JPS61143497A - Surfactant - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention consists of an N-(2-alkyl-2- and droxyethyl)-jetanolamine diphosphate salt represented by the general formula (1) below. Concerning a new surfactant.

(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, shampoos that people come into direct contact with.

In the case of cosmetics and household emulsions such as rinses and soaps, there is a need to develop active agents that are safer and can be used in the neutral range due to problems such as irritation to the skin. Fatty acid soaps are widely used as active agents that have a mild effect on dermatitis, but their cleaning effect is significantly reduced in neutral and acidic conditions. Furthermore, alkylbenzene sulfonates, higher alcohol sulfuric ester salts, and the like also exhibit excellent cleaning effects, but cannot be said to be satisfactory in terms of their effect on 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 a highly safe anionic surfactant can be developed that has less skin irritation and toxicity than monoalkyl phosphate ester salts, it can be used in cosmetics for direct use on the human body,
It can be used in a wide range of applications as a raw material for cosmetics.

(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.

The object of the present invention is to provide N-(2-
An object of the present invention is to provide a surfactant comprising an alkyl-2-hydroxyethyl)-jetanolamine diphosphate ester salt.

(Means for Solving the Problems) That is, the present invention has the following general formula (1) (wherein L is a caprylic 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)-jetanolamine diphosphate ester salt.

N-(2-alkyl-
2-hydroxyethyl)-jetanolamine diphosphate ester salt is N-(2-lauryl-2-hydroxyethyl)-jetanolamine diphosphate disodium salt (hereinafter referred to as compound 1 of the present invention), N- (2-
lauryl-2-hydroxyethyl)-jetanolamine diphosphate ester dianthonium salt (compound 2 of the present invention), N-(2-lauryl-2-hydroxyethyl)-
Jetanolamine diphosphate 2 triethanolamine salt (compound 8 of the present invention), N-(2-capryl-
2-hydroxyethyl)-jetanolamine diphosphate disodium salt (compound 4 of the present invention), N-(
2-Capryl-2-hydroxyethyl)-jetanolamine diphosphate 2-ammonium salt (Compound 5 of the invention), N-(2-capryl-2-hydroxyethyl)-jetanolamine diphosphate 2-triethanolamine salt (Compound 6 of the present invention), N-(2-myristyl-2-hydroxyethyl)-jetanolamine diphosphate disodium salt (Compound 7 of the present invention),
N-C2-1 listyl-2-hydroxyethyl)-jetanolamine diphosphate 2 ammonium salt (compound of the present invention 8), N-(2-myristyl-2-hydroxyethyl)-jetanolamine diphosphate 2
Triethanolamine salt (compound 9 of the invention), N-(
2-palmityl-2-hydroxyethyl)-jetanolamine diphosphate disodium salt (compound 10 of the present invention), N-(2-palmityl-2-hydroxyethyl)-jetanolamine diphosphate disodium salt (the present invention) Compound 11), N-(2-valmityl-2-hydroxyethyl)-jetanolamine diphosphate 2 triethanolamine salt (compound 12 of the present invention), N-(2-stearyl-2-hydroxyethyl)-jetanolamine diphosphate Tanolamine diphosphate disodium salt (Compound 18 of the present invention), N-(-2-stearyl-2-hydroxyethyl)-jetanolamine diphosphate diammonium salt (Compound 14 of the present invention),
N-(2-stearyl-2-hydroxyethyl)-jetanolamine diphosphate 2 triethanolamine salt (compound 15 of the present invention), N-(2-oleyl-2
-hydroxyethyl)-jetanolamine diphosphate disodium salt (compound 16 of the present invention), N-(
2-Oleyl-2-hydroxyethyl)-jetanolamine diphosphate 2-ammonium salt (compound 17 of the invention) and N-(2-oleyl-2-hydroxyethyl)-jetanolamine diphosphate 2-triethanolamine salt (compound 18 of the present invention), and the like.

