JPH0557968B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel moisturizing agent for cosmetics, and more specifically, to a moisturizing agent for cosmetics that has an excellent moisturizing effect and is composed of a combination of a specific water-soluble silicon compound and a water-soluble polymeric substance. The skin is located at the interface between the outside world and the living body, and its function is to protect the living body from humidity, light, microorganisms, chemicals, mechanical stimuli, etc., and maintain homeostasis of the living body by appropriately controlling moisture evaporation. . The stratum corneum is the outermost layer of the skin and normally retains a moderate amount of moisture, but when it is no longer able to retain moisture due to various external and internal factors, the skin becomes dry and rough. The flexibility and extensibility are reduced and the above-mentioned functions cannot be fulfilled. To achieve this, it is necessary to supply and retain moisture in the stratum corneum in some way, or to prevent the moisture in the stratum corneum from evaporating excessively. agent is included. Conventionally, such moisturizers include propylene glycol, glycerin, sodium pyrrolidone carboxylate, sodium lactate, and sorbitol.
It is used in relatively large amounts in cosmetics because of its affinity for the skin and its feel when used. However, these moisturizers tend to leave the skin feeling sticky, and when used at low humidity, moisture may be absorbed from the skin into the moisturizer-containing cosmetics, drying out the skin. It also has some drawbacks. Recently, mucopolysaccharides such as chondroitin sulfate, hyaluronic acid, mucoitin sulfate, and caronine sulfate, collagen, and polypeptides have been discovered as compounds that exist in the skin and have a moisturizing effect, and are used in cosmetics. It is being However, although these have the effect of preventing the aging phenomenon of the skin to some extent, their moisturizing effect is not necessarily sufficient. In view of these circumstances, the present inventors have conducted extensive research to provide a moisturizing agent for cosmetics that does not have a sticky feeling and has an excellent moisturizing effect. The inventors have discovered that a compound consisting of a combination with a polymeric substance can be suitable for the purpose, and based on this knowledge, they have completed the present invention. That is, the present invention is based on the general formula R _o Si (OH) _4-o () (wherein R is an alkyl group having 1 to 6 carbon atoms, an aralkyl group, an alkenyl group, a cycloalkyl group, or an alkoxy group). (If two or more R's are included, they may be the same or different, and n is 0 or an integer of 1 to 3), a dimer thereof, or A water-soluble compound containing 1 to 3 silicon atoms in the molecule and at least one silanol group, selected from trimers and those in which some of the hydrogen atoms of their hydroxyl groups have been replaced with basic substances. The present invention provides a moisturizing agent for cosmetics comprising a combination of at least one silicon compound and (B) a water-soluble polymeric substance. In the present invention, the water-soluble silicon compound used as component (A) has at least one silanol group in the molecule, that is, the formula It is necessary to have a group represented by When two or more silanol groups are present, a portion of the hydrogen atoms of the hydroxyl group is substituted with a basic substance such as an alkali metal, an alkaline earth metal, or an amine,
It may be cyanoate. As the compound represented by the general formula (),
For example, silanol, trimethylsilanol, dimethylsilanediol, methylethylsilanediol, methylsilanetriol, triethylsilanol, diethylsilanediol, ethylsilanetriol, di-n-propylsilanediol, diisopropylsilanediol, di-n-butylsilanediol, Examples include diisobutylsilanediol, di-tert-butylsilanediol, diallysilanediol, triphenylsilanol, diphenylsilanediol, phenylsilanetriol, methylcyclohexylsilanediol, dicyclohexylsilanediol, and the like. Also,
Examples of these dimers and trimers include tetramethyldisiloxane-1,3-diol, tetraethyldisiloxane-1,3-diol, bis(methylvinyl)disiloxane-1,3-diol, and hexamethyldisiloxane-1,3-diol. Methyltrisiloxane-1,5-diol, hexaethyltrisiloxane-1,5-
Examples include diol. These silanol compounds are generally unstable and easily polymerized, but they can be stabilized by combining them with the water-soluble polymeric substance of component (B). Although the mechanism of this stabilization is not necessarily clear, it is believed that hydrogen bonds are formed between the -OH or _-NH2 groups in the water-soluble polymer and the SiOH in the silanol compound. Seem. The water-soluble polymeric substance used as component (B) in the cosmetic moisturizer of the present invention is preferably one having at least one hydroxyl group or amino group or both in the molecule. Examples include water-soluble biopolymer substances such as mucopolysaccharides and water-soluble proteins, cellulose derivatives, starch derivatives, polyvinyl alcohol, etc. Each of these may be used alone or in combination of two or more. good. The mucopolysaccharides refer to mucopolysaccharides in a broad sense, and examples include acidic mucopolysaccharides such as neutral mucopolysaccharides, hyaluronic acid, chondroitin, chondroitin sulfate, heparin, and heparan sulfate, mucoproteins, glycoproteins, and glycolipids. As water-soluble proteins, for example, lipopeptides obtained by condensing amino groups of protein hydrolysates and carboxyl groups of fatty acids, soluble collagen, soluble elastin, soluble keratin, etc. can be used. As a cellulose derivative,
Examples include carboxymethyl cellulose (CMC), methyl cellulose (MC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose, etc. As starch derivatives, those that are more water-soluble than normal starch are preferred, such as slightly hydrolyzed dextrin, Examples include acetic acid derivatives, phosphoric acid derivatives, and hydroxyalkyl derivatives of starch. Furthermore, the solubility of polyvinyl alcohol in water varies depending on the degree of polymerization and saponification, but generally polyvinyl alcohol has a not very high degree of saponification (approximately
79 mol% or less) is desirable. Among these water-soluble polymer substances, water-soluble biopolymer substances such as mucopolysaccharides and water-soluble proteins are suitable because they themselves have effective pharmacological effects on the skin and have a moisturizing effect. It is. In the moisturizing agent for cosmetics of the present invention, the preferred blending ratio of the silanol compound as the component (A) and the water-soluble polymer substance as the component (B) is 1:10 to 1:10 on a weight basis.
