JPH06298850A - Fluorinated vinyl alcohol polymer and its production - Google Patents

Abstract

PURPOSE:To provide a fluorinated vinyl alcohol polymer useful as a polymeric surfactant by reacting a fluoroalkanoyl peroxide with a specified vinyl ester or both this ester and a specified monomer and treating the reaction product with an acid or an alkali. CONSTITUTION:The polymer is represented by formula I (wherein R<1> is H, 1-5C alkyl or the like; R<2> is H, halogen or the like; a is an integer of 1-10000; b is 0 or an integer of 1-10000; Rf is -(CF2)hX or a group of formula III; X is H, chlorine or fluorine; h is an integer of 1-10; and i is 0 or an integer of 1-8). The production process of the polymer comprises reacting a fluoroalkanoyl peroxide of formula II (wherein Rf is as defined above) with a vinyl ester of the formula: CH2=CHOCOR<11> (wherein R<11> is H, 1-18C alkyl or the like) or both this ester and a monomer of the formula: CH2=CR<1>R<2> (wherein R<1> and R<2> are as defined above) and treating the reaction mixture with an acid or an alkali.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel fluorine-containing vinyl alcohol polymer and a method for producing the same.
More specifically, the present invention is useful as a surfactant, particularly as a polymer surfactant having a low surface tension property, and also as a curable composition because it has a hydroxyl group as a curable group. Fluorine-containing vinyl alcohol polymer,
And a method for efficiently producing the same.

[0002]

2. Description of the Related Art A compound containing a fluoroalkyl group in an organic compound has recently attracted attention as a compound having useful properties such as weather resistance, water and oil repellency, and physiological activity. In particular, a fluoroalkyl group-containing polymer in which a fluoroalkyl group is introduced into an organic compound has low surface tension, low refractivity, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, releasability, and resistance. Due to its excellent properties such as chemical properties, in various fields, for example, surfaces for imparting water and oil repellency and stain resistance to the surfaces of optical lenses, eyeglass lenses, glass equipment, paints, etc. It is considered to be useful in the fields of treatment agents, biomaterials, raw materials for pharmaceuticals and agricultural chemicals, and materials that impart releasability. However, a conventional fluoroalkyl group-containing polymer is one in which a fluoroalkyl group is introduced into acrylic acid or methacrylic acid through an ester bond or an amino bond [for example, a fluoroalkyl group-containing polymer is introduced through an amino bond. Fluorine epoxy compound; "J. Fluorine Chemistry (J. Fluorine
Chem. ), Vol. 55, page 1 (1991)]
However, there is a problem in that it generally has drawbacks such as low weather resistance. In the acrylic resin coating material containing a fluoroalkyl group, since the fluoroalkyl group is introduced by an ester bond, there is a problem that the fluoroalkyl group is easily released by hydrolysis and the water and oil repellency deteriorates. There is also a problem that the stain resistance is insufficient. Fluororesin coatings using chlorotrifluoroethylene developed for the purpose of improving weather resistance [Organic Synthetic Chemistry, Vol. 42, page 841 (1984)].
Has a weather resistance, but has a problem of low water and oil repellency and insufficient stain resistance. Fluororesin having a fluoroalkyl group such as a fluoroacrylate polymer in which a fluoroalkyl group is introduced by an ester bond also forms a film on the surface of the equipment and protects the equipment, cosmetics, water and oil repellency, insulation, and release. It has been widely used as a surface treatment agent that imparts characteristics such as moldability and antifouling property.
However, the fluororesin has problems such as poor adhesion to inorganic materials such as metals, glass and cement, various plastics, organic materials such as base materials, and further, fluoroalkyl groups in the molecule due to ester bonds. Therefore, there is also a problem that the stability against acid and alkali is poor. On the other hand, in order to improve the adhesion, a fluoroalkyl group-containing silicone compound is proposed in JP-A-59-10280.
However, the above-mentioned silicone compounds have the drawbacks that sufficient adhesiveness has not yet been obtained, and that the water and oil repellency is reduced. More recently,
Fluorine compounds used as SR processing agents, antifogging agents, surfactants, and various surface treatment agents, etc., with a fluoroalkyl group exhibiting water and oil repellency in the same molecule, and an amphiphilic activity exhibiting hydrophilicity. Agents and surface treatment agents are considered to be useful and have been attracting attention, and the current situation is that their development is strongly desired. Therefore, the fluoroalkyl group has high carbon-carbon bond directly and has high weather resistance,
Furthermore, the development of materials having high water and oil repellency is strongly desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention is directed to low surface tension, low refractivity, heat resistance, cold resistance, oil resistance, electrical insulation,
It has excellent properties such as water repellency, releasability, water repellency and oil repellency and stain resistance on the surface of optical lenses, spectacle lenses, glass instruments, paints, etc., and as a biomaterial, Alternatively, the object is to provide a fluorine-containing vinyl alcohol polymer in which a fluoroalkyl group useful as a raw material for medicines and agricultural chemicals is introduced by a carbon-carbon bond, and a method for producing the same.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a vinyl alcohol polymer having a specific structure having fluoroalkyl groups at both ends meets the above-mentioned object. And that this is obtained by reacting a fluoroalkanoyl peroxide with a specific vinyl ester or a specific vinyl ester and a specific monomer and then treating with an acid or an alkali. The present invention has been completed based on this finding. That is, the present invention has the general formula

