JPS6214933A - Surfactant - Google Patents

Abstract

PURPOSE:To obtain a low irritant surfactant having excellent washing power, foaming power and emulsifying power, by using potassium salt of N-(2-alkyl-2- hydroxyethyl)-N-methylaminoethanol phosphate. CONSTITUTION:A compound potassium phosphate of N-(2-alkyl-2-hydroxyethyl)- N-methylaminoethanol represented by formula I (wherein R is a capryl group, a lauryl group, a myristyl group, a palmityl group, a stearyl group or an oleyl group and M is potassium) is prepared, for example, by a method wherein pyrophosphoric acid is added to a solution of N-(2-alkyl-2-hydroxyethyl)-N- methylaminoethanol represented by formula II (wherein R is the same meaning as the formula I) in benzene to perform phosphoric esterification reaction and an aqueous potassium hydroxide solution is subsequently added to an aqueous solution prepared by dissolving the taken-out reaction product in water to form a potassium salt. This compound has reduced irritability and toxity to the skin and a wide range of utilization and use are considered as a stock material for cosmetics or aromatic products.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an N-(binary surfactant) represented by the general formula (1) below.

(Prior Art) Many types of compounds have been known and used as surfactants. Among them, anionic activators have high detergency and excellent foaming power, and are used in various applications such as detergents, emulsifiers, and foaming agents. However, in the case of cosmetics and household detergents that people come into direct contact with, such as shampoos, conditioners, and soaps, due to issues such as irritation to the skin, the development of safer and more neutral active agents. is required. Fatty acid soaps are widely used as active agents that have a soothing effect on the skin, but their cleansing effectiveness is significantly reduced in neutral and acidic environments. Furthermore, alkylbenzene sulfonates, higher alcohol sulfuric acid ester salts, and the like also exhibit excellent cleaning effects, but cannot be said to be satisfactory in terms of action on the skin.

On the other hand, phosphate ester salts of various organic hydroxy compounds having surface activity are used as detergents, emulsifiers, antistatic agents,
Widely used as a rust inhibitor.

In particular, monoalkyl phosphate ester salts have extremely low toxicity and skin irritation, and are useful as anionic surfactants that are highly safe for the human body, such as cleaning agents used directly on the human body, and raw materials for other cosmetics and cosmetics. It is known that there is.

However, as living standards have become more sophisticated in recent years, there has been an increasing demand for the development of raw materials for cosmetics and cosmetics that have even higher levels of safety for the human body.

Therefore, if an anionic surfactant that is less irritating to the skin, less toxic, and more safe than monoalkyl phosphate ester salts can be developed, it will have a wide range of applications as a raw material for cosmetics and cosmetics that can be used directly on the human body. is possible.

(Problems to be Solved by the Invention) In view of the current situation, as a result of intensive research, it was found that the compound represented by the general formula (1) below has low irritation and excellent cleaning power.
It was discovered that it has surface tension lowering ability, foaming power, and emulsifying power, and the present invention was completed.

Therefore, the object of the present invention is to
An object of the present invention is to provide a surfactant comprising -(2-alkyl-2-hydroxyethyl)-N-methylaminoethanol phosphate potassium salt.

(Means for solving the problem) That is, the present invention has the following general formula (1) (wherein, 几 is a capryl group, a lauryl group, a myristyl group, a palmityl group, a stearyl group, or an oleyl group, and M is a N-(2-alkyl-
2-Hydroxyethyl)-N-methylaminoethanol phosphate potassium salt.

N-(2-arauryl-2-hydroxyethyl)-N-methylaminoethanol phosphate monopotassium salt (hereinafter referred to as compound 1 of the present invention) represented by the above general formula of the present invention, N-(2-caprylic 2-hydroxyethyl)-N-methylaminoethanol phosphate monopotassium salt (referred to as compound 2 of the invention), N-(2-t listyl-2- and droxyethyl)-N-methylaminoethanol phosphate monopotassium salt salt (referred to as compound 3 of the invention), N-(2-palmityl-2-hydroxyethyl)-N-methylaminoethanol phosphate ester 1
Potassium salt (referred to as compound 4 of the invention), N-(2-stearyl-2-hydroxyethyl)-N-methylaminoethanol phosphate monopotassium salt (referred to as compound 5 of the invention), N-(2-oleyl -2-hydroxyethyl)-N-methylaminoethanol phosphate ester 1
potassium salt (referred to as compound 6 of the present invention), and the like.

The N-(2-alkyl-2-hydroxyethyl)-N-methylaminoethanol phosphate potassium salt represented by the general formula (1) of the present invention is produced, for example, as follows.

