JPH0713114B2 - Fluoroalkyl-substituted styrene copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is a material for a coating material capable of treating the surface of glass or the like with water repellency, oil repellency treatment, antireflection treatment or chemical resistance treatment without impairing its light transmittance. And a novel fluoroalkyl-substituted styrene copolymer useful as

The fluoroalkyl-substituted styrene copolymer of the present invention is a novel compound which has not been published in the literature. The polymer can be used as a coating material capable of treating the surface of glass or the like with water repellency, oil repellency, antireflection treatment or chemical resistance without impairing its light transmission property.

[Conventional technology]

Conventionally, fluoropolymers have excellent corrosion resistance and chemical resistance as compared with hydrocarbon-based polymers, and further have water repellency and oil repellency, and therefore, these properties can be used for antifouling materials and non-adhesive materials. Has been applied.

[Problems to be solved by the invention]

However, polymers such as polytetrafluoroethylene and polyvinylidene fluoride in which a fluorine atom is introduced into the main chain are insoluble in ordinary organic solvents, and therefore, for example, when coating on a substrate such as glass or metal. Requires the operation of pressure-bonding after heating and melting, and cannot coat on a substrate having a complicated shape. Further, a polymer of a fluorinated acrylic ester or a fluorinated methacrylic ester is soluble in an organic solvent such as ethyl acetate, and by coating this polymer solution, water repellent treatment, antifouling treatment or optical fiber treatment of the fiber is performed. Although they are used as coating materials and the like, these polymers have an ester bond having a hydrolyzability, and therefore, when used for a long period of time, it is unavoidable that characteristic abilities such as water repellency and light transmittance are deteriorated.

The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the fluoroalkyl-substituted styrene copolymer of the present invention has high water repellency, oil repellency, and light transmittance as well as excellent coating properties and stability. Heading out, the present invention has been completed.

[Means for solving problems]

The fluoroalkyl-substituted styrene copolymer of the present invention has the general formula (In the formula, R ¹ represents a hydrogen atom or a lower alkyl group,
R ² represents a hydrogen atom or a lower polyfluoroalkyl group, R ³ represents a polyfluoroalkyl group, Y ^{1 to} Y ⁴ each represent a hydrogen atom or a halogen atom, and n represents 0 or 1
Is an integer. ) And the general formula [In the formula, R ⁶ represents a hydrogen atom or a lower alkyl group,
Z is an unsubstituted or lower alkyl group, a lower haloalkyl group, a lower alkyloxy group, or a phenyl group substituted with a halogen atom, a hydrogen atom, a lower alkyl group,
Alkyoxy group, cyano group, group represented by -COOR ⁷ or A group represented by (provided that R ⁷ and R ⁸ are a hydrogen atom or a carbon number 1 to
15 represents an alkyl group, a phenyl group or a cycloalkyl group, and R ⁹ represents a hydrogen atom or a lower alkyl group. )
Represents ] The composition of the repeating unit represented by the general formula (I) is 1 mol% to 99 mol.
The range is l% and the molecular weight is 1000 or more.

Examples of the lower polyfluoroalkyl group represented by R ² include a difluoromethyl group, a trifluoromethyl group, an ethyl group substituted with 2 to 4 fluorine atoms, a perfluoroethyl group and 2 to 6 fluorine atoms. Examples thereof include a propyl group, a perfluoropropyl group, a butyl group substituted with 2 to 8 fluorine atoms, and a perfluorobutyl group. Particularly, a perfluoromethyl group and a perfluoroethyl group are preferable in the sense that they give suitable reactivity, water repellency and oil repellency. The polyfluoroalkyl group represented by R ³ may have an ether bond in the alkyl chain, and may include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, and a perfluoroheptyl group. Group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, difluoromethyl group, 2
To an ethyl group substituted with 4 fluorine atoms from 2 to 6
Propyl group substituted with 1 fluorine atom, butyl group substituted with 2 to 8 fluorine atoms, 3-oxa-2-trifluoromethyl-2,4,4,5,5,6,6,6 -Octafluorohexyl group and the like can be exemplified. In particular, perfluoroalkyl groups or alkyl groups whose alkyl terminals are completely fluorinated such as 2,2,3,3,4,4,5,5,5-nonafluoropentyl groups exhibit high water and oil repellency. It is preferable in terms.

When R ⁷ and R ⁸ are an alkyl group or a cycloalkyl group, the alkyl group or the cycloalkyl group may be substituted with a hydroxyl group, an alkoxy group, an epoxy group, a cyano group, a carbonyl group, a halogen atom or the like. When R ⁷ and R ⁸ are phenyl groups, the phenyl group has a substituent such as an alkyl group, an alkoxy group, a halogen atom, an epoxyalkyl group, a cyano group, a carbonyl group, or a dialkylamino group. Good.

The fluoroalkyl-substituted styrene copolymer of the present invention has the general formula (In the formula, R ¹ , R ² , R ³ , Y ¹ , Y ² , Y ³ , Y ⁴ and n are the same as above.) And the general formula. (In the formula, R ⁶ and Z are the same as the above.) It can be easily produced by mixing one or more kinds of the monomers represented by the above and copolymerizing by a usual radical polymerization method. . As the method used for the polymerization reaction, known methods such as bulk polymerization, solution polymerization and emulsion polymerization can be used. The radical polymerization reaction is rapidly initiated simply by irradiation with heat, ultraviolet rays or addition of a radical initiator. As the radical initiator preferably used in the reaction,
Examples thereof include organic peroxides such as dilauroyl peroxide and benzoyl peroxide, and azo compounds such as α, α′-azobisisobutyronitrile. The organic solvent that can be used in the polymerization reaction is preferably soluble in the resulting polymer in order to obtain a high molecular weight polymer,
For example, benzene, toluene, chlorobenzene, tetrahydrofuran, carbon tetrachloride, chloroform, methyl ethyl ketone, fluorobenzene, hexafluorobenzene,
Benzotrifluoride, 1,4-bis (trifluoromethyl) benzene, N, 6-dimethylformamide and the like can be used, but are not limited thereto. The reaction is usually performed in the range of 40 ° C to 100 ° C.

The fluoroalkyl-substituted styrene derivative represented by the general formula (III) is a compound that can be easily produced from, for example, chloromethylethylene, chlorostyrene, fluoroacetophenone, hydroxyacetophenone, pentafluorostyrene, etc. (see Reference Example).