[0005]

[Chemical 7]

[Wherein R ¹ is a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, R ² is a hydrogen atom, a halogen atom, a cyano group or

[0007]

[Chemical 8]

R _F is-(CF ₂ ) _h X or

[0009]

[Chemical 9]

A is an integer of 1 to 10000, b is 0 or an integer of 1 to 10000 (provided that
R ³ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms, R ⁴ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, R ⁵ is an alkylene group having 1 to 10 carbon atoms or — (CH ₂ CH ₂ O) _j CH ₂ —, R ⁶ and R ⁷ are the same or different hydrogen atoms or alkyl groups having 1 to 18 carbon atoms, R ⁸ , R ⁹ and R ¹⁰ are the same or different hydrogen atoms or methyl groups, X is a hydrogen atom, chlorine atom or fluorine atom, c is 0 or an integer of 1 to 5, d is an integer of 1 to 20, and e and f are 0. Or an integer of 1 to 20, g is 1 or 2,
h is an integer of 1 to 10, i is 0 or an integer of 1 to 8, and j is 1.
It is an integer of 10]]]. According to the invention,
The fluorine-containing vinyl alcohol polymer, the general formula

[0011]

[Chemical 10]

Fluoroalkanoyl peroxide represented by the formula (R _F has the same meaning as described above) and the general formula CH ₂ ═CHOCOR ¹¹ ... [3] (R ¹¹ in the formula is a hydrogen atom or a carbon number. A vinyl ester represented by an alkyl group having 1 to 18 or a hydroxyalkyl group having 1 to 4 carbon atoms or the vinyl ester and the general formula CH ₂ = CR ¹ R ² ... [4] (R in the formula ¹ and R ² have the same meaning as described above), and can be produced by reacting with a monomer represented by the formula ( ¹ ) and then treating with an acid or an alkali. Hereinafter, the present invention will be described in detail. The fluorine-containing vinyl alcohol polymer of the present invention has the general formula

[0013]

[Chemical 11]

(In the formula, R ¹ , R ² , R _F , a and b have the same meanings as described above), and applicable R in the general formula [1] _F , that is-(CF
₂ ) _h X or

[0015]

[Chemical 12]

For example, CF ₃ , F (CF ₂ ) ₂ , F
(CF ₂ ) ₃ , F (CF ₂ ) ₄ , F (CF ₂ ) ₅ , F (CF ₂ ) ₆ , F
(CF ₂ ) ₇ , F (CF ₂ ) ₈ , F (CF ₂ ) ₉ , F (CF ₂ ) ₁₀ , H
CF ₂ , H (CF ₂ ) ₂ , H (CF ₂ ) ₃ , H (CF ₂ ) ₄ , H (CF
₂ ) ₅ , H (CF ₂ ) ₆ , H (CF ₂ ) ₇ , H (CF ₂ ) ₈ , H (CF ₂ )
₉ , H (CF ₂ ) ₁₀ , ClCF ₂ , Cl (CF ₂ ) ₂ , Cl (CF
₂ ) ₃ , Cl (CF ₂ ) ₄ , Cl (CF ₂ ) ₅ , Cl (CF ₂ ) ₆ , C
l (CF ₂ ) ₇ , Cl (CF ₂ ) ₈ , Cl (CF ₂ ) ₉ , Cl (C
F ₂ ) ₁₀ ,

[0017]

[Chemical 13]

Examples thereof include groups represented by:
At this time, the carbon number of R _F , that is, h and i are 1
If it exceeds 0 or 8, the solubility in a solvent decreases. Specific examples of the fluorine-containing vinyl alcohol polymer represented by the general formula [1] include compounds represented by the formula:

[0019]

[Chemical 14]

[0020]

[Chemical 15]

Preferred examples include those represented by: The fluorine-containing vinyl alcohol polymer of the present invention preferably has a molecular weight in the range of 500 to 1,000,000, and may partially contain a polymer having a fluoroalkyl group only at one terminal. The fluorine-containing vinyl alcohol polymer represented by the above general formula [1] of the present invention has the general formula

[0022]

[Chemical 16]

Fluoroalkanoyl peroxide represented by the formula (R _F has the same meaning as described above) and the general formula CH ₂ ═CHOCOR ¹¹ ... [3] (R ¹¹ in the formula has the same meaning as described above). Or a monomer represented by the general formula CH ₂ ═CR ¹ R ² ... [4] (wherein R ¹ and R ² have the same meanings as described above) It can be produced by reacting with a compound and then treating with an acid or an alkali. Specific examples of the vinyl esters and monomers represented by the general formulas [3] and [4] include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, Acrylonitrile, (meth) acrylic acid, methyl (meth) acrylate, (meth)
Acrylic acid-t-butyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-2-ethylhexyl, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,

[0024]

[Chemical 17]

[0025]

[Chemical 18]

[0026]

[Chemical 19]

Preferred examples include: In the above formula, k is an integer of 1 to 10, m is an integer of 1 to 20, n is an integer of 0 or 1 to 20, and when used, k or m and n are different integers. It may be a mixture. In the fluoroalkanoyl peroxide represented by the general formula [2], when h is 11 or more, or i is 9 or more, when the reaction is performed in the presence of a solvent, the compound represented by the general formula [2] is used. It is not preferable because the solubility of fluoroalkanoyl peroxide is insufficient. The fluoroalkanoyl peroxide has the above general formula [1].
It can be appropriately selected and used according to the fluoroalkyl group in. In the present invention, when the fluoroalkanoyl peroxide is reacted with the vinyl ester represented by the general formula [3] or the vinyl ester and the monomers represented by the general formula [4], The mixing molar ratio of the vinyl ester and the monomer can be any ratio, but is preferably in the range of 1: 0.01 to 100, and the fluoroalkanoyl peroxide and the vinyl ester or the vinyl are mixed. The charge molar ratio of the ester and the monomer is usually selected in the range of 1: 0.1 to 5000, preferably 1: 0.5 to 1000. When the charged molar ratio of vinyl esters or vinyl esters and monomers is less than 0.1, a large amount of products resulting from the self-decomposition of peroxides are produced, and when it exceeds 5,000, it is aimed. It is not preferable because the yield of the fluorine-containing vinyl alcohol polymer is lowered. Further, the molecular weight of the obtained polymer can be adjusted by adjusting the charged molar ratio of the fluoroalkanoyl peroxide. That is, if the charged molar ratio of the fluoroalkanoyl peroxide is increased, a polymer having a low molecular weight can be obtained, and if it is decreased, a polymer having a high molecular weight can be obtained. Further, the above reaction can be carried out at normal pressure, and the reaction temperature is usually selected in the range of -20 to 150 ° C, preferably 0 to 100 ° C. If the reaction temperature is lower than -20 ° C, the reaction time tends to be long, whereas if it exceeds 150 ° C, the pressure during the reaction is high, and the reaction operation is difficult, which is not preferable. Further, the reaction time is usually in the range of 30 minutes to 20 hours, but it is desirable to set the conditions so as to be practically 1 to 10 hours. In the present invention, the fluoroalkanoyl peroxide is reacted with the vinyl ester represented by the general formula [3] or the vinyl ester and the monomers represented by the general formula [4], and then an acid or an acid or A desired fluorine-containing vinyl alcohol polymer represented by the above general formula [1] is produced by treating with an alkali. As the acid used at this time, a usual inorganic acid or organic acid can be used. , For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, citric acid, boric acid, hydrofluoric acid, acetic acid, butyric acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid,
Preferable examples include trifluoromethanesulfonic acid and p-toluenesulfonic acid. On the other hand, as an alkali,
Usual inorganic alkali and organic bases can be used, for example sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, pyridine, triethylamine,
Preferred examples include tributylamine, lutidine, triethanolamine and the like. Further, upon use, it is usually preferable to dissolve these acids or alkalis and use as a diluted solution. As the solvent used for the diluted solution,
Examples thereof include water and organic solvents for general use such as methanol, ethanol, xylene, toluene, benzene and acetonitrile, which can be further diluted to an arbitrary concentration before use. The amount of these acids or alkalis used is 1 part by weight of the fluorine-containing vinyl alcohol polymer obtained by reacting the fluoroalkanoyl peroxide with the vinyl ester or the vinyl ester and the monomers. The range of 0.01 to 1000 parts by weight is preferable, and the reaction temperature is usually selected in the range of -20 to 250 ° C, while the reaction time is about 1 minute to 72 hours. The fluorine-containing vinyl alcohol polymer thus obtained can be purified by a conventional purification method such as reprecipitation. It is preferable to use a solvent in order to more smoothly handle and react the fluoroalkanoyl peroxide used in the production of the fluorine-containing vinyl alcohol polymer of the present invention. As the solvent, an aliphatic ester solvent, an aliphatic alcohol solvent, a halogenated aliphatic solvent and a halogenated aromatic solvent are particularly preferable, and for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl. Alcohol, isobutyl alcohol, sec-butyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, 1 , 2-Dibromohexafluoropropane, 1,2-
Dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-
2,3,3-trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1, -trichloropentafluoropropane, 1,1,2-trichlorotrifluoroethane, 1,1, 1,2,2-pentafluoro-3,
3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, benzotrifluoride, hexafluoroxylene, etc. can be used,
Particularly industrially, 1,1,2-trichlorotrifluoroethane, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro- 1,
Solvents such as 3-dichloropropane, benzotrifluoride and hexafluoroxylene can be preferably mentioned. When using these solvents, the concentration of the fluoroalkanoyl peroxide in the solvent is usually 0.1 to 30% by weight.
It is desirable that it is a degree.