The N-(2-alkyl-2-hydroxyethyl)-jetanolamine diphosphate salt represented by the general formula (11) of the present invention is produced, for example, as follows.

N-(2-alkyl-2-hydroxyethyl) represented by the following general formula (2) (In the above formula, R is a caprylic group, a lauryl group, a myristyl group, a palmityl group, a stearyl group, or an oleyl group.) - Jetanolamine in benzene solvent (concentration is 1
．． 0 to 8.0% by weight), 1 to 10 times the molar amount of birophosphoric acid is added, and the phosphoric acid esterification reaction is carried out under stirring at room temperature for 2 to 10 hours.

Next, the generated N-(2-alkyl-2-hydroxyethyl)-jetanolamine diphosphate is removed by decantation, then dissolved in water, and the base described below or its aqueous solution is stirred into this aqueous solution. Adjust the pH to 6.0 while adding to the bottom. Thereafter, the desired N-(2-alkyl-2-hydroxyethyl)-jetanolamine diphosphate salt is obtained by concentrating it using an evaporator and purifying it using preparative high-performance liquid chromatography.

In addition, as the base, sodium hydroxide, aqueous ammonia, triethanolamine, etc. are applicable.

The N-(2-alkyl-2-hydroxyethyl)-jetanolamine diphosphate salts of the present invention represented by the general formula (1) and obtained in the Examples below are shown in Table 1 below. The present invention will be described in detail with reference to Examples below.

Note that the parts shown in the Examples mean parts by weight.

Example I Synthesis of N-(2-lauryl-2-hydroxyethyl)-jetanolamine diphosphate disodium salt In 11 flasks equipped with a stirrer, N-(2-lauryl-2-hydroxyethyl)-
2-Hydroxyethyl)-jetanolamine817.
F (1 mol), birophosphoric acid 4821 (2.4 mol) and benzene 800 mI! and react at room temperature for 8 hours with vigorous stirring.

After the reaction, the resulting N-(2-lauryl-2-hydroxyethyl)-jetanolamine diphosphate is removed by decantation. Using this as a sample, N-C2-lauryl-hydroxyethyl)-jetanolamine diphosphate was continuously separated and purified by preparative high-performance liquid chromatography under the following conditions. After distilling off the solvent from the preparative fraction of kerosene using an evaporator, ethanol 11! is added, the precipitate formed at this time is removed by a decantation machine, and the solvent is removed by an evaporator to obtain N-(2-laurylhydroxyethyl)-jetanolamine diphosphate.

This is 11! of water, and the pH was adjusted to 6.0 by adding dropwise an 80% aqueous solution of sodium hydroxide under stirring. Thereafter, water was removed using an evaporator to obtain white powder 474I. The obtained white powder was confirmed to be the target compound, N-(2-lauryl-2-hydroxyethyl)-jetanolamine diphosphate disodium salt, from the analysis results shown in Table 1 above. (Yield: 91
%) 0 Conditions for preparative high performance liquid chromatography Stationary phase:
A stainless steel column with an inner diameter of 20 U and a length of 25 cm was filled with 0D8-silica gel (5sEII).

Add 0.02 to an equal volume suspension of mobile phase niacetonitrile and water.
Dissolve 5M potassium dihydrogen phosphate and adjust the pH to 2.0 with phosphoric acid.

Detector: An ultraviolet detector (22Qnm) and a differential refractive index detector are used in conjunction.

