JP2011213903A - Hydrophilic polymer and cosmetic or external preparation for skin combined with the polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrophilic polymer for a cosmetic or an external preparation for skin, which is capable of maintaining moistness even under low humidity conditions and being capable of remaining on skin for long periods of time because of its high film plasticity without imparting none of viscosity, spinnability, stickiness, and the like to the formulation.SOLUTION: The hydrophilic polymer having 1, 2, or more types of unit structure represented by the following formula, wherein X denotes -NHRor OM (a case in which both Xs are OM is excluded, R1 denotes a 1-3C alkyl group, M denotes a hydrogen atom, an alkali metal atom, or an organic base group), one of Rs denotes a hydrogen atom, the other R denotes one type or more selected from among a hydrogen atom, a 1-3C alkyl group, a 1-3C alkoxy group, a phenyl group, an acetoxy group, a carboxy group, a salt type carboxy group, an amide group, and an N monoalkyl-substituted amide group.

Description

  The present invention relates to a novel hydrophilic polymer and a cosmetic or skin external preparation containing the same, and more specifically, a hydrophilic polymer having high film-forming properties and excellent moisturizing properties, and a cosmetic containing the same or It relates to an external preparation for skin.

  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 lines 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. Hydrating effect with water present in the stratum corneum using low molecular weight compounds such as water-soluble polyhydric alcohols such as glycerin and 1,3-butylene glycol, organic acid salts such as pyrrolidone carboxylate soda and lactate soda Although a method for enhancing the moisture content has been found, these moisturizers are easy to diffuse on the skin and often have a temporary effect. There are still challenges.

  On the other hand, high molecular weight compounds are also used as humectants. For example, acetylated hyaluronic acid having a hyaluronic acid or a hydrophobic group (see, for example, Patent Document 1), and 2-methacryloyloxy having the same structure as the polar group of phosphatidylcholine focused on the structure of the cell membrane Polymers having ethylphosphorylcholine as a structural unit (for example, see Patent Document 2), amino acid-modified γ-polyglutamic acid having moisturizing property formed by amide bond between a side chain α-carboxyl group and an amino group of a hydrophilic amino acid (for example, High molecular weight compounds such as Patent Document 3) have 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 (for example, see Patent Document 4), an aqueous gel resin (see, for example, Patent Document 5), a water separation and retention agent containing a (meth) acrylamide-derived polymer (for example, see Patent Document 4). For example, Patent Document 6), water vapor absorption and release agents (for example, see Patent Document 7) have been proposed, and water-soluble ethylenically unsaturated monomers such as dialkylacrylamide and ionic acrylamide derivatives are dissolved in the dispersion layer. And a thickener comprising a microgel obtained by radical polymerization in the dispersed phase (see, for example, Patent Document 8) and an oily phase dispersed in an aqueous solution A medium-oil type nanoemulsion composition comprising an acrylic acid homopolymer neutral (e.g., see Patent Document 9) have been proposed, and the like.

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 low molecular weight humectants represented by glycerin, pyrrolidone carboxylate soda, lactic acid soda, etc. absorb moisture at high humidity, but release moisture molecules at low humidity, and the moisture retention may not be maintained. Many. Moreover, since the solubility to water is high, it is easy to diffuse on the skin and the outflow from the skin cannot be prevented. As a result, the moisturizing effect cannot be expected. In addition, high molecular weight moisturizers have high water solubility in the same way as low molecular weight moisturizers, and cannot completely prevent diffusion and outflow on the skin. Further, the high molecular weight humectant sometimes imparts undesirable properties such as viscosity, spinnability, and stickiness to the blended preparation. The object of the present invention is to maintain moisture retention even under conditions of low humidity, do not impart viscosity, stringiness, stickiness, etc. to the formulated preparation, and have high film-forming properties and can stay on the skin for a long time. Another object of the present invention is to provide a hydrophilic polymer for cosmetics or an external preparation for skin.

  In view of the above-mentioned problems, the present inventors modify a part of maleic acid-based copolymer and maleic anhydride-based copolymer that are excellent in film-forming property, and maintain the film-forming property while maintaining the moisturizing effect. Thus, the present inventors have found that a hydrophilic polymer having a high retention rate on the skin without adversely affecting the blended preparation and having good retention on the skin can be obtained.