[0028]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1 360 g of a 1,1,2-trifluorotrichloroethane solution containing 25.8 g (300 mmol) of vinyl acetate and 9.9 g (10 mmol) of perfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide. Under a nitrogen stream for 30
The reaction was carried out at ℃ for 7 hours. After completion of the reaction, 1,1,2-trifluorotrichloroethane was removed and then dried under reduced pressure to obtain a fluorine-containing vinyl acetate polymer represented by the following structure in a yield of 22.1 g.

[0029]

[Chemical 20]

Then, 2 g of the fluorine-containing vinyl acetate polymer was dissolved in 100 ml of methanol, and 2.5 ml of a 40 wt% sodium hydroxide aqueous solution was added at room temperature. The obtained white precipitate was washed with methanol and further dried under vacuum to obtain a fluorovinyl alcohol polymer represented by the following formula in a yield of 1.6 g.

[0031]

[Chemical 21]

IR (cm ^-1 ) ν3430 (OH), 1330
_{(CF 3), 1240 (CF} 2) 1 H-NMR (D 2 O) δ1.40 (-CH 2 -), 3.81 (=
CH-) ¹⁹ F-NMR (D ₂ O, ext.CF ₃ CO ₂ H) δ-4.2
5--9.10 (26F), -55.0 (6F), -70.0
(2F) Molecular weight: Mn = 8800 (Mw / Mn = 1.91) Example 2 Instead of vinyl acetate, vinyl acetate 5.2 (60 mmol)
When the reaction was carried out according to Example 1 except that a mixture of acrylic acid and 4.3 g (60 mmol) of acrylic acid was used, the following polymer was obtained in a yield of 7.6 g.

[0033]

[Chemical formula 22]

Then, 2 g of the fluoropolymer was dissolved in 100 ml of methanol, and 2.5 ml of 40 wt% sodium hydroxide aqueous solution was added at room temperature. The obtained white precipitate was washed with methanol and further dried under vacuum to obtain a fluorovinyl alcohol polymer represented by the following formula in a yield of 1.6 g.

[0035]

[Chemical formula 23]

IR (cm ^-1 ) ν3350 (OH), 1740
(C = O), 1320 ( CF 3), 1240 (CF 2) 1 H-NMR (D 2 O) δ1.45 (-CH 2 -), 1.68 (-
CH _2- ), 2.45 (= CH-), 3.81 (= CH-) ¹⁹ F-NMR (D ₂ O, ext.CF ₃ CO ₂ H) δ-4.2.
5--9.19 (26F), -55.5 (6F), -70.1
(2F) Copolymerization ratio x: y = 60: 40 Molecular weight: Mn = 10500 (Mw / Mn = 2.30) Example 3 Instead of vinyl acetate, 1.7 g of vinyl acetate (20 mmo)
When the reaction was carried out according to Example 1 except that a mixture of l) and 4.3 g (60 mmol) of acrylic acid was used, the following polymer was obtained in a yield of 7.6 g.

