JPH0920615A - Solubilizing agent composed of water-soluble and amphiphilic polyelectrolyte, solubilized composition and solubilized cosmetic containing the same - Google Patents

Abstract

PURPOSE: To obtain a solubilizing agend good in safety and usability by using a water-soluble and amphiphilic polyelectrolyte obtained by copolymerizing two kinds of specified (meth)acrylamide-based monomers or further neutralizing the resultant copolymer with an alkaline agent. CONSTITUTION: This solubilizing agent uses a water-soluble and amphiphilic polyelectrolyte obtained by copolymerizing a (meth)acrylamidoalkylsulfonic acid and/or its salt with an N-substituted (meth)acrylamide or further neutralizing the resultant copolymer with an alkaline agent. The polyelectrolyte preferably contains at least >=15wt.% (meth)acrylamidoalkylsulfonic acid unit based on the total weight. Further, the polyelectrolyte preferably contains at least >=40wt.% N-substituted (meth)acrylamide unit based on the total weight. The solubilized composition is preferably obtained by blending 0.01-20wt.% solubilizing agent therein. The solubilized cosmetic can be produced by blending the solubilized composition therein.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solubilizer comprising a water-soluble amphiphilic polyelectrolyte.

The present invention also relates to a solubilizing composition and a solubilizing cosmetic composition containing a solubilizing agent composed of a water-soluble amphiphilic polyelectrolyte.

[0003]

2. Description of the Related Art Heretofore, many studies on solubilization have been conducted, many solubilizing agents have been developed, and very stable solubilizing systems have been widely used in all industries.

[0004]

However, most of them are nonionic containing polyoxyethylene chains such as polyoxyethylene stearic acid derivatives, polyoxyethylene oleyl ether, polyoxyethylene sorbitan oleate, polyoxyethylene hydrogenated castor oil and the like. Surfactants are used as solubilizers, and many of them are concerned about safety, especially among general consumers.

Therefore, in recent years, a method using a polymer surfactant, which is expected to have higher safety than conventional surfactants, has begun to be studied, but the solubilization process is complicated and the process is inexpensive. Easy products have not been put on the market yet.

Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that a water-soluble amphiphilic polymer obtained by copolymerizing (meth) acrylamidoalkylsulfonic acid and N-substituted (meth) acrylamide The inventors have found that the electrolyte can be a solubilizer capable of preparing a solubilized composition that is easy to manufacture, has good safety, and has good usability, and has completed the present invention.

[0007]

That is, the present invention provides:
Water-soluble obtained by copolymerizing (meth) acrylamide alkyl sulfonic acid and / or its salt with N-substituted (meth) acrylamide, or obtained by further neutralizing the obtained copolymer with an alkali agent. The present invention provides a solubilizer characterized by comprising an amphipathic polymer electrolyte.

Further, the present invention provides the above-mentioned solubilizer, characterized in that the water-soluble amphiphilic polyelectrolyte contains (meth) acrylamidoalkylsulfonic acid units in an amount of at least 15% by weight based on the total amount. To do.

Further, in the present invention, the N-substituted (meth) acrylamide unit of the above water-soluble amphiphilic polyelectrolyte is
The present invention provides the above-mentioned solubilizer, characterized in that it is contained at least 40% by weight of the whole.

The present invention also provides a solubilizing composition containing the above-mentioned solubilizing agent.

Further, the present invention provides the above-mentioned solubilizing composition, wherein the solubilizing agent is blended in an amount of 0.01 to 20% by weight.

The present invention also provides a solubilized cosmetic composition containing the solubilized composition described above.

The structure of the present invention will be described in detail below. The water-soluble amphiphilic polyelectrolyte used in the present invention comprises (meth) acrylamidoalkylsulfonic acid and / or its salt, and N-
It is a copolymer obtained by copolymerizing a substituted (meth) acrylamide. As the (meth) acrylamidoalkylsulfonic acid, its salt may be used, or the salt may be copolymerized alone or in combination with the (meth) acrylamidoalkylsulfonic acid. As the salt of (meth) acrylamidoalkyl sulfonic acid, for example, salts of alkali metals, ammonia, organic amines such as triethylamine, triethanolamine and the like can be used. Further, the (meth) acrylamidoalkylsulfonic acid unit of the resulting copolymer may be neutralized with an alkaline agent to obtain the water-soluble amphiphilic polymer electrolyte of the present invention.

