JP2010196048A - Novel water-soluble polymer, and cosmetic material or skin preparation for external use containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-soluble polymer for cosmetic materials or skin preparations for external use with maintaining water retention under low humidity conditions, without giving sticky feeling under high humidity conditions, having no or almost no viscosity and without affecting sense or function of other ingredients. <P>SOLUTION: A water soluble (meth)acrylamide polymer for cosmetic materials or skin preparations for external use comprises one kind or more kinds of repeating units expressed by formula (1), and has 5,000-150,000 weight average molecular weight (Mw) and &le;25 wt.% weight reduction rate after 50 wt.% aqueous solution of the polymer is allowed to stand for 6 hours at 30&deg;C and 60% relative humidity. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a novel water-soluble polymer and a cosmetic or skin external preparation containing the same, and more particularly, a water-soluble poly (meth) acrylic amide having novel water retention properties and a cosmetic containing the same. Or it relates to a skin external preparation.

  Generally, skin dryness occurs when the amount of skin secretions, especially sebum secretion, decreases the stratum corneum barrier function and increases transepidermal water loss. When the skin becomes dry, the gloss of the skin decreases, and harmful effects such as fine wrinkles appear. Therefore, maintaining the moisture content of the skin is an important issue, and various studies on moisturizing agents for maintaining the moisture content of the skin have been conducted. Hydration with water present in the stratum corneum using water-soluble polyhydric alcohols such as glycerin and 1,3-butylene glycol, organic acid salts such as sodium pyrrolidonecarboxylate and sodium lactate, and polysaccharides such as chitin Although a method for enhancing the effect has been found, these moisturizing effects are often transient and excellent in increasing the moisture content of the skin, but there are still problems with its sustainability. Yes.

  On the other hand, many compounds have been used to improve rheology such as usability and appearance stability by serving as a moisturizer and imparting viscosity. For example, in addition to water-soluble hyaluronic acid characterized by having thickening properties and spinnability, and acetyl hyaluronic acid that has a hydrophobic group and can be blended in an oily base material (see, for example, Patent Document 1), A polymer substance (lipid) having 2-methacryloyloxyethyl phosphorylcholine having the same structure as the polar group of phosphatidylcholine focused on the constitution as a constitutional unit and excellent in film-forming ability (for example, see Patent Document 2), α-side chain α- A polymer such as an amino acid-modified γ-polyglutamic acid having moisturizing properties (for example, see Patent Document 3) having a amide bond between a carboxyl group and an amino group of a hydrophilic amino acid has been proposed.

  Further, as a (meth) acrylamide derivative, an N-alkyl or N-alkylene-substituted (meth) acrylamide homopolymer or copolymer is copolymerized with, for example, a crosslinkable monomer having two or more double bonds in the molecule. A water separation and retention agent containing a humidity control resin (see, for example, Patent Document 4), an aqueous gel resin (see, for example, Patent Document 5), and a (meth) acrylamide-derived polymer. (For example, refer to Patent Document 6) and water vapor absorption and release agents (for example, refer to Patent Document 7), water-soluble ethylenically unsaturated monomers such as dialkyl acrylamide and ionic acrylamide derivatives are used in the dispersion layer. It contains a thickener (see, for example, Patent Document 8) made of microgel obtained by dissolution and radical polymerization in the dispersed phase, and an oily phase dispersed in water. A oil-in-water nanoemulsion, a composition comprising an acrylic acid homopolymer neutral (e.g., see Patent Document 9) have been proposed.

Japanese Patent No. 3557044 Japanese Patent No. 2832119 JP 2007-297559 A Japanese Unexamined Patent Publication No. 60-250013 JP 60-250019 A JP-A-60-9010 JP-A-61-263639 Japanese Patent Laying-Open No. 2005-289831 JP 2002-68935 A

  Conventional moisturizers have a high moisture absorption under high humidity, and moisturizers feel sticky.On the other hand, under low humidity, water molecules are often released and water retention is not maintained. In some cases, other undesirable properties such as spinnability and the like may be imparted with the viscosity. Further, imparting the viscosity may affect the feel and sensuality of other components of the cosmetic. The object of the present invention is to maintain water retention even under low humidity conditions, not to feel sticky even under high humidity conditions, to have little or no viscosity, and to affect the feel and sensation of other components. It is to provide a water-soluble polymer for cosmetics or skin external preparations.

The inventors of the present invention have proposed the acetamide moiety of theanine (Japanese Patent No. 3543478), which has been proposed as a moisturizing agent that has a high moisturizing effect, maintains water retention even under low humidity conditions, and has low moisture absorption under high humidity and low stickiness. As a result of examining whether or not monoethylacetamide can be used as a moisturizing agent, it was confirmed that it was volatile and difficult to be blended into cosmetics as a moisturizing agent. However, since it was found that monoethylacetamide interacts with water molecules, (meth) acrylic acid was selected as the skeleton of the polymer, an amide compound was selected as the introduction group, and polymerization was performed without using a crosslinking agent. However, the obtained water-soluble polymer exhibits excellent water retention and has very low viscosity, and when blended in cosmetics, it feels sufficient moisture retention without affecting the feel and sensation of other ingredients. The present invention has been completed.
The inventors have also found that the coexistence of the water-soluble polymer of the present invention with phospholipids, particularly liposomes formed therefrom, improves the moisturizing effect as compared to phospholipids or liposomes alone.

That is, the present invention
[1] The following formula (1)

（式中、Ｒ_１は水素原子又はメチル基を示し、Ｒ_２は水素原子又は炭素数１〜３のアルキル基を示し、Ｒ_３は炭素数１〜３のアルキル基又は炭素数１〜３のヒドロキシアルキル基を示す）で表される繰返し単位の１種又は２種以上からなり、重量平均分子量（Ｍｗ）が５，０００〜１５０，０００であり、温度３０℃、相対湿度６０％における当該ポリマーの５０重量％水溶液の６時間放置後の重量減少率が２５重量％以下である化粧料又は皮膚外用剤用水溶性（メタ）アクリルアミドポリマー、
[２]さらに、温度３０℃において相対湿度を６０％から４０％に下げたときの当該ポリマーの５０質量％水溶液の質量減少率が３質量％未満であることを特徴とする上記[１]記載の水溶性（メタ）アクリルアミドポリマー、
[３]さらに、温度３０℃において相対湿度を４０％から６０％に上げたときの当該ポリマーの５０質量％水溶液の質量増加率が３質量％未満であることを特徴とする上記[１]又は[２]記載の水溶性（メタ）アクリルアミドポリマー、及び
[４]水溶性（メタ）アクリルアミドポリマーがポリＮ，Ｎ−ジエチルアクリルアミドであることを特徴とする上記[１]〜[３]のいずれかに記載の水溶性（メタ）アクリルアミドポリマーに関する。

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₃ represents an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. A polymer having 1 to 2 or more of repeating units represented by a hydroxyalkyl group, having a weight average molecular weight (Mw) of 5,000 to 150,000, a temperature of 30 ° C. and a relative humidity of 60%. A water-soluble (meth) acrylamide polymer for cosmetics or topical skin preparations, wherein the weight reduction rate after standing for 6 hours in a 50% by weight aqueous solution is 25% by weight or less,
[2] The above-mentioned [1], wherein, when the relative humidity is lowered from 60% to 40% at a temperature of 30 ° C., the mass reduction rate of the 50% by mass aqueous solution of the polymer is less than 3% by mass Water-soluble (meth) acrylamide polymer,
[3] Further, the above-mentioned [1], wherein the mass increase rate of a 50% by mass aqueous solution of the polymer is less than 3% by mass when the relative humidity is increased from 40% to 60% at a temperature of 30 ° C. [2] The water-soluble (meth) acrylamide polymer according to [2], and
[4] The water-soluble (meth) acrylamide polymer as described in any one of [1] to [3] above, wherein the water-soluble (meth) acrylamide polymer is poly N, N-diethylacrylamide.