Examples of the copolymerizable monomer represented by the general formula (IV) include styrene such as styrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, pentafluorostyrene and p-aminostyrene. Derivatives, alkenes such as ethylene, propylene and butylene, ethyl vinyl ether, propyl vinyl ether,
Vinyl ethers such as butyl vinyl ether, hexyl vinyl ether and octyl vinyl ether, methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, butyl acrylate, 2,3-dihydroxypropyl acrylate, polyfluoroalkyl acrylate, p-fluorophenyl acrylate, m-tri Acrylic esters such as fluoromethylphenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid esters such as perfluoroalkyl methacrylate, acrylonitrile, Acrylamide, - -methoxyacrylic anilide,
N-hydroxymethyl acrylamide, N- (1,1-dimethyl-3-octylbutyl) acrylamide, methacrylamide, N-hydroxyethyl methacrylamide, acrolein, acrylic acid, methacrylic acid and the like can be used. Further, the repeating unit represented by the general formula (I) contained in the copolymer is at least 1 mol% or more, and 5 mol% or more for obtaining suitable water repellency, oil repellency and light transmittance. Is desirable.

Further, the fluoroalkyl-substituted styrene copolymer of the present invention, (In the formula, Y ⁵ represents a halogen atom, and R ¹ , Y ¹ , Y ² , Y ³ ,
Y ⁴ and n are the same as above. ) The monomer obtained by the copolymerization reaction of one or more kinds of the monomer represented by the general formula (IV) with the general formula (R ² and R ³ are the same as above), and can be obtained by reacting in the presence of a base. The reaction is preferably carried out in a solvent, and usable solvents include tetrahydrofuran and 1,4-
Examples thereof include bis (trifluoromethyl) benzene and the like. As the base used in the reaction, alkali metal hydrides such as sodium hydroxide, potassium hydroxide, sodium hydride and potassium hydride, alkali metals such as sodium, potassium and lithium and diazabicyclo [3.4.0] nonene-5 ( Examples include amines such as DBN) and 1,5-diazabicyclo [5.4.0] undecene-5- (DBU). It is also possible to use a phase transfer catalyst such as tetra-n-butylammonium hydrogen sulfate to react in a two-phase system of an organic phase and an aqueous phase.

Further, as the fluorine-containing alcohol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-1-propanol, 2,2,3,3,4,4,4-hepta Fluoro-1-butanol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol, 2,2,2- Trifluoro-1- (trifluoromethyl) ethanol, 2,2-difluoroethanol, 2,2,3,3,4,4-hexafluoro-1
-Butanol, 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 3,3,4,4, 4-pentafluoro-1-butanol, 4,4,4-trifluoro-1-butanol, 1,1,1,3,
3,3-hexafluoro-2-propanol, 4,4,5,5,6,
6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanol, 1,1,1,6,6,7,7,7-octafluoro-2-heptanol , 3-oxa-2-trifluoromethyl-2,
Examples include 4,4,5,5,6,6,6-octafluorohexanol and the like.

Further, as the reaction solvent and the organic phase in the two-phase system reaction,
Examples thereof include benzene, toluene, xylene, diethyl ether, cyclohexane and the like.

The reaction temperature is in the range of 0 ° C to 150 ° C, preferably 10 ° C to 100 ° C.

The polymer having a repeating unit represented by the general formula (V), which is a raw material polymer, is obtained by homopolymerizing a styrene derivative substituted with a haloalkyl group or a halogen atom, or by combining the styrene derivative with the general formula (IV). It can be easily synthesized by mixing one or more kinds of the indicated monomers and copolymerizing them by an ordinary radical polymerization method. As the method used for the polymerization reaction, known methods such as bulk polymerization, solution polymerization and emulsion polymerization can be used.
The radical polymerization reaction is rapidly initiated simply by irradiation with heat, ultraviolet rays or addition of a radical initiator. Examples of the radical initiator preferably used in the reaction include organic peroxides such as dilauroyl peroxide and benzoyl peroxide, and azo compounds such as α, α′-azobisisobutylnitrile. The organic solvent that can be used in the polymerization reaction is preferably soluble in the polymer to be obtained in order to obtain a high molecular weight polymer, for example, benzene, toluene, chlorobenzene, tetrahydrofuran, carbon tetrachloride, chloroform, methyl ethyl ketone, fluorobenzene, hexa Fluorobenzene, N, N-dimethylformamide and the like can be used, but not limited thereto.

The reaction is usually performed in the range of 40 ° C to 100 ° C. Examples of the styrene derivative substituted with a haloalkyl group or a halogen atom include p-chloromethylstyrene and 4-chloromethyl-2.
-Fluorostyrene, p- (2-chloroethyl) styrene, m-chloromethylstyrene, p-bromomethylstyrene, p-chloromethyl-α-methylstyrene, m-
(2-Bromoethyl) styrene, p- (3-chloropropyl) styrene, m-chloromethyl-α-ethylstyrene, p-iodomethylstyrene, pentafluorostyrene, pentachlorostyrene and the like can be mentioned.

Further, the repeating unit represented by the general formula (V) contained in the polymer is at least 1 mol% or more, and 5 mol% or more for obtaining suitable water repellency, oil repellency and light transmittance. Is desirable. Further, the fluoroalkyl-substituted styrene copolymer obtained by the production method of the present invention has a molecular weight of 10
It is preferably 00 or more, and the molecular weight is preferably 10,000 or more when the copolymer is used as a coating material.

The present invention will be specifically described below with reference to Reference Examples, Examples, Test Examples, and Comparative Examples.

Reference example 1 2,2,2-Trifluoroethanol 9g and tetra-n-butylammonium hydrogen sulfate (TBAS) 20.37g and toluene 30
0 ml was placed in a three-necked flask and stirred under a stream of argon. Next, add 17.5 ml of 50 wt% sodium hydroxide solution.
After stirring for 15 minutes, 9.15 g of p-chloromethylstyrene was added, and the mixture was stirred overnight at room temperature. The reaction mixture was neutralized by adding dilute hydrochloric acid, and then the organic layer was placed in a separating funnel and thoroughly washed with water. Then, it was dried over anhydrous magnesium sulfate, and toluene was distilled off under reduced pressure. The residue was purified by passing through a silica gel column using n-hexane as an eluent, and n-hexane was distilled off to give 5.8 g of 27% yield of p- (2,2,2-
Trifluoroethyloxymethyl) styrene (p-TFE
S) got.

Elemental analysis value (%); Actual value: C: 61.5, H: 5.2 Calculated value: C: 61.1, H: 5.1 IR (cm ^-1 ); 2800 to 3000,1610,1510 (aromatic ring), 1630 (CH
₂ = CH), 1210, 1150 (CF), 1100 to 1180 (-O-). NMR (ppm); 3.6-4.0 (2H), 4.6 (2H), 5.1-5.8 (2
H), 6.5 to 6.8 (1H). Reference Examples 2 to 9 (Results of Synthesis of Fluoroalkyl-Substituted Styrene Derivatives) Fluoroalkyl-substituted styrene derivatives were synthesized in the same manner as in Reference Example 1 except that the types of fluorine-containing alcohol, haloalkylstyrene and solvent were changed. The results are shown in Table 1.

