JP2001316427A - Copolymer and composition containing it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer which is useful as a treatment for the body surface, such as external preparations for skin, represented by cosmetics, is uniformly dissolved in an aqueous carrier and, when applied, forms a water- resistant coating film. SOLUTION: The polymer comprises a copolymer containing as the constituent monomers a monomer represented by general formula (I) (wherein R1 is H or a 1-4C alkyl; and R2 is a 1-20C alkyl having a fluorine atom) and a monomer represented by general formula (II) (wherein R3 is H or a 1-4C alkyl; R4 is alkyloxy, acyloxy, or a 2-4C alkyl which may have a hydroxyl group; R5 is H, a 1-8C aromatic or aliphatic hydrocarbon group, or acyl; and n is 1 to 40), wherein the content of the compound represented by formula (1) is 7-9.5 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolymer having plasticity and having improved solubility in water while being hydrophobic at the time of film formation, and a skin external preparation such as a cosmetic containing the copolymer.

[0002]

2. Description of the Related Art In processing various materials, surface treatment is an important factor for maintaining the material of each member. For this reason, various varnishes, paints, and the like have been developed as construction materials, and cosmetics that form a water-retaining film can be recognized as a kind of surface treatment agent from such a viewpoint. As materials usually used in such surface treatment, there are usually many polymers and many water-insoluble materials. This is because the coating is often intended to block off aqueous components. Therefore, in such a treatment, the polymer is usually used by dispersing it in an aqueous carrier or the like, or by dissolving it in an organic solvent or the like. However, in the case of dispersion in an aqueous carrier or the like, the usability of the composition may be significantly reduced due to agglomeration or the like, and the organic solvent system has a problem that the use of the organic solvent itself is restricted. In particular, in the field of cosmetics for the skin, hair, and nails, it was an essential condition to be able to apply using an aqueous carrier. That is, there has been a demand for a polymer which is uniformly dissolved in an aqueous carrier and forms a film having excellent water resistance after coating. Furthermore, conventional polymers require a plasticizer because of their hard film properties, but some of these plasticizers are suspected of acting as endocrine disruptors, such as phthalates. There was something.

On the other hand, the compound represented by the following general formula (I) and the compound represented by the following general formula (II) are already known in the literature, and are commercially available as monomers for producing polymers. By combining these, they have not been produced at all by dissolving in an aqueous carrier to form a polymer having excellent water resistance after application, not requiring a plasticizer or the like, and forming a plastic film. Further, no water-soluble plastic polymer containing the compound represented by the general formula (I) and the compound represented by the general formula (II) as constituent monomers has been known at all.

[0004]

DISCLOSURE OF THE INVENTION The present invention is useful as an agent for treating the surface of a living body such as an external preparation for skin represented by cosmetics. An object of the present invention is to provide a polymer that forms a water-resistant film.

[0005]

In view of such circumstances, the present inventors have uniformly dissolved in an aqueous carrier which is useful as a treatment agent for the surface of a living body such as an external preparation for skin represented by cosmetics. After coating, an excellent water-resistant film is formed. As a result of intensive research efforts for a polymer, one or two or more monomers selected from the monomers represented by the following general formula (I) are obtained. Is contained in a total amount of 7 to 9.5% by weight with respect to the total amount of the constituent monomers, and a copolymer containing the monomer represented by the general formula (II) as a constituent monomer is found to have such characteristics. The invention has been completed. That is,
The present invention relates to the following technology. (1) 1 selected from monomers represented by the general formula (I)
A copolymer containing, as constituent monomers, at least one kind or two or more kinds and at least one kind selected from the monomers represented by the general formula (II), containing the compound represented by the general formula (I); The amount is 7 with respect to all the constituent monomers.
9.5% by weight. (2) When the content of the monomer represented by the general formula (II) is
The copolymer according to (1), wherein the total amount is 30 to 90.5% by weight based on the total amount of the monomers. (3) The copolymer according to (1) or (2), wherein all the monomers represented by the general formula (I) are monomers represented by the general formula (III). (4) The monomers represented by the general formula (II) are all those represented by the general formula (IV),
(1) The copolymer according to any one of (1) to (3). (5) having water solubility and plasticity,
(1) The copolymer according to any one of (1) to (4). (6) An external preparation for skin, comprising the copolymer according to any one of (1) to (5). (7) The external preparation for skin according to (6), which is a cosmetic. Hereinafter, the present invention will be described in detail focusing on embodiments.