The present invention also provides
[5] A liposome-containing water-soluble (meth) acrylamide comprising (A) the water-soluble (meth) acrylamide polymer according to any one of [1] to [4] above, and (B) a phospholipid. Polymer composition,
[6] The liposome-containing water-soluble (meta) according to the above [5], further comprising (C) one or more selected from the group consisting of cholesterol, cholesterol derivatives, phytosterols and phytosterol derivatives An acrylamide polymer composition, and
[7] The liposome-containing water-soluble solution as described in [5] or [6] above, further comprising (D) one or more selected from the group consisting of glycerin and 1,3-butylene glycol. The present invention relates to a (meth) acrylamide polymer composition.

Furthermore, the present invention provides
[8] A cosmetic or skin external preparation containing the water-soluble (meth) acrylamide homopolymer according to any one of [1] to [4] above, and
[9] A cosmetic or skin external preparation comprising the liposome-containing composition according to any one of [5] to [7] above.

  The water-soluble (meth) acrylamide polymer of the present invention has a mass reduction rate of less than 25% by mass after standing for 5 hours in a 50% by mass aqueous solution of the polymer at a temperature of 30 ° C. and a relative humidity of 60%. When the relative humidity is reduced from 60% to 40% in FIG. 1, the mass reduction rate of the 50% by weight aqueous solution of the polymer is less than 3% by weight, and the relative humidity is increased from 40% to 60% at 30 ° C. A mass increase rate of a 50% by mass aqueous solution of the polymer is less than 3% by mass, which is excellent in water retention. By using a water-soluble (meth) acrylamide polymer having such characteristics, an oil-in-water nanoemulsion containing an oily phase dispersed in an aqueous phase, compared with the method described in JP-A-2002-68935 Therefore, it is possible to impart moisture retention to the blended cosmetics and the like, and hardly affect the feel and sensation of other components.

  Furthermore, when phospholipids are allowed to coexist, particularly when phospholipids form liposomes, the water-soluble (meth) acrylamide polymer of the present invention contributes to improvement of the temporal stability of the liposomes, thereby The storage property is enhanced, and the moisturizing effect over time of the skin of the phospholipid and the water-soluble (meth) acrylamide polymer of the present invention can be remarkably enhanced.

It is a figure which shows the measurement result of the skin moisture content by continuous use about this invention products 6 and 7 and comparative products 6-8.

((Meth) acrylamide polymer)
The (meth) acrylamide polymer of the present invention is a homopolymer or copolymer composed of one or more repeating units represented by the formula (1) and does not have a crosslinked structure.
In formula (1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₃ represents an alkyl group having 1 to 3 carbon atoms, 1 or An alkyl group substituted with two or more hydroxy groups is represented. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. As the hydroxyalkyl group having 1 to 3 carbon atoms, _-CH 2 OH _group, -CH 2 _CH 2 OH group, -CH (OH) CH _{3 group,} -CH _{2 CH 2} CH ₂ OH group, -CH ₂ CH (OH) CH ₃ group, —CH (OH) CH ₂ CH ₃ group, —CH (OH) ₂ group, —CH (OH) CH ₂ OH group, —CH ₂ CH (OH) CH ₂ OH group, — CH ₂ C (OH) ₂ CH ₃ group, —CH (OH) CH (OH) CH ₂ OH and the like can be exemplified.

Specific examples of the monomer corresponding to the repeating unit represented by the above formula (1) include N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, and N, N-dimethyl. Acrylamide, N, N-diethylacrylamide, N, N-di-n-propylacrylamide, N, N-diisopropylacrylamide, N-hydroxymethylacrylamide, N-2-hydroxyethylacrylamide, N-3-hydroxyn-propylacrylamide, Acrylamide-based polymerizable monomers such as N-methyl-N-ethylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-hydroxymethylacrylamide, N-ethyl-N-2-hydroxyethylacrylamide, or , -Methyl methacrylamide, N-ethyl methacrylamide, Nn-propyl methacrylamide, N-isopropyl methacrylamide, N, N-cymethyl methacrylamide, N, N-diethyl methacrylamide, N, N-di-n-propyl Methacrylamide, N, N-diisopropylmethacrylamide, N-hydroxymethylmethacrylamide, N-2-hydroxyethylmethacrylamide, N-3-hydroxyn-propylmethacrylamide, N-methyl-N-ethylmethacrylamide, N- Methyl
Examples include methacrylamide-based polymerizable monomers such as Nn-propyl methacrylamide, N-methyl-N-hydroxymethyl methacrylamide, N-ethyl-N-2-hydroxyethyl methacrylamide, and the like. The (meth) acrylamide polymer used in the present invention can be produced by polymerizing with one or two or more monomers without using.

  Examples of the acrylamide polymer or methacrylamide polymer that can be prepared by polymerizing the monomer used in the present invention include poly N-methyl acrylamide, poly N-ethyl acrylamide, poly Nn-propyl acrylamide, and poly N. -Isopropylacrylamide, polyN, N-dimethylacrylamide, polyN, N-diethylacrylamide, polyN, N-di-n-propylacrylamide, polyN, N-diisopropylacrylamide, polyN-hydroxymethylacrylamide, polyN-hydroxy Ethyl acrylamide, Poly N-hydroxypropyl acrylamide, Poly N-methyl-N-ethyl acrylamide, Poly N-methyl-Nn-propyl acrylamide, Poly N-methyl-N-hydroxy acrylamide Acrylamide homopolymers such as polyacrylamide, poly N-ethyl-N-2-hydroxyethyl acrylamide, poly N-methyl methacrylamide, poly N-ethyl methacrylamide, poly Nn-propyl methacrylamide, poly N-isopropyl methacrylamide , Poly N, N-dimethyl methacrylamide, poly N, N-diethyl methacrylamide, poly N, N-di-n-propyl methacrylamide, poly N, N-diisopropyl methacrylamide, poly N-hydroxymethyl methacrylamide, poly N -Hydroxyethyl methacrylamide, poly N-hydroxy n-propyl methacrylamide, poly N-methyl-N-ethyl methacrylamide, poly N-methyl-Nn-propyl methacrylamide, poly N-methyl-N-hydroxy Methacrylamide homopolymers such as til methacrylamide, poly N-ethyl-N-2-hydroxyethyl methacrylamide, (N-methylacrylamide / N-ethylacrylamide) copolymer, (N-methylacrylamide / N, N-di-n-) Propyl acrylamide) copolymer, (N-methyl methacrylamide / N-ethyl methacrylamide) copolymer, (N-methyl methacrylamide / N, N-di-n-propyl methacrylamide) copolymer, and the like. Is preferable in that it is superior in terms of the flexibility of the film of the polymer composition and the affinity to the skin, and polyN, N-diethylacrylamide, polyN-ethylacrylamide, and polyN, N-dimethylacrylamide are particularly good in water retention. It is more preferable in that .

  The weight average molecular weight of the water-soluble (meth) acrylamide polymer of the present invention is not particularly limited as long as the target effect of the present invention is exhibited, but tetrahydrofuran is used as an eluent, and a calibration curve prepared with a linear polystyrene standard product and The polystyrene equivalent weight average molecular weight (Mw) measured by a liquid gel permeation chromatography (GPC) method using a refractive index detector is preferably 5,000 to 150,000, and preferably 10,000 to 100,000. A range is more preferable.