Reference example 10 2.6 g of 50% sodium hydride (oil-based) was added to 50 ml of hexamethylphosphoramide (HMPA), and the mixture was stirred under an argon stream. This is cooled to 10 ° C or lower, 10.0 g of 2,2,2-trifluoroethanol is added, and the mixture is stirred for 30 minutes. Next, 6.06 ml of p-fluoroacetophenin was added, and stirring was continued for 2.5 hours at 10 ° C. or lower and further for 15 hours at room temperature. The reaction mixture was poured into water, and the organic layer was extracted with ether. It is dried over magnesium sulphate and the ether is distilled off under reduced pressure. The crude product was purified by a silica gel column using a chloroform / ethyl acetate (10/1) mixture as an eluent. The eluate was distilled off under reduced pressure to obtain p- (2,2,2-trifluoroethoxy) acetophenone (p-TFEA) at a yield of 8.54 g and a yield of 77.6%.

Elemental analysis value (%); Theoretical value: C: 55.1, H: 4.2 Actual value: C: 55.1, H: 4.1 IR (cm ^-1 ); 3000-2800,1610, (aromatic ring), 1690 (C =
O), 1280, 1240 (CF ₃ ). NMR (ppm); 2.56 (3H), 4.19 to 4.63 (2H), 6.80 to 7.07
(2H), 7.75 to 8.06 (2H). Reference example 11 P- (2,2,3,3,4, by the same method as in Reference Example 10 except that the fluorinated alcohol was changed to 2,2,3,3,4,4,4-heptafluoro-1-butanol. 4,4-Heptafluorobutoxy) acetophenone (p-HFBA) was obtained with a yield of 50%.

Elemental analysis value (%); Theoretical value: C: 45.3, H: 2.9 Actual value: C: 45.2, H: 2.7 NMR (ppm); 2.53 (3H), 4.33 to 4.72 (2H), 6.83 to 7.11
(2H), 7.8 to 8.07 (2H). Reference Example 12 p- (3,3,3) was prepared in the same manner as in Reference Example 10 except that the fluorinated alcohol was changed to 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexanol. 4,4,5,5,6,6,6-Nonafluorohexaoxy) acetophenone (p-NFHA) was obtained with a yield of 57%.

Elemental analysis value (%); Theoretical value: C: 44.0, H: 2.9 Actual value: C: 43.7, H: 2.7 NMR (ppm); 2.52 (3H), 2.3 to 3.0 (2H), 4.1 to 4.4 (2
H), 6.7 to 7.0 (2H), 7.9 to 8.1 (2H). Reference example 13 To 1.26 g of 50% sodium hydride (oil), 4.76 g of p-hydroxyacetophenone dissolved in 30 ml of HMPA was added dropwise under an argon stream. This was stirred for 20 minutes, and 12.8 g of 2,2,3,3,4,4,4-heptafluorobutyl trifluoromethanesulfonate (TFHB) was dissolved. 10 ml of HMPA was added dropwise.
This was stirred at 140 ° C. for 20 hours, the reaction mixture was poured into ice water, and the organic layer was extracted with ether. After the ether was distilled off under reduced pressure, the crude product was converted into chloroform / ethyl acetate (20
/ 1) Purification was performed by a silica gel column using the mixed solution as an eluent to obtain p-HFPA at a yield of 8.0 g and a yield of 71.8%.

Elemental analysis value (%); Theoretical value: C: 45.3, H: 2.9 Actual value: C: 45.5, H: 2.8 IR (cm ^-1 ); 3000-2800,1610, (aromatic ring), 1690 (C =
O), 1280 to 1160 (C-F). NMR (ppm); 2.54 (3H), 4.33 to 4.71 (2H), 6.78 to 7.09
(2H), 7.78 to 8.04 (2H). Reference Example 14 TFHB with trifluoromethanesulfonic acid 2,2,3,3,4,4,5,5,
P- (2,23,3,4,4,5,5,
6,6,7,7,8,8,8-pentadecafluorooctyloxy)
Acetophenone (p-PFOA) was obtained with a yield of 94%.

Elemental analysis value (%); Theoretical value: C: 37.1, H: 1.8 Actual value: C: 37.2, H: 2.0 NMR (ppm); 2.52 (3H), 4.33 to 4.73 (2H), 6.9 to 7.1 (2
H), 7.87 to 8.1 (2H). Reference example 15 40 ml of ether in which 8.54 g of p-TFEA obtained in Reference Example 10 was dissolved
Was dropped into 40 ml of ether containing 0.52 g of lithium aluminum hydride under an argon stream. 1 at room temperature
After stirring for an hour, 5.8 ml of water was added, and 3m hydrochloric acid 78m was added.
l was added. The organic layer was extracted with ether, the ether was distilled off under reduced pressure, and the crude product was purified on a silica gel column using a chloroform / ethyl acetate (10/1) mixture as an eluent. 92% p- (2,2,2-trifluoroethoxy) phenylmethylcarbinol (p-TFEC)
Got

Elemental analysis value (%); Theoretical value: C: 54.5, H: 5.0 Actual value: C: 54.8, H: 5.2 IR (cm ^-1 ); 3700-3100 (OH), 1610,1510, (aromatic ring), 1
070 (C-O), 1280,1240 (CF 3). NMR (ppm); 1.42 to 4.49 (3H), 1.93 (1H, OH), 4.12 to 4.
46 (2H), 4.67 ~ 4.97 (1H), 6.77 ~ 6.99 (2H), 7.17 ~
7.41 (2H). Reference Example 16 p-2,2,3,3,4,4,4 in the same manner as in Reference Example 15 except that p-TFHA was replaced with p-HFBA obtained in Reference Examples 11 and 13.
-Heptafluorobutoxy) phenylmethylcarbinol (p-HFBC) was obtained at a yield of 75%.

IR (cm ^-1 ); 3700-3100 (OH), 1620, 1520, (aromatic ring), 1
300-1160 (C-F). NMR (ppm); 1.27 to 1.53 (3H), 2.37 (1H), 4.17 to 4.6
(2H), 4.6 ~ 4.92 (1H), 6.7 ~ 6.97 (2H), 7.1 ~ 7.37
(2H). Reference Example 17 p- (2,2,3,3,4,4,5,5,6,6) was prepared in the same manner as in Reference Example 15, except that p-TFEA was replaced with p-PFOA obtained in Reference Example 14. 6,7,7,8,
8,8-Pentadecafluorooctyloxy) phenylmethylcarbinol (p-PFOC) was obtained with a yield of 72%.

