TW201207029A - Curable resin composition, cured material and fluorinated polymer - Google Patents

Abstract

Disclosed is a curable resin composition that is easy to produce and in which the cross-link density can be easily adjusted. Specifically disclosed is a curable resin composition formed from a fluorinated polymer (A) and a hydrosilylated cross-linking agent (B). The curable resin composition is characterized in that the fluorinated polymer (A) is formed from a polymerization unit originating in a fluorinated monomer and a polymerization unit originating in a norbornene monomer having two or more carbon-carbon double bonds. The hydrosilylated cross-linking agent (B) is a siloxane compound having two or more groups where a hydrogen atom is directly bonded to a silicon atom in the molecule.

Description

201207029 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a curable resin composition, a cured product, and a fluorine-containing polymer. More specifically, the curable resin composition which is cured by a hydrogenation reaction, the cured product obtained by curing the curable resin composition, and the fluorine-containing polymer which is suitable for the curable resin composition. [Prior Art] A curable resin composition containing a fluoropolymer, for example, a composition formed of a curable fluorine-containing polymer having an ethylenic carbon-carbon double bond at a side chain side as proposed in Patent Document 1 is used. Patent Document 2 discloses a curable composition containing a specific fluorine-containing guanamine compound having a vinyl group at both terminals and a specific fluorine-containing organohydrogen siloxane and a catalytic amount of an aromatic compound. [Patent Document 1] [Patent Document 1] International Publication No. 02/1 8457 [Patent Document 2] Japanese Laid-Open Patent Publication No. Hei No. Hei 8- No. Hei. The crosslinking reaction disclosed in Patent Document 1 is a photohardening reaction, which does not reveal a curing system which does not pass through a sand hydrogenation reaction. Further, the curable fluorine-containing polymer is formed of a chain monomer having a specific structure. 201207029 The fluorine-containing guanamine compound described in Patent Document 2, which is obtained by introducing a carbon-carbon double bond into a terminal after the production of a polymer, has no improvement in the portion in which the amount of crosslinking cannot be easily adjusted. SUMMARY OF THE INVENTION An object of the present invention is to provide a curable resin composition which is easy to manufacture and which is easy to adjust the crosslinking density. [Means for Solving the Problem] The present invention is a curable resin composition comprising a fluoropolymer (A) and a hydrazine hydrogenation crosslinking agent (B), characterized in that the fluoropolymer (A) is fluorine-containing. a polymerization unit formed by a monomer, and a fluoropolymer formed by a polymerization unit formed by a norbornene monomer having two or more carbon-carbon double bonds, and a ruthenium hydrogenation crosslinking agent (B) is intramolecular. A curable resin composition having a siloxane compound in which two or more hydrogen atoms are directly bonded to a ruthenium atom. The present invention is also a cured product obtained by curing the above curable resin composition. The present invention is also a perfluorocarbon represented by tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CFpCF-ORf1 (wherein, Rf1 represents a perfluoroalkyl group having 1 to 8 carbon atoms) a polymerization unit formed by at least one fluorine-containing ethylenic monomer selected from the group consisting of (alkyl vinyl ether), and the following formula (a): -6-201207029 [Chemical Formula 1]

(wherein R1 is a hydrogen atom or may contain a carbon number of 1 to 1 group; R2 is a hydrogen atom or an ice-forming polymerization unit having two or more carbon-carbon double bonds represented by oxygen having a carbon number of 1 to 10; A fluoropolymer formed as a feature. The present invention is also a perfluoro(alkane) represented by tetrafluoroethylene, vinylidene fluoride hexafluoropropylene, and CFeCF-ORf1 (wherein, a perfluoroalkyl group of Rf1) The following formula (b) produced by at least one fluorine-containing ethylenic monomer derived from a vinyl ether: [Chemical 2]