The water-soluble (meth) acrylamide polymer in the present invention has the above-mentioned chemical structure and the following characteristics.
(1) Soluble in water and lower alcohols such as ethanol and isopropanol, polyhydric alcohols such as propylene glycol and 1,3-butylene glycol.
(2) The mass reduction rate after standing for 6 hours of a 50% by mass aqueous solution of the polymer at a temperature of 30 ° C. and a relative humidity of 60% is less than 25% by mass, preferably less than 20% by mass. The mass reduction rate of the 50% by mass aqueous solution of the polymer after 6 hours when it is lowered from 60% to 40% is less than 3% by mass, preferably less than 2% by mass. Furthermore, when the relative humidity is increased from 40% to 60% at a temperature of 30 ° C., the mass increase rate of the 50% by mass aqueous solution of the polymer is less than 3% by mass, preferably less than 1% by mass.

In the present invention, the mass change rate (mass increase rate / mass decrease rate) is calculated as follows.
(1) “Mass reduction rate after standing for 6 hours of 50% aqueous solution of the polymer at 30 ° C. and 60% relative humidity” is a sample comprising a 50% aqueous solution of the water-soluble (meth) acrylamide polymer of the present invention. This is obtained by measuring the mass, measuring the mass again after putting it in a constant temperature and humidity chamber of 30 ° C. and 60% humidity and allowing it to stand for 6 hours, and calculating the decrease in mass.
(2) “Mass reduction rate of 50% aqueous solution of the polymer when the relative humidity is lowered from 60% to 40% at a temperature of 30 ° C.” refers to the 50% aqueous solution of the water-soluble (meth) acrylamide polymer of the present invention. The sample is prepared, put in a constant temperature and humidity chamber at 30 ° C. and 60% humidity, and after 48 hours, the mass is measured. Then, the sample is transferred to a constant temperature and humidity chamber at 30 ° C. and 40% humidity. The mass after 6 hours is measured, and the increase in mass is calculated.
(3) “Mass increase rate of 50% by weight aqueous solution of the polymer when the relative humidity is increased from 40% to 60% at a temperature of 30 ° C.” is a 50% by weight aqueous solution of the water-soluble (meth) acrylamide polymer of the present invention. 48 hours after putting the sample in a constant temperature and humidity chamber having a temperature of 30 ° C. and a humidity of 60%, the sample was transferred to a constant temperature and humidity chamber having a temperature of 30 ° C. and a humidity of 40%. The mass is measured, and then the sample is transferred to a constant temperature and humidity chamber with a temperature of 30 ° C. and a humidity of 60%, the mass after 6 hours is measured, and the increase in mass is calculated.

(Production method)
The method for producing an acrylamide or methacrylamide polymerizable monomer corresponding to the repeating unit represented by the above formula (1) is not particularly limited including a known method. For example, the amine is dissolved in acetonitrile. Then, after adding triethylamine as appropriate, the mixture was cooled, and while maintaining 0 ° C., a known method such as a chemical method such as a method of slowly dropping acrylic acid chloride or methacrylic acid chloride under stirring and concentrating under reduced pressure was included. A synthesis method can be mentioned, and the product may be purified by a purification means including known methods such as recrystallization and column chromatography. In addition, as a method for producing an acrylamide polymer or a methacrylamide polymer using the acrylamide or methacrylamide polymerizable monomer, the characteristics described above are obtained using one kind of the acrylamide or methacrylamide polymerizable monomer (monomer). As long as the water-soluble (meth) acrylamide polymer of the present invention can be produced, there is no particular limitation, and examples thereof include a radical polymerization method, an anionic polymerization method, a cationic polymerization method, and the like. A radical polymerization method using a radical generator such as an azo compound can be suitably shown. The amount of the radical generator used is 0.01 to 10% by mass, preferably 0.1 to 0.1%, based on the total amount of monomers. 8% by mass. In addition, as the radical polymerization method, any of known bulk polymerization, emulsion polymerization, solution polymerization, and the like can be used. In the production method for obtaining a water-soluble (meth) acrylamide polymer in the present invention, solution polymerization is preferable. Examples of the method for performing the solution polymerization include a method for performing a polymerization reaction under an atmosphere of an inert gas such as nitrogen or argon at a temperature of 50 to 100 ° C, preferably 65 to 75 ° C. In addition, as the organic solvent in the case of performing the above solution polymerization, aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate and butyl acetate, ethers such as dioxane, methyl ethyl ketone and methyl isobutyl Examples include ketones such as ketone and cyclohexanone, alcohols such as ethanol and isopropyl alcohol, and alicyclic hydrocarbons such as cyclohexane. Further, as another method for producing the water-soluble (meth) acrylamide polymer of the present invention, a method of reacting polyacrylic acid and an alkylamine to form an amide can be used, but is not limited thereto.

(Cosmetics and skin preparations)
The cosmetic / skin external preparation of the present invention contains an acrylamide polymer or a methacrylamide polymer (hereinafter also referred to as “(meth) acrylamide polymer”) having a repeating unit represented by the above formula (1), The (meth) acrylamide polymer is not particularly limited as long as it is an acrylamide-based or methacrylamide-based polymer that can be produced by polymerizing the corresponding monomer, which is an acrylamide-based polymerizable monomer or a methacrylamide-based polymerizable monomer. First, one or more of the above polymers can be blended in cosmetics or skin external preparations.

  The water-soluble (meth) acrylamide polymer in the present invention can be used for various applications in addition to cosmetics and skin external preparations, but is preferably used for cosmetics and skin external preparations, and is incorporated into cosmetics. It is more preferable. The cosmetics in the present invention include basic cosmetics such as lotions, creams, milky lotions, and beauty essences, hair cosmetics such as shampoos, rinses, and treatments, makeup cosmetics such as liquid foundations, base emulsions, and tanning. Cosmetics such as stop cosmetics (including quasi-drugs) can be exemplified, and examples of external skin preparations include external medicines such as liniments, lotions and ointments.

  The blending ratio of the water-soluble (meth) acrylamide polymer in the present invention to the cosmetic or skin external preparation of the present invention is not particularly limited as long as the effect of the present invention is exhibited, but usually the cosmetic or skin external preparation. 0.01-10 mass% is preferable with respect to the whole, 0.1-5 mass% is more preferable, and it may mix | blend 1 type or 2 types or more suitably.

  In the cosmetic and skin external preparation of the present invention, components commonly used in cosmetics and skin external preparations together with the water-soluble (meth) acrylamide polymer, for example, the following oily components, surfactants, alcohols, moisturizing agents 1 type or 2 or more types of agents, gelling agents, powders, ultraviolet absorbers, antiseptics, antibacterial agents, antioxidants, pH adjusters, skin beautifying ingredients, fragrances, etc. You may mix | blend suitably in the range which does not impair the effect of this.

  The oil component (oil agent) is not particularly limited as long as it is an oil agent used in regular cosmetics, and has properties such as animal oil, vegetable oil, synthetic oil and the like and solid oil, semi-solid oil, liquid oil, volatile oil and the like. Regardless, for example, hydrocarbon oils, ester oils, glyceride oils, silicone oils, higher alcohols, fatty acids, lanolin derivatives, waxes, hardened oils, fluorinated oils, etc. The oil agent can give an emollient feeling to the skin. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.

  Examples of the alcohols include lower alcohols such as ethanol and isopropanol, and various alcohols such as glycerin, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, and erythritol. Examples thereof include monohydric alcohols, sugar alcohols such as sorbitol, maltose, xylitol, and maltitol, and sterols such as cholesterol, sitosterol, phytosterol, and lanosterol. Examples of the humectant include urea, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate and the like.