[0006]

Embedded image General formula (I) (wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 has 1 to 20 carbon atoms having a fluorine atom.
Represents an alkyl group. )

[0007]

Embedded image Formula (II) (wherein, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 may have an alkyloxy group, an acyloxy group, or a hydroxyl group, and has 2 to 4 carbon atoms. R5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and n represents 1 to 4
Represents a numerical value of 0. )

[0008]

Embedded image General formula (III) (wherein, R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, O represents a numerical value of 1 to 4, P represents a numerical value of 1 to 10, and R7 represents a fluorine atom. Or a hydrogen atom.)

[0009]

Embedded image General formula (IV) (wherein, R8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R9 represents an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom, Q represents a numerical value of 5 to 30.)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION (1) Compound represented by the general formula (I) used in the polymer of the present invention The copolymer of the present invention is a compound selected from monomers represented by the general formula (I) Or two or more kinds as constituent monomers, in a total amount of 7 to 9.5% by weight, more preferably 7.5 to 9.3% by weight, based on the total amount of the constituent monomers. This is because, due to the water resistance of the copolymer in this portion, if the portion due to the monomer of the general formula (I) is too small or if the hydrophobicity of this portion is too low, the polymer film as This is because the water resistance is reduced. or,
If the amount is too large, the solubility in water may be hindered. In the general formula (I), R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 represents an alkyl group having 1 to 20 carbon atoms having a fluorine atom. R1 is particularly preferably a hydrogen atom or a methyl group. This is the structure of acrylic acid or methacrylic acid, which is widely used in polymers and the like, because many things such as safety have already been confirmed, and many commercial products are easily available as raw materials. . R2 is particularly preferably a compound containing as a partial structure a methylene group having a structure substituted with a fluorine atom except for a bond to carbon. The number of carbon atoms is preferably from 5 to 10, more preferably from 6 to 10. This is because, in the polymer of the present invention, the partial structure of R2 realizes the water resistance of the coated film. As a particularly preferred form, the monomer which carries the hydrophobic portion in the polymer is selected from those having extremely high hydrophobicity, and the content of the monomer is suppressed to a small value, but the solution shows water solubility, and the film has plasticity. It is preferable because it exhibits functional properties such as hydrophobicity. Among these, it is preferable that the compound represented by the general formula (III) is contained as one kind or two or more kinds selected from the general formula (I). R of such general formula (I)
Specific examples of preferred alkyl groups having a fluorine atom represented by 2 include a 2,2,2-trifluoroethyl group, 2,2,3,3,4.4,5,5
-Octafluoropentyl group, 3.3, 4, 4, 5,
5,6,6,7,7,8,8,9,9,10,10,1
0-heptadecafluorodecanyl group, 2,2,2,
2 ′, 2 ′, 2′-hexafluoroisopropyl group,
Examples thereof include a 2,2,3,3-tetrafluoropropyl group. Particularly preferred among these are 2,2,3
3,4.4,5,5-octafluoropentyl group and 3.
3,4,4,5,5,6,6,7,7,8,8,9,
It is a 9,10,10,10-heptadecafluorodecanyl group. Of these, 3.3, 4, 4, 5, 5, 6,
The 6,7,7,8,8,9,9,10,10,10-heptadecafluorodecanyl group is particularly preferred. Like this,
The monomer represented by the general formula (I), which is a constituent monomer of the copolymer of the present invention, can be obtained in high yield by reacting acrylic acid or methacrylic acid acid chloride with the corresponding alkali metal alcoholate. Can be done. Further, it can also be obtained by treating the corresponding alcohol with thionyl chloride, phosphorus oxychloride or the like, converting it to chloride, and reacting it with sodium acrylate or sodium methacrylate. Since there are already many commercially available products of such compounds, such commercially available products can also be used.