(wherein R3 is a hydrogen atom or may have a carbon number of 1 to 5; R4 is a hydrogen atom or an oxygen atom which may have a carbon number of 1 to 1 Torr is a hydrogen atom or may have an oxygen atom having 1 to 5 carbon atoms; a hydrocarbon group of a hydrocarbon atom having an oxygen atom of hail, which has two or more carbon-carbon double bonds, a sulfonate monomer, and a chlorotrifluoroethylene (carbon number: 1 to 8) a polymerization unit, and (b) a hydrocarbon group of a hydrocarbon atom of an oxygen atom; R5; a group; η is a fluoropolymer characterized by a polymerization unit of 201207029 formed by a monomer of a olefin. Also known as tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CFz^CF-ORf1 (wherein, Rf1 represents a perfluoroalkyl group having 1 to 8 carbon atoms) a polymerization unit formed by at least one fluorine-containing ethylenic monomer selected from the group consisting of (alkyl vinyl ether) and 'the following formula (c):

(wherein R6 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 5 carbon atoms), and a polymerization unit formed of a norbornene monomer having two or more carbon-carbon double bonds is characterized by Fluoropolymer. [Effects of the Invention] The curable resin composition of the present invention can be easily adjusted by including a polymer in which a norbornene monomer having two or more carbon-carbon double bonds is polymerized and introduced into a crosslinking site. The amount of the crosslinked portion is also easy to manufacture. Further, a cured product having a high crosslinking density can be obtained. Further, since it can be produced without a solvent, it is not necessary to have a step of removing the solvent from the obtained carbide. -8 - 201207029 The cured product of the present invention is highly transparent because it is obtained by hardening the above curable resin composition, and can be easily and economically produced. Further, the fluoropolymer of the present invention can be suitably used because it has an easy-to-manufacture, easy adjustment of the amount of the crosslinking site, and is easily dissolved or dispersed in the ruthenium hydrogenation crosslinking agent. The above curable resin composition. [Embodiment of the Invention] The curable resin composition of the present invention is a polymerization unit (hereinafter referred to as "fluorinated monomer unit") formed of (A) a fluorine-containing monomer, and has two or more carbons. a fluoropolymer formed of a polymerization unit (hereinafter, also referred to as "norbornene monomer unit") formed by a norbornene monomer having a carbon double bond, and a (B) hydrazine hydrogenation crosslinking agent. Since the curable resin composition of the present invention is formed of a fluorine-containing polymer (A) containing a fluorine-containing monomer unit, the obtained cured product has excellent refractive index or transparency in the ultraviolet to near-infrared region. Optical properties, light resistance, weather resistance, heat resistance, water absorption, water and oil repellency, and drug resistance. The crosslinking reaction of the curable resin composition of the present invention is not a reaction of generating a dissociated component such as water or a salt, and is an additional reaction, so that the step of removing by-products is not required. Further, when a hydrogenation crosslinking agent is appropriately selected, 'a composition having a specific viscosity can be produced even without using a solvent, and crosslinking (hardening) can be easily carried out. Further, it is also not necessary to remove the solvent from the obtained cured product -9 - 201207029. Further, since it can be produced without using a solvent, the transparency of the obtained cured product can be improved. In the curable resin composition of the present invention, since the norbornene monomer unit has a carbon-carbon double bond (crosslinking site), the step of introducing the crosslinked portion in the fluoropolymer is not required, and the production step can be performed. Simplified. Further, since the amount of the crosslinking portion can be easily adjusted, a molded article having a high crosslinking density can be obtained. In addition, when compared with the fluorine-based sealing material described in the publication of the International Publication No. 2005/085 3 03 and International Publication No. 2009/096 3 42 , it is practical because it can be manufactured at low cost. (A) The fluoropolymer fluoropolymer (A) is a polymerization unit formed of a fluorinated monomer, and a polymerization unit formed by a norbornene monomer having two or more carbon-carbon double bonds. . Since the fluoropolymer (A) is a polymer having a cross-linking site, the amount of the cross-linking portion can be easily adjusted when the fluoropolymer (A) is produced. Further, the fluoropolymer (A) is more surprising in that it can be dissolved or dispersed in the sand gasification crosslinking agent, so that the curable resin composition of the present invention does not require the use of a solvent. The amount of the cross-linking site (carbon-carbon double bond) can be easily adjusted depending on the type of the norbornene monomer and the ratio of the norbornene monomer relative to the total monomer amount. The presence or absence of a crosslinking site in the fluoropolymer (A) can be confirmed, for example, by using 1 Η - N M R . A borneol monomer having two or more carbon-carbon double bonds is a single one having a carbon-carbon double bond in a portion other than the skeleton of the borneol. body. The norbornene monomer is preferably a norbornene monomer having two carbon-carbon double bonds. The norbornene monomer may be a fluorine atom or a fluorine atom, and it is preferred that the norbornene monomer has no fluorine atom. The norbornene monomer ' is preferably, for example, a monomer having a norbornene skeleton and a group having one or more carbon-carbon double bonds, and/or a dicyclopentadiene skeleton. The above norbornene skeleton is represented by the following formula: [Chemical 4]