NMR (ppm); 1.37 to 1.57 (3H), 1.92 (1H), 4.23 to 4.63
(2H), 4.63 to 4.98 (1H), 6.8 to 7.05 (2H), 7.2 to 7.47
(2H). Reference Example 18 p- (3,3,4,4,5,5,6,6,6- in the same manner as in Reference Example 15 except that p-TFEA was replaced with p-NFHA obtained in Reference Example 12. Nonafluorohexyloxy) phenylmethylcarbinol (p-NFHC) was obtained with a yield of 69%.

NMR (ppm); 1.30 to 1.55 (3H), 2.20 (1H), 2.2 to 2.9 (2
H), 3.8 to 4.2 (2H), 4.52 to 4.85 (1H), 6.75 to 7.0 (2
H), 7.13 to 7.41 (2H). Reference example 19 One drop of 48% aqueous hydrogen bromide was added to 5.7 g of tribromophosphine, and p-TFEC obtained in Reference Example 14 was added thereto under an argon stream.
11 g was added dropwise, and the mixture was stirred at 10 ° C for 1 hour. Then at room temperature 1
After continuing stirring for 5 hours, 20 ml of ice water was added to the reaction mixture, and the organic layer was extracted with ether. After the ether was distilled off under reduced pressure, 12.4 ml of quinoline and a small amount of p-tert-butylcatechol were added, and the mixture was distilled at 120 ° C. and 2 mmHg. After adding dilute hydrochloric acid to the distillate, the organic layer was extracted with ether. The ether was distilled off under reduced pressure, and the crude product was purified by a silica gel column using an n-hexane / ether (2/1) mixture as an eluent to give 3.68 g and 52% yield of p- (2,2,2). -Trifluoroethoxy) styrene (TFES) was obtained.

Elemental analysis value (%); Theoretical value: C: 59.4, H: 4.5 Actual value: C: 59.1, H: 4.4 IR (cm ^-1 ); 3000 to 2800,1610, (aromatic ring), 1615 (CH ₂ = C
H), 1280, 1240 (CF ₃ ). NMR (ppm); 4.12 to 4.47 (2H), 5.03 to 5.73 (2H), 6.43
~ 6.77 (1H), 6.77 ~ 7.00 (2H), 7.17 ~ 7.45 (2H). Reference Example 20 p- (2,2,3,3,4,4,4-heptafluorobutoxy) was prepared in the same manner as in Reference Example 19 except that p-TFEC was replaced with p-HFBC obtained in Reference Example 16. Styrene (HFBS) was obtained with a yield of 36%.

Elemental analysis value (%); Theoretical value: C: 47.7, H: 3.0 Actual value: C: 47.1, H: 3.1 NMR (ppm); 4.2 to 4.6 (2H), 5.03 to 5.27 (1H), 5.47 to
5.75 (1H), 6.47 ~ 6.8 (2H), 6.8 ~ 6.98 (2H), 7.1 ~ 7.
47 (2H). Reference Example 21 p-TFEC stomach p- (2,2,3,3,4,4,5,5,6, by the same method as in Reference Example 19 except that p-PFOC obtained in Reference Example 17 was replaced. 6,7,
7,8,8,8-Pentadecafluorooctyloxy) styrene (PFOS) was obtained in a yield of 26%.

Elemental analysis value (%); Theoretical value: C: 38.3, H: 1.8 Actual value: C: 38.2, H: 1.9 NMR (ppm); 4.23 to 4.65 (2H), 5.03 to 5.29 (1H), 5.45
~ 5.77 (1H), 6.45 ~ 6.77 (1H), 6.77 ~ 7.03 (2H), 7.2
3 to 7.47 (2H). Reference Example 22 p- (3,3,4,4,5,5,6,6,6- was prepared in the same manner as in Reference Example 19 except that p-TFEC was replaced with p-NFHC obtained in Reference Example 18. Nonafluorohexyloxy) styrene (NFHS) yield 30
Earned in%.

Elemental analysis value (%); Theoretical value: C: 45.9, H: 3.0 Actual value: C: 45.7, H: 2.9 NMR (ppm); 2.2-3.0 (2H), 4.0-4.3 (2H), 4.95-5.2
(1H), 5.4 to 5.7 (1H), 6.4 to 6.7 (1H), 6.7 to 6.9 (2
H), 7.2 to 7.45 (2H). Reference example 23 0.78 g of 60% sodium hydride (oil) was added to 80 ml of tetrahydrofuran (THF), and the mixture was stirred under an argon stream.
To this, 7.8 g of 2,2,3,3,4,4,4-heptadecafluoro-1-butanol was added, and the mixture was stirred at room temperature for 15 minutes. Next, after adding 2.91 g of pentafluorostyrene and reacting overnight at room temperature, a large amount of the reaction mixture was poured into water. The organic layer was extracted with ether, washed thoroughly with diluted hydrochloric acid and water, and dried over magnesium sulfate. After distilling off the ether under reduced pressure, the residue was distilled under reduced pressure to give a yield of 3.79 g and a yield of 67.
4- (2,2,3,3,4,4,4-heptafluorobutoxy) at 5%
-2,3,5,6-Tetrafluorostyrene (HFBS) was obtained.

Boiling point; 91-93 ° C / 6.5 mmHg. NMR (ppm); 4.46 ~ 4.83 (2H), 5.57 ~ 6.2 (2H), 6.47 ~
6.87 (1H). Mass Spec; 374 (M ⁺ ), 205 (M ⁺ −CF ₂ CF ₂ CF ₃ ), 191 (M ⁺ −C
F ₂ CF ₂ CF ₂ CF ₃ ). Reference Examples 24 to 26 Fluoroalkyl-substituted styrene derivatives were obtained in the same manner as in Reference Example 23 except that the type of fluorinated alcohol was changed. The compounds of Reference Examples 24 and 25 were purified by silica gel column. The results are shown in Table 2.

Example 1 Synthesis of Copolymer with p-TFES 324 mg and St 625 mg of p-TFES obtained in Reference Example 1 were charged into a glass-made polymerization ampoule so that the molar ratio of p-TFES and styrene (St) was 20/80. THF6.5m
l, 6.2 mg of α, α'-azobisisobutylnitrile (AIBN) was added as a polymerization initiator, degassed by a conventional method, and the tube was sealed under a high vacuum. A copolymerization reaction was performed by shaking this at 60 ° C. for 21 hours. The reaction mixture was poured into a large amount of methanol to precipitate the polymer and yield 188 mg, 19.8%.
To obtain a polymer. As a result of elemental analysis, the p-TFES molar composition of the copolymer was 22.8%, and the molecular weight was 2.7 × 10 ⁴ . The glass transition temperature (Tg) was found to be 83 ° C by DSC measurement.