The characteristic feature of the water-soluble amphiphilic polyelectrolyte that is the copolymer obtained is that the (meth) acrylamidoalkylsulfonic acid unit {(meth) acrylamidoalkylsulfonic acid and / or the A salt-derived copolymerized unit} and a hydrophobicity-imparting N-substituted (meth) acrylamide unit {N-substituted (meth) acrylamide-derived copolymerized unit} in its components, and It functions as a water-soluble solubilizing agent with a certain composition.

The component composition of the water-soluble amphiphilic polyelectrolyte having this constituent component is such that the resulting copolymer is water-soluble and functions as a solubilizing agent, (Meth) acrylamidoalkyl sulfonic acid unit is at least 15% by weight or more of the whole copolymer, 60
Less than 20% by weight, preferably 20% by weight or more, 50% by weight
Is less than. On the other hand, the N-substituted (meth) acrylamide unit is at least 40% by weight or more and 85% by weight or more of the whole copolymer.
Less than wt%, preferably 50 wt% or more, 80 wt%
Is less than.

Examples of the above-mentioned (meth) acrylamidoalkylsulfonic acid include acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and 2-methacrylamido-2-.
Methylpropanesulfonic acid, 2-acrylamido-n-
Butanesulfonic acid and the like can be mentioned.

The N-substituted (meth) acrylamide is not particularly limited, but for example, cyclohexylacrylamide, cyclohexylmethacrylamide, laurylacrylamide, laurylmethacrylamide, phenylacrylamide, phenylmethacrylamide, 2-
Naphthylacrylamide, 2-naphthylmethacrylamide, Nn-dodecyl-N-methylacrylamide, N
Examples include -n-dodecyl-N-methylmethacrylamide.

The copolymer may be polymerized by a known polymerization method such as a solution polymerization method, a bulk polymerization method or a precipitation polymerization method.

The polymerization initiator is not particularly limited as long as it has the ability to initiate radical polymerization. For example, benzoyl peroxide, azobisisobutyronitrile,
Examples thereof include potassium persulfate and ammonium persulfate.

The water-soluble amphiphilic polyelectrolyte of the copolymer obtained by the above-mentioned method is a (meth) acrylamidoalkylsulfonic acid unit within a range not impairing the effect of the present invention as a water-soluble solubilizing agent. In addition to the N-substituted (meth) acrylamide units, units containing other vinyl monomers may be included.

The solubilizing composition comprising the water-soluble amphiphilic polyelectrolyte of the present invention is blended to obtain the solubilizing composition and the solubilizing cosmetic of the present invention. 0
It is from 01 to 30% by weight, preferably from 0.01 to 20% by weight. If it is less than 0.001% by weight, solubilization is not sufficient, and if it exceeds 30% by weight, gelation occurs. The solubilizer comprising the water-soluble amphipathic polymer electrolyte of the present invention is preferably used as a solubilizer for solubilizing perfumes, drugs and the like.

The solubilized composition and the solubilized cosmetic of the present invention include, as long as the effects of the present invention are not impaired, oils and surfactants which are components usually added to the solubilized composition and the solubilized cosmetic. , Moisturizers, UV absorbers, chelating agents, pH adjusters, anti-fading agents, preservatives, thickeners, dyes, pigments, fragrances,
Dyes, plasticizers, organic solvents and the like can be appropriately blended.

[0023]

EXAMPLES Next, the present invention will be described in more detail with reference to Synthesis Examples and Examples and Comparative Examples of the water-soluble amphiphilic polymer electrolyte of the present invention, but the present invention is not limited to these examples. Absent.

[Synthesis Example 1] 25.9 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 74.0 parts by weight of laurylmethacrylamide, and azobis in a reactor equipped with a stirrer, a reflux condenser and a nitrogen inlet tube. 0.1 parts by weight of isobutyronitrile and 100 parts by weight of N, N-dimethylformamide were charged, and the mixture was stirred at room temperature under a nitrogen stream for 2 hours. The reaction system was heated to 60 ° C. and reacted for 20 hours. The product liquid was taken out of the reactor and then reprecipitated 3 times with ether to obtain a polymer powder. This powder was dissolved in a NaOH aqueous solution and dialyzed for about 7 days. Then, the aqueous solution was concentrated and freeze-dried to obtain a water-soluble amphiphilic polymer electrolyte.