Selected in a 10:1 ratio. The moisturizing agent for cosmetics of the present invention is obtained by stabilizing the silanol compound as the component (A) with the water-soluble polymer substance as the component (B). As for this stabilization method, a silanol compound may be added to the aqueous solution of the water-soluble polymer substance, but since the silanol compound is generally unstable and easily polymerized, the following method should be used. is preferred. That is, first, a relatively stable aqueous solution of a silanoate compound is prepared, an aqueous solution of a water-soluble polymer substance is added thereto, and then the silanoate compound is converted into a silanol compound using an H-type cation exchange resin or the like. As a result, the silanol compound is stabilized, and the moisturizing agent for cosmetics of the present invention is obtained. The aqueous solution of the silanoate compound can be prepared by, for example, using a halogen-containing hydrocarbon-substituted silane derivative as a starting material, recovering a hydrolyzate produced by hydrolyzing the silane derivative, and converting this hydrolyzate into a silicon atom. A method in which the alkali metal hydroxide is added to an aqueous solution in such a proportion that at least 1 equivalent of base is present per base [Journal.
Journal of the Chemical Society
chemical society), Vol. 105, p. 679], a hydrocarbon-substituted silane derivative containing a halogen is prepared in such a way that at least one equivalent of base is present per silicon atom in addition to the neutralization equivalent derived from the halogen of the derivative. It is prepared by adding it to an aqueous solution of an alkali metal hydroxide prepared in Examples of starting materials such as halogen-containing hydrocarbon-substituted silane derivatives used in preparing an aqueous solution of a silanoate compound include silicon tetrachloride, methyltrichlorosilane, phenyl Examples include trichlorosilane, diphenyldichlorosilane, dimethyldichlorosilane, chloromethytrulichlorosilane, trimethylchlorosilane, chlorophenyltrichlorosilane, methylcyclohexyldichlorosilane, and benzyltrichlorosilane. The moisturizing agent for cosmetics of the present invention can be used, for example, in addition to ordinary skin conditioning and nutritional lotions, water-based cosmetic lotions such as astringent lotions, shave lotions, body lotions, and liquid packs, nutritional creams, and eye care lotions. It is used in creams such as creams, body creams, hand creams, pine surge creams, cold creams, and emollient creams, emulsions such as nutritional emulsions, body emulsions, netsuku emulsions, and hand emulsions, and skin cosmetics such as packs. It can also be used in hair cosmetics such as shampoo and conditioner. When using the moisturizing agent for cosmetics of the present invention for such purposes, the moisturizing agent for cosmetics may be used with the necessary ingredients added, or the moisturizing agent for cosmetics may be used as an aqueous moisturizer containing the necessary ingredients. An appropriate amount may be added to a solution, an aqueous dispersion, or a solid base, and the amount is usually preferably used in the range of 0.1 to 10% by weight based on the cosmetic composition. Next, the present invention will be explained in further detail by reference examples and examples. Reference Example 1 Collect the precipitate generated by hydrolyzing methyltrichlorosilane, add an equimolar aqueous sodium hydroxide solution to it, stir to dissolve it, and obtain silanoate (CH ₃ Si (OH)) with a concentration of 10% (in terms of silanol). ₂・
ONa) aqueous solution was obtained. On the other hand, in another beaker, prepare 100 c.c. of a 1% aqueous solution of purified hyaluronic acid (manufactured by Kewpie Corporation), which is a type of mucopolysaccharide, and add the above-mentioned cyanoate 10
After adding 10 c.c. of an aqueous solution, the mixture was neutralized to pH 6.5 with an H-type cation exchange resin, and then, after removing the ion exchange resin, water was added to make a total volume of about 200 c.c. to obtain a moisturizing agent.
