JP3242880B2 - Cosmetic base - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an emulsifier comprising a polyoxyethylenated polypropylene glycol,
The present invention relates to a cosmetic base used as a humectant or the like. More particularly, the present invention relates to a cosmetic base free of odor during production and after long-term storage.

[0002]

2. Description of the Related Art Polyoxyethylene-polyoxypropylene block copolymers are used in various industrial fields as surfactants such as emulsifiers, dispersants and defoamers. Particularly, a polyoxyethylene-polyoxypropylene block copolymer is used as a base for cosmetics because of its excellent safety, emulsifiability, moisture retention and the like. However, many of the polyoxyethylene-polyoxypropylene block copolymers have a peculiar odor, and since this odor becomes particularly strong with the lapse of time after production, improvement has been demanded.

Conventionally, there has been known a method of adding a stabilizer such as an antioxidant or a photo-deterioration inhibitor to suppress generation of odor during production and during long-term storage. However, regarding the polyoxyethylene-polyoxypropylene block copolymer used for the cosmetic base, the type and amount of the stabilizer are limited, and an effective effect cannot be expected within the limit. In Japanese Patent Publication No. 52-33000,
A method of neutralizing with carbon dioxide to remove neutralized salts is described. However, the neutralized salt produced by this method has a very small particle size and requires a great deal of labor and time for removal. Japanese Patent Publication No. 56-5414 describes a method of deodorizing using steam or nitrogen gas. However, in this method, even if the odor is temporarily reduced, the odor reduction effect during long-term storage is low. JP 5
JP-A-6-104936 discloses a method in which a polyether is treated under acidic conditions to decompose a propenyl ether group, and then dealdehyde is obtained.
No. 4720 describes a method in which a polyether is treated with phosphorus pentoxide under acidic conditions and then neutralized. However, any of these methods is insufficient to suppress the generation of odor over time. Tokuho 3-4145
No. 4 describes a method of adding lactic acid and / or lactate to an alkylene oxide adduct. This method has the effect of suppressing the generation of odor over time as compared with the conventional method containing acetic acid or the like, but is still insufficient. JP-A-5-294880 describes a method using a fatty acid metal salt as a reaction catalyst.
However, since the catalyst of this method has a lower catalytic activity than a conventional alkali metal hydroxide catalyst or the like, when this method is carried out on the polyoxyethylene-polyoxypropylene block copolymer of the present invention, a great deal of Takes time.

[0004]

As described above, as described above,
Without using stabilizers such as antioxidants and light deterioration inhibitors,
It is difficult to produce a polyoxyethylene-polyoxypropylene block copolymer having no odor during production and during long-term storage, and it is difficult to use a polyoxyethylene-polyoxypropylene block copolymer as a cosmetic base. , Need to mask with fragrance,
The compounding amount in cosmetics is limited.

[0005]

Means for Solving the Problems The present inventors do not use a stabilizer such as an antioxidant or a photo-deterioration inhibitor, have no odor at the time of production and at the time of long-term storage, and therefore mask by using a fragrance. Or, as a result of intensive research on a base that does not need to set a limit on the blending amount, it was manufactured under specific conditions,
The present inventors have found that a cosmetic base comprising a polyoxyethylene-polyoxypropylene block copolymer having a low content of a propenyl ether group as an unsaturated ether group solves this problem, and completed the present invention. That is, the present invention comprises a polyoxyethylenated polypropylene glycol (A), and (A) converts propylene oxide to a glycol compound at a temperature of 60 to 90 ° C. in the presence of a potassium-based and / or cesium-based catalyst. An ethylene oxide adduct of polypropylene glycol obtained by an addition reaction, wherein the content of the propenyl ether group in (A) is 0.001 meq / g or less. .

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the cosmetic base comprising the polyoxyethylenated polypropylene glycol (A) of the present invention, the number average molecular weight of the polypropylene glycol portion is a value exceeding 1000, preferably 1500.
４4500. When the number average molecular weight of the polypropylene glycol part is less than 1000, the function of the polypropylene glycol part as a hydrophobic group is small, and the emulsifying performance is low. The proportion of polyoxyethylene in the polyoxyethylenated polypropylene glycol (A) is 10 to 9
0% by weight. When the proportion of polyoxyethylene is less than 10% by weight or more than 90% by weight, the polypropylene glycol (A) has low emulsifying performance.