The carbon skeleton represented. The above dicyclopentadiene skeleton is represented by the following formula:

The carbon skeleton represented. In the case where the norbornene monomer is a monomer having a group having one or more carbon-carbon double bonds, the norbornene monomer may have one group having one or more carbon-carbon double bonds, or have 2 More than one can be. It is better to have a norbornene skeleton and a base with more than one carbon-carbon double bond with -11 - 201207029 to have a norbornene skeleton and a carbon The basis of the carbon double bond is better. a group having one or more carbon-carbon double bonds, for example, an alkenyl group such as a vinyl group, a propyl group, an isopropanyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptyl group, an octenyl group; An alkenyl group-containing aryl group such as a vinylphenyl group or an isopropenylphenyl group: an alkenyl group-containing aralkyl group such as a vinyl phenylmethyl group; an alkylene group such as an ethylene group: and the like. a group having one or more carbon-carbon double bonds, for example, at least one selected from the group consisting of an alkenyl group, an alkenyl group-containing aryl group, an alkenyl group-containing aralkyl group, and an alkylene group It is better. More preferably, it is an alkenyl group, and/or an alkylene group; and a group having two or more carbon-carbon double bonds, for example, a compound such as KARENZU BEI manufactured by Showa Denko Co., Ltd., and a norbornene monomer having an OH group. Two groups of two or more carbon-carbon double bonds introduced in the reaction are introduced. The above norbornene monomer, for example, the following formula (a):

(wherein R1 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 10 carbon atoms: R2 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 10 carbon atoms), and has two or more carbon-carbons A double bond of norbornene monomer is preferred. It is more preferable that R1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R2 is a hydrogen atom or carbon -12-201207029 The alkyl group of 1 to 5 is more preferably. R1, specifically, for example, a hydrogen atom; methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, sec. butyl, t-butyl, η-pentyl, isoprene Base, t-pentyl, neopentyl, hexyl, isohexyl, heptyl, octyl, decyl, decyl and the like. R1 is preferably a methyl group. R2 is the same as R1. R2 is preferably a hydrogen atom. Further, in the present specification, the "hydrocarbon group which may contain an oxygen atom" is preferably an alkyl group, an alkenyl group, an alkyl ether group or an alkenyl group. The norbornene monomer represented by the above formula (a) is, for example, the following formula (1)

(In the formula, R7 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), and a norbornene monomer having two carbon-carbon double bonds is preferred. R7 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and preferably a methyl group. The above norbornene monomer, for example, the following formula (b):

—C—CH—R 5 (wherein R 3 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 5 carbon atoms; R 4 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom having 1 to 10 carbon atoms; R 5 —13- 201207029 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom having 1 to 5 carbon atoms; η is an integer of 0 to 10), and a norbornene monomer having two or more carbon-carbon double bonds is also preferable. R3 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R4 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R5 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and preferably a hydrogen atom. η is preferably an integer of 0 to 5, and preferably 0 or 1. The norbornene monomer represented by the above formula (b), for example, the following formula (2)

