JPS592287B2 - Method for producing phosphate esters of polyoxyalkylene glycols - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a stable phosphoric ester of polyoxyalkylene glycols that has excellent performance for use in cosmetics and does not change over time.

It is already known that phosphoric acid esters of polyoxyalkylene glycols have excellent performance as cosmetics. For example, in Japanese Patent Publication No. 48-11955, phosphoric acid esters of polyalkylene glycol and polyalkylene glycol monoalkyl ether were used as liquid hair conditioners.
No. 29141 describes the use of a phosphorylated polymer of polypropylene glycol in hair cosmetics.
However, ingredients that can be widely used in cosmetics, including hair cosmetics, must not change over a long period of time and must always be stable and usable as cosmetics. However, among phosphoric acid esters, monoesters are very stable and preferable, but diesters are unstable and decompose into monoesters and alcohol components, i.e. polyoxyalkylene glycols, which not only change the solubility but also change the pH. It has a fatal flaw as a cosmetic. Furthermore, triester is not only unstable like diester, but also hardly improves hydrophilicity, and has little effect on converting polyoxyalkylene glycol into phosphate ester. Special Publication No. 11955 of 1977 states that monoester, diester, or triester may be used;
129141 describes it as a phosphorylated polymer, which seems to be mainly composed of diesters and triesters. In addition, various methods for producing phosphoric acid monoesters with good yield are known, but in general, in conventional methods, monoesters containing a large amount of monoester produce a large amount of inorganic phosphoric acid as a by-product.
When used as a cosmetic, inorganic phosphate inhibits its performance.

Furthermore, when the molecular weight of polyoxyalkylene glycols is about 1000 or more, it is difficult to react with phosphoric anhydride, and in severe cases, only tar-like substances are produced, and the phosphoric acid esters of polyoxyalkylene glycols are almost completely removed. I can't get it. In view of the current situation, the present inventors believed that even more excellent cosmetics could be obtained by establishing a method for producing phosphoric acid monoester in high yield, and as a result of various studies, they completed the present invention.

That is, the object of the present invention is to obtain a phosphoric ester of polyoxyalkylene glycols with a large monoester content, and when used in cosmetics, it has excellent performance and does not change over time. The present invention provides a stable cosmetic and solves the problems of the conventional manufacturing methods mentioned above. Hereinafter, to explain the present invention, ethyl alcohol, propyl alcohol, or a mixture thereof is added to polyoxyalkylene glycols in advance, and phosphoric anhydride is added thereto at a temperature of about 60°C or less to form a phosphoric acid ester. become

The addition of ethyl alcohol, etc. not only allows the esterification reaction to proceed uniformly and suppresses excessive elevation of the molecular weight and the formation of complex polymers, but also prevents polyoxyalkylene glycols with a molecular weight of 1000 or more. Even if you use
It has the extremely important effect of not producing tar-like substances and producing phosphoric acid esters without coloring or odor. Next, add water and heat at a temperature of 60 to 100°C to about 0.
Heat for 5 hours or more to decompose.

This step is also extremely important, as it not only moderately lowers the molecular weight of the produced phosphoric acid ester, but also selectively decomposes the ester moiety mainly due to lower alkyl groups such as ethyl alcohol or propyl alcohol. Decomposes into phosphoric acid monoester and ethyl or propyl alcohol. The raw materials used in these reaction steps are 1 mol of phosphoric anhydride to 0.0 mol of polyoxyalkylene glycols.
5-3 mol, 0.1-3 mol of ethyl alcohol or propyl alcohol or a mixture thereof, 0.5 mol of water
It is more effective to use it in a molar or higher proportion.

The phosphoric acid ester of polyoxyalkylene glycols thus obtained contains a large amount of monoester, is stable and has good properties and appearance, and can be used in cosmetics by converting it into an appropriate salt. The present invention provides cosmetics such as basic cosmetics for use as hair cosmetics or moisturizers that do not change over time and are stable, which is not found in conventional products.

Polyoxyalkylene glycols that can be used in the present invention include polypropylene glycol consisting of a homopolymer of propylene oxide or butylene oxide, polybutylene glycol or a copolymer consisting of two or three of ethylene oxide, propylene oxide, butylene oxide, and methyl Alcohol, monohydric alcohols such as ethyl alcohol, propyl alcohol, butyl alcohol, polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, sugars such as xylose, glucose, sugar rose, propylene oxide, butylene oxide, each alone or Polyoxyalkylene glycols having a molecular weight of 500 or more are added with two or three of ethylene oxide, propylene oxide, and butylene oxide, and it does not matter whether they are used alone or in combination.