  The gelling agent is not particularly limited as long as it is an aqueous gelling agent or oily gelling agent that is generally used for external preparations for skin or cosmetics. Examples of the aqueous gelling agent include gum arabic, gum tragacanth, galactan, Plant-based polymers such as carob gum, guar gum, caraya gum, carrageenan, pectin, agar, quince seed (derived from quince), starch (derived from rice, corn, potato, wheat, etc.), algae colloid, trant gum, locust bean gum, , Microbial polymers such as xanthan gum, dextran, succinoglucan and pullulan, animal polymers such as collagen, casein, albumin and gelatin, starch polymers such as carboxymethyl starch and methylhydroxypropyl starch, and methylcellulose , Hydro Cellulose polymers such as cyclopropylmethylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, alginic acid polymers such as sodium alginate and propylene glycol alginate, sodium polyacrylate, carboxy Vinyl polymers such as vinyl polymers, alkyl-modified carboxyvinyl polymers, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, ethylene oxide propylene oxide copolymer, bentonite, magnesium aluminum silicate, laponite, hectorite, anhydrous silica Inorganic gelling agent thickeners such as acids can be mentioned, Examples of the gelling agent include metal soaps such as aluminum stearate, magnesium stearate and zinc myristate, amino acid derivatives such as N-lauroyl-L-glutamic acid and α, γ-di-n-butylamine, and dextrin palmitic acid. Dextrin derivatives such as esters, dextrin stearates, dextrin 2-ethylhexanoic acid palmitic acid mixed esters, sucrose fatty acid esters such as fatty acid esters, sucrose palmitic acid esters, sucrose stearic acid esters, monobenzylidene sorbitol, di Organic modifications such as benzylidene derivatives of sorbitol such as benzylidene sorbitol, dimethylbenzyl dodecyl ammonium montmorillonite clay, dimethyl dioctadecyl ammonium montmorillonite clay Or the like can be mentioned soil mineral.

  Examples of the powder include inorganic powders, organic powders, metal soap powders, colored pigments, pearl pigments, metal powders, tar dyes, natural dyes, and the like, and their particle shapes (spherical, needle-like, Plate shape, etc.), particle diameter (smoke, fine particles, pigment grade, etc.) and particle structure (porous, non-porous, etc.). These powders may be used as they are, but a composite of two or more powders may be used, and surface treatment may be performed with an oil agent, a silicone compound, a fluorine compound, or the like.

  Examples of the ultraviolet absorber include benzoic acid ultraviolet absorbers such as paraaminobenzoic acid, anthranilic acid ultraviolet absorbers such as methyl anthranilate, salicylic acid ultraviolet absorbers such as methyl salicylate, and paramethoxy cinnamon. Examples thereof include cinnamic acid UV absorbers such as octyl acid, benzophenone UV absorbers such as 2,4-dihydroxybenzophenone, and urocanic acid UV absorbers such as ethyl urocanate. Examples of antiseptics and antibacterial agents include paraoxybenzoic acid esters, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, salicylic acid, coalic acid, sorbic acid, parachlormetacresol, hexachlorophene, benzalkonium chloride Chlorohexidine chloride, trichlorocarbanilide, photosensitizer, isopropylmethylphenol, and the like.

  Examples of the antioxidant include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene and the like. Examples of the pH adjuster include lactic acid, lactate, citric acid, citrate, glycolic acid, succinic acid, tartaric acid, malic acid, potassium carbonate, sodium bicarbonate, ammonium bicarbonate and the like.

  Examples of the above skin beautifying ingredients include whitening agents such as arbutin, glutathione, and yukinoshita extract, cell activating agents / skin roughening agents such as royal jelly, photosensitizer, and cholesterol derivatives, nonyl acid wallenyl amide, nicotinic acid benzyl ester, Nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, caffeine, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin , Blood circulation promoters such as γ-oryzanol, skin astringents such as zinc oxide and tannic acid, and antiseborrheic agents such as sulfur and thianthol.

  Although it does not specifically limit as a dosage form of the cosmetics and skin external preparation of this invention, Aqueous, an oil-in-water type, a water-in-oil type etc. can be mentioned. Examples of the cosmetic and skin external preparations of the present invention can include cream, gel, and liquid. The effects of the present invention are most effective in lotions, creams, milks, and cosmetics. Basic cosmetics such as shampoos, rinses, hair cosmetics such as treatments, liquid foundations, base emulsions and the like.

(Liposome-containing water-soluble (meth) acrylamide polymer composition)
In addition, the water-soluble (meth) acrylamide polymer of the present invention can improve the moisturizing effect when used in combination with phospholipids, but the moisturizing effect is further improved by coexisting with liposomes formed from phospholipids. Can be made.
Liposomes, which are closed vesicles composed of phospholipid bilayers, have been used in research as biological membrane models and have been applied to pharmaceuticals and cosmetics as microcapsules that encapsulate and deliver drugs for a long time. In particular, in the cosmetics field, when liposomes are applied to the skin, a high moisturizing effect can be obtained because the liposomes have the property of staying in the stratum corneum for a long time.

  The liposome-containing water-soluble (meth) acrylamide polymer composition of the present invention contains the water-soluble (meth) acrylamide polymer of the present invention and at least a phospholipid in an aqueous solution such as purified water, and preferably further contains cholesterol. 1 or 2 or more types chosen from the group which consists of a cholesterol derivative, a phytosterol and a phytosterol derivative, and / or 1 type or 2 or more types chosen from the group which consists of glycerol and 1, 3- butylene glycol It is.

Examples of phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinositol, lysophosphatidylcholine, natural phospholipids such as sphingomyelin, egg yolk lecithin, soybean lecithin, and phospholipids such as dioleoylphosphatidylcholine, or naturally derived phospholipids. Examples thereof include hydrogenated phospholipids in which unsaturated carbon chains of phospholipids are saturated with hydrogen, and other phospholipids extracted from microorganisms such as Escherichia coli. These can be used alone or in combination of two or more.
Among these, one or more selected from hydrogenated soybean phospholipid, hydrogenated egg yolk phospholipid, hydrogenated phosphatidylcholine, and hydrogenated phosphatidylserine are preferable.

  Examples of cholesterol or a cholesterol derivative include cholesteryl hydroxystearate, cholesterol, cholestanol, dehydrocholesterol, lanolin fatty acid cholesteryl, isostearic acid cholesteryl, ricinoleic acid cholesteryl, macadamia nut oil fatty acid cholesteryl, and the like. It can be used in combination of more than one species.

  Examples of phytosterol or phytosterol induction include β-sitosterol, stigmasterol, campesterol, ergosterol, macadamia nut fatty acid phytosteryl, phytosteryl oleate, and the like, and these can be used alone or in combination.

  The liposome-containing water-soluble (meth) acrylamide polymer composition of the present invention can be produced according to a known method for producing a liposome-containing aqueous dispersion, except that the water-soluble (meth) acrylamide polymer of the present invention coexists. It can be produced by a known method such as a bangham method, a pH gradient method, a freeze-thaw method, a reverse phase evaporation method, a mechanochemical method, a supercritical carbon dioxide method, or a film loading method (see JP-A-8-183726). ).

  Although the compounding quantity of each component in a composition can be suitably set according to a use, the following ranges are preferable. The water-soluble (meth) acrylamide polymer of this invention is 0.01-10 mass%, More preferably, it is 0.1-5 mass%. A phospholipid is 0.005-10 mass%, More preferably, it is 0.01-5 mass%. Outside this range, the temporal stability when liposomes are formed is not preferred. Cholesterol, cholesterol derivative, phytosterol or phytosterol derivative is not always necessary, but when used, it is 0.01 to 10% by mass, preferably 0.05 to 5% by mass. Glycerin or 1,3-butylene glycol is not always necessary, but when used, it is 1 to 50% by mass, preferably 5 to 40% by mass.

  Hereinafter, the present invention will be described with reference to examples. In addition, these do not limit this invention at all.