Examples 2 to 13 A copolymerization reaction between a fluoroalkyl-substituted styrene derivative and styrene was carried out in the same manner as in Example 1. The results are shown in Table 3.

Example 14 m-TFES 247 mg so that the molar ratio of m- (2,2,2-trifluoroethyloxymethyl) styrene (m-TFES) and methyl methacrylate (MMA) obtained in Reference Example 6 was 10/90.
Then, 238 mg of MMA was charged in a glass polymerization ampoule, 3.7 ml of benzene as a solvent and 3.2 mg of AIBN as a polymerization initiator were added thereto, and after degassing by a conventional method, the tube was sealed under a high vacuum. 60 this
The copolymerization reaction was carried out by shaking at 12 ° C for 12 hours. The reaction mixture was poured into a large amount of methanol to precipitate the polymer, and the polymer was obtained at a yield of 121 mg and a yield of 24.9%. As a result of elemental analysis, the molar composition of m-TFES in the copolymer was 6.8%.
And the molecular weight was 3.6 × 10 ⁴ .

Example 15 The molar ratio of p- (1,1,1,3,3,3-hexafluoroisopropyloxymethyl) styrene (p-HFPS) obtained in Reference Example 5 to butyl acrylate (BA) was p-HFPS /. 204 mg of p-HFPS and 215 mg of BA were charged into a glass-made polymerization ampoule so that BA = 30/70, THF4.0 ml as a solvent, and a polymerization initiator
AIBN (2.8 mg) was added and the mixture was degassed by a conventional method and then sealed under high vacuum. A copolymerization reaction was performed by shaking this at 60 ° C. for 4 hours. The reaction mixture was poured into a large amount of methanol to precipitate the polymer, and the polymer was obtained at a yield of 97 mg and a yield of 23.2%. As a result of elemental analysis, the molar composition of p-HFPS was 27.1%, and the molecular weight was 4.3 × 10 ⁴ .

Example 16 m- (2,2,3,3,3-pentafluoropropyloxymethyl) -α-methylstyrene (m-PFPM) obtained in Reference Example 7
S) and acrylonitrile (AN) charge molar ratio is m-PFP
MS-AN = 30/70 m-PFP MS 84 mg and AN 37 mg were charged into a glass polymerization ampoule, N, N-dimethylformamide 1 ml was added as a solvent, and AIBN 0.13 mg was added as a polymerization initiator. The tube was sealed under vacuum. 60 ° C
Then, the copolymerization reaction was carried out by shaking for 10 hours. The reaction mixture was poured into a large amount of methanol to precipitate the polymer, and the polymer was obtained at a yield of 41 mg and a yield of 33.9%. As a result of elemental analysis, the molar composition of m-PFPMS in the copolymer was 23.7%.
And the molecular weight was 7.7 × 10 ⁴ .

Example 17 The charged molar composition ratio of TFES and styrene (St) obtained in Reference Example 19 was 1.05 g and respectively so that TFES / St = 0.8 / 0.2.
0.14 g was charged into a polymerization ampoule, AIBN 5.34 mg and THF 5.3 ml were added thereto, and after deaeration according to a conventional method, the tube was sealed under a high vacuum. A copolymerization reaction was carried out by shaking this at 60 ° C. for 22 hours, and the reaction mixture was poured into a large amount of methanol to precipitate the polymer. This was filtered off and dried in vacuum to obtain a TFES-St copolymer with a yield of 62 mg and a yield of 5.2%. From the elemental analysis value, the TFES mole fraction in the copolymer is 0.80
Met.

Elemental analysis value (%); C; 63.2, H; 5.0 IR (cm ^-1 ); 1600 (aromatic ring), 1280, 1240 (CF ₃ ). Molecular weight: 5.1 × 10 ⁴ (in terms of polystyrene) Examples 18 to 25 Copolymers were synthesized by variously changing the molar composition ratio of the fluoroalkyl-substituted styrene derivatives obtained in Reference Examples 19 to 22 and St. The results are shown in Table 4.

Example 26 The molar ratio of HFBS and styrene (St) obtained in Reference Example 23 was HF.
BFBS1.05g, St0.13g so that BS / St = 0.70 / 0.30
Was charged into a glass ampoule for polymerization, and AIBN3.29mg
Then, 2.8 ml of THF was added and the mixture was degassed according to a conventional method and then sealed under high vacuum. This was shaken at 60 ° C. for 23 hours to carry out a copolymerization reaction. After completion of the reaction, the polymer was precipitated by throwing the mixture in a large amount of methanol. This was separated by filtration, sufficiently washed with methanol and then vacuum dried to obtain an HFBS-St copolymer at a yield of 0.78 g and a yield of 66.8%. The HFBS mole fraction of the copolymer was 0.72 based on the elemental analysis values. The molecular weight was 3.2 × 10 ⁴ (polystyrene conversion).

Elemental analysis value (%); C: 43.8, H: 2.2 IR (cm ^-1 ); 3000 ~ 2800, 1650, 1510 (benzene ring), 1300
~ 1100 (C-F). Examples 27 to 32 Fluoroalkyl-substituted styrene derivative-styrene copolymers were obtained in the same manner as in Example 26, except that the type of fluoroalkyl-substituted styrene derivative and the molar composition charged with styrene were variously changed.

The results are shown in Table 5.

Example 33 Charge HFBS and acrylonitrile (AN) obtained in Reference Example 23 so that the molar composition ratio is HFBS / AN = 0.50 / 0.50.
0.75g, AN0.10g was charged into a polymerization ampoule, and AIBN
3.29 mg and THF 3.2 ml were added. This was degassed and sealed under high vacuum according to a conventional method. This was shaken at 60 ° C. for 33.5 hours to carry out a copolymerization reaction. After completion of the reaction, the polymer was precipitated by throwing the reaction mixture into a large amount of methanol. This was filtered off, washed thoroughly with methanol and then vacuum dried to yield 19 mg and 2.2% of HFB.
An S-AN copolymer was obtained. The HFBS mole fraction in the copolymer was 0.87 by elemental analysis.