(2) The monomer represented by the general formula (II) used in the polymer of the present invention: The polymer of the present invention contains a monomer represented by the general formula (II) as a constituent monomer. Features. Here, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 represents an alkyl group having 2 to 4 carbon atoms, which may have an alkyloxy group, an acyloxy group or a hydroxyl group, R5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and n represents 1 to 40.
Represents the numerical value of. R3 is particularly preferably a hydrogen atom or a methyl group. This is the structure of acrylic acid or methacrylic acid commonly used in polymers and the like,
This is because safety and the like have already been confirmed for many products, and many commercially available products are easily available as raw materials. (R4-O) n can be exemplified by a polyoxyethylene group, a polyoxypropylene group, a polyoxybutene group, a polyoxy (hydroxypropylene) group, a part or all of its acylated product, and an alkyl ether. As the acyl group, those having 1 to 20 carbon atoms such as an acetyl group, a benzoyl group, a stearoyl group and an oleoyl group can be preferably exemplified.
Preferred examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms. Among these, a polyoxyethylene group is preferable. This terminal hydroxyl group may be left free, or it may be blocked with an acyl group or an alkyl group. As such an acyl group, an acetyl group,
A benzoyl group, an acryloyl group, a methacryloyl group and the like can be preferably exemplified, and an alkyl group having 1 to 4 carbon atoms can be preferably exemplified. Preferred (R4-O) n groups are methylpolyoxyethylene (9), methylpolyoxyethylene (23), methoxyethyl,
-Methoxybutyl group, ethyl polyoxyethylene (2)
Group, phenoxytyl group, phenyl polyoxyethylene (2) group, methyl polyoxyethylene (3) group, acrylic polyoxyethylene (4) group, acrylic polyoxypropylene (3) group, acrylic polyoxypropylene (7) group And the like can be preferably exemplified. Such a general formula (I
As the monomer represented by I), those represented by the general formula (IV) are particularly preferred. The proportion of the monomer represented by the general formula (II) as a constituent monomer in the polymer of the present invention is 30 to 90.0.5% by weight, as an average weight percentage of the total amount in one molecule, More preferably 40 to
90.1% by weight. This is because the solubility of the copolymer of the present invention in water depends on the constituent part represented by the general formula (II). If the amount is too small, the solubility of the polymer in water may be impaired. If it is too much, the water resistance of the formed film may be impaired.

(3) Copolymer of the Present Invention The copolymer of the present invention comprises one or two or more monomers selected from the monomers represented by the above general formula (I) and the general formula (II)
Or one or more selected from monomers represented by the formula (1) as constituent monomers. That is, it is characterized by having the following partial structural formula 1 and partial structural formula 2 in one molecule. In the copolymer of the present invention, in addition to these essential constituent monomers, monomers commonly used in copolymers can be contained as constituent monomers as long as the effects of the present invention are not impaired. Such optional monomers include, for example, acrylic acid, methacrylic acid, their alkyl esters, vinyl acetate, vinyl alcohol, alkyl ethers of vinyl alcohol, styrene, α-alkylstyrene, butadiene, isoprene, propene, vinyl chloride, acrylonitrile Etc. can be exemplified. The polymer of the present invention can be produced by treating these monomers according to a conventional method.
That is, the monomers may be dissolved in a solvent or the like, a polymerization initiator or the like may be added, and heating may be performed. As the polymerization initiator,
It can be used without any particular limitation as long as it is commonly used, for example, peroxides such as benzoyl peroxide, azo compounds such as azobisisobutyronitrile, The polymerization may be started using a persulfate, a persulfate and a sulfite (redox initiator), or the like. Since the polymer of the present invention has water solubility, if the solvent is miscible with water, it can be concentrated as it is, or if the solvent is immiscible with water, after the reaction, water can be added to flush. The copolymer migrates towards the water. Thereafter, the aqueous phase is removed and concentrated to obtain the copolymer of the present invention. Here, the term "water-soluble" as used in the present invention refers to a state of solubility in water.
When a uniform system is created by adding 99 parts by weight of water to parts by weight,
It means that the transmittance of the liquid to visible light is 90% or more. The copolymer of the present invention may be a random type copolymer, a graft type copolymer, a block type or a combination thereof. The polymer thus obtained is not only water-soluble, but also has the property of forming a flexible film without a plasticizer when a film is formed. It is not necessary to use an acid ester or the like as a plasticizer. Further, since it has water solubility as described above, water can be used as a solvent in formulating, and a composition without an organic solvent can be prepared. Therefore, it can be used in cosmetics such as hair cosmetics, skin cosmetics, nail cosmetics, and the like, and can also be used as a surface treatment agent for aqueous paints, metals, glass, fibers, and the like. At present, there is no known substance capable of forming a hydrophobic and plastic film after drying and forming a film.