[0037]

[Chemical formula 24]

Then, 2 g of the fluoropolymer was dissolved in 100 ml of methanol, and 2.5 ml of 40 wt% sodium hydroxide aqueous solution was added at room temperature. The obtained white precipitate was washed with methanol and further dried under vacuum to obtain a fluorine-containing vinyl alcohol polymer represented by the following formula in a yield of 1.4 g.

[0039]

[Chemical 25]

IR (cm ^-1 ) ν3350 (OH), 1740
(C = O), 1320 ( CF 3), 1240 (CF 2) 1 H-NMR (D 2 O) δ1.47 (-CH 2 -), 1.61 (-
_{CH 2 -), 2.43 (=} CH -), 3.92 (= CH-) 19 F-NMR (D 2 O, ext.CF 3 CO 2 H) δ-4.2
3 to -9.10 (26F), -55.1 (6F), -70.5
(2F) Copolymerization ratio x: y = 33: 67 Molecular weight: Mn = 11500 (Mw / Mn = 2.11) Example 4 Instead of vinyl acetate, 1.7 g of vinyl acetate (20 mmo)
When the reaction was carried out according to Example 1 except that a mixture of l) and 5.2 g (60 mmol) of methacrylic acid was used, the polymer shown below was obtained in a yield of 9.1 g.

[0041]

[Chemical formula 26]

Next, 2 g of the fluoropolymer was dissolved in 100 ml of methanol, and 2.5 ml of 40 wt% sodium hydroxide aqueous solution was added at room temperature. The obtained white precipitate was washed with methanol and further dried under vacuum to obtain a fluorovinyl alcohol polymer represented by the following formula in a yield of 1.6 g.

[0043]

[Chemical 27]

IR (cm ^-1 ) ν 3350 (OH), 1740
(C = O), 1320 ( CF 3), 1240 (CF 2) 1 H-NMR (D 2 O) δ1.10 (CH 3 -), 1.61 (-C
_{H 2 -), 3.88 (=} CH-), 19 F-NMR (D 2 O, e
xt.CF ₃ CO ₂ H) δ−4.20 to −9.12 (26F),
-55.0 (6F), -70.1 (2F) Copolymerization ratio x: y = 29: 71 Molecular weight: Mn = 5630 (Mw / Mn = 1.53) Example 5 40 wt% sodium hydroxide aqueous solution 2. Instead of 5 ml,
When the reaction was carried out according to Example 1 except that 0.5 ml of a 40 wt% aqueous solution of sodium was used, the following polymer was obtained in a yield of 1.7 g.

[0045]

[Chemical 28]

IR (cm ^-1 ) ν3430 (OH), 1335
_{(CF 3), 1250 (CF} 2) 1 H-NMR (D 2 O) δ1.44 (-CH 2 -), 1.70 (-
_{CH 2 -), 1.98 (CH} 3 -), 3.89 (= CH-) 19 F-NMR (D 2 O, ext.CF 3 CO 2 H) δ-4.2
1--9.19 (26F), -55.3 (6F), -70.6
(2F) Copolymerization ratio x: y = 79: 21 Molecular weight: Mn = 9100 (Mw / Mn = 1.89) Example 6 Perfluoroperfluoro-2,5-dimethyl-3,6-dioxanonanoyl 9. The reaction was carried out according to Example 1 except that 4.3 g (10 mmol) of perfluorobutyryl peroxide was used instead of 9 g (10 mmol), and the fluorine-containing vinyl alcohol polymer shown below was obtained in a yield of 1.2 g. It was

[0047]

[Chemical 29]

IR (cm ^-1 ) ν3430 (OH), 1335
_{(CF 3), 1250 (CF} 2) 1 H-NMR (D 2 O) δ1.45 (-CH 2 -), 3.90 (=
CH-) ¹⁹ F-NMR (D ₂ O, ext.CF ₃ CO ₂ H) δ-5.1
0 (6F), −36.21 (4F), −51.00 (4F) Molecular weight: Mn = 7990 (Mw / Mn = 1.88) Example 7 2w instead of 2.5 wt% 40 wt% sodium hydroxide aqueous solution.
The reaction was carried out in accordance with Example 1 except that a t% sulfuric acid-methanol solution was used and the treatment conditions were changed from room temperature to reflux under stirring for 3 hours. Obtained at 0.7 g.