That is, the present invention provides the following formula (1):
[In the formula (1), X represents —NHR ₁ or OM (except when both X are simultaneously OM; R ₁ is an alkyl group having 1 to 3 carbon atoms; M is a hydrogen atom or an alkali metal atom) Or an organic base group). One of R is a hydrogen atom, the other is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, an acetoxy group, a carboxy group, a salt-type carboxy group, an amide group, N mono 1 type chosen from an alkyl substituted amide group is shown. And a hydrophilic polymer having one or more unit structures.
Moreover, this invention provides the cosmetics or skin external preparation which mix | blends the above-mentioned hydrophilic polymer.

  The hydrophilic polymer of the present invention has a high moisturizing effect, does not adversely affect the blended preparation, and has a good film-forming ability and also has good retention on the skin. Moreover, the cosmetic or external preparation for skin according to the present invention containing the hydrophilic polymer also has a long-lasting moisturizing effect.

(Hydrophilic polymer)
The hydrophilic polymer of the present invention is a polymer compound having one or more unit structures represented by the formula (1).

[In the formula (1), X represents —NHR ₁ or OM (except when both X are simultaneously OM; R ₁ is an alkyl group having 1 to 3 carbon atoms; M is a hydrogen atom or an alkali metal atom) Or an organic base group). One of R is a hydrogen atom, the other is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, an acetoxy group, a carboxy group, a salt-type carboxy group, an amide group, N mono 1 type chosen from an alkyl substituted amide group is shown. ]

The unit structure represented by the formula (1) will be described in more detail. X represents —NHR ₁ or OM, and R ₁ represents any of a methyl group, an ethyl group, a propyl group, and an isopropyl group. When the carbon number of R ₁ is 4 or more, the hydrophilicity of the polymer provided by the unit may be reduced, and sufficient moisturizing ability may not be exhibited. M represents a hydrogen atom, an alkali metal atom, or an organic base group, and the alkali metal atom represents a sodium atom or a potassium atom. Organic base groups, ammonia, alkyl-substituted amines, shows the alkanol-substituted amines such as, if specifically illustrated in the form of a ^{_{-OM, -O - N + H 4}} , -O - N + H 3 R a, -O ^{_{- N + H 2 R a2,}} -O - N + HR a3 (. , where _{R a} is a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group). However, in the present invention, units in which both X are simultaneously represented by OM are not subject to the invention. One of R is a hydrogen atom, the other is a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, phenyl group, acetoxy group (—OC (═O) CH ₃ ), a carboxy group (—C (═O) OH), a salt-type carboxy group (—C (═O) OM: where M is the same as M above), an amide group (—CONH ₂ ), N A monoalkyl-substituted amide group (—CONHR _b, where R _b represents a methyl group, an ethyl group, a propyl group, or an isopropyl group).

Of these unit structure, the unit structure the effect of the present invention can be attained high, one of X is -NHCH ₂ CH _3, the other is _{-NHCH 2 CH 3, -OH, -ONa} , -OK, -O - ^{_{N + H 4, -O - N}} + H 3 (CH 2 CH 2 OH), - O - N + H 2 (CH 2 CH 2 OH) 2, -O - N + H (CH 2 CH 2 OH) 3 R is one type selected from a hydrogen atom, the other being a hydrogen atom, a methoxy group, a carboxy group, a salt-type carboxy group, an amide group, and an N monoalkyl-substituted amide group. In the unit structure in which the effect of the present invention is further enhanced, both of X are —NHCH ₂ CH ₃ , and one of R is a hydrogen atom, and the other is a methoxy group, a carboxy group, a salt-type carboxy group, an N-mono group. This is one type selected from alkyl-substituted amide groups. Furthermore, in the unit structure in which the effect of the present invention is most highly exhibited, both X are —NHCH ₂ CH ₃ , and one of R is a hydrogen atom, the other is a methoxy group, a carboxy group, and an N monoethyl-substituted amide group (— This is one case selected from CONHCH ₂ CH ₃ ).