(In the formula, R8 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), and a norbornene monomer having two carbon-carbon double bonds is preferred. R8 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and preferably a hydrogen atom. a norbornene monomer represented by the above formula (a) or (b), for example, 5-methyl-2-norbornene, 5-vinyl-2-norbornene 5-(2-propane burn) )-2-norbornene, 5-(3-butenyl)-2-norbornene, 5_(丨_methyl-2-propene)_2-norbornene, 5-(4-pentenyl)- 2-norborn, 5-(1-methyl-3-butenyl)-2-norbornene, 5-(5-hexenyl)_2_norbornene, 5-(1-methyl-4 -pentenyl)-2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, 5-(2-ethyl-3-butenyl)-2 -norbornene, 5-(6-heptene)-2_norbornene, %(3-methyl·5_hex-14- 201207029 alkenyl)-2-norbornene, 5-(3,4 -dimethyl-4-pentenyl)-2-norbornene, 5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2- Norbornene, 5-(2-methyl-6-heptene)·2-norbornene, 5-( 1,2-dimethyl-5-hexenyl)-2-norbornene, 5_( 5-ethyl-5-hexenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, 5-ethylene- 2-norbornene, 5-isopropylidene-2-norbornene, 2,3 - Isopropylidene-5-norbornene, 2-ethyl-3-isopropylidene-5-norbornene and the like. These norbornene monomers may be used singly or in combination of two or more. The above norbornene monomer, for example, the following formula (c): [Chemical 1 〇]

(In the formula, R6 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 5 carbon atoms), and a norbornene monomer having two or more carbon-carbon double bonds is also preferable. The norbornene monomer represented by the above formula (c) is, for example, the following formula: -15- (3) 201207029 [Chemical Formula 1]

The norbornene monomer having two carbon-carbon double bonds is a preferred norbornene monomer, and is easily dissolved or dispersed in the viewpoint of hydrazine cross-linking B) by using the formula (a). Preferably, the norbornene monomer represented by the norbornene monomer (b) and at least one monomer selected from the group consisting of the olefin monomers represented by the formula (c) are preferred. More preferably, the norbornene monomer represented by the formula (1), the olefin monomer represented by the formula (2), and at least one selected from the norbornene monomers represented by the formula (3) monomer. More preferably, it is a olefin-reducing monomer represented by the formula (1). The fluorine-containing monomer in the present invention is a monomer having a fluorine atom which is compatible with the above-mentioned norbornene monomer. The above fluorine-containing monomer is preferably one which does not have an ice-reducing skeleton. More preferably, it is a monomer having no norbornene skeleton and having a carbon double bond. The above fluorine-containing monomer is, for example, tetrafluoroethylene [TFE], meta-diene [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropyl HFP], hexafluoroisobutylene, CHpCZUCF^jy (wherein Or F, Z2 is H, F or Cl, and η1 is an integer of 1 to 1 )), CFzsCF-ORf1 (wherein Rf1 represents a perfluorocarbon represented by a perfluorocarbon number of 1 to 8 carbon atoms) (vinyl alcohol ether) [PAVE], and, CF2 agent (, type of ice-falling, borneol bornerene-fluorofluoroethylene in the ice group [Η 单体 monomer group] = CF- -16- 201207029 OCH2-Rf2 (form In the above, Rf2 is preferably a fluorine-containing ethylenic monomer selected from the group consisting of alkyl perfluorovinyl ether derivatives represented by a perfluoroalkyl ether having 1 to 5 carbon atoms. Perfluoro(methyl vinyl ether) [PMVE], perfluoro(ethyl vinyl ether) [PEVE], perfluoro(propyl vinyl ether) [PPVE], perfluoro(butyl vinyl ether), etc., among which PMVE Further, PEVE or PP VE is more preferable. The above alkyl perfluorovinyl ether derivative is preferably a perfluoroalkyl group having Rf2 of 1 to 3 carbon atoms, more preferably CF2 = CF-OCH2-CF2CF3.