(Reference example)
[Synthesis of N-ethylacrylamide]
15 g of ethylamine (NH ₂ (CH ₂ CH ₃ ): 45.1) was dissolved in 250 mL of acetonitrile, 26 g of triethylamine (N (CH ₂ CH ₃ ) 3: 77.2) was added, and the mixture was cooled to 0 ° C. While maintaining 0 ° C., 30 g of acrylic acid chloride (CH ₂ CHCOCl: 90.51) was slowly added dropwise thereto with stirring. After completion of the dropwise addition, the cooling was released, and when the liquid temperature became the same as the room temperature, the stirring was stopped and the solution was concentrated under reduced pressure. 200 mL of purified water and 20 g of sodium chloride were added to the concentrate, adjusted to pH 6.5 with 1N hydrochloric acid, and partitioned with ethyl acetate. The aqueous layer after ethyl acetate partitioning was further added with 10 g of sodium chloride and partitioned with ethyl acetate. The ethyl acetate partition was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain about 25.5 g of a crude reaction product. The crude reaction was purified by column chromatography (carrier: ODS silica gel, developing solvent: water: methanol (9: 1)) after deployment at, purified, N- ethyl acrylamide _{(CH 2 CHCONH (CH 2 CH} 3): 99 .15) 22.8 g (yield approximately 69%) was obtained. The obtained N-ethylacrylamide had an elemental analysis value of carbon 58.58%, hydrogen 9.15%, nitrogen 14.13%, oxygen 16.14% (calculated residue), (theoretical value: carbon 60.58). %, Hydrogen 9.151%, nitrogen 14.129%, oxygen 16.139%), H-NMR (in deuterated chloroform solution), δ = 6.7 (1H, b), 6.2 (2H, m ), 5.6 (1H, dd), 3.3 (2H, qq), 1.1 (3H, m). In C-NMR (in deuterated chloroform solution), δ = 165.6 (166.7), 131.1 (131.1), 125.7 (128.9), 34.3 (34.1) 14.5 (15.0). (Numerical values in parentheses are theoretical values) In mass spectrometry, a peak (theoretical value: 99.13) of m / e = 99.07 (M +) was observed.

1) Synthesis of polymer (Example 1)
[Synthesis of N-ethylacrylamide homopolymer]
10 g of N-ethylacrylamide and 30 g of toluene were added to a four-necked separable flask (hereinafter also simply referred to as “flask”) equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a stirring device, and nitrogen gas was added. After introduction and sufficient nitrogen atmosphere, the mixture was heated to 70 ° C., 0.5 g of α, α′-azobisisobutyronitrile (hereinafter referred to as AIBN) was added, and the mixture was refluxed for 1 hour for polymerization. . After the reaction, the precipitated solid content was collected, dissolved in methanol, and then injected with ethyl acetate to cause precipitation. The precipitate was filtered off and dried in vacuo to give 8.12 g of N-ethylacrylamide homopolymer (yield). 81.2%). The weight average molecular weight in terms of polystyrene by GPC was 61,900. This N-ethylacrylamide homopolymer dissolved transparently in water and became a viscous solution.

(Example 2)
[Synthesis of N-ethylacrylamide homopolymer]
To the flask, 5 g of N-ethylacrylamide and 45 g of ethyl acetate were added, nitrogen gas was introduced to make a nitrogen atmosphere sufficiently, then the mixture was heated to 70 ° C., 0.25 g of AIBN was added and refluxed for 1 hour to polymerize. I let you. After the reaction, the precipitated solid was collected, dissolved in methanol, and then injected with ethyl acetate to cause precipitation. The precipitate was filtered off and dried in vacuo to give 3.4 g of N-ethylacrylamide homopolymer (yield) 68%). The weight average molecular weight in terms of polystyrene by GPC was 83,200. This N-ethylacrylamide homopolymer dissolved transparently in water and became a viscous solution.

(Example 3)
[Synthesis of N-ethylacrylamide homopolymer]
To the flask, 7.5 g of N-ethylacrylamide and 42.5 g of toluene were added, and nitrogen gas was introduced to make a nitrogen atmosphere sufficiently. Then, the mixture was heated to 70 ° C., and 0.375 g of AIBN was added for 15 minutes. Refluxed and polymerized. After the reaction, the precipitated solid content is collected, dissolved in ethanol, and injected with hexane to cause precipitation. The precipitate is filtered off and dried in vacuo to yield 5.56 g of N-ethylacrylamide homopolymer (yield 74). %). The weight average molecular weight in terms of polystyrene by GPC was 51,600. This N-ethylacrylamide homopolymer was transparently dissolved in water and became a viscous solution.

Example 4
[Synthesis of N-ethylacrylamide homopolymer]
Add 5 g of N-ethylacrylamide and 45 g of toluene to the flask, introduce nitrogen gas into a nitrogen atmosphere, heat to 70 ° C., add 0.15 g of AIBN and reflux for 30 minutes for polymerization. It was. After the reaction, the precipitated solid was collected, dissolved in methanol, and then injected with ethyl acetate to cause precipitation. The precipitate was filtered off and dried in vacuo to give 3.61 g of N-ethylacrylamide homopolymer (yield) 72.2%). The weight average molecular weight in terms of polystyrene by GPC was 11,900. This N-ethylacrylamide homopolymer dissolved transparently in water and became a viscous solution.

(Example 5)
[Synthesis of N-ethylacrylamide homopolymer]
Add 5 g of N-ethylacrylamide and 45 g of methyl isobutyl ketone to the flask, introduce nitrogen gas to make it sufficiently nitrogen atmosphere, warm to 70 ° C., add 0.25 g of AIBN and reflux for 5 hours. Polymerized. After the reaction, the precipitated solid was collected, dissolved in methanol, and then injected with ethyl acetate to cause precipitation. The precipitate was filtered and dried in vacuo to give 3.57 g of N-ethylacrylamide homopolymer (yield). 71.4%). The weight average molecular weight in terms of polystyrene by GPC was 20,700. This N-ethylacrylamide homopolymer dissolved transparently in water and became a viscous solution.

(Example 6)
[Synthesis of N, N-dimethylacrylamide homopolymer]
Add 10 g of N, N-dimethylacrylamide and 90 g of toluene to the flask, introduce nitrogen gas into a nitrogen atmosphere, heat to 70 ° C., add 0.3 g of AIBN and reflux for 2 hours. Polymerized. After the reaction, the reaction solution is concentrated with an evaporator, and then hexane is injected to cause precipitation. The precipitate is filtered off and dried in vacuo to give 8.42 g of N, N-dimethylacrylamide homopolymer (yield 84.2%). ) The weight average molecular weight in terms of polystyrene by GPC was 28,400. This N, N-dimethylacrylamide homopolymer was transparently dissolved in water and became a viscous solution.

(Example 7)
[Synthesis of N, N-diethylacrylamide homopolymer]
To the flask, 10 g of N, N-diethylacrylamide (manufactured by Kojin Co., Ltd.) and 90 g of toluene were added, and nitrogen gas was introduced to make a sufficient nitrogen atmosphere. 3 g was added and refluxed for 2 hours for polymerization. After the reaction, the reaction solution is concentrated with an evaporator, and then hexane is injected to cause precipitation. The precipitate is filtered off and dried in vacuo to give 8.03 g of N, N-diethylacrylamide homopolymer (yield 80.3%). ) The weight average molecular weight in terms of polystyrene by GPC was 40,600. The N, N-diethylacrylamide homopolymer was transparently dissolved in water and became a viscous solution.