The hydrophilic polymer having a unit structure represented by the formula (1) of the present invention can be obtained, for example, by chemically modifying a maleic acid copolymer or a maleic anhydride copolymer. As a specific example, both R in formula (1) are hydrogen atoms by reacting a maleic acid-derived carboxy group of an ethylene-maleic acid copolymer with ammonia or an alkyl-substituted amine for amidation. A hydrophilic polymer having a unit structure in which X is changed to —NH ₂ , —NHR _C (wherein R _C represents an alkyl group of an alkyl-substituted amine used for the reaction) can be obtained. Similarly, by reacting a carboxyl group derived from acrylic acid and maleic acid in an acrylic acid-maleic acid copolymer with ammonia or an alkyl-substituted amine and amidating, one of R in formula (1) is a hydrogen atom, Is —CONH ₂ , —CONHR _C (wherein R _C is the same as above), and X is changed to —NH ₂ , —NHR _C (where R _C is the same as above). A hydrophilic polymer having can be obtained. In addition, by reacting ammonia or an alkyl-substituted amine with the ring-closing acid anhydride group of the methyl vinyl ether-maleic anhydride copolymer to cause ring-opening amidation, one of R in formula (1) is a hydrogen atom and the other is methoxy. It is possible to obtain a hydrophilic polymer having a unit structure in which X is —NH ₂ and —NHR _C (wherein R _C is the same as described above). The amidation may be performed by a direct dehydration condensation reaction between a carboxyl group and an amino group, a condensation reaction using a condensing agent such as carbonyldiimidazole or dialkylcarbodiimide, or an amidation reaction using urea or alkylated urea. However, the hydrophilic polymer of the present invention may be obtained by methods other than those described above.

  The hydrophilic polymer of the present invention needs to be a hydrophilic polymer in order to have both film forming properties and moisture retention. The hydrophilicity in the present invention means that the polymer is soluble in any one of water, a water-ethanol mixture and ethanol.

  The hydrophilic polymer of the present invention is not limited as long as it has one or more unit structures represented by the formula (1), but the formula occupying the hydrophilic polymer molecule. The ratio of the unit structure represented by (1) is preferably 75 mol% or more, and more preferably 90 mol% or more. Most preferably, the hydrophilic polymer of the present invention is composed of one or more unit structures all represented by the formula (1). When the proportion of the unit structure represented by the formula (1) in the hydrophilic polymer molecule is less than 75 mol%, the moisture retention ability of the hydrophilic polymer of the present invention may be inferior.

The structural unit other than the structural unit represented by the formula (1) in the hydrophilic polymer of the present invention is not particularly limited as long as the effects of the present invention can be maintained, but the hydrophilicity is greatly reduced. The structural unit is not preferred, and the homopolymer of the structural unit preferably exhibits hydrophilicity in the present invention. Specific examples of the structural unit other than the structural unit represented by the formula (1) in the hydrophilic polymer of the present invention include the structural unit (—CH ₂ CH (COOH) —) and methacrylic acid provided by acrylic acid. The structural unit (—CH ₂ C (CH ₃ ) (COOH) —), acrylamide provides (—CH ₂ CH (CONH ₂ ) —), and the structural unit (—CH ₂ C (CH ₃ ) gives methacrylamide. ) (CONH ₂₎ -), a structural unit hydroxyethyl acrylate gives _{(-CH 2 CH (COOCH 2 CH} 2 OH) -), a structural unit hydroxyethyl methacrylate gives _{(-CH 2 C (CH 3)} (COOCH 2 CH ₂ OH) -), a structural unit given by N- monomethyl acrylamide _{(-CH 2 CH (CONH (CH} 3)) -), N- Monomechi Structural units Le methacrylamide gives _{(-CH 2 C (CH 3)} (CONH (CH 3)) -), a structural unit given by N- monoethyl acrylamide _{(-CH 2 CH (CONH (CH} 2 CH 3)) - ), A structural unit given by N-monoethylmethacrylamide (—CH ₂ C (CH ₃ ) (CONH (CH ₂ CH ₃ )) —), a structural unit given by N-monopropylacrylamide (—CH ₂ CH (CONH ( CH ₂ CH ₂ CH ₃ ))-), N-monopropylmethacrylamide gives the structural unit (—CH ₂ C (CH ₃ ) (CONH (CH ₂ CH ₂ CH ₃ )) —), N-vinylpyrrolidone gives A structural unit etc. are mentioned, Those 1 type (s) or 2 or more types can be used.