[0013]

Embedded image Partial structural formula 1 (wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 has 1 to 20 carbon atoms having a fluorine atom.
Represents an alkyl group. )

[0014]

Embedded image Partial structural formula 2 (wherein, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 is an alkyl having 2 to 4 carbon atoms which may have an alkyloxy group, an acyloxy group or a hydroxyl group. R5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and n represents 1 to 4
Represents a numerical value of 0. )

(4) External preparation for skin of the present invention The copolymer of the present invention is particularly preferably applied to the field of external preparation for skin. This is because the characteristic of the copolymer of the present invention is to form a film having plasticity even without a plasticizer, and the property that the film has hydrophobicity is particularly required for cosmetics and the like in which endocrine disrupting substances must be avoided. This is because it is suitable for a skin external preparation. In view of this, it is particularly preferable to apply a skin external preparation to cosmetics having a long use period. In the external preparation for skin of the present invention, the above-mentioned copolymer is a make-up applied on the skin by a physical force such as sebum or wind, or as a protective film such as a skin to prevent moisture from escaping from the skin or the like. It has a function as a fixing medium for a coloring material or the like in makeup cosmetics or the like, which prevents collapse. As an example specifically applied, for example, in cosmetics, cream, milky lotion, lotion,
Basic cosmetics such as packs, make-up cosmetics such as nail color, lip color, mascara, eyeliner, foundation and under-makeup, and cosmetics for hair such as hair liquid, set lotion, hair color, and hair mascara. Preferred examples of the external medicine for skin include lotion-type or nail-lacquer-type antifungal agents and liquid plaster for wounds. In the skin external preparation of the present invention, the above copolymer may contain only one kind, or may contain two or more kinds in combination. The preferred content of the copolymer in the skin external preparation of the present invention is 0.01 to
30% by weight, more preferably 0.1 to 10% by weight
It is.

The external preparation for skin of the present invention may contain optional components usually used in external preparations for skin, in addition to the above-mentioned copolymer which is an essential component. Such optional components include, for example, hydrocarbons such as squalane, petrolatum, microcrystalline wax, jojoba oil, carnauba wax, esters such as octyldodecyl oleate, triglycerides such as olive oil, tallow, coconut oil, and stearin. Acid, oleic acid, fatty acids such as ritinoleic acid, oleyl alcohol, stearyl alcohol,
Higher alcohols such as octyldodecanol; anionic surfactants such as sulfosuccinates and sodium polyoxyethylene alkyl sulfate; amphoteric surfactants such as alkyl betaine salts; cationic surfactants such as dialkylammonium salts; sorbitan fatty acids Nonionic surfactants such as esters, fatty acid monoglycerides, their polyoxyethylene adducts, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, and polyhydric alcohols such as polyethylene glycol, glycerin, and 1,3-butanediol , A thickening / gelling agent, an antioxidant, an ultraviolet absorber, a coloring material, a preservative, a powder, and the like. The external preparation for skin of the present invention is produced by treating these optional components and essential components according to a conventional method.

[0017]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to only these Examples.