Elemental analysis value (%); C: 39.13, H: 1.49, N: 0.59. IR (cm ^-1 ); 3000 ~ 2800, 1650, 1510 (benzene ring), 2200
(C≡N) 1300 to 1100 (C-F). Example 34 HFBS and methyl methacrylate (MMA) obtained in Reference Example 23 were charged, and HFBS 0.75 g and MMA 0.20 g were charged to a polymerization ampoule so that the molar composition ratio would be HFBS / MMA = 0.50 / 0.50,
Further, AIBN 3.29 mg and THF 3.0 ml were added. This was degassed and sealed under high vacuum according to a conventional method. This was shaken at 60 ° C. for 33.5 hours to carry out a copolymerization reaction. After completion of the reaction, the polymer was precipitated by throwing the reaction mixture into a large amount of methanol. This was filtered off, washed thoroughly with methanol, and then vacuum dried to yield 39 mg.
An HFBS-MMA copolymer was obtained at 4.1%. The HFBS mole fraction of the copolymer was 0.61 according to elemental analysis.

Elemental analysis value (%); C: 41.8, H: 2.5, IR (cm ^-1 ); 3000 to 2800, 1650, 1510 (benzene ring), 1740
(C = O) 1300 to 1100 (CF). Reference Example 27 p-chloromethylstyrene (p-CMS), styrene (S
t) in a molar ratio of 50/50 and a total monomer concentration of 3 mol /, 27.5 g and 18.5 g were charged into a glass polymerization ampoule, respectively, and 74 ml of toluene as a diluent and AINBN0 as a polymerization disclosure agent. Further, 0.16 g was placed in the ampoule, sufficiently deaerated according to a conventional method, and then sealed under high vacuum (10 ^-5 mmHg or less). This was shaken at 60 ° C. for 20 hours to carry out a polymerization reaction. The reaction mixture was poured into a large amount of hexane to precipitate the polymer. This was separated by filtration, dissolved in toluene and precipitated again in hexane to purify the p-CMS-St copolymer. Yield 10.
8 g (yield 23.5%). Elemental analysis value (%) is C: 77.8, H: 6.9, C
l: 15.4, and the molar composition ratio of the polymer determined from the Cl content is p
-CMS / St = 57.8 / 42.2. The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is Mw = 1.49 × 10
^{Was 5} .

IR (cm ^-1 ); 2850 ~ 2950 (CH ₂ ), 1600 (benzene ring), 12
50,750 (CH ₂ Cl). Example 35 2.7 g of 2,2,2-trifluoroethanol was dissolved in 20 ml of benzene, 3 ml of 30% aqueous sodium hydroxide solution and 2.4 g of tetra-n-butylammonium bromide were added and stirred.
0.5 g of the p-CMS-St copolymer obtained in Reference Example 27 was added to this solution, and stirring was continued for 3 days at room temperature under light blocking. The reaction mixture was washed with water and then poured into a large amount of methanol to precipitate the polymer. This was separated by filtration and dried to obtain a fluoroalkyl-substituted styrene copolymer. Yield 0.39g
(Yield 77.6%). The trifluoroethoxy group introduction rate determined from elemental analysis was 99%.

Elemental analysis value (%); C: 69.2, H: 5.6 Cl: 0.2 IR (cm ^-1 ); 2850 to 2950 (CH ₂ ), 1600 (benzene ring), 11
50 to 1200 (CF ₂ CF ₃ ). Mw: 1.68 × 10 ^5. Glass transition point (Tg): 56 ° C. (measured by DSC) Example 36 2,2,2-trifluoroethanol was added to 2,2,3,3,4,4,4-hepta A fluoroalkyl-substituted styrene copolymer was obtained in the same manner as in Example 35 except that fluorobutyl alcohol was used instead.

The heptafluorobutoxy group introduction rate determined by NMR was 95.
%Met.

Elemental analysis value (%); C: 59.1, H: 4.5 Cl: 1.2 IR (cm ^-1 ); 2850 to 2950 (CH ₂ ), 1600 (benzene ring), 11
50 to 1200 (CF ₂ CF ₃ ). Mw: 2.23 × 10 ⁵ .Tg: 49 ° C. (measured by DSC) Example 37 A fluoroalkyl-substituted styrene copolymer was obtained in the same manner as in Example 36 except that the reaction time was 1 day.

The introduction rate of heptafluorobutoxy group determined by NMR is 43.
It was 7%.

Elemental analysis value (%); C: 67.2, H: 5.4 Cl: 7.2 IR (cm ^-1 ); 2850 to 2950 (CH ₂ ), 1600 (benzene ring), 11
50 to 1200 (CF ₂ CF ₃ ). 1250,750 (CH ₂ Cl). Mw: 1.71 × 10 ⁵ .Reference Example 28 m-chloromethylstyrene (m-CMS), p-methylstyrene (p-MSt) molar ratio of 50/50, and total monomer concentration of 2mol / 7.6g and 5.9g respectively into a glass polymerization ampoule, and 37 ml of benzene as a diluent.
Further, 0.034 g of AIBN as a polymerization initiator was placed in the ampoule, sufficiently degassed by a conventional method, and then sealed under a high vacuum. This was shaken at 60 ° C. for 10 hours to carry out a polymerization reaction. The reaction mixture was poured into a large amount of diethyl ether to precipitate the polymer. This was filtered off and dried to yield 3.9 g (yield
(28.9%) to obtain an m-CMS-p-MSt copolymer.

The elemental analysis value (%) was C: 77.6, H: 6.7Cl: 15.5, and the molar composition ratio of the polymer determined from the Cl content was m-CMS = p-MSt = 6.
It was 1.0 / 39.0. The Mw was 8.30 × 10 ⁴ .

IR (cm ^-1 ); 2850 ~ 2950 (CH ₂ ), 1600 (benzene ring), 12
50~750 (CH ₂ Cl). Example 38 4.12 g of 2,2,3,3,3-pentafluoropropanol was dissolved in 15 ml of toluene, and 2.7 m of 30% aqueous potassium hydroxide solution was added thereto.
and 2.1 g of tetra-n-butylammonium sulfate were added and stirred. M-CMS-p-M obtained in Reference Example 28 was added to this solution.
10 ml of benzene in which 0.4 g of St copolymer was dissolved was added, and stirring was continued at 60 ° C for 1 day. After thoroughly washing the reaction mixture with water,
Precipitated in diethyl ether. This was separated by filtration and dried to obtain a fluoroalkyl-substituted styrene copolymer. NMR
Introduced rate of pentafluoropropyl group is 100%
Met.

Elemental analysis value (%); C: 33.9, H: 4.9 Cl: 0 IR (cm ^-1 ); 2850 to 2950 (CH ₂ ), 1600 (benzene ring), 11
50 to 1200 (CF ₂ CF ₃ ). Mw: 1.12 × 10 ⁵ , Tg: 51 ° C. Example 39 1,2,3,3,3-pentafluoropropanol was added to 1,1,1,3,3,3
-A fluoroalkyl-substituted styrene copolymer was obtained in the same manner as in Example 38 except that hexafluoro-2-propanol was used instead.