The above fluorine-containing monomer is preferably TFE and/or CTFE, and more preferably TFE. The fluoropolymer (A) may be a norbornene monomer unit formed from a fluorinated monomer unit and a norbornene monomer having two or more carbon-carbon double bonds, and may be combined with the above fluorine A monomer unit formed by a monomer and another monomer copolymerized with a norbornene monomer having two or more carbon-carbon double bonds may be formed. The other monomer described above is a monomer having no fluorine atom. The above other monomers are preferably a halogenated vinyl monomer other than the norbornene monomer having two or more carbon-carbon double bonds. The other monomers mentioned above, for example, ethylene, propylene, 1-butene, 2-butene, vinyl chloride, ethylene chloride, alkyl vinyl ether, hydroxyl group-containing vinyl ether monomer, vinyl ester monomer Preferably, the unsaturated carboxylic acid and the at least one selected from the group consisting of norbornene monomers having one carbon-carbon double bond are fluorine-free ethylenic monomers. The above alkyl vinyl ether is, for example, methyl vinyl ether or ethyl vinyl ether. A hydroxyl group-containing vinyl ether monomer such as 4-hydroxybutylethyl-7-201207029 olefin ether, 2-hydroxyethyl vinyl ether or the like. The vinyl ester monomer is, for example, ethyl t-acetate, vinyl lauric acid, vinyl stearate, vinyl cyclohexylcarboxylate, vinyl acetate or the like. Among other monomers, it is preferable to use a norbornene monomer having one carbon-carbon double bond. The norbornene monomer having one carbon-carbon double bond is a monomer having a norbornene skeleton and a norbornene skeleton and having no carbon-carbon double bond. a norbornene monomer having one carbon-carbon double bond, for example, by the following formula [Chemical Formula 1 2]

(wherein R14 is an alkyl group having 1 to 10 carbon atoms. X is an integer of 〇~2) Preferably, the norbornene monomer is represented by the following formula: [Chemical Formula 1]