(Example 8)
[Synthesis of N-isopropylacrylamide homopolymer]
Add 10 g of N-isopropylacrylamide and 90 g of toluene to the flask, introduce nitrogen gas into a nitrogen atmosphere, heat to 70 ° C., add 0.3 g of AIBN and reflux for 3 hours for polymerization. It was. After the reaction, the solvent was distilled off with an evaporator to obtain 6.77 g (yield 67.7%) of N-isopropylacrylamide homopolymer. The weight average molecular weight in terms of polystyrene by GPC was 54,100. This N-isopropylacrylamide homopolymer was transparently dissolved in water and became a viscous solution.

Example 9
[Synthesis of N-hydroxyethylacrylamide homopolymer]
To the flask, 10 g of N-hydroxyethyl acrylamide (manufactured by Kojin Co., Ltd.) and 90 g of methyl isobutyl ketone were added, and nitrogen gas was introduced to make a sufficient nitrogen atmosphere. .3 g was added and refluxed for 2 hours for polymerization. After the reaction, the precipitated solid content was collected, dissolved in ethanol, hexane was injected to precipitate the precipitate, the precipitate was filtered off, dried in vacuo, and 9.04 g of N-hydroxyethylacrylamide homopolymer (yield) 90.4%). The weight average molecular weight in terms of polystyrene by GPC was 37,800. The N-hydroxyethylacrylamide homopolymer dissolved in water and became a viscous solution.

(Example 10)
[Synthesis of N-ethylacrylamide homopolymer]
7.2 g of polyacrylic acid (molecular weight 5000, manufactured by Wako Pure Chemical Industries, Ltd.), 100 mL of distilled tetrahydrofuran, and 20 g of activated molecular sieve (3A 1/8) are charged into a glass-lined pressure-resistant reaction vessel having an internal volume of 500 mL. A gas introduction valve was installed. From the gas introduction valve, ethylamine gas (manufactured by Tokyo Chemical Industry Co., Ltd.) was press-fitted until the total mass increased by 5 g and sealed. Thereafter, the reaction vessel itself was heated to 105 ° C. while shaking and reacted for 6 hours. After the reaction, return to normal temperature, release the pressure, filter the molecular sieve, concentrate under reduced pressure until it is about half volume, inject ethyl acetate to precipitate, filter the precipitate, and vacuum dry. 8.85 g (yield 89.4%) of N-ethylacrylamide homopolymer was obtained. The weight average molecular weight in terms of polystyrene by GPC was 6,800. This N-ethylacrylamide homopolymer dissolved transparently in water and became a viscous solution.

(Example 11)
[Synthesis of N-ethylacrylamide homopolymer]
To a 500 mL three-necked separable flask (hereinafter simply referred to as “flask”) equipped with a reflux condenser, a thermometer and a stirrer, 7.2 g of polyacrylic acid (molecular weight 25,000, manufactured by Wako Pure Chemical Industries, Ltd.) Then, 150 mL of distilled tetrahydrofuran and 10 g of activated molecular sieve (3A 1/8) were added and heated to dissolve polyacrylic acid in tetrahydrofuran, and then 1,3-diethylurea (manufactured by Tokyo Chemical Industry Co., Ltd.). ) 6 g was added and refluxed at the boiling point of tetrahydrofuran for 24 hours. After cooling, the molecular sieve was filtered off and concentrated under reduced pressure to about half volume, and then ethyl acetate was injected for precipitation. The precipitate was filtered off and dried in vacuo to give 7.98 g of N-ethylacrylamide homopolymer. (Yield 80.1%) was obtained. The weight average molecular weight in terms of polystyrene by GPC was 34,000. This N-ethylacrylamide homopolymer dissolved transparently in water and became a viscous solution.

2) Evaluation test [Water retention evaluation 1 (mass reduction test)]
Prepare 50% by weight aqueous solutions of the water-soluble homopolymers of the present invention prepared in Examples 1 to 9 above, glycerin, sodium PCA, sodium lactate, serine, glutamine as comparative examples, and theanine as a positive control. Then, using this as a test sample, the water retention was evaluated by measuring the change in mass by leaving it in a constant temperature and humidity chamber set at a temperature of 30 ° C. and a relative humidity of 60% for 6 hours. The results obtained here are shown in Table 1.

[result]
Glycerin, PCA sodium, sodium lactate, serine, and glutamine, which are said to have high water retention, were shown to rapidly evaporate under conditions of a temperature of 30 ° C. and a relative humidity of 60%. On the other hand, the polymers produced in Examples 1 to 9 have a small mass change rate, have excellent water retention, and are presumed to be able to impart moisture retention when blended in cosmetics.

[Water retention evaluation 2 (humidity dependency test)]
1 g each of poly N-ethyl acrylamide, poly N, N-dimethyl acrylamide, poly N, N-diethyl acrylamide, poly N-isopropyl acrylamide and poly N-hydroxyethyl acrylamide prepared in each of the above Examples 1 to 9, Each sample was added to 1 g of purified water in a container having a diameter of 25 mm and a height of 10 mm to prepare a 50% by mass aqueous solution sample of each polymer. After mass measurement, the sample was transferred to a constant temperature and humidity chamber at 30 ° C. and 60% relative humidity. The mass after the time was measured. The sample was transferred to a constant temperature and humidity chamber with a relative humidity of 40%, and the mass change rate was evaluated by measuring the mass after 6 hours. Further, a 50% by mass aqueous solution sample of each polymer was transferred to a constant temperature and humidity chamber having a temperature of 30 ° C. and a relative humidity of 60%, the mass after 6 hours was measured, and water retention was evaluated from each mass change rate. Further, with respect to glycerin, sodium PCA, sodium lactate, serine, glutamine as comparative compounds and theanine as a positive control, 50 mass% aqueous solution samples of each polymer were evaluated in the same manner.

[result]
Regarding the mass change rate when the relative humidity was changed from 60% to 40%, the 50% by mass aqueous solution sample of the polymer prepared in Examples 1 to 9 was reduced by 1.4% or less at most, and glycerin , And sodium lactate showed a decrease of 2% or more, and it was speculated that when incorporated in cosmetics, rheology changes due to humidity. Furthermore, about 50 mass% aqueous solution sample of each polymer, when the relative humidity was changed from 40% to 60%, about mass change rate after 6 hours, 50 mass% aqueous solution of the polymer produced in Examples 1-9 The sample falls within the range of -1.0 to 0.2%, and even under high humidity conditions, it hardly infers hygroscopicity, and it is presumed that it will not cause stickiness even when blended into cosmetics. On the other hand, glycerin, PCA sodium and sodium lactate all show a mass increase of 1.5% or more, especially when moisture is taken in under high humidity conditions and blended into cosmetics due to such hygroscopicity. It was inferred that it would feel sticky.

[Viscosity evaluation]
A 10% by mass poly N-ethylacrylamide solution of Example 1 was prepared and allowed to stand in a constant temperature bath at 30 ° C. for 24 hours. The measurement was performed under conditions of 6 rotations per minute and a viscosity value after 1 minute.
[result]
It was in a state of no viscosity at all.

[Skin lotion sensory evaluation]
A lotion was prepared according to the formulation shown in Table 2 using the polymers prepared in Example 1 and Example 3, and sensory evaluation was performed. A lotion was prepared in the same manner as described above except that a (alkyl acrylate / octylacrylamide) copolymer and carboxyvinyl polymer were used, and sensory evaluation was performed for comparison. The results are shown in Table 2.

[result]
The skin lotion using the polymers prepared in Example 1 and Example 3 was excellent in skin familiarity, moist feeling, non-stickiness, and uniform spread, whereas the comparative polymer was Was also inferior.