The hexafluoro-2-propyloxy group introduction rate determined by NMR was 53.1%.

Elemental analysis value (%); C: 54.4, H: 5.7 Cl: 8.2 IR (cm ^-1 ); 2850 to 2950 (CH ₂ ), 1600 (benzene ring), 11
50 to 1250,750 (CH ₂ Cl) .. Mw: 9.73 × 10 ⁴ , Tg: 81 ° C. Reference Example 29 p-Bromomethylstyrene (p-BMS) and n-octyl vinyl ether (OVE) at a molar ratio of 70 / 30, and 20.7g and 7.7g were charged to a glass polymerization ampoule so that the total concentration of the monomers would be 3mol /, and then toluene 22ml and AI.
0.04 g of BN was added and the tube was sealed under high vacuum. This was shaken at 60 ° C. for 7 hours to carry out a reaction. The reaction mixture was poured into diethyl ether to precipitate the polymer. This was separated by filtration and dried to obtain p-BMS- with a yield of 4.35 g (15.3% yield).
An OVE copolymer was obtained. Elemental analysis value (%) is C: 59.8, H: 6.5,
It was Br: 27.8, and the molar composition ratio of the polymer determined from the Br content was p-BMS / OVE = 65.3 / 34.7. Also Mw = 7.21 x 10
^{Was 4} .

IR (cm ^-1 ); 2850-3000 (CH ₂ CH ₃ ), 1600 (benzene ring), 1200 (CH ₂ Br). Example 40 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentafluorodecafluoro-1-octanol 8.0 g was dissolved in toluene 20 ml, To this, 3 ml of 30% aqueous sodium hydroxide solution and 3.0 g of tetra-n-butylammonium iodide were added and stirred.
This solution was obtained in Reference Example 29. 0.3g of p-BMS-OVE copolymer
Was added and stirring was continued at 80 ° C for 1 day. The reaction mixture was washed with water and then poured into diethyl ether to precipitate the polymer.
This was separated by filtration and dried to obtain a fluoroalkyl-substituted styrene copolymer. The introduction rate of pentadecafluorooctyloxy group determined by NMR was 99%.

Elemental analysis value (%); C: 44.2, H: 3.4 Br: 0 IR (cm ^-1 ); 2850 to 2950 (CH ₂ CH ₃ ), 1600 (benzene ring), 1150 to 1200 (CH ₂ Br). Mw: 1.24 × 10 ⁵ , Tg: −20 ° C. Reference Example 30 p- (2-chloroethyl) styrene (p-CES), p−
Ethylstyrene (BSt) was charged into a glass polymerization ampoule with 10.0 g and 3.2 g, respectively, so that the molar ratio was 70/30 and the total monomer concentration was 2 mol /, and toluene 36.8 ml and AI
BN 0.04 g was added and the tube was sealed under vacuum. 5 at 60 ℃
The polymerization reaction was carried out by shaking for a period of time. The reaction mixture was poured into a mixture of n-hexane / diethyl ether (3: 1) to precipitate the polymer. This is filtered off and dried to yield 4.
A p-CES-ESt copolymer was obtained with 11 g (yield 31.1%). The elemental analysis values (%) were C: 73.8, H: 8.7, and Cl: 9.8. The polymer molar composition ratio calculated from the Cl content was p-CES / ESt = 64.1 / 3.
It was 5.9. Further, it was Mw = 1.21 × 10 ⁵ .

IR (cm ^-1 ); 2800-3000 (CH ₂ CH ₃ ), 1600 (benzene ring), 1200 (CH ₂ Br). Reference Example 41 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-1-octanol 7.1 g dissolved in fully dehydrated THF 18 ml Then, 0.4 g of sodium was added thereto. Gas is generated,
Stir slowly until the sodium is completely dissolved.
P-CES-ESt copolymer obtained in Reference Example 30 in this solution 3.
A solution of 5 g dissolved in 10 ml of THF was added, and stirring was continued at room temperature for 2 days. The reaction mixture was poured into a large amount of water, and the obtained precipitate was filtered and dissolved in THF again. This was poured into methanol to purify the polymer. The pentadecafluorooctyloxy group introduction ratio determined by NMR was 100%.

Elemental analysis value (%); C: 43.6, H: 3.5 Cl: 0 IR (cm ^-1 ); 2850 to 2900 (CH ₂ CH ₃ ), 1605 (benzene ring), 1150 to 1200 (CF ₂ CF ₃ ). Mw: 1.31 × 10 ⁵ , Tg: 4 ° C Example 42 183 mg of 60% sodium hydride (oily) and 2 in 15 ml of THF,
1.35 g of 2,3,3,3-pentafluoro-1-propanol was dissolved and stirred under an argon stream for 20 minutes. To this, 30 ml of THF containing 994 mg of pentafluorostyrene-styrene copolymer (pentafluorostyrene mole fraction 0.463) was added.
Stir at room temperature for days. The reaction mixture was poured into a large amount of methanol to precipitate the polymer. This was filtered off and dried under vacuum to give 4- (2,2,3,3,3-pentafluorooxy) -2,3,5,6-tetrafluorostyrene- with a yield of 604 mg.
A styrene copolymer was obtained.

Elemental analysis value (%) Theoretical value: C; 54.7, H; 2.9 Actual value: C; 54.7, H; 2.9 Example 43 1.96 g and 0.02 g of the fluoroalkyl-substituted styrene derivative (DFOS) obtained in Reference Example 4 and N-methyl roll-N-acrylamide were charged into a polymerization ampoule so that the molar composition ratio was 0.95: 0.05. BPO (10 mg), Freon 113 (5 ml) and ethanol (1 ml) were added, and the mixture was degassed according to a conventional method and then sealed under a high vacuum. This was shaken at 60 ° C. for 20 hours to carry out a copolymerization reaction, and the reaction mixture was poured into a large amount of methanol to precipitate the polymer.
This was separated by filtration and vacuum dried to obtain a copolymer with a yield of 58%. The DFOS mole fraction in the copolymer was 0.96 based on the elemental analysis values.

Elemental analysis value (%): C; 39.63 C; 2.21 N; 0.11 IR (cm ^-1 ): 1730 (C = O), 1240,1210, (CF ₃ ), 1150
(-O-). Molecular weight: 3.2 × 10 ⁴ (polystyrene conversion) Example 44 Styrene derivative (DFOS) obtained in Reference Example 4 and N- (1,1-
The charge molar ratio of dimethyl-3-oxobutyl) acrylamide was 1.96 g and 0.034 g, respectively, so that the molar ratio was 0.95: 0.05.
To a polymerization ampoule and use 10 mg of BPO as a polymerization initiator.
And as a solvent, Freon 113 (5 ml) and ethanol (1 m
l) was added and degassed according to the usual method, and the tube was sealed under high vacuum (10 ^-5 mmHg or less). This was shaken at 60 ° C. for 20 hours to carry out a polymerization reaction. The copolymer was precipitated by pouring the reaction mixture into a large amount of methanol, which was filtered off and dried under vacuum. Yield 820 mg Yield 41% Elemental analysis value (%): C; 39.98 H; 2.28 N; 0.11 From this, it was confirmed that the DFOS mole fraction in the copolymer was 0.96.