The polypropylene glycol (A) of the present invention
Is obtained by addition polymerization of ethylene oxide to polypropylene glycol. Polypropylene glycol is obtained by addition polymerization of propylene oxide to a glycol compound in the presence of a catalyst. As the glycol compound, propylene glycol, dipropylene glycol or a propylene oxide adduct thereof is used. Examples of the potassium-based catalyst and the cesium-based catalyst used as the catalyst include potassium and cesium hydroxides, oxides, alcoholates, hydrides, and metals.
In addition, these aqueous solutions and solvent-diluted products can also be used. Of these, potassium hydroxide and cesium hydroxide are preferred. The amount of the catalyst used is usually 0.01 to 5% by weight, and preferably 0.03 to 3% by weight, based on the polypropylene glycol obtained by addition polymerization. If the amount of the catalyst used is less than 0.01% by weight, the time required for the reaction becomes longer. If the amount of the catalyst exceeds 5% by weight, it is difficult to remove the catalyst, and when the catalyst is neutralized, many neutralized salts are present in the system, which is not preferable. In the addition polymerization of propylene oxide to a glycol compound in the presence of a catalyst to obtain polypropylene glycol (A),
The reaction temperature is from 60 to 90 ° C, preferably from 70 to 80 ° C.
° C. When the reaction temperature is lower than 60 ° C., the time required for the reaction is prolonged. When the reaction temperature is higher than 90 ° C., the allyl ether group is easily formed, and the allyl ether group is easily rearranged into a propenyl ether group. The content of the propenyl ether group in the polyoxyethylenated polyoxypropylene glycol (A) is 0.001.
It is difficult to obtain a cosmetic base having a milliequivalent / g or less.

[0008] Polypropylene glycol obtained by addition polymerization of propylene oxide to a glycol compound in the presence of a catalyst may be subjected to addition polymerization of ethylene oxide as it is, removal of the catalyst or neutralization, or addition polymerization. After removing and purifying impurities produced as byproducts,
Ethylene oxide may be subjected to addition polymerization.

As a method of removing and purifying the catalyst, there is a known method of filtering with a filter aid and / or an adsorbent. As a method of neutralizing the catalyst, there is a method of neutralizing with a carboxylic acid such as acetic acid or lactic acid, a mineral acid such as hydrochloric acid or sulfuric acid, an acid such as carbonic acid, phosphoric acid, or paratoluenesulfonic acid. Salt generated by neutralizing the catalyst may be removed by filtration or the like. As a method for removing and purifying impurities in polypropylene glycol obtained by addition polymerization of propylene oxide to a glycol compound in the presence of a catalyst, there is a method of stripping under reduced pressure.
This method is particularly effective when the impurities are low volatile compounds. In stripping, an inert gas such as nitrogen or water vapor may be introduced, or a low-boiling solvent or water may be added. Alternatively, a method of causing a reducing agent to act may be used.
This method uses impurities such as aldehydes and carboxyl compounds,
It is particularly effective when it is an oxygen-containing group such as a peroxide or an ester. As the reducing agent, sodium boron hydride, lithium aluminum hydride, hydrogen or the like is used. There is also a method in which water acts in the presence of an acid. This method is effective when the impurity is a compound containing a propenyl ether group. When the impurity is an allyl ether group-containing compound, there are also a method of reacting with hydrogen and a method of transferring water to propenyl ether by applying heat and then reacting with water in the presence of an acid.

[0010] The method of obtaining the polypropylene glycol (A) of the present invention by addition-polymerizing ethylene oxide to polypropylene glycol is carried out in the presence of a catalyst. As the catalyst, those similar to the potassium-based catalyst and the cesium-based catalyst described above can be used. Of these, hydroxides of potassium and cesium are preferred. The amount of catalyst used is
Usually, 0.005 to 5% by weight, preferably 0.1 to 5% by weight, based on the polypropylene glycol (A) obtained by addition polymerization.
01 to 0.5% by weight. 0.005 of catalyst used
If the amount is less than 5% by weight, the reaction time will be prolonged. If the amount is more than 5% by weight, it will be difficult to remove the catalyst. In order to obtain the terminal polyoxyethylenated polypropylene glycol (A) of the present invention in the presence of a catalyst, the reaction temperature is usually from 60 to 120C, preferably from 70 to 110C. If the reaction temperature is lower than 60 ° C., the reaction time becomes longer,
At a temperature exceeding 120 ° C., the already formed allyl ether group is easily rearranged into a propenyl ether group. It is difficult to obtain a cosmetic base having 0.001 meq / g or less.

