JPH0747597B2 - Process for producing arginine salt of phosphoric acid monoester - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an arginine salt of a phosphoric acid monoester useful as an emulsifying agent for cosmetics and the like.

[Conventional technology]

Alkyl phosphates and their alkali metal salts, alkanolamine salts are widely used as detergents, emulsifiers, antistatic agents, fiber oils, rust preventives, lubricant additives, etc. It is widely used in cosmetics and cosmetics as a surfactant with extremely low toxicity and skin irritation and high safety for the human body. However, when an emulsified system is prepared by using a salt of phosphoric acid monoester, crystallization with time occurs, and the yield value and the viscosity are drastically reduced accordingly, which is a drawback that it is difficult to use as a cosmetic emulsifier. It was being done.

However, a salt of a specific phosphoric acid monoester, for example, an arginine salt of a phosphoric acid monoester is known to be useful as an emulsifier that forms a stable and good emulsion over time regardless of the type of oil, Further, since it forms a stable gel regardless of the type of oil, it is also useful as a raw material for perfumed cosmetics.

Thus, the arginine salt of phosphoric acid monoester useful as a raw material for fragrance cosmetics is conventionally prepared by dissolving phosphoric acid monoester in methanol and then adding arginine dissolved in ion-exchanged water and stirring to obtain a paste form. It was manufactured by filtering a solid substance and washing with methanol.

[Problems to be Solved by the Invention]

However, when the arginine salt of phosphoric acid monoester is produced by this method, the crystallinity of the paste-like solid is poor, the viscosity is high, and the handling is difficult, and moreover, with a normal filtration device (pressure filtration, vacuum filtration). Since the filter cloth or the filter paper is clogged, filtration is difficult, and a great amount of labor is required for pulverization, it is not satisfactory as a method for industrial mass production.

Therefore, a method for industrially producing a large amount of an arginine salt of a phosphoric acid monoester in a simple manner has been desired.

[Means for Solving the Problems]

Under such circumstances, as a result of intensive studies, the present inventors have found that the amount of water at the time of neutralization has a great influence on the filterability of the arginine salt of the phosphoric acid monoester to be produced. It was found that the filterability can be significantly improved by neutralizing the amount of water or the amount of water to a minimum and then pulverizing the salt in a specific organic solvent, and completed the present invention.

That is, the present invention relates to the following phosphoric acid monoester (II)
In an alcohol or a saturated or unsaturated hydrocarbon solvent which may contain 0.5 times by weight or less of water, a compound represented by the general formula (II) (In the formula, m represents 0 or 1. Here, when m is 0,
R ¹ is a linear or branched alkyl group or alkenyl group having 1 to 36 carbon atoms in which one or more hydrogen atoms may be substituted with a fluorine atom, or a linear or branched alkyl group having 1 to 15 carbon atoms. A phenyl group substituted with a group, R ² represents an alkylene group having 2 to 3 carbon atoms, and n represents a number of 0 to 30. When m is 1, n represents 0, l represents 0 or 1, and l
When is 0, R ¹ represents a straight-chain alkyl group having 1 to 22 carbon atoms in which one or more hydrogen atoms may be substituted with a fluorine atom,
1 is 1 and R ¹ is a linear or branched alkyl or alkenyl group having 1 to 36 carbon atoms in which one or more hydrogen atoms may be replaced by fluorine atoms. Is neutralized with arginine to obtain a liquid or emulsion containing the arginine salt of phosphoric acid monoester, and then contacting this liquid or emulsion with a solvent in which the arginine salt of phosphoric acid monoester is sparingly soluble, A general formula (I) characterized by precipitating a powder of an arginine salt of a phosphoric acid monoester and filtering the powder. (Wherein R ¹ , R ² , 1, m and n have the same meaning as described above), and a method for producing an arginine salt of a phosphoric acid monoester represented by the formula.

Examples of the phosphoric acid monoester (II) used in the present invention include monooctyl phosphoric acid, monolauryl phosphoric acid, monostearyl phosphoric acid, monononylfluorohexyl phosphoric acid,
Mono-linear alkyl phosphates such as monotridecyl fluorooctyl phosphate and monoheptadecyl fluorodecyl phosphate; monoisostearyl phosphate, mono 8-methyl-heptadecyl phosphate, mono 2-hexyldecyl phosphate, etc. Monoalkylphenylphosphoric acid such as branched-chain alkylphosphoric acid, monooctylphenylphosphoric acid and monononylphenylphosphoric acid; monopolyoxyethylene (3 mol) lauryl ether phosphoric acid, monopolyoxypropylene (3 mol) decyl ether phosphoric acid, monopoly Oxyethylene (8 mol) polyoxypropylene (3 mol) monopolyoxyalkylene alkyl ether phosphoric acid such as lauryl ether phosphoric acid; monopolyoxyethylene (5 mol) nonylphenyl ether phosphoric acid, monopolyoxypropylene (2 mol) octyl Monopoli oxyalkyl phenyl ether phosphoric acid, such as E alkenyl ether phosphate; 1-octyl-glycerophosphate 3-phosphate, 1 Rauringurisero -3
-Phosphoric acid, hydroxydecyl phosphoric acid, 2-hydroxylauryl phosphoric acid, etc. may be mentioned.