(Prescription)
[Lotion]
Components 1 to 7 shown below were mixed and dissolved while stirring at normal temperatures at respective ratios to prepare a lotion.
(Ingredient) (mass%)
1. Ethanol 10.0
2. Polyoxyethylene hydrogenated castor oil (60 EO) 0.1
3. Perfume appropriate amount 4. N-ethylacrylamide homopolymer (Example 1) 0.5
5). 1,3-butylene glycol 15.0
6). Preservative 0.1
7). Purified water remaining amount The skin lotion prepared according to the above formulation had a fresh feeling of use without stickiness and was excellent in moisturizing feeling.

[Moisturizing serum-1]
Components 1 to 6 and components 7 to 15 shown below are stirred and mixed at respective ratios and heated to 80 ° C. The latter is added dropwise to the former and stirred to emulsify. Subsequently, it was cooled to prepare a moisturizing serum.
(Ingredient) (mass%)
1. Sucrose fatty acid ester 0.6
2. Glyceryl monostearate 0.1
3. Polyethylene glycol monostearate 0.1
4). Batyl alcohol 0.1
5). Liquid paraffin 4.5
6). Glyceryl trioctanoate 1.5
7). N-ethylacrylamide homopolymer (Example 3) 1.0
8). 1,3-butylene glycol 6.0
9. Glycerin 2.0
10. Ethanol 13.0
11. Carboxyvinyl polymer 0.1
12 Sodium hydroxide 0.01
13. Preservative 0.1
14 Perfume appropriate amount 15. Purified water remaining amount The moisturizing serum prepared according to the above formulation had a fresh feeling of use without stickiness and was excellent in moisturizing feeling.

[Emulsion]
The components 1-4 shown below and the components 5-12 are stirred and mixed in each ratio, and it heats at 80 degreeC. The latter is added dropwise to the former and stirred to emulsify. Subsequently, it was cooled to prepare an emulsion.
(Ingredient) (mass%)
1. Squalane 5.0
2. Cetanol 1.0
3. Polyethylene ethylene sorbitan monooleate (20E.O.) 2.0
4). Sorbitan sesquioleate 0.8
5). Glycerin 5.0
6). 1,3-butylene glycol 10.0
7). N-ethylacrylamide homopolymer (Example 5) 1.0
8). Carboxyvinyl polymer 0.2
9. Potassium hydroxide 0.1
10. Preservative 0.1
11. Perfume appropriate amount 12. Purified water remaining amount The emulsion prepared according to the above formulation had a fresh feeling of use without stickiness, and was excellent in moisturizing feeling.

[Cream pack]
The components 1-4 shown below and the components 5-12 are stirred and mixed in each ratio, and it heats at 80 degreeC. The latter is added dropwise to the former and stirred to emulsify. Subsequently, the mixture was cooled to prepare a cream pack.
(Ingredient) (mass%)
1. Polyoxyethylene polyoxypropylene cetyl ether (20EO, 4PO)
0.8
2. Diglyceryl monostearate 0.2
3. Glyceryl tri-2-ethylhexanoate 1.0
4). Medu home oil 1.0
5). Glycerin 5.0
6). 1,3-butylene glycol 3.0
7). N-ethylacrylamide homopolymer (Example 1) 1.0
8). Sodium hydroxide 0.28
9. Hydroxyethyl cellulose 0.3
10. Ascorbic acid 2-glucoside 2.0
11. Preservative 0.1
12 Purified Water Remaining The cream pack prepared by the above formulation had a fresh feeling without stickiness and was excellent in moisturizing feeling after use.

[Impregnation mask]
Components 1 to 9 shown below were stirred and mixed at respective ratios to obtain an aqueous composition. An impregnation mask was prepared by impregnating this aqueous composition into a nonwoven fabric (substantially facial shape having holes and cuts in the eyes, nose and mouth) about 10 times the mass of the nonwoven fabric.
(Ingredient) (mass%)
1. Polyoxyethylene (60E.O.) hydrogenated castor oil 0.1
2. Preservative 0.1
3. Alcohol 5.0
4). Dipropylene glycol 7.0
5). Glycerin 3.0
6). N-ethylacrylamide homopolymer (Example 4) 0.5
7). Phosphorus monohydrogen phosphate 0.1
8). Monosodium dihydrogen phosphate 0.1
9. Purified Water Remaining The impregnated mask prepared by the above formulation had a fresh feeling with no stickiness and excellent moisturizing feeling after removing the mask.

[Funny]
97 parts of talc is mixed with 3 parts of N-ethylacrylamide homopolymer and ethanol at room temperature, and then heated to 80 ° C. to recover ethanol under reduced pressure. After cooling, the mixture was pulverized with a hammer mill to obtain N-ethylacrylamide homopolymer 3 wt% treated talc. Ingredients 1 to 9 shown below were stirred and mixed in their respective proportions, and pulverized with a hammer mill to prepare an interesting one.
(Ingredient) (mass%)
1. N-ethylacrylamide homopolymer (Example 1) 3 wt% treated talc
70.0
2. 2. Silicon processing sericite Perfluoroalkyl polyether-treated mica titanium 5.0
4). Magnesium stearate 2.0
5). Gunjo 0.2
6). Bengala 0.1
7). Preservative 0.1
8). Silicic anhydride 5.0
9. Perfume Appropriate amount Oshiroi prepared by the above formulation was excellent in moisturizing feeling during use.

[Powder Foundation]
Components 1 to 11 and components 12 to 16 shown below are mixed in respective proportions. The latter was dropped and mixed with the former, pulverized with a hammer mill, pressed into a mold and molded to prepare a powder foundation.
(Ingredient) (mass%)
1. Titanium oxide 10.0
2. Zinc oxide 5.0
3. Mica 20.0
4). 4. Sericite remaining amount Talc 20.0
6). Silicic anhydride 2.0
7). Bengala 0.5
8). Yellow iron oxide 2.0
9. Black iron oxide 0.3
10. Mica titanium 5.0
11. Polystyrene 3.0
12 Preservative 0.1
13. N-ethylacrylamide homopolymer (Example 1) 1.0
14 Glyceryl trioctanoate 1.0
15. Dimethylpolysiloxane 1.0
16. 2-Ethylhexyl paramethoxycinnamate 3.0
The powder foundation prepared by the above formulation was excellent in moisturizing feeling during use.

[Liquid Foundation]
Components 1 to 8 and Components 9 to 13 shown below are stirred and mixed at respective ratios and heated to 80 ° C. Add the latter to the former and mix. Subsequently, the mixture was cooled to prepare a liquid foundation.
(Ingredient) (mass%)
1. Squalane 10.0
2. Decamethylcyclopentasiloxane 20.0
3. Polyoxyethylene-modified dimethylpolysiloxane 5.0
4). Talc 5.0
5). Bengala 0.5
6). Yellow iron oxide 1.0
7). Black iron oxide 0.1
8). Titanium oxide 10.0
9. Propylene glycol 10.0
10. N-ethylacrylamide homopolymer (Example 1) 1.0
11. Preservative 0.1
12 Perfume appropriate amount13. Purified water remaining amount The liquid foundation prepared by the above formulation was excellent in moisturizing feeling during use.

[lipstick]
Components 1 to 16 shown below are added in respective proportions and dispersed by roller treatment. The lipstick was prepared by pouring into a mold at a high temperature, filling the container with the molded product after cooling.
(Ingredient) (mass%)
1. Carnauba wax 10.0
2. Heavy liquid isoparaffin 20.0
3. α-olefin oligomer 20.0
4). Liquid paraffin 25.0
5). 5. Diglyceryl triisostearate remaining amount Cetyl isooctanoate 5.0
7). Ozoquelite wax 1.0
8). Hydrogenated rosin acid pentaerythritol 1.0
9. (Ethylene / Propylene) Copolymer 0.1
10. N-ethylacrylamide homopolymer (Example 1) 0.5
11. Red No. 202 0.3
12 Yellow No. 4 aluminum rake 0.7
13. Titanium oxide 0.5
14 Iron oxide coated mica titanium 3.0
15. Dibutylhydroxytoluene 0.01
16. Preservative 0.1
The lipstick prepared by the above formulation was excellent in moisturizing feeling during use.