  The hydrophilic polymer of the present invention is not limited as long as it has one or more unit structures represented by the formula (1), but the hydrophilic polymer has a crosslinked structure. It does not matter. However, as the cross-linked structure increases, the solubility of the hydrophilic polymer decreases and the film formation also decreases. Therefore, the cross-linked structure is preferably 5% or less as the molar fraction in the hydrophilic polymer of the present invention. . When the molar fraction of the cross-linked structure exceeds 5%, the solubility of the hydrophilic polymer of the present invention in water decreases, so that swelling occurs instead of dissolution. However, the swollen material has no film-forming property but has moisture retention.

  The molecular weight of the hydrophilic polymer of the present invention is generally in the range of 50,000 to 5,000,000, although there are differences depending on the difference between R and X in formula (1). If the molecular weight is less than 50,000, the film-forming property may be reduced. If the molecular weight exceeds 5,000,000, the film-forming property and the moisturizing ability are not affected, but another cosmetic according to the present invention. Or, when blended into a skin external preparation, viscosity or stickiness may occur, and the feel of the cosmetic or the skin external preparation may be impaired.

(Cosmetics and skin preparations)
The cosmetic or external preparation for skin of the present invention is formed by blending a hydrophilic polymer having one or more unit structures represented by the formula (1), and the hydrophilic polymer is: It mix | blends by 1 type or the combination of 2 or more types.

  The hydrophilic polymer of the present invention can be blended in cosmetics and other external preparations for skin, as well as other preparations to be moisturized, but is preferably used in cosmetics and external skin preparations. It is more preferable to blend in. 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 hydrophilic polymer of the present invention in the cosmetic or skin external preparation of the present invention is not particularly limited as long as the effects of the present invention are exhibited, but usually, for the cosmetic and the entire skin external preparation, 0.01-10 mass% is preferable and 0.1-5 mass% is more preferable.

  The cosmetic or skin external preparation of the present invention includes components generally used in cosmetics and skin external preparations together with the hydrophilic polymer of the present invention, such as the following oily components, surfactants, alcohols, and humectants. , Gelling agents, powders, ultraviolet absorbers, antiseptics, antibacterial agents, antioxidants, pH adjusters, skin-beautifying ingredients, perfumes, and the like, as long as the effects of the present invention are not impaired You may mix | blend suitably combining.

  The oily component (oil agent) is not particularly limited as long as it is an oil agent generally used for cosmetics and skin external preparations, and is derived from animal oil, vegetable oil, synthetic oil and the like, solid oil, semi-solid oil, liquid oil, Regardless of the nature of volatile oils, for example, hydrocarbon oils, ester oils, glyceride oils, silicone oils, higher alcohols, fatty acids, lanolin derivatives, waxes, hardened oils, fluorinated oils, etc. These oil agents 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 , Hi Cellulose polymers such as loxypropylmethylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, alginic acid polymers such as sodium alginate and propylene glycol alginate, sodium polyacrylate, carboxy Vinyl polymers, alkyl-modified carboxyvinyl polymers, vinyl polymers such as polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, ethylene oxide propylene oxide copolymer, bentonite, magnesium aluminum silicate, laponite, hectorite, List inorganic gelling agent thickeners such as silicic anhydride As oily gelling agents, metal soaps such as aluminum stearate, magnesium stearate, zinc myristate, amino acid derivatives such as N-lauroyl-L-glutamic acid, α, γ-di-n-butylamine, Dextrin derivatives such as dextrin palmitic acid ester, dextrin stearic acid ester, dextrin 2-ethylhexanoic acid palmitic acid mixed ester, sucrose fatty acid ester such as fatty acid ester, sucrose palmitic acid ester, sucrose stearic acid ester, monobenzylidene Benzylidene derivatives of sorbitol such as sorbitol, dibenzylidene sorbitol, dimethylbenzyl dodecyl ammonium montmorillonite clay, dimethyl dioctadecyl ammonium montmorillonite clay, etc. , And the like organic modified clay 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 UV absorber include benzoic acid UV absorbers such as paraaminobenzoic acid, anthranilic UV absorbers such as methyl anthranilate, salicylic acid UV absorbers such as methyl salicylate, and paramethoxy cinnamon. Examples thereof include cinnamic acid ultraviolet absorbers such as octyl acid, benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone, and urocanic acid ultraviolet 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-mentioned skin beautifying ingredients include whitening agents such as arbutin, glutathione and yukinoshita extract, cell activators and rough skin improving 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.