Example 1 Production Example 26.6 g of methyl polyoxyethylene (9) methacrylate, 11.4 g of methacrylic acid, 10, 10, 10, 9, 9, 8 in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube. ,
A mixed solvent of 8,7,7,6,6,5,5,4,4,3,3-heptadecafluorodecanyl acrylate, 100 ml of isopropyl alcohol and 100 ml of water was taken and mixed with stirring. After a solution of 0.1 g of ammonium persulfate dissolved in 10 ml of water was added thereto, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. 80
The polymerization was performed by heating to 12 ° C. for 12 hours. After adding and mixing an aqueous solution in which 5.2 g of sodium hydroxide was dissolved, isopropyl alcohol was removed to obtain an aqueous solution of a desired copolymer. This was freeze-dried to obtain Copolymer 1 of the present invention.

[0019]

Embedded image Methyl polyoxyethylene (9) methacrylate

[0020]

Embedded image 10, 10, 10, 9, 9, 8, 8, 7, 7, 6, 6, 6,
5,5,4,4,3,3-heptadecafluorodecanyl acrylate

Example 2 Preparation Example 10 g of 2-hydroxy-3-phenoxypropyl acrylate and 50 g of methyl polyoxyethylene (23) methacrylate were placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube.
A mixed solvent of 0 g, 4 g of styrene, 35.0 g of 2,2,2-trifluoroethyl methacrylate, 100 ml of isopropyl alcohol and 100 ml of ethyl acetate was taken and mixed with stirring. After adding a solution of 0.1 g of benzoyl peroxide dissolved in 10 ml of isopropyl alcohol, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Polymerization was carried out at the boiling point of the solvent for 10 hours. The mixed solvent was flushed with water to obtain an aqueous solution of the copolymer. This was freeze-dried to obtain Copolymer 2 of the present invention.

[0022]

Embedded image 2-hydroxy-3-phenoxypropyl acrylate

[0023]

Embedded image Methyl polyoxyethylene (23) methacrylate

[0024]

Embedded image 2,2,2-trifluoroethyl methacrylate

Example 3 Production Example In a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube, 24.3 g of methyl polyoxyethylene (23) methacrylate, 12.0 g of hydroxyethyl methacrylate, 18.0 g of methyl methacrylate, 10, 10, 10, 9, 9,
A mixed solvent of 8.7 g of 8,8,7,7,6,6,5,5,4,4,3,3-heptadecafluorodecanyl acrylate, 180 ml of isopropyl alcohol and 120 ml of water was taken and mixed with stirring. A solution of 0.7 g of ammonium persulfate dissolved in 10 ml of water was added thereto, and the mixture was sufficiently replaced with a nitrogen stream while stirring. 80 ℃
And polymerized for 12 hours. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain Copolymer 3 of the present invention.

Example 4 Production Example A flask equipped with a cooler, a stirrer, and a nitrogen inlet tube was charged with 20.0 g of methyl polyoxyethylene (9) methacrylate,
Hydroxy-3-phenoxypropyl acrylate 1
2.8 g, n-butyl acrylate 4.0 g, 5, 5,
3.4 g of 4,4,3,3,2,2-octafluoropentyl methacrylate and isopropyl alcohol 10
A mixed solvent of 0 ml and 100 ml of ethyl acetate was taken and mixed with stirring. A solution of 0.2 g of benzoyl peroxide dissolved in 10 ml of isopropyl alcohol was added thereto, and the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Polymerization was carried out at the boiling point of the solvent for 10 hours. Flushing from the mixed solvent to water was performed to obtain an aqueous solution of the desired copolymer.
This was freeze-dried to obtain Polymer 4 of the present invention.

[0027]

Embedded image 5,5,4,4,3,3,2,2-octafluoropentyl methacrylate

Example 5 Production Example In a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube, 24.0 g of methyl polyoxyethylene (23) methacrylate, 12.1 g of methyl methacrylate, 2,2,3,3-tetrafluoro A mixed solvent of 3.9 g of propyl acrylate, 150 ml of isopropyl alcohol and 50 ml of water was taken and mixed with stirring. Add 0.3% ammonium persulfate
g was dissolved in 10 ml of water, and the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Heat to 80 ° C and 8
Polymerization was carried out for hours. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain Polymer 5 of the present invention.