N-(2-alkyl-2- and droxyethyl)-N-methylaminoethanol in benzene solvent (
The concentration is 1.0 to 8.0% by weight).
Add 10 times the mole of pyrophosphoric acid and mix 2 to 10 times at room temperature.
The phosphoric acid esterification reaction is carried out under stirring for a period of time.

Next, the generated N-(2-alkyl-2-hydroxyethyl)-N-methylaminoethanol phosphoric acid ester was taken out using a decantation bottle, and then dissolved in water.
I)H was adjusted to 6.0 while adding 30% potassium hydroxide/aqueous solution to this aqueous solution while stirring. Thereafter, the desired N-
(2-Alkyl-2-hydroxyethyl)-N-methylaminoethano-2relic acid ester potassium salt is obtained.

The N-(2-alkyl-2-hydroxyethyl)-N-methylaminoethanol phosphate potassium salt of the present invention represented by the general formula (1) and obtained in the Examples described below is Example I Synthesis of N-(2-lauryl-2-hydroxyethyl)-N-methylaminoethanol phosphate monopotassium salt In 11 flasks equipped with a stirrer, N-(2-lauryl-2-hydroxyethyl)-N-(2-lauryl-
2-and droxyethyl)-N-methylaminoethanol 317f (1 mol) pyrophosphoric acid 432fC2.4 mol)
and 800 ml of benzene, and the mixture was allowed to react at room temperature for 8 hours with vigorous stirring. After the reaction, the obtained N-(
2-Lauryl-2-hydroxyethyl)-N-methylaminoethanol phosphate ester is removed by decanting. Using this as a sample, N-(2-lauryl-hydroxyethyl)-N-methylaminoethanol phosphoric acid ester was continuously collected and purified by preparative high-performance liquid chromatography under the following conditions. After distilling off the solvent from this preparative fraction using an evaporator, ethanol 11 was added, and the precipitate that opened at this time was removed by decantation (2-laurylhydroxyethyl)-N
- Obtain methylaminoethanol phosphate ester.

This was dissolved in 11 water, and a 30% aqueous solution of potassium hydroxide was added dropwise with stirring to adjust the pH to 6.0. After that, when water is removed using an evaporator, white powder 35
I got 0f. From the analysis results shown in Table 1 above, this white powder obtained has the target compound N-(2-lauryl-2
-Hydroxyethyl)-N-methylaminoethanol phosphate monopotassium salt. (Yield: 90
%) Q preparative high performance liquid chromatography conditions stationary phase:
0D8-silica gel (5n) with an inner diameter of 20j! I11 Packed in a stainless steel column with a length of 251 mm.

0.02 to a mixture of equal volumes of mobile phase niacetonitrile and water.
Dissolve 5M potassium dihydrogen phosphate and adjust the pH to 2.0 with phosphoric acid.

Detector: Ultraviolet detector (220 nm) and differential refraction Synthesis of N-(2-capryl-2-hydroxyethyl)-N-methylaminoethanol phosphate monopotassium salt N-(2-lauryl-2 -Hydroxyethyl)-N-methylaminoethanol instead of N-(2-capryl-
A white powder 352f was obtained in the same manner as in Example 1 except that 29 (1 (1 mol)) -N-methylaminoethanol (2-hydroxyethyl)-N-methylaminoethanol was used. From the analysis results shown in Table 1, the target compound N-(,2-capryl-2-hydroxyethyl)-N-
It was confirmed that it was methylaminoethanol phosphate monopotassium salt. (Yield: 98%) Example 3 N-(2-myristyl-2-hydroxyethyl)-N-
Synthesis of methylaminoethanol phosphate monopotassium salt Instead of N-(2-lauryl-2-hydroxyethyl)-N-methylaminoethanol, N-(2-myristyl-2-hydroxyethyl)-N-methylamino A white powder 400f was obtained in the same manner as in Example 1 except that ethanol 316F (1 mol) was used. From the analysis results shown in Table 1 above, this white powder obtained was found to contain the target compound N-(2-myristyl-2- and droxyethyl)-N.
- It was confirmed that it was methylaminoethanol phosphate monopotassium salt. (Yield: 96%) Example 4 N-(2-harmothyl-2-hydroxyethyl)-N
- Synthesis of methylaminoethanol phosphate monopotassium salt N-(2-lauryl-2- and droxyethyl)-N-methylaminoethanol was replaced with N-(2-palmitel-2-hydroxyethyl)-N-methylamino A white powder 428f was obtained in the same manner as in Example 1 except that ethanol 360f (1 mol) was used. From the analysis results shown in Table 1 above, this white powder obtained has the target compound N-(2-palmityl-2-hydroxyethyl)-N
- It was confirmed that it was methylaminoethanol phosphate monopotassium salt. (Yield: 96%) Example 5 N-(2-stearyl-2- and droxyethyl)-N-
Synthesis of methylaminoethanol phosphate monopotassium salt N-(2-stearyl-
A white powder 453f was obtained in the same manner as in Example 1, except that 2-hydroxyethyl)-N-methylaminoethanol 4049 (1 mol) was used. From the analysis results shown in Table 1 above, this white powder obtained has the target compound N-(2-stearyl-2-hydroxyethyl)-N
- It was confirmed that it was methylaminoethanol phosphate monopotassium salt. (Yield: 89%) Example 6 Synthesis of N-(2-oleyl-2-hydroxyethyl)-N-methylaminoethanol phosphoric acid ester 1 ammonium salt N-(2-oleyl −
After obtaining 2-hydroxyethyl)-N-methylaminoethanol phosphoric acid ester, a colorless viscous substance 460f was obtained by the same operation as in Example 1. From the analysis results shown in Table 1 above, this colorless viscous substance obtained was found to contain the target compound N.
It was confirmed that it was -(2-oleyl-2-hydroxyethyl)-N-methylaminoethanol monopotassium salt.