These phosphoric acid monoesters can be obtained by reacting the corresponding organic hydroxy compound or glycidyl ether compound, or α-olefin epoxide with a phosphorylating agent such as phosphorus pentoxide, phosphorus oxychloride and polyphosphoric acid by a known method. You can

In the present invention, first, phosphoric acid monoester (II),
Mix with alcohol or saturated or unsaturated hydrocarbon and raise the temperature to 30 ° C or higher, preferably 30 to 80 ° C.
The alcohol or saturated or unsaturated hydrocarbon used here may contain water in advance, and the amount of water contained is 0 to 0.5 part by weight, preferably 0 to 0.3 part by weight with respect to the phosphoric acid monoester. It may be within the range of parts. Examples of alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, isopropanol, and cyclohexanol. Examples of saturated hydrocarbons include pentane, hexane, heptane, and the like, and unsaturated hydrocarbons include benzene. , Toluene, xylene and the like, among which ethanol, isopropanol, hexane and xylene are preferable.

After the temperature is raised, the arginine powder is added in an equimolar amount to the phosphoric acid monoester, and the mixture is stirred until no floating arginine powder is observed to complete the neutralization. Here, the arginine to be charged may be any of L-form, D-form, and DL-form, and may be not only powder but also an arginine aqueous solution. The amount of water in the aqueous arginine solution may be 0.5 weight times or less of the total amount of the water in the solvent and the phosphoric acid monoester (II). The powder or the aqueous solution may be charged all at once or in several times.

Next, the obtained liquid or emulsion containing the arginine salt of phosphoric acid monoester is mixed with a solvent in which the arginine salt of phosphoric acid monoester is sparingly soluble, and 0 to 60 ° C., preferably
Stir at 20-40 ° C. to precipitate the arginine salt of phosphoric acid monoester as a powder. Here, the sparingly soluble refers to those having a solubility at 25 ° C. of 30% by weight or less, and examples of the solvent in which the arginine salt of phosphoric acid monoester is sparingly soluble include acetone, dimethylformamide, dimethylsulfoxide, and methylethylketone. Of these, acetone is particularly preferable. These solvents are used in an amount of 1 to 10 times by weight, preferably 1 to 5 times by weight, based on the weight of the phosphoric acid monoester.

The powder obtained by precipitating in this way has very good filterability, and by operations such as pressure filtration and vacuum filtration,
It can be easily filtered. After filtration and drying under reduced pressure at 20 to 60 ° C, the desired powder of arginine salt of phosphoric acid monoester can be obtained.

〔The invention's effect〕

According to the present invention, arginine salt of phosphoric acid monoester useful as a raw material for perfume cosmetics is industrially produced in large quantity and easily by pulverizing in a specific organic solvent and improving filterability. be able to.

〔Example〕

Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.

Example 1 Monolauryl phosphoric acid 100 g (first equivalence point acid value 208.3, second equivalence point acid value 418.2, 0.371 mol) was dissolved in ethanol 100 g and heated to 60 ° C., and then L-arginine 64.6 g (0.371 mol). And stir until there is no floating L-arginine powder. The neutralized product thus obtained is put into 300 g of acetone with stirring, and the mixture is pulverized by stirring at 30 ° C. for 3 hours. The precipitated powder was filtered by vacuum filtration and dried to obtain 162 g of L-arginine monolaurylphosphate salt.

Elemental analysis value Theoretical value C: 49.1 H: 9.4 N: 12.7 P: 7.0 Actual value C: 48.5 H: 9.5 N: 12.5 P: 7.2 Example 2 100 g of mono-2-hexyldecyl phosphate (first equivalent point acid value 17
2.8, second equivalent point acid value 342.8, 0.308 mol) ethanol 1
After dissolving in 00g and heating to 60 ° C, L-arginine 53.6g (0.30
8 mol) and stir until there are no floating L-arginine powders. The neutralized product obtained in this way
Pour into 300 g of acetone with stirring and stir at 30 ° C. for 3 hours to pulverize. The precipitated powder was filtered by vacuum filtration and dried to obtain 150 g of L-arginine salt of mono-2-hexyldecylphosphoric acid.

