacted in the same manner as in Production Example 1 to obtain 23.1 g of crude coconut oil fatty acid chloride. This product had a free fatty acid content of 2.0%, a phosphorus content of 0.8%, and a purity of 96.5%. This crude coconut oil fatty acid chloride was distilled using a glass distillation apparatus to obtain 20.0 g of distilled coconut oil fatty acid chloride. This product has free fatty acids of 0.16% and phosphorus content of 0.0.
The purity was 99.2%.

17.6 g (0.12 mol) of DL-glutamic acid and 9.6 g (0.24 mol) of sodium hydroxide were mixed with 80 g (0.24 mol) of water.
1. Dissolve in a mixed solution of 351 tetrahydrofuran and
23.0 g (0.1 mol) of the distilled coconut oil fatty acid chloride and 2
0% w/w sodium hydroxide aqueous solution 30g (0,1
, 5 mol) were simultaneously added dropwise over a period of approximately 2 hours. After dropping, the mixture was stirred at the same temperature for 2 hours. 100ml of reaction condensate
In addition, the pH was adjusted to 1 with 6N hydrochloric acid to obtain 32.6 g of crude crystals of N-cocoyl-DL-glutamic acid that did not precipitate.

Example 7 N-Cocoyl Lucosine Rosarcosine 1.3.4g (0.15 mol) 20% w/
w Sodium hydroxide aqueous solution 60g (0.3 mol), water 1
After the reaction, 23.0 g (0.1 mol) of the distilled coconut oil fatty acid chloride of Example 6 was cleaved and added dropwise while maintaining the temperature at 10 to 15°C. After the reaction, the mixture was cooled to 5°C.
The pH was adjusted to 1 with N-hydrochloric acid, and the precipitated N-cocoyl-sarcosine was filtered off and dried. 27.0 g of crude crystals were obtained.

Example 8 Using 59.6 g of beef tallow fatty acid (neutralization value 188.3.0.2 mol) of N-taloyl DL-asparan, a reaction treatment was carried out in the same manner as in Production Example 1 to obtain distilled beef tallow fatty acid chloride of 64.6 g. Obtained 0g. This one has free fatty acids 0.31
%, phosphorus content 0.06%, and purity 98.9%.

DL-aspartic acid 19.9 g (0.15 mol)
was suspended in a mixed solvent of 701 acetone and 70ffi1 water, 16.9 g (0.3 mol) of potassium hydroxide was added and dissolved, and the beef tallow fatty acid chloride 3 was dissolved while maintaining the temperature at 10 to 15°C.
2.9 g (0.1 mol) and an alkaline aqueous solution prepared by dissolving 2.9 g (0.1 mol) of potassium hydroxide and 8.4 g (0.1.5 mol) of potassium hydroxide in 201 g of water were simultaneously added dropwise over about 2 hours. After the reaction, the reaction mixture was cooled to 5° C. and adjusted to pH 1 with a 10% aqueous sulfuric acid solution, and the precipitated crude crystals were filtered off and dried to obtain 43.4 g of crude N-taloyl-DL-aspartic acid.

Example 9 A post-reaction treatment was carried out in the same manner as in Production Example 1 using 56.5 g of oleic acid (neutralization value: 198.8.0.2 mol) of N-silyl lucosine, and 61.0 g of distilled oleic acid chloride. The obtained product had a free fatty acid content of 1.7%, a phosphorus content of 0.04%, and a purity of 98%.

Sarcosine 13.4g (0.15mol) 20%w
/w sodium hydroxide aqueous solution 60g (0.3 mol),
Dissolved in 120ml of water, 50ml of tetrahydrofuran, 1
While maintaining the temperature at 5 to 20°C, the oleic acid chloride 30
．． 7. g (0.1 mol) was added dropwise at about 1 hour. After the dropwise addition, the mixture was further stirred at the same temperature for 5 hours. 20%w after reaction
/w sulfuric acid aqueous solution 38g''C' The pH was adjusted to 4, the lower layer was separated, and the upper layer solvent was removed under reduced pressure to obtain 34.7g of viscous crude N-oleoyl-sarcosine.