(Yield: 90%) Example 7 This example is for explaining the surface tension lowering ability, foaming property, detergency and safety of the surfactant of the present invention.

Surface tension, foam height, foam half-life, detergency, and skin irritation were measured for the surfactants obtained in Examples 1 to 6.

Similar measurements were carried out using lauryl phosphate monopotassium salt as a control substance for comparison.

Surface tension was measured using a Fischer surface tension meter, and the results are shown in Table 2 in dynes/ax at 28.5°C. The surface tension of the surfactant of the present invention is about 2096 smaller than the surface tension of monopotassium lauryl phosphate.

Foam height and foam half-life were measured using the Ross Miles test (A
STMD1173-53). The measurement results are shown in Table 2. High values indicate good foam stability.

As shown in Table 2, the foam height CM of the surfactant of the present invention
(initial and after 5 minutes) and foam half-life are in each case slightly higher than the corresponding values for the monopotassium lauryl phosphate salt.

The detergency was measured by uniformly applying 0.4 ml of a chloroform solution containing 7% lanolin and 0,0 s% of Sudan to a 5cm x 5cm wool muslin cloth and drying it. Approximately 1 containing
The cloth was placed in a 00 ml glass cylinder and shaken for 15 minutes in a constant temperature bath at 40° C. The contaminated cloth was thoroughly rinsed under running water, dried, and the reflectance was examined, and the cleaning rate was determined using the following formula.

The results are shown in Table 2. The cleaning efficiency of the surfactant of the present invention is slightly superior to that of lauryl phosphate l-potassium salt.

As a test method for skin irritation, a 24-hour occlusion patch test was conducted on humans. That is, a patch test plaster impregnated with 1 xi of a 0.2% aqueous solution of a surfactant was applied to 20 subjects for 24 hours, and 24 hours after the patch was removed.
Irritation was determined after a period of time.

The test result is positive if it shows clear erythema.
It is shown in the positive rate. As can be seen from Table 2, the measurement results are as follows:
The safety of the surfactants of the present invention is almost the same.

Application Example 1 (Application as an emulsifier in the production of emulsion) 5 parts of each of the compounds 1 to 18 of the present invention and monopotassium lauryl phosphate as an analogous compound and 30 parts each of liquid paraffin were mixed as emulsifiers. 70
Heat to °C and stir.

This was gradually added to 65 parts of water at 70°C to disperse and emulsify. Next, each emulsion was heated at 30°C while being gently stirred.
A 0/W emulsion was obtained.

Each of these emulsions was left in a constant temperature room at 45°C to examine their oral stability. The results are shown in Table 3.

Table 3 As shown, the emulsion using the compound (surfactant) of the present invention as an emulsifier is stable even after 6 months, but the oil content of the emulsion using a related compound separates after 6 months. The emulsifying power of the surfactant of the present invention is excellent.

Claims (1)

[Claims] The following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...(1) (In the formula, R is a caprylic group, a lauryl group, a myristyl group, a palmityl group, a stearyl group, or an oleyl group, and M is potassium.) N-(2-alkyl-2 -Hydroxyethyl)-N-methylaminoethanol phosphate ester potassium salt.