Elemental analysis value Theoretical value C: 53.2 H: 9.9 N: 11.3 P: 6.2 Measured value C: 53.0 H: 10.1 N: 11.0 P: 6.2 Example 3 100 g of monotrioxyethylene lauryl phosphoric acid (first equivalent point acid value 141.8 , Second equivalent point acid value 283.0, 0.253 mol) was dissolved in 100 g of ethanol and the temperature was raised to 60 ° C., then L-arginine 4
Add 4.0 g (0.253 mol) and stir until there is no floating L-arginine powder. The neutralized product thus obtained was added to 300 g of acetone while stirring, and the temperature was adjusted to 30 ° C.
Stir for 3 hours to pulverize. The precipitated powder was filtered off under reduced pressure and dried to obtain 143 g of L-arginine salt of monotrioxyethylene lauryl phosphoric acid.

Elemental analysis value Theoretical value C: 50.2 H: 9.5 N: 9.8 P: 5.4 Actual value C: 49.7 H: 9.3 N: 9.5 P: 5.5 Example 4 Mono 1-lauryl glycero-3-phosphate 100 g (first equivalent point) Acid value 165.0, second equivalent point acid value 326.4, 0.294 mol) was dissolved in 100 g of ethanol and the temperature was raised to 60 ° C., then L-arginine 5
Add 1.2 g (0.294 mol) and stir until there is no floating L-arginine powder. The neutralized product thus obtained was added to 300 g of acetone while stirring, and the temperature was adjusted to 30 ° C.
Stir for 3 hours to pulverize. The precipitated powder was filtered by vacuum filtration, dried and mono-1-laurylglycero-3-.
150 g of L-arginine salt of phosphoric acid was obtained.

Elemental analysis value Theoretical value C: 49.0 H: 9.2 N: 10.9 P: 6.0 Measured value C: 48.6 H: 9.1 N: 10.6 P: 5.8 Example 5 100 g of mono-2-hydroxylauryl phosphate (first equivalent point acid value 199.5) , Second equivalent point acid value 395.0, 0.355 mol) was dissolved in 100 g of ethanol and the temperature was raised to 60 ° C., and then 61.9 g of L-arginine.
(0.355 mol) is added and floating L-arginine 61.9g
(0.355 mol), and stir until there is no floating L-arginine powder. The neutralized product thus obtained was added to 300 g of acetone while stirring, and the mixture was stirred at 30 ° C. for 3 days.
Stir for time to pulverize. The powder thus precipitated was filtered off by vacuum filtration and dried to obtain 159 g of L-arginine salt of mono-2-hydroxylauryl phosphoric acid.

Elemental analysis value Theoretical value C: 47.4 H: 9.1 N: 12.3 P: 6.8 Measured value C: 47.6 H: 9.0 N: 12.6 P: 6.3 Example 6 Monolauryl phosphoric acid 100 g (first equivalent point acid value 208.3, second Equivalent point acid value 418.2, 0.371 mol) 10% hydrous ethanol 10
After being dissolved in 0 g and heated to 60 ° C., L-arginine 64.6 g (0.371
Mol) and stir until there is no floating L-arginine powder. The neutralized product thus obtained is
Pour into 0 g of acetone with stirring and stir at 30 ° C. for 3 hours to pulverize. The precipitated powder is filtered off by vacuum filtration,
After drying, 160 g of L-arginine salt of monolauryl phosphoric acid was obtained.

Elemental analysis value Theoretical value C: 49.1 H: 9.4 N: 12.7 P: 7.0 Actual value C: 48.4 H: 9.5 N: 12.5 P: 7.1 Example 7 Mono-2-hexyldecylphosphoric acid 100 g (first equivalent point acid value 17
2.8, second equivalent point acid value 342.8, 0.308 mol) was dissolved in 100 g of 5% hydrous ethanol and the temperature was raised to 60 ° C., then L-arginine 5
Add 3.6 g (0.308 mol) and stir until there is no floating L-arginine powder. The neutralized product thus obtained was added to 300 g of acetone while stirring, and the temperature was adjusted to 30 ° C.
Stir for 3 hours to pulverize. The precipitated powder was filtered by vacuum filtration and dried to obtain 151 g of L-arginine salt of mono-2-hexyldecylphosphoric acid.