Hereinafter, the present invention will be described with reference to examples. In addition, these do not limit this invention at all.
Example 1 [Synthesis of hydrophilic polymer having unit structure represented by formula (2)]
Into a glass flask having an internal volume of 200 mL, 1.56 g of methyl vinyl ether-maleic anhydride copolymer (“Gantrez AN-119” average molecular weight of about 130,000 manufactured by ISP) dried at 105 ° C. for 2 hours was charged. Dissolved in 50 mL of distilled dry tetrahydrofuran. Then, 2.25 g of a tetrahydrofuran solution (20% by mass) of ethylamine was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at room temperature for 12 hours. Thereafter, the precipitated white solid was collected, washed three times with distilled tetrahydrofuran, and dried under reduced pressure to obtain 1.77 g of a colorless solid hydrophilic polymer having a unit structure represented by the formula (2) (yield) 88%). This hydrophilic polymer was soluble in water. The hydrophilic polymer had a weight average molecular weight in terms of polystyrene of about 200,000.

[In the formula, one of R represents a hydrogen atom and the other represents a methoxy group (—OCH ₃ ). X represents a group in which either one is a hydroxyl group and the other is represented by —NHCH ₂ CH ₃ . ]

Example 2 [Synthesis of hydrophilic polymer having unit structure represented by formula (3)]
Distilled water (50 mL) was added to 2.50 g of methyl vinyl ether-maleic anhydride copolymer (“Gantrez AN-169” (average molecular weight: about 2,500,000) manufactured by ISP), and the mixture was refluxed for 10 hours for hydrolysis. Then, the colorless solid obtained by distilling off distilled water under reduced pressure was dried at 105 ° C. for 2 hours to obtain 2.78 g of a compound having a unit structure represented by the formula (4). 1.74 g of this product was dissolved in 50 mL of distilled and dried N-methylpyrrolidone, 3.3 g of carbonyldiimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature for 5 hours. Next, 5 g of a tetrahydrofuran solution (20% by mass) of ethylamine was added dropwise over 1 hour, and after the addition, the mixture was further stirred at room temperature for 3 hours. After completion of the reaction, N-methylpyrrolidone, tetrahydrofuran and excess ethylamine were distilled off by heating under reduced pressure to obtain a colorless solid. This was purified by removing imidazole by column chromatography, and 1.58 g (yield 69%) of a colorless solid hydrophilic polymer having a unit structure represented by formula (3) was obtained. This hydrophilic polymer was soluble in water. The hydrophilic polymer had a weight average molecular weight in terms of polystyrene of about 3,600,000.

[In the formula, one of R represents a hydrogen atom and the other represents a methoxy group (—OCH ₃ ). Me represents a methyl group. ]

[In the formula, one of R represents a hydrogen atom and the other represents a methoxy group (—OCH ₃ ). ]

Example 3 [Synthesis of hydrophilic polymer having unit structure represented by formula (5)]
950 mL of distilled water is added to 50 g of an acrylic acid-maleic acid copolymer salt solution (“AQUALIC TL” manufactured by Nippon Shokubai Co., Ltd.), treated with a cation exchange resin (strongly acidic type), and the carboxylate in the copolymer Was converted to the free acid form, and then the water was distilled off under reduced pressure to obtain a colorless powder. 1.5 g of this was dissolved by adding 100 mL of distilled and dried tetrahydrofuran, and 7 g of a tetrahydrofuran solution (20% by mass) of ethylamine and 6 g of dicyclohexylcarbodiimide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at room temperature for 10 hours. After completion of the reaction, tetrahydrofuran and excess ethylamine were removed by heating under reduced pressure and purified by column chromatography to obtain 1.75 g of a colorless solid hydrophilic polymer having a unit structure represented by the formula (5) (yield). 76%). This hydrophilic polymer was soluble in water.

[In the formula, one of R represents a hydrogen atom and the other represents an N monoethyl-substituted amide group (—CONHCH ₂ CH). Me represents a methyl group. ]

Example 4 [Evaluation of Film Formability and Moisturizing Property]
The compound having the unit structure represented by the formula (4) obtained in the production process of Example 2 (sample 1) and the carboxy group of the compound having the unit structure represented by the formula (4) are triethanolamine. Using the neutralized salt (Sample 2) and the compound of Example 2 (Sample 3), the film-forming property and the moisturizing property were compared.
(Method for evaluating film formability)
A 2% by mass aqueous solution of each of Samples 1 to 3 was prepared, and 20 mL thereof was put into a glass petri dish having a diameter of 10 cm, covered with a nonwoven fabric, then air-dried, and the state after air-drying was evaluated. In the evaluation, “surface is whitened and no film is formed” (×), “partial whitening is observed” (Δ), and “uniform film without whitening” is (◯). The results are shown in Table 2.
(Moisturizing evaluation method)
Samples 1 to 3 were used to prepare lotions having the prescriptions shown in Table 1 (samples 4 to 6 respectively), and each of the lotions was subjected to a “moisturizing” sensory function by 20 cosmetic specialists inside the forearm. Evaluation was performed. In the sensory evaluation, 3 hours after using the skin lotion, “not feeling moisturizing” (×), “feeling slightly moisturizing” (Δ), and “feeling high moisturizing” (◯). The results are shown in Table 2. In addition, the skin moisture content before use of the skin lotion and the skin moisture content after 3 hours of use of the skin lotion were measured using a skin surface angle layer moisture content measuring device (SKICON-200EX manufactured by IBI S Co., Ltd.). Measured value is ("Measured value of skin moisture after 3 hours of use of lotion"-"Measured value of skin moisture before use of lotion") / "Measured value of skin moisture before use of lotion" x 100 Processed. The results are shown in Table 2.

[Lotion preparation method]
A. Components 1 to 9 are mixed and dissolved.
B. Components 10-12 are mixed and dissolved.
C. After adding A to B and dissolving, it was filled in a container to make a lotion.

  As is clear from the results in Table 2, the hydrophilic polymer of the present invention has high film-forming properties and excellent moisturizing effect.

Example 5 [Cosmetic (Lotion)]
[Prescription]
Ingredient Ingredient name (Unit: mass%)
1. Ethanol 10.0
2. Polyoxyethylene (60 mol) hydrogenated castor oil 0.1
3. Perfume appropriate amount 4. Compound of Example 3 0.5
5). 1,3-butylene glycol 15.0
6). Preservative 0.1
7). Purified water balance

[Production method]
A. Components 1 to 6 were mixed and dissolved.
B. A was added to Component 7, mixed and dissolved, and then filled into a container to prepare a cosmetic (lotion).
[Evaluation]
The cosmetic (skin lotion) of Example 5 had a fresh feeling of use without stickiness, was excellent in moisturizing feeling, and the effect was sustained.

Example 6 [Cosmetic (Moisturizing Essence)]
[Prescription]
Ingredient Ingredient name (Unit: 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). Compound of 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 0.02
13. Preservative 0.1
14 Perfume appropriate amount 15. Purified water balance

[Production method]
A. Components 1 to 6 were heated and mixed and dissolved to 80 ° C.
B. Ingredients 7 to 13 and 15 were mixed by heating and dissolved to 80 ° C.
C. B was added to A, emulsified by stirring, component 14 was added during cooling, and then the mixture was filled in a container to prepare a cosmetic (moisturizing serum).
[Evaluation]
The cosmetic of Example 6 (moisturizing serum) was excellent in moisturizing feeling and the effect was sustained.

Example 7 [Cosmetic (Emulsion)]
[Prescription]
Ingredient Ingredient name (Unit: mass%)
1. Squalane 5.0
2. Cetanol 1.0
3. Polyethylene (20 mol) sorbitan monooleate 2.0
4). Sorbitan sesquioleate 0.8
5). Glycerin 5.0
6). 1,3-butylene glycol 10.0
7). Compound of Example 1 1.0
8). Carboxyvinyl polymer 0.2
9. Potassium hydroxide 0.1
10. Preservative 0.1
11. Perfume appropriate amount 12. Purified water balance

[Production method]
A. Ingredients 1 to 4 were heated, mixed and dissolved to 80 ° C.
B. Ingredients 5 to 10 and 12 were heated and mixed and dissolved to 80 ° C.
C. B was added to A, emulsified by stirring, component 11 was added during cooling, and the mixture was filled in a container to prepare a cosmetic (emulsion).
[Evaluation]
The cosmetic (milky lotion) of Example 7 was excellent in moisturizing feeling and the effect was sustained.