When this product was dried under reduced pressure, the solid content concentration was about 1%. Reference Example 2 A 4-aqueous solution of water-soluble atelocollagen was prepared by dissolving calf skin insoluble collagen with pepsin and purifying it. To 80 c.c. of this aqueous solution, 10 c.c. of a 10% (silanol equivalent) aqueous solution of silanoate prepared in the same manner as in Reference Example 1 was added, and then the pH was adjusted using an H-type cation exchange resin.
6.5, and then added water to make a total volume of 100 c.c. to obtain a moisturizer. When this product was dried under reduced pressure, the solid content concentration was 5. Example 1 Commercially available pig skin was cut into 2 cm square pieces lengthwise and widthwise. Separately, various moisturizing agent aqueous solutions as shown in Table 1 were prepared, and a fixed amount of each of these moisturizing agents was applied to two pieces of pig skin, and each was placed in a desiccator maintained at relative humidity of 65% and 30%. After leaving it for 24 hours, the moisture content on the surface of the pig's skin was determined by impedance measurement. The results are shown in Table 2. An impedance measuring device manufactured by IBS was used, and the moisture content was determined from the obtained impedance value using a calibration curve, and the average value of the two sheets was used.

【table】

[Table] It is clear from Table 2 that the hyaluronic acid-stabilized moisturizer of the present invention can be used as well as other moisturizers.
It turns out that it has a better moisturizing effect than hyaluronic acid. Example 2 Commercially available pig skin was cut into squares of 2 cm lengthwise and widthwise. Two pieces of this pig skin were immersed in the moisturizer aqueous solution (solid content 5%) prepared in Reference Example 2, the collagen 5% aqueous solution, and water, and then left in a desiccator at a relative humidity of 50% for 6 hours. As in Example 1, the amount of moisture on the surface of pig skin was determined by impedance measurement. As a result, the moisture content of the moisturizer of the present invention obtained in Reference Example 2 was 75, whereas the water content was 55% for the 5% collagen aqueous solution and 5% for water alone. Example 3 In the same manner as in Reference Example 2, a 5% aqueous solution of dimethylsilanediol-chondroitin sulfate B (weight ratio 1:4) was prepared as a humectant, and using this,
A lotion with the following composition was prepared. Ingredient content (wt%) Dimethylsilanediol-chondroitin sulfate B 5 Propylene glycol 1 Ethanol 6 Methyl p-hydroxybenzoate 0.1 Disodium hydrogen phosphate 0.06 Fragrance 0.2 Purified water Balance When this lotion was used by 20 women, An improvement effect was observed with a risk rate of 1% for skin moisturization and smoothness. Example 4 In the same manner as in Reference Example 1, ethylsilane triol-hyaluronic acid (weight ratio 1:1) was used as a humectant.
A 1% aqueous solution was prepared and used to prepare an emollient cream having the following composition. Ingredient content (wt%) Ethylsilanetriol - Hyaluronic acid 1 Liquid paraffin 6 Squalane 3 Cetyl palmitate 2 Setanol 2 Stearic acid 2 Antioxidant 3 Purified water Balance When this cream was used by 20 women,
An improvement effect was observed at a risk rate of 1% for the moisturized and smooth skin. Example 5 In the same manner as in Reference Example 1, phenylsilane triol-hyaluronic acid (weight ratio 1:
1) When a 1% aqueous solution was prepared and used to prepare a shampoo having the composition shown below, it showed an excellent moisturizing effect on hair. Ingredient content (wt%) Phenylsilanetriol - Hyaluronic acid 1 C ₁₄ - Sodium α-olefin sulfonate 10 Triethanol lauryl sulfate Amine 5 Fragrance 0.1 Purified water Balance example 6 Trimethylsilanol - in the same manner as in Reference example 2
When a 2% aqueous solution of collagen (weight ratio 1:1.5) was prepared and used to prepare a rinse having the composition shown below, it showed an excellent moisturizing effect on hair. Ingredient content (wt%) Trimethylsilanol - Collagen 2 Alucard 2HT 2 Setanol 3 Stearyl ethoxylate (5 moles of EO) 1 Fragrance 0.1 Purified water Balance

Claims (1)

[Claims] 1 (A) General formula R _o Si (OH) _4-o (R in the formula is an alkyl group having 1 to 6 carbon atoms, an aralkyl group, an alkenyl group, a cycloalkyl group, or an alkoxy group) and when two or more R's are included, they may be the same or different, and n is 0 or an integer of 1 to 3), a dimer or a trimer thereof, A water-soluble compound containing 1 to 3 silicon atoms in the molecule and at least one silanol group, selected from mercury and those in which some of the hydrogen atoms of their hydroxyl groups have been replaced with basic substances. A moisturizing agent for cosmetics comprising a combination of at least one silicon compound and (B) a water-soluble polymer substance. 2. The moisturizing agent for cosmetics according to claim 1, wherein the water-soluble polymeric substance has at least one hydroxyl group, one amino group, or both in the molecule. 3. The moisturizing agent for cosmetics according to claim 1, wherein the water-soluble polymer substance is a water-soluble biopolymer substance.