[Synthesis Example 2] 28.9 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 70.9 parts by weight of t-butylacrylamide, and azo were added to a reactor equipped with a stirrer, a reflux condenser and a nitrogen introducing tube. 0.2 parts by weight of bisisobutyronitrile and 260 parts by weight of N, N-dimethylformamide were charged, and the mixture was stirred at room temperature for 2 hours under a nitrogen stream. The reaction system was heated to 60 ° C. and reacted for 40 hours. The product liquid was taken out of the reactor and then reprecipitated 3 times with ether to obtain a polymer powder. This powder was dissolved in a NaOH aqueous solution and dialyzed for about 7 days. Then, the aqueous solution was concentrated and freeze-dried to obtain a water-soluble amphiphilic polymer electrolyte.

[Synthesis Example 3] 53.5 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 46.3 parts by weight of adamantylmethacrylamide, and azobis in a reactor equipped with a stirrer, a reflux condenser and a nitrogen inlet tube. 0.2 parts by weight of isobutyronitrile, N, N-dimethylformamide 15
0 part by weight was charged, and the mixture was stirred under a nitrogen stream at room temperature for 2 hours. The reaction system was heated to 60 ° C. and reacted for 30 hours. The product liquid was taken out of the reactor and then reprecipitated 3 times with ether to obtain a polymer powder. This powder is NaO
It was dissolved in an aqueous solution of H and dialyzed for about 7 days. Then, the aqueous solution was concentrated and freeze-dried to obtain a water-soluble amphiphilic polymer electrolyte.

Next, examples of the present invention will be shown, and the performance test thereof was measured by the following method, and the results are shown in Table 1.

<Solubilizing ability> Sample 0.1 g, preservative 0.
A test amount of 1 g of an oil-soluble drug (vitamin E acetate) was uniformly dissolved in 10 g of ethanol, and this was added to purified water to make the total amount 100 g. The transmittance of this system at 700 nm is 8
The compounding amount of the oil-soluble drug which becomes 0% was evaluated according to the following four stages. A: Equal to or more than the sample amount. ◯: Half or more of the sample amount and less than the same amount. Δ: 1/3 or more and less than half of the sample amount. X: Less than one third of the sample amount.

<Kasumi> The sample in the solubilized state was heated to 50 ° C.
The state of generation of a smear after standing for 4 weeks was evaluated according to the following three grades. The term "smear" refers to a state in which the system is slightly turbid and slightly fogged. ◯: No stain. Δ: Slightly stained. X: There is a stain.

<Defoaming property> 10 ml of a 1% aqueous solution was sampled in a test tube, and the defoaming state after shaking vigorously for 30 seconds was evaluated in the following three stages. ○: Excellent. B: Good. X: Poor.

<PH drop> The pH drop after leaving a 1% aqueous solution at 50 ° C. for 2 months was evaluated according to the following three grades. ◯: pH decrease is less than 1. (Triangle | delta): pH fall is 1 or more and less than 2. X: pH decrease of 2 or more.

[0032]

[Table 1]

From the results shown in Table 1, it was found that the performance of the product of the present invention was excellent. Conventional polyoxyethylene (3
0) It is understood that hydrogenated castor oil has a high solubilizing ability but is inferior to the product of the present invention in terms of defoaming property and pH decrease. It can be seen that polyoxyethylene (20) oleyl ether and polyoxyethylene (35) polyoxypropylene glycol (40) are inferior to the products of the present invention in all performance tests.

Example 1 Beauty Serum (Formulation) Wt% Glycerin 4.0 1,3-Butylene Glycol 6.0 Solubilizing Agent Obtained in Synthesis Example 1.0 Ethanol 10.0 Arbutin 0.1 Olive Oil 0.1 Hydroxyethyl cellulose 0.1 Sequestering agent Appropriate amount Anti-fading agent Appropriate amount Perfume Appropriate amount Preservative Appropriate amount Purified water Residual amount The solubilized cosmetic of the present invention prepared according to the conventional production method is 50 The condition was stable even after being left at 1 ° C and 5 ° C for 1 month, and the usability was good.