The polypropylene glycol (A) thus obtained is usually stored after removing or neutralizing the catalyst. The catalyst can be removed by filtering with a filter aid and / or an adsorbent. When the catalyst is a basic compound, the catalyst is neutralized with a carboxylic acid such as acetic acid or lactic acid, a mineral acid such as hydrochloric acid or sulfuric acid, an acid such as carbonic acid, phosphoric acid, or paratoluenesulfonic acid. There is a way. In removing or neutralizing the catalyst, the temperature is usually lower than 120 ° C, preferably lower than 100 ° C, and most preferably 60 to 100 ° C. Temperature 12
If it exceeds 0, it is difficult to obtain a cosmetic base characterized by having no odor during the production and during long-term storage of the present invention.

In order for the polypropylene glycol (A) obtained as described above to function as a cosmetic base free of odor at the time of production and during long-term storage, the purpose of the present invention is to use polypropylene glycol (A). A)
It is necessary that the content of propenyl ether groups therein is 0.001 meq / g or less, preferably 0.001 meq / g.
It is not more than 05 meq / g.

The content (equivalent) of the propenyl ether group in the polypropylene glycol (A) can be determined according to a known method. That is, first, about 0.5 g of 2,4 dinitrophenylhydrazine (special grade reagent, about 50% water mixture) is placed in a 100 ml glass bottle, and about 20 ml of a 3 mol / l hydrochloric acid aqueous solution is added.
2,4 dinitrophenylhydrazine-hydrochloric acid aqueous solution (a)
Create Next, 2 g of the sample was precisely weighed in a 20 ml volumetric flask, and dissolved by adding about 10 ml of methanol. Then, about 1 ml of 2,4 dinitrophenylhydrazine-hydrochloric acid aqueous solution (a) was added, and methanol was added to add exactly 20 ml. Milliliter. Thereafter, the measuring flask is placed in a water bath at 50 to 55 ° C. for 30 minutes, and then cooled to room temperature. Set an ODS-based column in high-performance liquid chromatography and set the mobile phase (acetonyl / water = by volume ratio).
(50/50) at a flow rate of 1 milliliter per minute. The reaction product of propionaldehyde and 2,4-dinitrophenylhydrazine is separated using high performance liquid chromatography,
Determine the peak area of the reactants. The equivalent of propionaldehyde can be determined from the concentration-peak area relational expression prepared using a standard concentration solution of propionaldehyde. Since the content (equivalent) of propenyl ether group in the sample corresponds to the equivalent of propionaldehyde determined by this measurement method, the equivalent of propionaldehyde is the equivalent of propenyl ether group.

The cosmetic base of the present invention can be used in all fields used as cosmetics. That is, cleansing cosmetics used exclusively for washing off such as toilet soaps, facial cleansers, shampoos and rinses; hair cosmetics used exclusively for hair or scalp such as hair dyes and hair cosmetics; creams, colognes, lotions, cosmetic oils Basic cosmetics used for the purpose of keeping skin healthy, such as creams, packs, shaving creams, etc .; Make-up cosmetics such as whitening, foundation, blusher, eyeshadow, etc .; Fragrances used for flavoring, such as perfumes Cosmetics;
Sunburn / sunscreen cosmetics used exclusively for sunburn or sunscreen, such as suntan or sunscreen cream; nail cosmetics used exclusively for nail protection, make-up effect or removal, such as nail cream An eyeliner cosmetic used along with the eyelashes solely for the purpose of make-up effect, such as an eyeliner; a usage such as a bath additive put in or similar to a bathtub for the purpose of cleaning the body Bath cosmetics and the like used in the above. In particular, since the cosmetic base of the present invention has good odor and no bitterness or irritating taste when contained in the mouth, it is exclusively used for cleaning the oral cavity and preventing bad breath, such as tooth brushing and mouthwash. Oral cosmetics used for the purpose such as lipsticks, etc., exhibit particularly excellent effects when used for lip cosmetics used exclusively for the purpose of protecting the lips such as lipsticks, making-up effects and the like.