[Cleansing sheet]
Components 1 to 3 and components 4 to 8 shown below are stirred and mixed at respective ratios and heated to 80 ° C. The latter was dropped and stirred into the former to emulsify, and then components 9 to 11 were added and stirred and mixed to obtain an emulsion composition. A cleansing sheet was prepared by impregnating the emulsion composition into a nonwoven fabric about 10 times the mass of the nonwoven fabric.
(Ingredient) (mass%)
1. Hydrogenated soybean phospholipid 1.0
2. Phytosterol 0.1
3. Glycerin 5.0
4). Dipropylene glycol 5.0
5). N-ethylacrylamide homopolymer (Example 1) 0.5
6). Neopentyl glycol dicaprate 2.0
7). Liquid paraffin 5.0
8). Light liquid paraffin 0.5
9. Preservative 0.1
10. Ethanol 10.0
11. Purified water remaining amount The cleansing sheet prepared by the above formulation had a fresh, non-sticky feeling of use and was excellent in a moisturizing feeling after use.

[Moisturizing serum-2]
A moisturizing serum was prepared according to the following formulation for the components shown in Table 3.
(Invention products 1 to 4, comparative products 1 to 4)
A: Components 1 to 4 are uniformly dissolved at 80 ° C.
B: Components 5 to 11 are uniformly dissolved at 80 ° C.
C: B is dropped and mixed in A and emulsified.

(Invention product 5, comparative product 5) <Liposome-containing composition>
A: Components 1 to 4 are uniformly dissolved at 80 ° C.
B: Components 5 to 11 are uniformly dissolved at 80 ° C.
C: B is dropped and mixed in A, and finely emulsified with a disperse mill.

  As shown in Table 3, the liposome composition obtained by miniaturization had little stickiness at the time of application and was excellent in moisturizing feeling over time.

Evaluation was performed by the following method.
(Evaluation methods)
About this invention products 1-5, comparative products 1-5, a use test is conducted by a professional panel by 20 people, and the "stickiness" when the sample is applied to the skin is evaluated according to the following criteria, and the average score Judged.
(Evaluation item)
a. No stickiness (absolute evaluation criteria)
(Score): (Evaluation)
6: There is no stickiness at all 5: There is no stickiness at all 4: There is no stickiness at all 3: Normal 2: There is a feeling slightly sticky 1: There is a feeling of stickiness 0: There is a feeling of stickiness (judgment criteria)
(Judgment): (Average score)
: Over 5 points (very good)
○: 5 points or less exceeding 3.5 points (good)
Δ: 3 points or less exceeding 1.5 points (slightly poor)
×: 1.5 points or less (defect)

(Evaluation methods)
About the present invention products 1-5 and comparative products 1-5, a use test is performed by a professional panel by 20 people, and the “moist feeling” when the sample is applied to the skin is evaluated according to the following criteria, and the average score Judged.
(Evaluation item)
b. Moist feeling (absolute evaluation criteria)
(Score): (Evaluation)
6: Feels moist 5: Moist )
(Judgment): (Average score)
: Over 5 points (very good)
○: 5 points or less exceeding 3.5 points (good)
Δ: 3 points or less exceeding 1.5 points (slightly poor)
×: 1.5 points or less (defect)

(Evaluation methods)
The inventive products 1 to 5 and the comparative products 1 to 5 are subjected to a use test by a professional panel by 20 people, the sample is applied to the skin, and the “humidity feeling over time” after 6 hours is evaluated according to the following criteria. The average score was determined.
(Evaluation item)
c. Moisturizing feeling over time (absolute evaluation criteria)
(Score): (Evaluation)
6: Feels very moisturized 5: Feels moisturized 4: Feels slightly moisturized 3: Normal: Does not feel moisturized slightly 1: Does not feel moisturized 0: Does not feel moisturized at all (judgment criteria) )
(Judgment): (Average score)
: Over 5 points (very good)
○: 5 points or less exceeding 3.5 points (good)
Δ: 3 points or less exceeding 1.5 points (slightly poor)
×: 1.5 points or less (defect)

[Moisturizing serum-3]
A moisturizing serum was prepared according to the following formulation for the components shown in Table 4 below.
(Invention product 6, comparative products 6, 7) <Liposome-containing composition>
A: Components 1 to 4 are uniformly dissolved at 80 ° C.
B: Components 5 to 6 are uniformly dissolved at 80 ° C.
C: B is dropped and mixed in A, and finely emulsified with a disperse mill.
D: Components 7 to 9 are uniformly dissolved at room temperature and added to C and mixed.

(Invention product 7, comparative product 8)
A; Components 7 to 9 are uniformly dissolved at room temperature.

(Evaluation methods)
About this invention products 6 and 7, and comparative products 6-8, the skin moisture content by continuous use (used twice a day in the morning and evening) was measured. After washing the inside of the forearm of the panel with facial soap and acclimating for 20 minutes in an environment with a constant humidity and temperature, reflection measurement is performed with a near-infrared spectrometer (Spectrum 400 PerkinElmer). The amount of water was detected at the peak height. The skin moisture content before use (0 day) was plotted as 100%, and the skin moisture content after use was plotted. The results are shown in FIG.

[result]
The water retention when the sample of the water-soluble polymer of the present invention was applied to the skin showed the same water retention as theanine, which is a material for which the water retention effect is focused. In addition, the water-soluble polymer of the present invention can be synergistically imparted with moisture retention by being blended with the liposome-containing cosmetic.

Claims (9)

Formula (1)

(Wherein, _{R 1} represents a hydrogen atom or a methyl group, _{R 2} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, _{R 3} is alkyl or 1 to 3 carbon atoms having 1 to 3 carbon atoms A polymer having 1 to 2 or more of repeating units represented by a hydroxyalkyl group, having a weight average molecular weight (Mw) of 5,000 to 150,000, a temperature of 30 ° C. and a relative humidity of 60%. A water-soluble (meth) acrylamide polymer for cosmetics or topical skin preparations, wherein the mass reduction rate after standing for 50 hours in a 50% by weight aqueous solution is 25% by weight or less.   Furthermore, when the relative humidity is lowered from 60% to 40% at a temperature of 30 ° C., the mass reduction rate of the 50% by mass aqueous solution of the polymer is less than 3% by mass. (Meth) acrylamide polymer.   Further, the water increase rate according to claim 1 or 2, wherein the mass increase rate of a 50% by mass aqueous solution of the polymer is less than 3% by mass when the relative humidity is increased from 40% to 60% at a temperature of 30 ° C. Sex (meth) acrylamide polymer.   The water-soluble (meth) acrylamide polymer according to any one of claims 1 to 3, wherein the water-soluble (meth) acrylamide polymer is poly N, N-diethylacrylamide. (A) A liposome-containing water-soluble (meth) acrylamide polymer composition comprising the water-soluble (meth) acrylamide polymer according to any one of claims 1 to 4 and (B) a phospholipid.   The liposome-containing water-soluble (meth) acrylamide polymer composition according to claim 5, further comprising (C) one or more selected from the group consisting of cholesterol, cholesterol derivatives, phytosterols, and phytosterol derivatives. .   The liposome-containing water-soluble (meth) acrylamide polymer composition according to claim 5 or 6, further comprising (D) one or more selected from the group consisting of glycerin and 1,3-butylene glycol. object.   Cosmetics or skin external preparation containing the water-soluble (meth) acrylamide homopolymer according to any one of claims 1 to 4.   A cosmetic or external skin preparation comprising the liposome-containing composition according to any one of claims 5 to 7.

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