Example 2 Synthesis of N-(2-lauryl-2-hydroxyethyl)-jetanolamine diphosphate 2 ammonium salt N-(2-lauryl-2
After obtaining the -hydroxyethyl)-jetanolamine diphosphate ester, a colorless viscous substance 460.9 was obtained by the same procedure as in Example 1, except that aqueous ammonia was used instead of the 80% aqueous sodium hydroxide solution. . The obtained colorless viscous substance was found to be the target compound N-(2-lauryl-2-hydroxyethyl) from the analysis results shown in Table 1 above.
- It was confirmed that it was diammonium salt of jetanolamine diphosphate. (Yield 9o%) Example 8 Synthesis of N-(2-lauryl-2- and droxyethyl)-jetanolamine diphosphate 2-triethanolamine salt By the same operation as in Example 1, N-(2-lauryl-2- and droxyethyl)- 2
After obtaining the -hydroxyethyl)-jetanolamine diphosphate ester, a colorless viscous substance 719I was obtained by the same procedure as in Example 1, except that triethanolamine was used instead of the 80% aqueous sodium hydroxide solution. From the analysis results shown in Table 141 above, this colorless viscous substance obtained was confirmed to be the N-(2-lauryl-2-hydroxyethyl)-jetanolamine diphosphate 2-triethanolamine salt of the target compound. I approved.

(Yield: 92%) Example 4 Synthesis of disodium N-(2-capryl-2-hydroxyethyl)-diethanolamine diphosphate ester instead of N-(2-lauryl-2-hydroxyethyl)-jetanol as main , N-(2-capryl-2-hydroxyethyl)-jetanolamine 289. A white powder 468I was obtained in the same manner as in Example 1 except that p (1 mol) was used. This obtained white powder is
From the analysis results shown in the table, it was confirmed that the target compound was N-(2-capryl-2-hydroxyethyl)-jetanolamine diphosphate disodium salt.

(Yield: 95%) Example 5 Synthesis of N-(2-capryl-2-hydroxyethyl)-jetanolamine diphosphate 2 ammonium salt N-(2-caprylic 2-
-Hydroxyethyl)-jetanolamine diphosphate ester was obtained, and the same procedure as in Example 2 was carried out to obtain a colorless viscous substance 464! ! I got it. From the analysis results shown in Table 1 in Section 1, the obtained brown viscous substance has the target compound N-(8
-Caproxy-2-hydroxypropyl)-jetanolamine diphosphate ester diammonium salt. (Yield: 96%) Example 6 Synthesis of N-(2-capryl-2-hydroxyethyl)-jetanolamine diphosphate 2-triethanolamine salt N-(2-lauryl -2
After obtaining the -hydroxyethyl)-jetanolamine diphosphate ester, a colorless viscous substance 686Ii was obtained by the same operation as in Example 8. From the analysis results shown in Table 1 above, this colorless viscous substance obtained has the target compound N-(2
-Capryl 2-hydroxyethyl)-N-jetanolamine diphosphate 2-triethanolamine salt. (Yield: 91%) Example 7 Synthesis of N-(2-myristyl-2-hydroxyethyl)-diethanolamine diphosphate disodium salt Substitute for N-(2-lauryl-2-hydroxyethyl)-jetanolamine N-(2-myristyl-2-hydroxyethyl)-jetanolamine 845.9 (1
White powder 6211 was obtained in the same manner as in Example 1 except that mol) was used.

From the analysis results shown in Table 1 above, this white powder obtained was found to be the target compound N-(2-myristyl-2-hydroxyethyl)-jetanolamine diphosphate 2.
It was confirmed that it was a sodium salt. (Yield: 95%) Example 8 Synthesis of N-(2-myristyl-2-hydroxyethyl)-diethanolamine diphosphate ester diammonium salt N-(2-myristyl-2-hydroxyethyl) was synthesized in the same manner as in Example 7.
After obtaining 2-hydroxyethyl)-jetanolamine diphosphate ester, a colorless viscous substance 4851 was obtained by the same operation as in Example 2. This colorless viscous substance obtained is
From the analysis results shown in Table 1 above, the target compound N-(
It was confirmed that it was 2-myristyl-2-hydroxyethyl)-jetanolamine diphosphate diammonium salt. (Yield: 90%) Example 9 Synthesis of N-(2-myristyl-2-hydroxyethyl)-jetanolamine diphosphate 2-triethanolamine salt By the same procedure as Example 7, N-(2- Myristyl
After obtaining 2-hydroxyethyl)-jetanolamine diphosphate ester, a colorless viscous substance 744I was obtained by the same operation as in Example 8. From the analysis results shown in Table 1 above, this colorless viscous substance obtained has the target compound N-(2
-myristyl-2-hydroxyethyl)-jetanolamine diphosphate 2-triethanolamine salt. (Yield: 92%) Example 1O Synthesis of N-(2-palmityl-2-hydroxyethyl)-diethanolamine phosphate disodium salt Instead of N-(2-lauryl-2-hydroxyethyl)-jetanolamine , N-(2-palmityl-2-hydroxyethyl)-jetanolamine 84'FDI
(1 mol) was carried out in the same manner as in Example 1,
A white powder 55411 was obtained.