Elemental analysis value Theoretical value C: 53.2 H: 9.9 N: 11.3 P: 6.2 Actual value C: 52.7 H: 10.0 N: 11.1 P: 6.2 Example 8 Monotridecyl fluorooctyl phosphate 100 g (first equivalent point acid value 127.3 , Second equivalent point acid value 251.5, 0.227 mol) 5
% Dissolved in 100 g of water-containing ethanol, heated to 60 ° C., charged with 39.5 g (0.227 mol) of L-arginine, and stirred until floating L-arginine powder disappeared. The neutralized product thus obtained is put into 300 g of acetone with stirring, and the mixture is pulverized by stirring at 30 ° C. for 3 hours. The precipitated powder was filtered by vacuum filtration and dried to obtain 138 g of L-arginine salt of monotridecylfluorooctylphosphoric acid.

Elemental analysis value Theoretical value C: 27.2 H: 3.4 N: 9.1 P: 5.0 F: 39.9 Measured value C: 26.7 H: 3.2 N: 8.8 P: 5.1 F: 39.2 Example 9 Monolauryl phosphate 100 g (first equivalent point) Acid value 208.3, second equivalent point acid value 418.2, 0.371 mol) 25% hydrous ethanol 10
After being dissolved in 0 g and heated to 60 ° C., L-arginine 64.6 g (0.371
Mol) and stir until there is no floating L-arginine powder. The neutralized product thus obtained is
Pour into 0 g of acetone with stirring and stir at 30 ° C. for 3 hours to pulverize. The precipitated powder is filtered off by vacuum filtration,
After drying, 157 g of an L-arginine salt of monolauryl phosphoric acid was obtained.

Elemental analysis value Theoretical value C: 49.1 H: 9.4 N: 12.7 P: 7.0 Actual value C: 48.9 H: 9.2 N: 12.3 P: 7.1 Example 10 Monolauryl phosphoric acid 100 g (first equivalent point acid value 208.3, second Equivalent point acid value 418.2, 0.371 mol) was dissolved in 90 g of hexane, 10 g of water was added and the temperature was raised to 60 ° C, and then 64.6 g of L-arginine (0.
371 mol) and stir until there is no floating L-arginine powder. The neutralized product thus obtained is put into 300 g of acetone with stirring and stirred at 30 ° C. for 3 hours to be powdered. The precipitated powder was filtered by vacuum filtration and dried to obtain L-arginine salt of monolauryl phosphate.
I got 7g.

Elemental analysis value Theoretical value C: 49.1 H: 9.4 N: 12.7 P: 7.0 Actual value C: 48.7 H: 9.2 N: 12.5 P: 7.1 Example 11 100 g of mono-2-hexyldecyl phosphate (first equivalent point acid value 17
2.8, second equivalent point acid value 342.8, 0.308 mol) hexane 90 g
Dissolve in 10 g of water, add 10 g of water, raise the temperature to 60 ° C, and then add L-arginine 5
Add 3.6 g (0.308 mol) and stir until there is no floating L-arginine powder. The neutralized product thus obtained is put into 500 g of acetone with stirring and stirred at 30 ° C. for 3 hours to be powdered. The precipitated powder was filtered off under reduced pressure, dried, and dried with L of mono-2-hexyldecylphosphate.
-149 g of arginine salt are obtained.

Elemental analysis value Theoretical value C: 53.2 H: 9.9 N: 11.3 P: 6.2 Actual value C: 53.5 H: 9.7 N: 11.5 P: 6.0

Claims (1)

[Claims] 1. A compound of the general formula (II) in an alcohol or a saturated or unsaturated hydrocarbon solvent which may contain water in an amount not more than 0.5 times by weight the amount of the following phosphoric acid monoester (II). (In the formula, m represents 0 or 1. Here, when m is 0,
R ¹ is a linear or branched alkyl group or alkenyl group having 1 to 36 carbon atoms in which one or more hydrogen atoms may be substituted with a fluorine atom, or a linear or branched alkyl group having 1 to 15 carbon atoms. A phenyl group substituted with a group, R ² represents an alkylene group having 2 to 3 carbon atoms, and n represents a number of 0 to 30.
When m is 1, n is 0, l is 0 or 1, and l is 0
Then R ¹ represents a straight chain alkyl group having 1 to 22 carbon atoms in which one or more hydrogen atoms may be replaced by fluorine atoms, and when l is 1, R ¹ represents one or more hydrogen atoms as fluorine atoms. (A linear or branched alkyl or alkenyl group having 1 to 36 carbon atoms which may be substituted) is neutralized with arginine to contain an arginine salt of the monoester of phosphoric acid. A liquid or emulsion is obtained, and the liquid or emulsion is then contacted with a solvent in which the arginine salt of phosphoric acid monoester is sparingly soluble to precipitate a powder of the arginine salt of phosphoric acid monoester, and the powder is filtered. General formula (I) characterized by taking (Wherein R ¹ , R ² , 1, m and n have the same meanings as described above), and a method for producing an arginine salt of a phosphoric acid monoester represented by the formula: