JP2000226419A - Copolymer for surface modification - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a copolymer which is uniformly soluble in an aqueous carrier to form a solution which, when applied, can form a coating film having excellent water resistance by copolymerizing two specified monomers with each other. SOLUTION: A monomer (7-9.5 wt.%) of formula I is copolymerized with 30-90.5 wt.% monomer of formula II and, optionally, a monomer of formula III to obtain a polymer having plasticity. In the formulae, R1 is H or a 1-4C alkyl; R2 is a 1-20C alkyl optionally having a fluorine atom; R3 is H or a 1-4C alkyl; R4 is an alkyloxy, an acyloxy, or a 2-4C alkyl optionally containing hydroxy, R5 is H, an aromatic or aliphatic 1-8C hydrocarbon group, or an acyl; (n) is 1-40; R6 is H or a 1-4C alkyl; (o) and (p) are each 1-10; and R7 is F or H. When this polymer is in the form of a uniform system prepared by adding 1 pt.wt. polymer to 99 pts.wt. water, the solution has a transmittance of at least 90% to visible light.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer having plasticity, which is suitable for surface treatment and the like and has improved solubility in water while being hydrophobic at the time of film formation.

[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 forms a coating having excellent water resistance after application, which is uniformly dissolved in an aqueous carrier and is useful as a cosmetic, a paint or a fiber treatment agent. It is an object to provide a polymer.

[0005]

In view of such circumstances, the present inventors have found that the present inventors have found that water-soluble carriers, which are useful as cosmetics, paints and fiber treatment agents, are uniformly dissolved and have excellent water resistance after application. As a result of intensive research efforts for a polymer that forms a film having good properties and plasticity, one or two or more monomers selected from the monomers represented by the general formula (I), preferably the general formula (II)
A polymer containing, as constituent monomers, a compound represented by I) and one or more kinds selected from monomers represented by general formula (II), preferably a compound represented by general formula (IV) Have such characteristics, and have completed the invention. Hereinafter, the present invention will be described in detail focusing on embodiments.

[0006]

Embedded image Formula (I) (wherein R1 is a hydrogen atom or a carbon atom
And R2 represents an alkyl group having 1 to 20 carbon atoms which may have a fluorine atom. )

[0007]

Embedded image Formula (II) (wherein, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R4 represents an alkyloxy group,
Having 2 carbon atoms which may have an acyloxy group or a hydroxyl group;
Represents an alkyl group of 4 to 4, R5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group or an acyl group having 1 to 8 carbon atoms, and n represents a numerical value of 1 to 40. )

[0008]

Embedded image Formula (III) (wherein, R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, O and P each independently represent 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) The compound represented by the general formula (I) used in the polymer of the present invention The polymer of the present invention is a compound selected from the compounds represented by the general formula (I) One or more species are contained as constituent monomers. 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 which may have 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. . Also, as R2,
It preferably contains a fluorine atom, and particularly preferably contains, 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 means that in the polymer of the present invention,
This is because the partial structure of R2 realizes the water resistance of the coated film. When no fluorine atom is contained,
Instead, it is necessary to realize water resistance, and it is necessary that the alkyl group has a long-chain, branched or cyclic structure. The term “long chain” as used herein means one having 13 or more carbon atoms, more preferably 15 or more carbon atoms, and still more preferably 16 or more carbon atoms. 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). Specific examples of preferred alkyl groups represented by R2 in the general formula (I) include a 2,2,2-trifluoroethyl group, 2,2,2
3,3,4.4,5,5-octafluoropentyl group,
3.3,4,4,5,5,6,6,7,7,8,8,
9,9,10,10,10-heptadecafluorodecanyl group, 2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl group, 2,2,3,3-tetrafluoropropyl group, Examples include an isopalmityl group, an isostearyl group, and a 3-cyclohexylpentyl group. Of these, particularly preferred are 2,2,3,3,4.4,5,5-
Octafluoropentyl group and 3.3,4,4,5,5
6,6,7,7,8,8,9,9,10,10,10-
It is a heptadecafluorodecanyl group. Of these,
3.3,4,4,5,5,6,6,7,7,8,8,
The 9,9,10,10,10-heptadecafluorodecanyl group is particularly preferred. Such a compound represented by the general formula (I), which is a constituent monomer of the polymer of the present invention, is obtained by reacting an acid chloride of acrylic acid or methacrylic acid with a corresponding alkali metal alcoholate. It can be obtained in yield. 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. In the polymer of the present invention, the content of the compound represented by the general formula (I) as a constituent monomer is 5 to 9.9% by weight in total, and more preferably 7 to 9% by weight.
Preferably, 9.5% by weight is contained in one molecule. In this case, 3.3, 4, 4, 5, 5, 6, 6, 7, 7, 8,
It is preferable to contain an acrylic acid derivative having an 8,9,9,10,10,10-heptadecafluorodecanyl group as a constituent monomer represented by the general formula (I). This is due to the water resistance of the polymer in this part,
A portion derived from the compound of the general formula (I) is too small,
This is because if the hydrophobicity of this portion is too low, the water resistance of the polymer film decreases. If the amount is too large, the solubility in water may be impaired.

(2) Compound represented by the general formula (II) used in the polymer of the present invention The polymer of the present invention contains a compound 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 is a hydrogen atom, aromatic or aliphatic carbon number 1
Represents a hydrocarbon group or an acyl group of 8 to 8, and n represents a numerical value of 1 to 40. R3 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, etc., and safety and many others have already been confirmed.
This is because many commercial products are easily available as raw materials. R
4 is a polyoxyethylene group, a polyoxypropylene group,
Examples thereof include a polyoxybutene group, a polyoxy (hydroxypropylene) group, a part or all of an acylated product thereof, and an alkyl ether. The acyl group preferably has 1 to 20 carbon atoms such as an acetyl group, a benzoyl group, a stearoyl group and an oleoyl group, and the alkyl group preferably has 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. Preferred examples of such an acyl group include an acetyl group, a benzoyl group, an acryloyl group and a methacryloyl group, and preferred examples of the alkyl group include those having 1 to 4 carbon atoms. Preferred R4 groups are methylpolyoxyethylene (9) group and methylpolyoxyethylene (2
3) group, methoxyethyl group, 3-methoxybutyl group, ethylpolyoxyethylene (2) group, phenoxytyl group,
Preferable examples include a phenyl polyoxyethylene (2) group, a methyl polyoxyethylene (3) group, an acryl polyoxyethylene (4) group, an acryl polyoxypropylene (3) group, and an acryl polyoxypropylene (7) group. As the compound represented by the general formula (II), a compound represented by the general formula (IV) is particularly preferable.
In the polymer of the present invention, a monomer represented by the general formula (II):
Is 30 to 90.0.5% by weight, more preferably 40 to 90.1% by weight, as an average weight percentage of the total amount in one molecule. This is because the solubility of the polymer of the present invention in water is determined by the general formula (I)
If the amount is too small, the solubility of the polymer in water may be impaired. If the amount is too large, the water resistance of the formed film may be impaired.

(3) Polymer of the Present Invention The polymer of the present invention comprises one or more compounds selected from the compounds represented by the general formula (I) and a compound represented by the general formula (II) It is characterized in that one or more selected ones are contained as constituent monomers. That is, it is characterized by having the following partial structural formula 1 and partial structural formula 2 in one molecule. The polymer of the present invention may contain, in addition to these essential constituent monomers, monomers commonly used in copolymers as constituent monomers as long as the effects of the present invention are not impaired. Examples of such optional constituent monomers include acrylic acid, methacrylic acid, vinyl acetate, vinyl alcohol, alkyl ethers of vinyl alcohol, styrene, α-alkylstyrene, butadiene, isoprene, propene, vinyl chloride, acrylonitrile, and the like. 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. The polymerization initiator can be used without any particular limitation as long as it is generally used.For example, peroxides such as benzoyl peroxide, azobisisobutyronitrile, etc. The polymerization may be started using a suitable azo compound, a persulfate, a persulfate and a sulfite (redox-based 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 macromolecules migrate toward the water. Thereafter, the aqueous phase is taken and concentrated to obtain the polymer of the present invention. Here, the water-soluble referred to in the present invention is:
It refers to the solubility in water. Specifically, when 99 parts by weight of water is added to 1 part by weight of a polymer to form a uniform system, the transmittance of the liquid to visible light is 90% or more. . The polymer 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. Also, because it has water solubility as described above,
In formulating, water can be used as a solvent,
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 represents an alkyl group having 1 to 20 carbon atoms which may have a fluorine atom.)

[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. )

[0015]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but it goes without saying that the present invention is not limited to such examples.

Example 1 Production Example 26.6 g of methyl polyoxyethylene (9) methacrylate, 11.4 g of methacrylic acid, 10, 10, 10, 9, 9, and 8 were placed 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 Polymer 1 of the present invention.

[0017]

Embedded image Methyl polyoxyethylene (9) methacrylate

[0018]

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

Example 2 Production Example 19.6 g of methyl polyoxyethylene (23) methacrylate, 8.4 g of hydroxyethyl methacrylate, 2, 2, 3, and 3 were placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube.
12.0 g of 3-tetrafluoropropyl acrylate,
A mixed solvent of 120 ml of isopropyl alcohol and 80 ml of water was taken and mixed with stirring. After sufficient replacement with a nitrogen stream while continuing to stir, the mixture was heated to 60 ° C., a solution of 0.1 g of ammonium persulfate and 0.1 g of sodium sulfite dissolved in 10 ml of water was added, and heating was continued for 6 hours to carry out polymerization. . PH 7.0 with aqueous sodium hydroxide solution
Then, the isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain Polymer 2 of the present invention.

[0020]

Embedded image Methyl polyoxyethylene (23) methacrylate

[0021]

Embedded image Hydroxyethyl methacrylate

[0022]

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

Example 3 Production Example 60.0 g of methyl polyoxyethylene (23) methacrylate was placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube.
2,2,2-trifluoroethyl methacrylate
0 g and a mixed solvent of 100 ml of isopropyl alcohol and 100 ml of ethyl acetate were 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. 1 at the boiling point of the solvent
The polymerization was carried out for 0 hour. The mixed solvent was flushed with water to obtain an aqueous solution of the copolymer. This was freeze-dried to obtain Polymer 3 of the present invention.

[0024]

Embedded image 2,2,2-trifluoroethyl methacrylate

Example 4 Production Example 21.0 g of methyl polyoxyethylene (9) methacrylate was placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube.
8.0 g of 2,2-trifluoroethyl methacrylate,
10, 10, 10, 9, 9, 8, 8, 7, 7, 6, 6, 6,
2.0 g of 5,5,4,4,3,3-heptadecafluorodecanyl acrylate, 9.0 g of hydroxyethyl methacrylate, and 120 ml of isopropyl alcohol,
A mixed solvent of 80 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. The polymerization was carried out by heating to 80 ° C. 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 a copolymer. This was freeze-dried to obtain Polymer 4 of the present invention.

Example 5 Production Example In a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube, 10 g of 2-hydroxy-3-phenoxypropyl acrylate, methyl polyoxyethylene (23) methacrylate 50.
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 Polymer 5 of the present invention.

[0027]

Embedded image 2-hydroxy-3-phenoxypropyl acrylate

Example 6 Production Example In a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube, 5 g of polyoxypropylene (2) acrylate, 5 g of vinyl alcohol, 50.0 g of methyl polyoxyethylene (23) methacrylate, α-methylstyrene 4g, 2,2,2-
35.0 g of trifluoroethyl methacrylate, 100 ml of isopropyl alcohol, 100 m of ethyl acetate
1 mixed solvent 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. Flushing the water from the mixed solvent,
An aqueous solution of the copolymer was obtained. This was freeze-dried to obtain polymer 6 of the present invention.

[0029]

Embedded image Polyoxypropylene (2) acrylate

Example 7 Production Example 19.6 g of methyl polyoxyethylene (23) methacrylate, 8.4 g of hydroxyethyl methacrylate, 12.0 g of stearyl acrylate, and 12.0 g of isopropyl alcohol were placed in a flask equipped with a cooler, a stirrer, and a nitrogen inlet tube. 12
A mixed solvent of 0 ml and 80 ml of water was taken and mixed with stirring. After performing sufficient replacement with a nitrogen stream while stirring, 60
Then, a solution of 0.1 g of ammonium persulfate and 0.1 g of sodium sulfite dissolved in 10 ml of water was added, and heating was continued for 6 hours to carry out polymerization. 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 7 of the present invention.

[0031]

Embedded image Stearyl acrylate

Example 8 Production Example In a flask equipped with a cooler, a stirrer and a nitrogen inlet tube, 20.0 g of methyl polyoxyethylene (23) methacrylate, 16.4 g of hydroxyethyl methacrylate, 2, 2,
3.6 g of 2,2 ′, 2 ′, 2′-hexafluoroisopropyl acrylate and 120 m of ethyl alcohol
1 and water (80 ml) were mixed with stirring. Thereafter, the mixture was sufficiently replaced with a nitrogen stream while continuing to stir, and then heated to 60 ° C., and a solution obtained by dissolving 0.1 g of ammonium persulfate and 0.1 g of sodium hydrogen sulfite in 10 ml of water was added. Done. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, ethyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain Polymer 8 of the present invention.

Example 9 Production Example In a flask equipped with a cooler, 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. 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 Polymer 9 of the present invention.

Example 10 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 10 of the present invention.

Example 11 Production Example In a flask equipped with a condenser, 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 the polymer 11 of the present invention.

Example 12 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 12 of the present invention was obtained.

Example 13 Physical Properties of Polymer of the Present Invention (Water- and Oil-Repellent Properties) A 5% aqueous solution of Polymers 1 to 12 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 and 8 to 12 did not change at all from 60 to 70 degrees for water and oil for 48 hours. One hour after dropping the oil, the polymer 7 had the oil absorbed by the filter paper. Also, there was no change in water up to 4 hours, but it was absorbed by the filter paper within 24 hours. This indicates that the polymer of the present invention preferably contains a fluorine atom in the molecule. As for the solution state, Polymers 4, 8 to 12 were particularly excellent in water solubility.

Example 14 Physical Properties of Polymer of the Present Invention (Oil and Water Permeability) For polymers 1 to 12, polymer films were cast on filter paper in the same manner as in Example 13. The filter paper was set in a Fritz diffusion cell, and the lower portion was filled with water (aqueous solution of 0.5% sodium polyacrylate) and glyceryl triisooctanoate. A dye (R102) aqueous solution (0.5% aqueous solution of sodium polyacrylate) and a dye (R502) glyceryl triisooctanoate solution were added to the upper part, and the lower part was left for 30 minutes while stirring. The lower solution was taken and the absorbance was measured, but almost no permeation of the dye was observed. This indicates that the polymer film of the present invention has excellent water and oil repellency and suppresses water and oil permeation. This shows that such a film is useful as a protective film.

Example 15 Physical Properties of Polymer of the Present Invention For Polymers 1 to 12, a cast film was prepared in the same manner as in Example 14, and this was lightly squeezed twice and tested in the same manner. Met. From this, it is clear that the polymer film of the present invention has sufficient plasticity without a plasticizer.

Example 16 Coating of Polymer of the Present Invention The same test as in Example 14 was carried out, except that the filter paper was changed to cloth (Tetron). The same results were obtained.

Example 17 Coating of Polymer of the Present Invention A coating of polymers 1 to 12 was formed on a metal surface, and water and oil were dropped and the contact angle was measured. The results were the same as in Example 13. there were. When this was tested in the same manner as in Example 15, similar results were obtained, and here, the excellent plasticity of the polymer of the present invention was proved.

[0042]

According to the present invention, it is useful that it is uniformly dissolved in an aqueous carrier,
After application, a polymer that forms a coating with excellent water resistance can be provided.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09D 133/16 C09D 133/16 D06M 15/263 D06M 15/263 // A61K 7/00 A61K 7/00 J

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) A polymer having plasticity. Embedded image Formula (I) (wherein R1 is a hydrogen atom or a carbon atom
And R2 represents an alkyl group having 1 to 20 carbon atoms which may have a fluorine atom. ) Formula (II) (wherein, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R4 represents an alkyloxy group,
Having 2 carbon atoms which may have an acyloxy group or a hydroxyl group;
Represents an alkyl group of 4 to 4, R5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group or an acyl group having 1 to 8 carbon atoms, and n represents a numerical value of 1 to 40. ) 2. A compound represented by the general formula (I):
The water-soluble plastic polymer according to claim 1, comprising the compound represented by the general formula (III). Embedded image Formula (III) (wherein, R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, O and P each independently represent a numerical value of 1 to 10, and R7 represents a fluorine atom or a hydrogen atom. .) 3. The compound having the water-soluble plasticity according to claim 1, wherein the compound represented by the general formula (II) contains a compound represented by the general formula (IV). High molecular. 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.) 4. One or more selected from the compounds represented by the general formula (I), 7 to 9.5% by weight, and one or more selected from the compounds represented by the general formula (II) Is a polymer having water-soluble plasticity, characterized in that two or more kinds thereof are contained as constituent monomers at 30 to 90.5% by weight. 5. The method according to claim 1, wherein when a uniform system is prepared by adding 99 parts by weight of water to 1 part by weight of the polymer, the transmittance of the liquid to visible light is 90% or more. ~ 4
The polymer having water-soluble plasticity according to any one of the above. 6. The water-soluble plastic polymer according to claim 1, wherein the polymer is used for surface treatment. 7. The method according to claim 1, wherein the surface is a skin surface, a nail surface, a hair surface,
The water-soluble plastic polymer according to any one of claims 1 to 7, wherein the polymer is a fiber surface, a glass surface, or a metal surface.