The obtained white powder was confirmed to be the target compound N-(2-/f lumityl-2-hydroxyethyl)-jetanolamine diphosphate disodium salt from the analysis results shown in Table 1 above. did. (Yield: 96
94) Example 11 Synthesis of N-(2-palmityl-2-hydroxyethyl)-jetanolamine diphosphate diammonium salt N-(2-palmityl-2-hydroxyethyl-jetyl) was synthesized by the same procedure as in Example 1G. After obtaining the tanolamine diphosphate ester, a colorless viscous substance 589I was obtained by the same operation as in Example 2.The obtained colorless viscous substance ξ was determined from the analysis results shown in Table 1 above, and was the target compound. N-(2
-palmityl-2-hydroxyethyl)-jetanolamine diphosphate ester diammonium salt. (Yield: 95%) Example 12 Synthesis of N-(2-palmityl-2-hydroxyethyl)-jetanolamine diphosphate 2-triethanolamine salt In the same manner as in Example 11, N-(2- /"lumityl-2-hydroxyethyl)-jetanolamine diphosphoric acid ester, the same procedure as in Example 8 was carried out to obtain colorless viscous substance 762I.

From the analysis results shown in Table 1 above, this colorless viscous substance obtained was determined to be the target compound N-(2-/"lumityl-2-hydroxyethyl)-jetanolamine diphosphate 2-triethanolamine salt. I confirmed that there is. (
Yield: 91%) Example 18 Synthesis of N-(2-stearyl-2-hydroxyethyl)-jetanolamine diphosphate disodium salt.

-2-hydroxyethyl)-jetanolamine 401
．． White powder 5461 was obtained in the same manner as in Example 1 except that 9 (1 mol) was used. From the analysis results shown in Table 1 above, this white powder obtained has the target compound N-
It was confirmed that it was (2-stearyl-2-hydroxyethyl)-jetanolamine diphosphate disodium salt.

(Yield: 9θ%) Example 14 Synthesis of N-(2-stearyl-2-hydroxyethyl)-jetanolamine diphosphate ester diammonium salt N-(2-stearyl-2 After obtaining the -hydroxyethyl)-jetanolamine diphosphate ester, a colorless viscous substance 560I was obtained by the same operation as in Example 2.

The obtained colorless viscous substance was confirmed to be the target compound N-C2-stearyl-2-hydroxyethyl)-diethanolandiammonium salt from the analysis results shown in Table 111 above.

(Yield: 94%) Example 15 Synthesis of N-(2-stearyl-2-hydroxyethyl)-jetanolamine diphosphate 2-triethanolamine salt By the same operation as in Example 18, N-(2-stearyl After obtaining -2-hydroxyethyl)-jetanolamine diphosphate ester, the same procedure as in Example 8 was carried out to obtain a colorless viscous substance 88G! I got i.