Example 8 [Cosmetic (Cream Pack)]
[Prescription]
Ingredient Ingredient name (Unit: mass%)
1. Polyoxyethylene (20 mol) Polyoxypropylene (4 mol)
Cetyl ether 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). Compound of Example 1 2.0
8). Sodium hydroxide 0.4
9. Hydroxyethyl cellulose 0.3
10. Ascorbic acid 2-glucoside 2.0
11. Preservative 0.1
12 Purified water balance

[Production method]
A. Ingredients 1 to 4 were heated, mixed and dissolved to 80 ° C.
B. Ingredients 5 to 12 were heated and mixed and dissolved to 80 ° C.
C. B was added to A, emulsified by stirring, then cooled, and then filled into a container to prepare a cosmetic (cream pack).
[Evaluation]
The cosmetic material (cream pack) of Example 8 was excellent in the moisturizing feeling after use.

Example 9 [Cosmetic (white powder)]
[Prescription]
Ingredient Ingredient name (Unit: mass%)
1. Talc (* 1) surface-treated with the compound of Example 2 70.0
2. Water repellent mica titanium (* 2) 5.0
3. Magnesium stearate 2.0
4). Gunjo 0.2
5). Bengala 0.1
6). Methyl paraoxybenzoate 0.1
7). Fumed silicic acid anhydride (* 3) 5.0
8). Perfume appropriate amount 9. Silicone-treated sericite (* 4) Residual amount * 1: 5 parts by mass of the compound obtained in Example 2 was dissolved in 80 parts by mass of ethanol, and 95 parts by mass of talc (JA-24R: manufactured by Asada Flour Milling Co., Ltd.) was added thereto. In addition, after mixing uniformly, ethanol was distilled off by heating under reduced pressure and pulverized with a hammer mill to obtain surface-treated talc.
* 2: Mica titanium treated with 5% by mass perfluorooctyltriethoxysilane (manufactured by Daito Kasei Kogyo Co., Ltd.)
* 3: Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd.)
* 4: SA Sericite FSE (manufactured by Miyoshi Kasei)

[Production method]
A. Components 1 to 9 were mixed uniformly, pulverized with a hammer mill, and then filled into a container to prepare a cosmetic (white powder).
[Evaluation]
The cosmetic (white powder) of Example 9 was excellent in moisturizing feeling during and after use.

Example 10 [Cosmetic (powder foundation)]
[Prescription]
Ingredient Ingredient name
1. Titanium oxide 10.0
2. Zinc oxide 5.0
3. Mica surface-treated with the compound of Example 2 (* 5) 20.0
4). 4. Sericite surface-treated with the compound of Example 2 (* 6) Residual amount Talc treated with the compound of Example 2 (* 7) 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. Spherical nylon powder (* 8) 1.0
12 Spherical silicone powder (* 9) 1.0
13. Preservative 0.1
14 Glyceryl trioctanoate 1.0
15. Dimethylpolysiloxane (* 10) 1.0
16. 2-Ethylhexyl paramethoxycinnamate 3.0
* 5: 3 parts by mass of the compound obtained in Example 2 was dissolved in 80 parts by mass of ethanol, 97 parts by mass of mica (PDM-8W: manufactured by Topy Industries) was added and mixed uniformly, and then ethanol was added. The talc was subjected to distillation under reduced pressure and pulverized with a hammer mill to obtain a surface-treated talc.
* 6: 3 parts by mass of the compound obtained in Example 2 was dissolved in 80 parts by mass of ethanol, 97 parts by mass of sericite (FSE: manufactured by Sanshin Mining Co., Ltd.) was added and mixed uniformly, and then ethanol was heated. Distilled under reduced pressure and pulverized with a hammer mill to obtain surface-treated talc.
* 7: Dissolve 5 parts by mass of the compound obtained in Example 2 in 80 parts by mass of ethanol, add 95 parts by mass of talc (JA-46R: manufactured by Asada Flour Mills) and mix uniformly, and then add ethanol. The talc was subjected to distillation under reduced pressure and pulverized with a hammer mill to obtain a surface-treated talc.
* 8: Nylon 12 SP500 (Toray Industries, Inc.)
* 9: KSP-101 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 10: KF-96A-20cs (manufactured by Shin-Etsu Chemical Co., Ltd.)