According to the present invention, even polyoxyalkylene glycols having a relatively high molecular weight of about 1,000 to 4,000, which could not be easily esterified with phosphoric anhydride, can be sufficiently utilized. In addition, the alcohols to be added in advance to polyoxyalkylene glycols include not only pure ethyl alcohol, n-propyl alcohol, and isopropyl alcohol, but also geraniol,
Ethyl alcohol modified with 8-acetylated sucrose, brucine, etc. can also be used, and a mixture of these can also be used.

Furthermore, when preparing cosmetics from this phosphate ester, sodium, potassium, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-2-methyl-1 - Salts neutralized to near neutrality with propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, morpholine, etc. can be used, and these can be used in combination. is also possible.

In addition, there are various known phosphorylating agents other than phosphoric anhydride, but when polyphosphoric acid or phosphoric acid is used, a large amount of inorganic phosphoric acid remains after the esterification reaction, so it is difficult to use phosphorous oxychloride. In this case, treatment of by-produced hydrochloric acid becomes complicated, so neither is preferable. That is, phosphoric anhydride is most suitable as the phosphorylating agent in the present invention. As described above, in the present invention, when obtaining phosphoric esters of polyoxyalkylene glycols, in order to increase the yield of monoester, ethyl alcohol, propyl alcohol, etc. are added before and after esterification, respectively. and water decomposition process, and finally,
The purpose is to obtain stable cosmetics.

Hereinafter, comparative examples based on experiments are shown in Tables 1 and 2 to further clarify the present invention and also describe the effects of the present invention. That is, Table 1 shows the case where ethyl alcohol and water are used as in the present invention (Experiment 1) and the case where only ethyl alcohol is used (Experiment 2) using glycerin-propylene oxide adduct (molecular weight 3000) as a starting material. , when using only water (
Experiment 3) and the case in which neither ethyl alcohol nor water was used (Experiment 4) were compared in terms of the properties and composition of the phosphoric acid esters obtained. This paper compares the properties, appearance, stability over time, etc. of liquid hair preparations prepared using acid esters.

According to these, in Experiment 1, that is, in the present invention,
It can be seen that the yield of monoester is higher than that of diester, and the amount of by-product of inorganic phosphoric acid is extremely small.

In addition, the increase in molecular weight and the formation of complex polymers or tar-like byproducts are suppressed, and there is almost no color or odor, and the reaction between polyoxyalkylene glycols and phosphoric anhydride proceeds uniformly. It shows that there is. Furthermore, when a liquid hair conditioner is made using this phosphoric acid ester,
It is almost colorless and transparent with almost no change in pH over time, indicating that it has excellent performance as a cosmetic.

It is clear that even if ethyl alcohol, propyl alcohol, etc. remain in the phosphoric acid ester, there will be no problem as a cosmetic. Next, in Experiment 2, that is, when the step of decomposition with water is excluded, the increase in molecular weight is somewhat suppressed due to the effect of adding ethyl alcohol, and a light-colored phosphoric acid ester with less tar-like substances is obtained.
The yield of monoester is low, and when it is used as a liquid hairdressing product, it exhibits a pale yellow color, and a relatively large change in pH over time is observed.

Furthermore, in Experiment 3, that is, when the step of adding ethyl alcohol was excluded, the amount of by-product of inorganic phosphoric acid and the remaining amount of unesterified polyoxyalkylene glycol increased, and tar-like substances were generated. Discoloration is also observed.

When a liquid hair conditioner is prepared using this phosphoric acid ester, it not only contains a large amount of unesterified polyoxyalkylene glycol and has a yellow color and a strange odor, but also contains dissolved salts of inorganic phosphoric acid. Due to the lack of transparency, the liquid is not transparent, which is not desirable. In Experiment 4, that is, when neither ethyl alcohol nor water was used, a large amount of tar-like material was produced, making it impossible to obtain a uniform phosphoric acid ester.

Therefore, it is almost impossible to use this in cosmetics, and test results when cosmetics were prepared using this are excluded from Table 2. As is clear from these comparative examples, phosphoric acid esters, which have physical properties that should be used as the main ingredients of cosmetics with excellent performance and stability, do not require the addition of ethyl alcohol, propyl alcohol, etc. or water during the manufacturing process. This can only be achieved effectively by the presence of both decomposition steps.

In particular, when polyoxyalkylene glycols with high molecular weight are used as starting materials, the reaction will not proceed normally without these steps, and according to the present invention, cosmetics that are sufficiently good even with these steps can be obtained. can be obtained. As described above, according to the present invention, phosphoric acid esters of polyoxyalkylene glycols having a high monoester content and a small amount of inorganic phosphoric acid by-product can be obtained even from high molecular weight polyoxyalkylene glycols. By using this, it is possible to make a stable and excellent cosmetic that has almost no change in pH over time, is almost colorless and transparent, and has no off-odor.