[0029]

Embedded image 2,2,3,3-tetrafluoropropyl acrylate

Example 6 Production Example In a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube, 16.0 g of methyl polyoxyethylene (9) methacrylate, 12.0 g of methacrylic acid, 8.4 g of methyl methacrylate,
3.6 g of 2,2,2,2 ', 2', 2'-hexafluoroisopropyl acrylate and a mixed solvent of 100 ml of isopropyl alcohol and 100 ml of ethyl acetate were taken and mixed with stirring. Then, 0.2 g of 2,2-azobis (isobutyronitrile) was added to 10 m of isopropyl alcohol.
After the solution dissolved in 1 was added, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Polymerization was carried out at the boiling point of the solvent for 6 hours. Flushing from the mixed solvent to water was performed to obtain an aqueous solution of the desired copolymer. This is freeze-dried,
Polymer 6 of the present invention was obtained.

[0031]

Embedded image 2,2,2,2 ', 2', 2'-hexafluoroisopropyl acrylate

Example 7 Physical Properties of Polymer of the Present Invention (Water- and Oil-Repellency) A 5% aqueous solution of Polymers 1 to 6 was dropped on filter paper, dried, and a polymer film was cast on the filter paper. Water and oil (olive oil) were dropped on the polymer film cast on the filter paper, and the contact angle was measured. The measured values of polymers 1 to 6 did not change at all from 60 to 70 degrees for water and oil for 48 hours. As for the solution state, Polymers 2 to 6 were particularly excellent in water solubility.

<Example 8> Physical properties of the polymer of the present invention For polymers 1 to 6, cast films were prepared in the same manner as in Example 7, and this was lightly swirled twice and tested in the same manner. Met. From this, the polymer coating of the present invention,
It is evident that it is sufficiently plastic even without a plasticizer.

<Example 9> Coating of polymer of the present invention The same test as in Example 8 was carried out, except that the filter paper was changed to cloth (Tetron (registered trademark)), and similar results were obtained.

<Examples 10 and 11> According to the following formulation, an oil-in-water cream (cosmetic) of the composition of the present invention was used.
It was created. That is, the components (a) and (b) were each heated to 80 ° C., (b) was gradually added to (a), emulsified, and the particles were homogenized with a homogenizer, followed by stirring and cooling to obtain a cream. A comparative example 1 was prepared by replacing the polymer with sodium hyaluronate, which is known to have high water retention, and a group of 10 people suffering from rough skin, using a total of 30 panelists, for 3 weeks The evaluation of the improvement of the rough skin in the continuous use of was evaluated. Table 1 shows the results as the number of appearance cases. From this, it can be seen that the cosmetic of the present invention is excellent in the effect of supplementing the damaged stratum corneum function and improving the rough skin due to the excellent coating. Here, the evaluation criteria for the skin roughness improving effect were ++: markedly improved, +: clearly improved, ±: slightly improved,-: not improved. In addition, when an acrylic polymer component is contained in a cosmetic or the like, and a plasticizer is not contained, a tactile feeling is often exhibited due to the film properties thereof. There was no such feeling of tension. This is because the polymer compound, which is an essential component of the cosmetic of the present invention, has excellent plasticity. A Sucrose fatty acid ester 0.5 parts by weight Vaseline 1 part by weight Lanolin 3 parts by weight Liquid paraffin 8 parts by weight Low viscosity silicone 10 parts by weight Stearyl alcohol 0.5 parts by weight Stearic acid 0.55 parts by weight Undecylenic acid monoglyceride 2 parts by weight Polyoxy Ethylene (20) behenyl ether 2 parts by weight b 1,3-butanediol 5 parts by weight glycerin 5 parts by weight Copolymer * 1 part by weight Potassium hydroxide 0.05 parts by weight Water 61.4 parts by weight * Details are shown in Table 1.