This colorless viscous substance obtained was confirmed to be the target compound, N-(2-stearyl-2-hydroxyethyl)-jetanolamine 2-triethanolamine salt, from the analysis results shown in Table 1 above. . (Yield: 96%) Example 16 Synthesis of N-(2-oleyl-2-hydroxyethyl)-jetanolamine diphosphate disodium salt N-(2-lauroyl-2-hydroxyethyl)-jetanol 74 A white powder 544Ii was obtained in the same manner as in Example 1, except that N-(2-oleyl-2-hydroxyethyl)-jetanolamine 899# (1 mol) was used instead. This white powder that was not obtained was confirmed to be the target compound N-(2-oleyl-2-hydroxyethyl)-jetanolamine phosphate disodium salt from the analysis results shown in Table 1 above. .

(Yield 90%) Example 17 Synthesis of N-(2-,oleyl-2-hydroxyethyl)-jetanolamine phosphate ester diammonium salt By the same operation as Example 16, N-(2- Oreil
After obtaining 2-hydroxyethyl)-jetanolamine diphosphate ester, a colorless viscous substance 546I was obtained by the same operation as in Example 2. This colorless viscous material thus obtained was found to contain the target compound N-(
It was confirmed that it was 2-oleyl-2-hydroxyethyl)-jetanolamine diammonium salt. (Yield: 92%) Example 18 Synthesis of N-(2-oleyl-2-hydroxyethyl)-diethanolamine diphosphate 2-triethanolamine salt In the same manner as in Example 16, N-(2-oleyl-2-hydroxyethyl)-diethanolamine diphosphate −
After obtaining 2-hydroxyethyl)-jetanolamine diphosphate, a colorless viscous substance 820.9 was obtained by the same operation as in Example 8. This colorless viscous substance obtained is
From the analysis results shown in Table 1 above, the N-C of the target compound
It was confirmed that the product was 2-oleyl-2-hydroxyethyl)-jetanolamine 2-triethanol amine salt.

(Yield: 96%) Example 19 This example is for explaining the surface tension lowering ability, foaming property, detergency and safety of the 8-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 18. Similar measurements were performed using lauryl phosphate monosodium 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/country at 28.6°C. The surface tension of the surfactant of the present invention is about 20% lower than that of monosodium lauryl phosphate.

Foam height and foam half-life were measured using the Ross Miles test (Mu8TMD1178-58).

The measurement results are shown in Table 2. High values indicate good foam stability.

Table 2 shows that the foam height (initial and after 5 minutes) and foam half-life of the surfactants of the present invention are in each case slightly greater than the corresponding values for lauryl phosphate monosodium salt.

The detergency was measured by uniformly applying 0.4 m/ml of a chloroform solution of 7% lanolin and 5% Sudan InO to a 5egXS wool muslin cloth and drying it. Approximately 100 cnl entered!
Place it in a glass cylinder and heat it in a constant temperature bath at 40℃ for 1 hour.
After removing the color for 5 minutes, the contaminated cloth was thoroughly rinsed under running water, dried, and the reflectance was examined to determine the cleaning rate 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 monosodium lauryl phosphate.

As a test method for skin irritation, a 24-hour closed patch test was conducted on humans. That is, 1 ml of a 0.2% aqueous solution of surfactant to 20 subjects! A patch test bandage impregnated with
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. The measurement results are shown in Table 2.

As can be seen from Table 2, the safety of the surfactant of the present invention is almost the same as that of lauryl phosphate monosodium salt.

Application Example 1 (Application as an emulsifier in the production of a milky lotion) Using each of the compounds 1 to 18 of the present invention and monosodium lauric acid ester salt as an analogous compound as an emulsifier, 6 parts each and 80 parts each of liquid paraffin were mixed. ,7
Heat to 0°C and stir.

This was gradually added to 65 parts of water at 70°C to disperse and emulsify. Next, each emulsion was heated to 80°C while being stirred gently.
A 0/W emulsion was obtained.

Each of these emulsions was left in a constant temperature room at 45°C to examine their stability over time. The results are shown in Table 8.

Table 8 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 compounds of the present invention is excellent.

Claims (1)

[Claims] The following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(1) N-(2 -Alkyl-2-hydroxyethyl)-diethanolamine diphosphate ester salt.