[0049]

[Chemical 30]

IR (cm ^-1 ) ν3430 (OH), 1330
_{(CF 3), 1240 (CF} 2) 1 H-NMR (D 2 O) δ1.40 (-CH 2 -), 3.81 (=
CH-), ¹⁹ F-NMR (D ₂ O, ext.CF ₃ CO ₂ H)
δ -4.25 to -9.10 (26F), -55.0 (6F),
-70.0 (2F) molecular weight: Mn = 8850 (Mw / Mn = 1.90)

[0051]

INDUSTRIAL APPLICABILITY The fluorine-containing vinyl alcohol polymer of the present invention is a novel compound and is useful as a surfactant, particularly as a polymer surfactant having a low surface tension. Furthermore, since it has a hydroxyl group as a curable group,
It is also useful as a curable composition. The fluorine-containing vinyl alcohol polymer is capable of exhibiting a sufficient function of fluorine by addition in a small amount, does not deteriorate resin-specific properties such as resin hardness, and has a high compatibility with resin components and a resin or a base. It has characteristics such as excellent durability and less problems such as material deterioration. In particular, the fluorine-containing vinyl alcohol polymer of the present invention is excellent in surface hydrophilicity (anti-fogging property) and oil repellency, and can maintain its properties permanently, and various plastic materials, glass, transparent ceramics, etc. It has excellent adhesion to the surface of transparent materials and various mirror surface materials, and the coating film has very good water resistance and mechanical strength. Therefore, various plastic molding materials, vanity mirrors, bathroom mirrors, buildings, automobile window glass, curved mirrors, reflectors, agricultural films, food packaging films, antifouling agents such as paints, antifog materials, etc. Is effective for use as.

Claims (2)

[Claims] 1. A general formula: [Wherein R ¹ is a hydrogen atom, a halogen atom, or a carbon number of 1 to
An alkyl group of 5, R ² is a hydrogen atom, a halogen atom, a cyano group or And R _F is — (CF ₂ ) _h X or And a is an integer of 1 to 10000, b is an integer of 0 or 1 to 10000 (wherein R ³ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl having 2 to 6 carbon atoms). Group, R ⁴ is a hydrogen atom, having 1 to 18 carbon atoms
Is an alkyl group having 1 to 4 carbon atoms, R ⁵ is an alkylene group having 1 to 10 carbon atoms, or-(CH ₂
CH ₂ O) _j CH ₂ —, R ⁶ and R ⁷ are the same or different hydrogen atoms or alkyl groups having 1 to 18 carbon atoms,
R ⁸ , R ⁹ and R ¹⁰ are the same or different hydrogen atoms or methyl groups, X is a hydrogen atom, a chlorine atom or a fluorine atom, c is 0 or an integer of 1 to 5, d is an integer of 1 to 20 and e
And f is 0 or an integer of 1 to 20, g is 1 or 2, and h is 1.
-10, i is 0 or an integer of 1-8, j is 1-10
The fluorine-containing vinyl alcohol polymer represented by 2. A general formula: [Wherein R _F is-(CF ₂ ) _h X or A group represented by, X is a hydrogen atom, a chlorine atom or a fluorine atom, h is an integer of 1 to 10, i is 0 or an integer of 1 to 8], and a fluoroalkanoyl peroxide represented by the general formula CH ₂ = CHOCOR ¹¹ (wherein R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms) or the vinyl ester or the vinyl ester and the general formula CH ₂ = CR ¹ R ² [wherein R ¹ is a hydrogen atom, a halogen atom or a carbon number of 1 to
An alkyl group of 5, R ² is a hydrogen atom, a halogen atom, a cyano group or (Wherein R ³ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms, R ⁴ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or A hydroxyalkyl group having 1 to 4 carbon atoms, R ⁵ is an alkylene group having 1 to 10 carbon atoms, or — (CH ₂ CH ₂ O) _j C
H ₂ -, R ⁶ and R ⁷ are identical or different hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R ^8, R ⁹ and R
¹⁰ is the same or different hydrogen atom or methyl group, c is 0 or an integer of 1 to 5, d is an integer of 1 to 20, e
And f is 0 or an integer of 1 to 20, g is 1 or 2, and j is 1.
It is an integer of 10)], and then treated with an acid or an alkali, and the method for producing a fluorine-containing vinyl alcohol polymer according to claim 1.