The norbornene monomer shown is preferred. The unsaturated carboxylic acid preferably has at least one copolymerizable carbon-carbon double bond in one molecule, and preferably has at least one carbonyloxy group [-c(=o)-o-] in one molecule. It may be an aliphatic unsaturated monocarboxylic acid or an aliphatic unsaturated polycarboxylic acid having two or more carboxyl groups. The above aliphatic unsaturated carboxylic acid is composed of (meth)acrylic acid, croton -18-201207029 acid, maleic acid, maleic anhydride, fumaric acid, isaconic acid, isaconic anhydride, miconic acid, and micotinic anhydride. At least one selected from the group consisting of mesaconic acid and aconitic acid is preferred. In the fluoropolymer (A), the molar ratio of the fluorinated monomer unit to the norbornene monomer unit is 90: 10 〜1 〇: 90 is preferable, and more preferably 70: 30 〜 3 0 : 7 0 In the fluorinated polymer (A), the total of the fluorinated monomer unit and the norbornene monomer unit is preferably 3 〇 mol% or more based on the total polymerization unit. More preferably 50% by mole or more. In the fluoropolymer (A), the above other monomer units are preferably 70 mol% or less based on the total monomer unit. More preferably 50% by mole or less. The number average molecular weight of the fluoropolymer (A) is not particularly limited, and from the viewpoint of solubility or dispersibility of the hydrazine hydrogenation crosslinking agent (B) or the solvent (D), it is preferably from 1,000 to 1,000,000 to 1,000. ~500000 is preferred. The fluoropolymer (A) preferably has a glass transition temperature of from 3 Å to 200 ° C and preferably from 45 to 150 ° C. From the viewpoint of obtaining a cured product having a uniform crosslinking density with the fluoropolymer (A), it is preferred to use an intermediate copolymer of the above fluorine-containing monomer and a norbornene monomer. Among these cross-linking copolymers, since the monomer composition ratio in the polymerization is about 1:1, it is suitable for production. The fluoropolymer (A) can be produced by a method such as solution polymerization, suspension polymerization or emulsion polymerization. In the above polymerization, a polymerization initiator, a surfactant, a chain transfer agent, and a solvent can be used, and -19-201207029 can be used as a conventionally known material. As the above polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical initiator can be used. The oil-soluble radical polymerization initiator may be, for example, a known oil-soluble peroxide, such as diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, or di-sec-butyl. Dialkyl peroxycarbonates such as oxydicarbonate, peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxyvalerate, di-t-butyl peroxidation Dialkyl peroxides, etc., and further, bis(ω-hydro-dodecylheptyl) peroxide, bis(ω-hydro-tetradecafluoroheptyl) peroxide, and di(ω) -hydrogen-hexadecafluoroindenyl) peroxide, bis(perfluorobutylidene) peroxide, bis(perfluoropentenyl) peroxide, bis(perfluorohexyl) peroxide, two ( Perfluoroheptyl) peroxide, bis(perfluorooctyl) peroxide, bis(perfluorodecyl) peroxide, bis(ω-chlorohexafluorobutylidene) peroxide, di(ω) -Chloro-decafluorohexyl) peroxide, bis(ω-chloro-tetradecyl octyl) peroxide, ω-hydro-dodecylheptyl-ω-hydrogen-hexadecafluoroantimony- Peroxide, chlorine - six gas butyl base - chlorine - ten gas Peroxide, ω-hydrogen-dodecylheptyl-perfluorobutanyl-peroxide, bis(dichloropentafluorobutenyl) peroxide, bis(trichlorononafluorohexyl) peroxide , bis(tetrachloroundecylfluorenyl) peroxide, bis(pentachlorotetradecyl) peroxide, di-chlorotrioxane 22 oxime) peroxide [perfluoro (or fluorochloro)indolyl peroxides and the like are representative materials. The water-soluble radical polymerization initiator may be any known water-soluble peroxide, for example, persulfate, perboric acid, perchloric acid, perphosphoric acid, ammonium salt such as -20-201207029 carbonic acid, potassium salt, sodium Salt, t-butyl maleate, t-butyl peroxide, and the like. The reducing agent such as a sulfate or a sulfonium sulfate may be used in combination with a peroxide, and the amount thereof may be 0.1 to 20 times the amount of the peroxide. A well-known surfactant can be used for the surfactant, and for example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, or the like can be used. Among them, a fluorine-containing anionic surfactant is preferred. 