[0015]

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

Example 1 An autoclave having an internal volume of 2 liters was charged with a number average molecular weight of 4
Then, 400 parts of polypropylene glycol of No. 00 and 1.7 parts of potassium hydroxide were added to seal the mixture. After the gas phase in the vessel was replaced with nitrogen, stripping was performed under reduced pressure while maintaining the temperature at 120 ° C. to reduce the water content to 0.1% by weight or less. 1300 parts of propylene oxide were introduced at a pressure of 200 kPa (gauge pressure) or less while keeping the temperature in the vessel at 80 ° C., and reacted to obtain polypropylene glycol (a) having a number average molecular weight of 1700. In an autoclave with an internal volume of 2 liters,
300 parts of polypropylene glycol (A) was added and sealed. After replacing the gas phase in the autoclave with nitrogen, 1200 parts of ethylene oxide was introduced at a pressure of 300 kPa (gauge pressure) or less while keeping the temperature in the autoclave at 100 ° C., and reacted. Use phosphoric acid to pour the contents of the container.
By setting H to 7.5, the polyoxyethylenated polypropylene glycol (I) of the present invention having a number average molecular weight of about 8500 was obtained.

Example 2 An autoclave having an internal volume of 2 liters was charged with a number average molecular weight of 4
Then, 250 parts of polypropylene glycol and 1.7 parts of potassium hydroxide were added to seal the mixture. After the gas phase in the vessel was replaced with nitrogen, stripping was performed under reduced pressure while maintaining the temperature at 120 ° C. to reduce the water content to 0.1% by weight or less. 1250 parts of propylene oxide was introduced at a pressure of 200 kPa (gauge pressure) or less while keeping the temperature in the vessel at 80 ° C., and reacted to obtain polypropylene glycol (a) having a number average molecular weight of 2,400. Except that this polypropylene glycol (a) was used in place of the polypropylene glycol (a), ethylene oxide was reacted in the same manner as in Example 1 and neutralized with phosphoric acid to adjust the pH to 7.6. And a polyoxyethylenated polypropylene glycol (I) having a number average molecular weight of about 12,000.
I) was obtained.

Example 3 Propylene oxide was reacted in the same manner as in Example 2 except that 6.0 parts of 50% by weight of cesium hydroxide was used instead of 1.7 parts of potassium hydroxide to obtain polypropylene glycol. . Next, 30 parts of water and 30 parts of Kyoward 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) were added to the container, and 8
After stirring for 30 minutes while maintaining at 0 ° C., Kyoward 6
00 is removed by filtration using Radiolite 800, and the water in the container is further stripped under reduced pressure to obtain polypropylene glycol (C) having a number average molecular weight of 2400.
I got Ethylene oxide was reacted in the same manner as in Example 2 except that the polypropylene glycol (C) and 0.5 part of potassium hydroxide were used instead of the polypropylene glycol (A), and the pH was adjusted to 7.5 with phosphoric acid. As a result, a polyoxyethylenated polypropylene glycol (III) having a number average molecular weight of about 12,000 was obtained.

Comparative Example 1 The temperature at which propylene oxide was introduced was changed to 80 ° C.
Propylene oxide was introduced in the same manner as in Example 1 except that the temperature was 30 ° C., and polypropylene glycol (d) having a number average molecular weight of about 1700 was obtained. Then, polypropylene glycol (d) was replaced with polypropylene glycol (d). A polyoxyethylene for comparison having a number average molecular weight of about 8500 was obtained by introducing ethylene oxide under the same conditions as in Example 1 and adjusting the pH to 7.5 with phosphoric acid, except that it was used. Polypropylene glycol (IV) was obtained.

Comparative Example 2 Polyoxyethylenated polypropylene glycol was synthesized according to the examples described in JP-B-56-5414 introduced in the section of the prior art. That the temperature for introducing propylene oxide is 120 ° C. instead of 80 ° C.,
And polypropylene glycol (e) having a number average molecular weight of about 2400 in the same manner as in Example 1 except that 8.5 parts of sodium methylate was used instead of 1.7 parts of potassium hydroxide. Then, instead of using 300 parts of polypropylene glycol (A), 900 parts of polypropylene glycol (E) were used, and 600 parts were used instead of using 1200 parts of ethylene oxide.
Except that part was used, ethylene oxide was introduced and reacted under the same conditions as in Example 1 to obtain a crude polyoxyethylenated polypropylene glycol (f).
The crude polyoxyethylenated polypropylene glycol (f) was placed in a 2 liter reaction vessel, and the pH was adjusted to 7.0 with phosphoric acid. Then, steam distillation was performed by introducing steam while maintaining the vessel temperature of 105 ° C. and the vessel pressure of 5 kPa or less. After performing steam distillation for 3 hours, the temperature in the vessel was kept at 120 ° C.
The water in the container was stripped at the following pressure to obtain a polyoxyethylenated polypropylene glycol (V) having a number average molecular weight of about 8000 for comparison.