Finally, examples of the present invention will be described to further embody the structure and effects of the present invention.

Example 1 Butanol-propylene oxide adduct (molecular weight 13
00) 6507 (0.5 mol) and ethyl alcohol4.
67 (0.1 mol) was placed in a four-liter flask, and phosphoric anhydride 28.47 (0.2 mol) was added to the flask.
Add for 1 hour at 0'C.

After further stirring for 1 hour, 7.27 (0.4 mol) of water was added and heated at 80-85°C for 2 hours. The obtained phosphoric acid ester had a color (APHA) of 70 and almost no odor, and as a result of acid value measurement, it was found that the inorganic phosphoric acid was 0.2% and the monoester-diester ratio was 78%-22%. The following table shows a performance comparison between this Example 1 and various comparative examples that do not include the step of addition of alcohol and/or decomposition with water.

Next, when a liquid hair styling product was prepared using the phosphoric acid ester according to Example 1 according to the following formulation, a light colored hair styling product with no odor was obtained, and even after being left at 40°C for 50 days, the PH and other properties remained unchanged. No changes were observed.

Formulation Example 2 Glycerin-propylene oxide-butylene oxide adduct (molecular weight 27001, propylene oxide-butylene oxide molar ratio 40:60) 6487 (0.
24 mol) and ethyl alcohol 1.4 y (0.0
3 mol), isopropyl alcohol 1.8 t (0.0
3 mol) was placed in a 1 liter flask, and 30 to 2.6 y (0.3 mol) of phosphoric anhydride was added to it.
Add for 1 hour at 40°C.

After stirring for another hour, water 8. ly (0.4 5 mol)
was added and heated at 75 to 80°C for 3 hours. The obtained phosphoric acid ester had a color (APHA) of 50, almost no odor, 0.25% inorganic phosphoric acid, and a monoester to diester ratio of 82% to 18%. The following table shows a performance comparison between this Example 2 and various comparative examples that do not include the step of addition of alcohol and/or decomposition with water.

Next, when a liquid hair conditioner was prepared using the phosphoric acid ester according to Example 2 according to the following formulation, a good product was obtained and was stable and did not change over time.

Example 3 Butanol-propylene oxide adduct (molecular weight 13
00) 1O4t (0.08 mol), glycerin-propylene oxide adduct (molecular weight 4 8 0 0) 2 8
8 V (0.06 mol) and isopropyl alcohol 6y (0.1 mol) were placed in a 1-liter four-ton flask, and phosphoric anhydride 14.2y (0.1 mol) was added to it at 40 to 45°C. Add in 1 hour.

After further stirring for 1 hour, 3.6 y (0.2 mol) of water was added and heated at 80 to 85°C for 2 hours. The obtained phosphoric acid ester was almost colorless and odorless, and the monoester to diester ratio was 75% to 25%. The following table shows a performance comparison between this Example 3 and various comparative examples that do not include the step of addition of alcohol and/or decomposition with water.

Next, an aerosol hair conditioner prepared using the phosphoric acid ester according to Example 3 according to the following formulation had no off-odor and was heated to 40°C at 40°C.
When the aerosol can (made of tin) was opened after being left for 100 days, there was no corrosion of the can, and no abnormality was observed in terms of pH, color, or odor.

Formulation Example 4 Sorbitol-propylene oxide adduct (molecular weight 1
200) 5407 (0.45 mol), ethyl alcohol, and 16.67 (0.36 mol) were placed in a 1 liter four-bottle flask, and 42.67 (0.3 mol) of phosphoric anhydride was added to the flask.
mol) in 1.5 hours at 30-35°C.

After further stirring at 50°C for 2 hours, water 10.87 (0.6
mol) was added and heated at 70'C for 3 hours. The obtained phosphoric acid ester had a color (APHA) of 180 and almost no odor, and the monoester-diester ratio was 80%-20%. The following table shows a performance comparison between this Example 4 and various comparative examples that do not include the step of addition of alcohol and/or decomposition with water. Next, a cream prepared using the phosphate ester according to Example 4 according to the following formulation shows no change over time, has good stability, and has appropriate moisturizing properties due to the potassium salt of the phosphate ester. Ta.

Claims (1)

[Claims] 1. Polyoxyalkylene glycols characterized by esterifying polyoxyalkylene glycols by adding ethyl alcohol, propyl alcohol, or a mixture thereof when esterifying polyoxyalkylene glycols with phosphoric anhydride, and then decomposing by adding water. A method for producing a phosphoric acid ester.