Molecular weight: 2.8 × 10 ⁴ (in terms of polystyrene) Test Example 1 (Evaluation of water repellency and oil repellency) A 0.5 wt% THF solution of the fluoroalkyl-substituted styrene copolymer obtained in Examples 1 to 16 was prepared, and this solution was prepared. Was cast onto a glass plate. The mixture was kept at 40 ° C. for 24 hours, THF was distilled off, and then vacuum dried for 2 days. The contact angle of water and n-octane on the surface of the obtained glass plate was measured with a contact angle goniometer (manufactured by Kyowa Kagaku). The results are shown in Table 6.
For comparison, the results of measuring the contact angles of droplets on the surfaces of polystyrene and polydimethylsiloxane
The results are shown in Table 6 as Comparative Example 1 and Comparative Example 2, respectively.

Test Example 2 (Evaluation of water repellency and oil repellency) The pure water and n-octane contact angles of the surfaces of the fluoroalkyl-substituted styrene and styrene copolymers obtained in Examples 17 to 25 were measured in the same manner as in Test Example 1. It was measured by. The results are shown in Table 7.

Test Example 3 (Evaluation of water repellency and oil repellency) The droplet contact angle on the surface of the fluoroalkyl-substituted styrene copolymer obtained in Examples 26 to 32 was measured by the same method as in Test Example 1.

The results are shown in Table 8.

Test Example 4 (Evaluation of water repellency and oil repellency) A 0.5 wt% THF solution of the fluoroalkyl-substituted styrene copolymer obtained in Examples 35 to 41 was prepared, and this solution was cast on a glass plate. The mixture was kept at 40 ° C. for 24 hours, THF was distilled off, and then vacuum dried for 2 days. The contact angle of water and methylene iodide on the surface of the obtained glass plate was measured with a contact angle goniometer (manufactured by Kyowa Kagaku). The results are shown in Table 9. For comparison, the results of measuring the contact angles of liquid drops on the surfaces of polystyrene and polymethylmethacrylate are shown in Table 9 as Comparative Example 3 and Comparative Example 4, respectively.

Test Example 5 (Evaluation of Light Transmittance) (i) 0.5 wt% THF solution of the fluoroalkyl-substituted styrene copolymer obtained in Examples 1, 12, 13 and 15 was cast onto a quartz plate and co-loaded onto the surface. The coalescence was coated. The light transmittance of this quartz plate was measured by a spectrometer (UV240 manufactured by Shimadzu Corporation). The results are shown in Table 1. The copolymer obtained in Example 12 is also shown in FIG.

(Ii) Further, the quartz plate coated with the copolymer obtained in Example 12 in the same manner as in the above (i) was immersed in a 10 wt% sodium hydroxide aqueous solution at 60 ° C. for 7 days to be subjected to an alkali treatment. The permeability is shown in FIG.

(Iii) Further, as Comparative Example 5, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10, which is known as a conventional glass coating agent
-Light transmittance of a quartz plate coated with 0.5% by weight of a styrene copolymer (HdFDA-St) containing 76 mol% of heptadecafluorodecyl acrylate on the surface in the same manner as in (i) above. Also, FIG. 2 shows the light transmittance when the polymer was treated with alkali in the same manner as in (ii) above.
However, when measuring the light transmittance, a quartz plate having the same shape as the above was used without coating the polymer on the reference side.

〔The invention's effect〕

The fluoroalkyl-substituted styrene copolymer of the present invention has high water repellency, oil repellency, and extremely high light transmittance.
Further, since it is soluble in an organic solvent, a thin film coating can be easily performed by applying the polymer liquid on the glass surface, etc., and antifouling treatment and antireflection treatment are possible.

Furthermore, since it is chemically stable as compared with known fluorine-containing acrylic acid ester or fluorine-containing methacrylic acid ester, for example, even when the glass surface coated with the copolymer is contacted with an alkaline solution for a long time, Also, the antifouling property and the light transmitting property can be maintained without eroding the glass surface.

[Brief description of drawings]

FIG. 1 shows the light transmittance of the fluoroalkyl-substituted styrene copolymers obtained in Examples 1, 12, 13 and 15. FIG. 2 shows the light transmission properties of the fluoroalkyl-substituted styrene copolymer obtained in Example 12, the alkali-treated copolymer, the HdFDA-St copolymer, and the alkali-treated copolymer. . However, each of the polymers was a quartz plate coated. 1. The copolymer obtained in Example 1. The copolymer obtained in Example 12. The copolymer obtained in Example 13. The copolymer obtained in Example 15. Polymer 5 ....... Alkali-treated copolymer obtained in Example 6. HdFDA-St copolymer 7 ....... HdFDA-St copolymer alkali-treated

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C08F 220/10 MLZ 220/42 MMY 220/52 MND

Claims (2)

[Claims] 1. A general formula (In the formula, R ¹ represents a hydrogen atom or a lower alkyl group,
R ² represents a hydrogen atom or a lower polyfluoroalkyl group, R ³ represents a polyfluoroalkyl group, Y ^{1 to} Y ⁴ each represent a hydrogen atom or a halogen atom, and n represents 0 or 1
Is an integer. ) And the general formula [In the formula, R ⁶ represents a hydrogen atom or a lower alkyl group,
Z is an unsubstituted or lower alkyl group, a lower haloalkyl group, a lower alkyloxy group, or a phenyl group substituted with a halogen atom, a hydrogen atom, a lower alkyl group,
An alkyloxy group, a cyano group, a group represented by -COOR ⁷ , or A group represented by (provided that R ⁷ and R ⁸ are a hydrogen atom or a carbon number 1 to
15 represents an alkyl group, a phenyl group or a cycloalkyl group, and R ⁹ represents a hydrogen atom or a lower alkyl group. )
Represents ] The composition of the repeating unit represented by the general formula (I) is 1 mol% to 99 mol%
A fluoroalkyl-substituted styrene copolymer having a molecular weight of 1000 or more. 2. A fluoroalkyl-substituted styrene copolymer according to claim 1, wherein the composition of the repeating unit represented by the general formula (I) is in the range of 5 mol% to 99 mol%.