Comparative Example 3 Polyoxyethylenated polypropylene glycol was synthesized according to the examples described in JP-A-56-104936 introduced in the section of the prior art. 1000 parts of the crude polyoxyethylenated polypropylene glycol (f) obtained in Comparative Example 2 is placed in a 2 liter reaction vessel, and 20 parts of a 5% by weight aqueous sulfuric acid solution is added to adjust the pH to 2.8.
And treated at 80 ° C. for 30 minutes. Subsequently, 10 parts of Kyoward 600 (synthetic magnesium silicate, manufactured by Kyowa Chemical Industry) was added, and the mixture was treated for 1 hour. Further, nitrogen was introduced into the container while maintaining the temperature in the container at 120 ° C. and the pressure at 5 kPa or less, and dealdehyde was performed for 3 hours. And 8
After cooling to 0 ° C., the inorganic solids were removed using Radiolite 800 (manufactured by Showa Chemical Industry Co., Ltd.) to obtain a comparative polyoxyethylenated polypropylene glycol having a number average molecular weight of about 4000. (VI) was obtained.

Comparative Example 4 The crude polyoxyethylenated polypropylene glycol (f) obtained in Comparative Example 2 was prepared in accordance with the example described in Japanese Patent Publication No. 3-414454 introduced in the section of the prior art. By adjusting the pH to 6.5 using lactic acid, a polyoxyethylenated polypropylene glycol (VII) having a number average molecular weight of about 4000 was obtained.

Comparative Example 5 The temperature for introducing propylene oxide was changed to 80.degree.
Propylene oxide was introduced in the same manner as in Example 1 except that the temperature was changed to 15 ° C., and a polypropylene glycol (d) having a number average molecular weight of about 1700 was obtained. Then, polypropylene glycol (d) was replaced with polypropylene glycol (d). An ethylene oxide was introduced under the same conditions as in Example 1 except that the temperature was changed from 100 ° C. to 150 ° C., and the pH was adjusted to 7.5 with phosphoric acid. A polyoxyethylenated polypropylene glycol (VIII) having a number average molecular weight of about 8500 was obtained for comparison.

<Evaluation of Performance> Examples 1 to 3 and Comparative Example 1
Of the polyoxyethylenated polypropylene glycols (I) to (VIII) obtained in Steps (1) to (5), the measurement of the unsaturated ether group content and the odor sensation of the samples immediately after production and after storage at 30 ° C. for 3 months The test was performed.
Table 1 shows the results. The odor sensory test was performed on a total of 10 males and females aged 18 to under 50. The test was performed by taking 5 g of polyoxyethylenated polypropylene glycol in an odorless clean glass bottle, sealing it tightly, shaking it five times at room temperature, and then opening it, and evaluating it by a sensory test. The results were evaluated on the basis of 1 point where the odor was strongly felt, 3 points where the odor was slightly felt, and 5 points where the odor was not felt.

[0025]

[Table 1]

Samples (IV) to (VIII) for comparison in which the propylene oxide addition reaction was carried out at a temperature higher than the reaction temperature conditions of the present invention had a high propenyl ether group content and were stored for 3 months. The odor test was poor. The sample (V) produced by the method described in JP-B-56-5414 had a good odor immediately after production, but was still insufficient to suppress the generation of odor during storage for 3 months. there were. And Japanese Patent Application Laid-Open No. 56-104
The sample (VI) prepared by the method described in Japanese Patent No. 936 did not have a propenyl ether group content of 1 or less, and was insufficient to suppress the generation of odor during storage for 3 months. Was.

[0027]

The cosmetic base of the present invention has a particularly good odor, so that it can be used for various applications used in cosmetics. Further, it can be used for polyurethane resin, brake fluid, lubricating oil and the like.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-10-36499 (JP, A) JP-A-61-246140 (JP, A) JP-A-10-46024 (JP, A) JP-A 50-46 27895 (JP, A) JP 47-48366 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K ⁷ /00-7/50 C08G 65/10-65/32 C07C 41/03 C07C 43/11

Claims (2)

(57) [Claims] (1) a propenyl ether group content of 0.00
A polyoxyethylenated polypropylene glycol (A) having an amount of 1 meq / g or less, wherein (A) is
In the presence of a potassium-based and / or cesium-based catalyst,
A cosmetic base characterized by being an ethylene oxide adduct of polypropylene glycol obtained by adding propylene oxide to a glycol compound at a temperature of 60 to 90 ° C. 2. A cosmetic comprising the cosmetic base according to claim 1.