Comparative Example I N-Lauroyl-DL-Glutamine After dissolving 200 g (1 mol) of lauric acid at 50°C, 69 g (0.5 mol) of phosphorus trichloride was added dropwise over about 30 minutes, and then heated to 50-60°C. The mixture was stirred for 3 hours. After the reaction was allowed to stand for 8 hours, the lower layer of phosphorous acid was removed and the crude lauric acid chloride 2
28g was obtained. This product had a free fatty acid content of 1.2%, a phosphorus content of 0.9%, and a purity of 95%.

Using this undistilled lauric acid chloride, the reaction and treatment were carried out in the same manner as in Example 1 to obtain N-lauroyl-DL-glutamic acid.

Comparative Examples 2 to 5 Using the undistilled lauric acid chloride of Comparative Example 1, the reaction treatment was carried out in the same manner as in Examples 2 to 5 to produce N-lauroyl-N-methyl-β-alanine, N-lauroyl-shi-aspartic acid. , N-lauroylsarcosine, N-lauroyl-β
-Alanine was produced.

Comparative Example 6 21.0 g (0.1 mol) of N-cocoyl-DL-glutamine was reacted with phosphorus trichloride in the same manner as in Comparative Example 1, resulting in 23.8 g of crude coconut oil fatty acid chloride.
I got it. This one has a pre-fatty acid content of 1.9% and a phosphorus content of 1.1%.
%, and the purity was 94%.

Example 6 Using this undistilled coconut oil fatty acid chloride
The reaction and treatment were carried out in the same manner as above to obtain N-cocoyl-DL-glutamic acid.

Comparative Example 7 N-Cocoyl Sarcosine Using the undistilled coconut oil fatty acid chloride of Comparative Example 6, the reaction and treatment were carried out in the same manner as in Example 7 to obtain N-cocoyl sarcosine.

Table 1 shows the solubility when water was added to the products produced in Examples 1 to 9 and Comparative Examples 1 to 7 to obtain a predetermined concentration, and the pH was adjusted to 6.0 with sodium hydroxide.

Table 1 in the margin below ◎... Completely transparent liquid ×... Cloudy or precipitated liquid ○... Very faintly cloudy liquid △...
...The solubility of a slightly cloudy liquid was determined visually after storing it in a 40°C constant temperature bath for one month. However, if the temperature is 25℃, 4
After heating and dissolving at 0°C for 30 minutes, the product was stored in a constant temperature bath at 25°C for 2 days, and the appearance was visually judged.

As is clear from the results in Table 1, the product of the present invention has excellent solubility and good stability.

Next, Examples and Comparative Examples regarding liquid cleaning compositions will be shown.

Example 10, Comparative Example 8 Example 1, 2, 3, 6.7 and Comparative Example 1, 2.3, 6
．． A hair shampoo having the following formulation was prepared using the N-long chain acylamino acid obtained in Step 7 in the form of sodium salt or triethanolamine salt as shown in Table 2.

(Hair shampoo) - Sodiumra, uryl ether sulfate 8% - Coconut oil fatty acid jetanolamide 4 - N-long chain acylamino acid type surfactant 8 - Citric acid or sodium hydroxide pi (amount to 6) - Pigment (yellow 5 No./I color No. 205) 0.001 Distilled water Remaining 100% The results of the stability, cold resistance, and dye fading test of this hair shampoo composition are shown in Table 2.

Margin below (1) Stability: Appearance determined by naked eye when stored in a 40°C thermostatic chamber for 1 month ○: No change Δ: Slightly turbid ×: ... Turbidity or precipitation (2) Cold resistance ... Visually judge the appearance when stored in a -5℃ thermostat for one week ○ ... No change × ... - Turbidity or precipitation (3) Pigment fading property: Appearance after being left in sunlight for one week compared with a standard solution containing only distilled water and pigment.○: No difference from the standard solution. △・・・・・・Slightly faded from II ×・・・・・・
As is clear from Table 2, the products of the present invention have excellent stability and cold resistance, and have anti-fading properties even when incorporated into liquid detergent compositions.

Examples of formulations of various liquid cleaning agents are illustrated below.

=24-23-Example 11, Comparative Example 9 Hair shampoo/N-lauroylsarcosine sodium salt 6.Ndium lauryl sulfate 8.Coconut oil fatty acid jetanolamide Tocitric acid
Amount to adjust pH to 7/Distilled water
Remaining 100% This hair shampoo containing N-lauroyl-sarcosine in Example 4 and Comparative Example 4 was transparent both at the time of formulation, but after storage at 40°C for 1 month, the product used in Comparative Example 4 became cloudy. .