Example 2 A compound was prepared according to Example 1 except that the solubilizing agent obtained in Synthesis Example 1 of Example 1 was changed to the solubilizing agent obtained in Synthesis Example 2.

[Comparative Example 1] A comparative example 1 was prepared in the same manner as in Example 1 except that the solubilizing agent obtained in Synthesis Example 1 of Example 1 was changed to polyoxyethylene (30) hydrogenated castor oil.

Comparative Example 2 Preparation was carried out according to Example 1 except that the solubilizing agent obtained in Synthesis Example 1 of Example 1 was changed to polyoxyethylene (20) oleyl ether.

Comparative Example 3 Example 1 was repeated except that the solubilizing agent obtained in Synthesis Example 1 of Example 1 was changed to polyoxyethylene (35) polyoxypropylene glycol (40).
It was prepared according to.

The beauty essences prepared in Examples 1 and 2 and Comparative Examples 1, 2 and 3 were actually used by 10 expert panels to perform a sensory test, and the usability was evaluated according to the following four grades. ◎: Eight or more of the ten responded that they were good. ◯: 6 to 7 out of 10 people answered that they were good. Δ: 4 to 5 people out of 10 people answered that they were good. Poor: 3 or less of 10 respondents answered good.

[0040]

[Table 2]

From the results shown in Table 2, it was found that the solubilized cosmetics having good usability can be obtained in Examples 1 and 2 using the product of the present invention.

[Example 3] Lotion (prescription) wt% glycerin 6.0 sorbit 3.0 1,3-butylene glycol 5.0 hyaluronic acid 0.1 glyceryl tri-2-ethylhexanoate 0.2 vitamin E acetate 0.02 Solubilizing agent obtained in Synthesis Example 0.2 Ethanol 2.0 Glycerin 5.0 Sequestering agent Appropriate amount Anti-fading agent Appropriate amount Perfume Appropriate amount Preservative Appropriate amount Purified water Residual amount According to conventional production method The prepared lotion, which is the solubilized cosmetic of the present invention, was in a stable state even after standing at 50 ° C. and 5 ° C. for 1 month, and had good usability.

Example 4 Hair Tonic (Formulation) Wt% Ethanol 66.0 Solubilizing agent obtained in Synthesis Example 1 20.0 Propylene glycol 2.0 Hinokitiol 0.02 Pyridoxine hydrochloride 0.05 Pantothenyl ethyl ether 0.2 l-Menthol 0.6 Vitamin E acetate 0.2 pH adjuster Appropriate amount Coloring agent Appropriate amount Fragrance Appropriate amount Purified water Residual amount Hair Tonic, which is a solubilized cosmetic of the present invention prepared according to a conventional production method, The state was stable even after being left at 50 ° C. and 5 ° C. for 1 month, and the usability was good.

[0044]

INDUSTRIAL APPLICABILITY According to the present invention, a solubilizing agent comprising a water-soluble amphiphilic polyelectrolyte obtained by copolymerizing (meth) acrylamidoalkylsulfonic acid and N-substituted (meth) acrylamide is used. A solubilized composition and a solubilized cosmetic having good stability and usability can be provided.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Michihiro Yamaguchi 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Shiseido Daiichi Research Center Co., Ltd.

Claims (6)

[Claims] 1. A (meth) acrylamide alkyl sulfonic acid and / or a salt thereof and an N-substituted (meth) acrylamide obtained by copolymerization, or the obtained copolymer is further neutralized with an alkaline agent. A solubilizing agent comprising a water-soluble amphiphilic polyelectrolyte obtained as described above. 2. The solubilizer according to claim 1, wherein the (meth) acrylamidoalkylsulfonic acid unit of the water-soluble amphiphilic polyelectrolyte is contained in an amount of at least 15% by weight based on the whole amount. 3. N- of the water-soluble amphipathic polyelectrolyte
The solubilizing agent according to claim 1, wherein the substituted (meth) acrylamide unit is contained in an amount of at least 40% by weight based on the whole. 4. A solubilizing composition comprising the solubilizing agent according to claim 1, 2 or 3. 5. The compounding amount of the solubilizer is 0.01 to 20.
The solubilized composition according to claim 4, wherein the solubilized composition is in% by weight. 6. A solubilized cosmetic comprising the solubilized composition according to claim 4 or 5.