[Production method]
A. Components 1 to 13 were mixed uniformly and then pulverized with a hammer mill.
B. A mixture of components 14 to 16 was added to A, mixed uniformly, pulverized with a hammer mill, and press-molded into a container to prepare a cosmetic (powder foundation).
[Evaluation]
The cosmetic (powder foundation) of Example 10 was excellent in moisturizing feeling during and after use.

Example 11 [Cosmetic (Liquid Foundation)]
[Prescription]
Ingredient Ingredient name
1. Squalane 10.0
2. Decamethylcyclopentasiloxane 20.0
3. Lauryl PEG-9
Polydimethylsiloxyethyl dimethicone (* 11) 2.5
4). Lauryl polyglyceryl-3
Polydimethylsiloxyethyl dimethicone (* 12) 2.5
5). Talc 5.0
6). Bengala 0.5
7). Yellow iron oxide 1.0
8). Black iron oxide 0.1
9. Titanium oxide 10.0
10. Propylene glycol 10.0
11. Compound of Example 1 1.0
12 Triethanolamine 0.15
13. Preservative 0.1
14 Perfume appropriate amount 15. Purified water residue * 11: KF-6038 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 12: KF-6105 (Shin-Etsu Chemical Co., Ltd.)

[Production method]
A. After mixing components 1 to 4 uniformly, components 5 to 9 are added and a bead mill treatment is performed.
B. Ingredients 10-13 and 15 are mixed and dissolved uniformly.
C. After emulsification by adding B to A with stirring, component 14 was added and filled in a container to prepare a cosmetic (liquid foundation).
[Evaluation]
The cosmetic (Liquid Foundation) of Example 11 was excellent in moisturizing feeling during and after use.

Example 12 [Cosmetic (Lipstick)]
[Prescription]
Ingredient Ingredient name (Unit: mass%)
1. Carnauba wax 10.0
2. Heavy liquid isoparaffin (* 13) 20.0
3. α-olefin oligomer (* 14) 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. Dibutylhydroxytoluene 0.01
11. Red No. 202 0.3
12 Yellow No. 4 aluminum rake 0.7
13. Compound of Example 2 0.5
14 Titanium oxide 0.5
15. Iron oxide coated mica titanium 3.0
* 13: Pearl Dream 18 (manufactured by NOF Corporation)
* 14: Nom Coat HP-30 (Nisshin Oilio Co., Ltd.)

[Production method]
A. Components 13 to 15 were added to 10 times (mass) of ethanol-purified water (4: 1 mixed solution) of component 13 and mixed uniformly, and then ethanol-purified water (4: 1 mixed solution). Was distilled off under reduced pressure, and surface-treated titanium oxide and iron oxide mica titanium were obtained.
B. Components 1 to 10 are heated and mixed and dissolved, components 11, 12, and A are added and kneaded with a three-roll mill.
C. After B was melted and filled in a mold, it was cooled to prepare a cosmetic (lipstick).
[Evaluation]
The cosmetic (lipstick) of Example 12 was excellent in moisturizing feeling during and after use.

Claims (2)

[In the formula (1), X represents —NHR ₁ or OM (except when both X are simultaneously OM; R ₁ is an alkyl group having 1 to 3 carbon atoms; M is a hydrogen atom or an alkali metal atom) Or an organic base group). One of R is a hydrogen atom, the other is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, an acetoxy group, a carboxy group, a salt-type carboxy group, an amide group, N mono 1 type chosen from an alkyl substituted amide group is shown. ] The hydrophilic polymer which has 1 type, or 2 or more types of unit structures represented by these. A cosmetic or external preparation for skin containing the hydrophilic polymer according to claim 1.