[0036]

[Table 1]

<Example 12> (Production of copolymer of Comparative Example 2) 24.3 g of methyl polyoxyethylene (23) methacrylate, 12.0 g of hydroxyethyl methacrylate, 17.2 g of methyl methacrylate were placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube. 7g, 10, 10, 10, 9, 9,
A mixed solvent of 8,8,7,7,6,6,5,5,4,4,3,3-heptadecafluorodecanyl acrylate, 180 ml of isopropyl alcohol and 120 ml of water was taken and mixed with stirring. A solution of 0.7 g of ammonium persulfate dissolved in 10 ml of water was added thereto, and the mixture was sufficiently replaced with a nitrogen stream while stirring. The mixture was heated to 80 ° C. and polymerized for 12 hours. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain a copolymer of Comparative Example 2. (Production of the copolymer of Comparative Example 2) Methyl polyoxyethylene (23) was placed in a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube.
24.3 g of methacrylate, 12.0 g of hydroxyethyl methacrylate, 19.7 g of methyl methacrylate,
10, 10, 10, 9, 9, 8, 8, 7, 7, 6, 6, 6,
4,5,4,4,3,3-heptadecafluorodecanyl acrylate 4 g and isopropyl alcohol 180
A mixed solvent of 120 ml of water and 120 ml of water was taken and mixed with stirring. A solution of 0.7 g of ammonium persulfate dissolved in 10 ml of water was added thereto, and the mixture was sufficiently replaced with a nitrogen stream while stirring. The mixture was heated to 80 ° C. and polymerized for 12 hours. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain a copolymer of Comparative Example 3. Using the copolymers of Comparative Examples 2 and 3 and the copolymer 3 of Example 3 of the present invention,
Created nail color. That is, according to the following formulation, the ingredients were stirred, mixed well, and then rolled to obtain a nail color. This was stored at 40 ° C. for 2 months to confirm the stability. Furthermore, after being applied to a plastic plate and immersed in water for 24 hours, a rubbing test with a 3H pencil was performed. Table 2 shows the results. These results show that the copolymer of the present invention preferably contains the monomer represented by the general formula (I) as a constituent monomer in an amount of 7 to 9.5% by weight. (Formulation) Copolymer ** 20 parts by weight Water 75 parts by weight Pigment 5 parts by weight ** Details are shown in Table 2.

[0038]

[Table 2]

[0039]

Industrial Applicability According to the present invention, it is uniformly dissolved in an aqueous carrier and is excellent in water resistance after application, which is useful as a treatment agent for the surface of a living body such as an external preparation for skin represented by cosmetics. The present invention can provide a polymer that forms a film having a certain thickness.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C076 AA17 BB31 EE10 EE12 EE48 4C083 AB032 AC012 AC022 AC072 AC122 AC182 AC242 AC422 AD091 AD152 AD222 CC01 CC05 DD33 EE12 4J027 AC02 AC03 AC04 BA07 BA08 CD07 4J100 AL08P AL08QBA08 BA03 BA08 CA04 DA36 DA38

Claims (7)

[Claims] 1. A monomer comprising at least one kind selected from the monomers represented by the general formula (I) and at least one kind selected from the monomers represented by the general formula (II) Wherein the content of the compound represented by the general formula (I) is 7 to 9.5% by weight based on all the constituent monomers. Embedded image General formula (I) (wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 has 1 to 20 carbon atoms having a fluorine atom.
Represents an alkyl group. ) Formula (II) (wherein, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 may have an alkyloxy group, an acyloxy group, or a hydroxyl group, and has 2 to 4 carbon atoms. R5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and n represents 1 to 4
Represents a numerical value of 0. ) 2. The content of the monomer represented by the general formula (II) is from 30 to 90.5 with respect to the total amount of the monomer.
2. The copolymer according to claim 1, which is in weight%. 3. The copolymer according to claim 1, wherein all the monomers represented by the general formula (I) are monomers represented by the general formula (III). Embedded image General formula (III) (wherein, R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, O represents a numerical value of 1 to 4, P represents a numerical value of 1 to 10, and R7 represents a fluorine atom. Or a hydrogen atom.) 4. A monomer represented by the general formula (II):
The copolymer according to any one of claims 1 to 3, wherein the copolymer is all represented by the general formula (IV). Embedded image General formula (IV) (wherein, R8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R9 represents an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom, Q represents a numerical value of 5 to 30.) 5. The copolymer according to claim 1, which has water solubility and plasticity. 6. An external preparation for skin, comprising the copolymer according to any one of claims 1 to 5. 7. The external preparation for skin according to claim 6, which is a cosmetic.