Example 12, Comparative Example 10 Length tip Muni A - N-cocoi 4-DL-glutamic acid monotriethanolamine salt 8 - Lauric acid jetanolamide 3 - Cocoamidopropyl dimethylamine oxide 8 - Citric acid pH 5,5 Distilled water remaining 100% This liquid soap containing N-cocoyl-DL-glutamic acid monotriethanolamine salt in Example 6 had a transparent appearance and remained transparent even after storage at 40°C for 1 month. The one used in Comparative Example 6 was opaque from the time of blending and was 40
After storage at ℃ for 1 month, a white precipitate was formed.

Example 13 Body shampoo/N-oleoyl-sarcosine (Example 9) Triethanolamine 5/Sodium lauryl ether sulfate 8/N-cocoyl-D L-glutamic acid (Example 6) Monolysine salt 5
・Glycerin 3・Citric acid Amount to adjust pH to 6,'5 ・Distilled water 100% balance This body shampoo was transparent and had good storage stability.

Example 14 11 dishes 9 milligrams of N-lauroyl-DL-aspartic acid (Example 8)
Monoammonium salt 7. Sodium lauryl sulfate 9. Propylene glycol
5.Citric acid pH7
, Amount to be 0/Distilled water
Remaining 100% This kitchen detergent was transparent and had good stability for one month at 40°C.

Benri R and Sashimi - The N-long chain acylamino acid type surfactant produced by the method of the present invention does not cause turbidity or precipitation even when it is made into an aqueous solution or added to a liquid detergent, and does not cause turbidity or precipitation in a liquid detergent. It has the effect of not fading the pigment.

Patent Applicant: Kawaken Fine Chemicals Co., Ltd. Procedural Amendment (Radio) July 16, 1985 1, Case Description 1985 Patent Application No. 13363 2, Name of the Invention N-long chain acylamino acid type surfactant Manufacturing method and relationship to the incident Patent applicant postal code 103 Address 6-6 Kobune-cho, Nihonbashi, Chuo-ku, Tokyo Telephone (0)
3) 663-9521 June 3, 1988 (shipment date June 30, 1988)
5. Subject of amendment 6. Contents of amendment (]) As shown in the attached sheet.

(2) An engraving of the application and the specification originally attached to the application;
As shown in the attached sheet (no change in content).

Claims (1)

[Claims] 1. A method for producing an N-long chain acylamino acid type surfactant by reacting a fatty acid chloride and an amino acid in the presence of an alkali, in which phosphorus trichloride and a fatty acid are reacted and then distilled. 1. A method for producing an N-long chain acylamino acid surfactant, the method comprising using a distilled fatty acid chloride obtained by 2. The method according to claim 1, wherein the distilled fatty acid chloride is a fatty acid chloride having 8 to 20 carbon atoms. 3. The method according to claim 1, wherein the amino acid is at least one selected from glutamic acid, aspartic acid, sarcosine, β-alanine, and N-methyl-β-alanine. 4. The alkali is sodium hydroxide or The method according to claim 1, wherein potassium hydroxide is used. 5. The N-long chain acylamino acid type surfactant is N-
At least one selected from long chain acylamino acids, N-long chain acylamino acid alkali metal salts, N-long chain acylamino acid alkanolamine salts, N-long chain acylamino acid ammonium salts, and N-long chain acylamino acid basic amino acid salts. The method according to claim 1. 6. Contains an N-long chain acylamino acid type surfactant obtained by reacting distilled fatty acid chloride obtained by reacting phosphorus trichloride with a fatty acid and then distilling it and an amino acid in the presence of an alkali. A liquid cleaning composition. 7. Claim 6, wherein the long chain acyl group of the N-long chain acylamino acid type surfactant has 8 to 20 carbon atoms.
Compositions as described in Section. 8. The N-long chain acylamino acid type surfactant is N-long chain acylglutamic acid, N-long chain acylaspartic acid, N-long chain acylamino acid type surfactant,
- selected from long chain acyl sarcosine, N-long chain acyl-β-alanine, N-long chain acyl-N-methyl-β-alanine and alkali metal salts, ammonium salts, alkanolamine salts and basic amino acid salts thereof 7. The composition according to claim 6, which is at least one.