'An ether-bonded oxygen atom may be (that is, an oxygen atom may be intercalated between carbon atoms). A fluorine-containing anion having a linear or branched carbon number of 4 to 20 The surfactant is more preferred. The amount added (for the polymerization water) is preferably 50 to 5000 ppm. In solution polymerization, a polymer which is polymerized in a solvent obtained by dissolving a reactive monomer may be dissolved in a solvent or may be precipitated. The solvent for solution polymerization, for example, CF3CH2CF2CH3, cf3chfchfcf2cf3, the following formula: Compounds represented by CF2CF2CF2CFHCH2, CHF2CH3CF3, CF3CF2CHC12, CC1F2CF2CHC1F, CF3CF2CF2CF2OCH3, CF3CF2CF2CF2OCH2CH3, CHF2CF2OCH2CF3 and other fluorocarbon solvents such as octane, An aliphatic hydrocarbon such as an alkane, a ketone such as acetone or methyl isobutyl ketone, an ester such as ethyl acetate, an aromatic hydrocarbon such as xylene or toluene, a chlorocarbon such as chloroform or an alcohol such as t-butanol. Among these solvents, it is preferred to use a fluorocarbon-based solvent when it is considered to have less chain shifting. The solvent may be used singly or in combination of two or more. -21 - 201207029 Suspension polymerization can be added to water, and a fluorine-based solvent can also be used. The fluorine-based solvent is, for example, a hydrochlorofluorocarbon such as CH3CC1F2, CH3CC12F, cf3cf2cci2h, CF2C1CF2CFHC1 or the like; a perfluoroalkane such as perfluorocyclobutane, CF3CF2CF2CF3'CF3CF2CF2CF2CF3'CF3CF2CF2CF2CF2CF3 or the like. The polymerization temperature is not particularly limited and may be 0 to 100 °C. The polymerization pressure may be appropriately determined in accordance with the type and amount of the solvent to be used, and other polymerization conditions such as vapor pressure and polymerization temperature, and it is usually from 0 to 9.8 MPaG. For the polymerization system, if necessary, hydrocarbons such as ethane, isopentane, η-hexane, and cyclohexane may be used: aromatics such as toluene and xylene; ketones such as acetone; and acetates such as ethyl acetate and butyl acetate. Classes; alcohols such as methanol and ethanol; mercaptans such as methyl mercaptan; chain transfer agents such as carbon tetrachloride, chloroform, dichloromethane, methyl chloride and the like. (Β) 矽 hydrogenation crosslinking agent 矽 hydrogenation reaction, an additional reaction of a carbon-carbon double bond and a hydrogen atom directly bonded to a ruthenium atom, and the ruthenium hydrogenation crosslinking agent (Β) in the present invention has two or more molecules. A hydrogen atom compound in which a hydrogen atom is directly bonded to a base of a halogen atom. The rhodium hydrogenation crosslinker is preferably in the form of a liquid. For the hydrazine-based hydrogenation cross-linking agent (Β), for example, those described in the publications of International Publication No. 2008/1 53 002, International Publication No. 2008/044765, and International Publication No. 2008/0727-14 can be used. Specifically, for example, Bl, Β2 or Β3 described in the publication of International Publication No. 2008/044765 can be used. -22- 201207029 The hydrogenation cross-linking agent (B) has a structure of two or more of the following formula: -OS i R8H- (wherein R 8 is a hydrocarbon group having a monovalent number of carbon atoms of 1 to 10) An alkane compound is preferred. The above R8 may be the same or different, and is preferably an alkyl group having 1 to 10 carbon atoms, or an aryl group. R8 is preferably a methyl group, an ethyl group, and at least one selected from the group consisting of phenyl groups, more preferably a methyl group; and the hydrazine hydrogenation crosslinking agent (B) has the following formula:

-O-S i R%H (wherein 'R8 is a hydrocarbon group having the same or different carbon number of 1 to 10 carbon atoms), preferably a dioxane compound of the diorganoalkylene group (bl). The above R8 is preferably the same or different alkyl group having 1 to 10 carbon atoms, or an aryl group. R8 is preferably at least one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group, more preferably a methyl group; and a diorganoalkylene group (bl), for example,

- Ο-Si (CH3) 2H The base represented by the formula: -O-S i (c6h5) 2h The base represented by the formula: -O-S i (CH3) (c6h5) η represents the base and formula:

—〇— The base represented by S i (C2H5) 2H is exemplified. In the present invention, the hydrazine hydrogenation crosslinking agent (B) is a liquid hydrazine having two or more soluble -23-201207029 or a hydrogen atom of the dispersed fluoropolymer (A) directly bonded to a ruthenium atom. The oxane compound (hereinafter also referred to as "hydrazine hydrogenation crosslinking agent (B4)") may be a direct bond of a hydrogen atom having two or more liquid or solid solvents capable of dissolving or dispersing the fluoropolymer (A). a oxoxane compound obtained by a ruthenium atom (hereinafter, also referred to as "hydrazine hydrogenation crosslinking agent (B 5 ) j ) ° (B4 ) 矽 hydrogenation crosslinking agent 矽 hydrogenation crosslinking agent (B4) has 2 in the molecule More than one liquid siloxane compound capable of dissolving or dispersing a hydrogen atom of the fluoropolymer (A) directly bonded to a ruthenium atom. The ruthenium hydrogenation crosslinker (B 4 ) has a hydrogenation reaction via hydrazine In addition to the ability to crosslink (harden) the fluoropolymer (A), the fluorinated polymer of the fluoropolymer (A) can also be dissolved or dispersed. The use of the hydrazine hydrogenation crosslinker (B4) is not It is necessary to use a solvent (a solvent (D) to be described later) for the purpose of dissolving or dispersing the fluoropolymer (A) or the like. In the case of a solvent-free curable resin composition, the organic solvent is not required to be removed, and the molding step and the like can be simplified. Further, the relationship between the molding processing conditions is not allowed. In the case of containing a volatile component, it is also suitable to use a solvent-free curable resin composition. For example, it is advantageously used for filling, sealing, and the like in a closed container. The hydrogenation crosslinking agent (B4) can be used, for example. B1 or B2 described in International Publication No. 2008/044765. The hydrogenation crosslinking agent (B 4 ) can be, for example, the following formula (4): -24- 201207029 R9bS i (OR10) 4_b (4) (wherein R9 represents an alkyl group having 1 to 10 carbon atoms, an aryl group containing a (meth)acryl group, or an epoxy group-containing one or a part of hydrogen which may be substituted by fluorine. The organic group. R1() represents the same or different hydrogen atom, an alkyl group having 1 to 40 carbon atoms, or the following formula: -si r82h (wherein R8 represents the same or different carbon number 1 to 1 〇) a diorganofluorenyl group (b2) represented by a monovalent hydrocarbon group. However, at least 2 of 1 molecule The arsonane compound (hereinafter, also referred to as hydrazine hydrogenation crosslinking agent (B 6 )) represented by R1() is a diorganofluorenyl group (b2). 15 is an integer of 0 to 2). It is preferably the same or different alkyl group having 1 to 10 carbon atoms, or an aryl group. R8 is preferably at least one selected from the group consisting of methyl, ethyl, and phenyl groups. Preferably, it is a methyl group; R9 may be the same or different 'partial or all hydrogen atoms which may be substituted by fluorine and have a carbon number of 1 to 1 Å, or an aryl group. b is preferably 1 and 2 Ri〇 is the above-mentioned diorganofluorenyl group (b2), and one of R1Q is an argon atom, or three of R1Q are preferably a diorganofluorenyl group (b2). Further, the 'sand hydrogenation crosslinking agent (B4) may also be, for example, the following formula (5) R9ci (R10〇) 3-clS i-RH-s i R«c2 (〇ri〇) 3_c2 (5) (wherein R9 represents an alkyl group having 1 to 10 carbon atoms, an aryl group, a (meth)acrylic group-containing organic group, or an epoxy group-containing group, in which some or all of the same or different hydrogen may be substituted by fluorine. Organic base. R10 means the same or different

S -25- 201207029 A hydrogen atom, an alkyl group having a carbon number of 1 to 10, or the following formula: -S i r82h (wherein R8 represents the same or a different hydrocarbon group having 1 to 10 carbon atoms) The two organic sulfhydryl groups (b2) are represented. However, at least two of the 1 molecules of R1Q are diorganofluorenyl groups (b2). Rii is a divalent organic group; cl is an integer of 〇~3, and c2 is an integer of 0~3. However, neither ci nor C2 is a siloxane compound represented by 3) (hereinafter, also referred to as hydrazine hydrogenation crosslinking agent (B7)). The (meth)acrylic group-containing organic group is an alkyl group having a (meth)acrylic group having a carbon number of 1 to 10, or an alkyl ether group having a (meth)acrylic group having a carbon number of 1 to 10; good. The epoxy group-containing organic group is preferably an alkyl group having 1 to 10 carbon atoms having an epoxy group, or an alkyl ether group having 1 to 1 carbon atom. The hydrazine hydrogenation crosslinking agent (B) is preferably at least one compound selected from the group consisting of hydrazine hydrogenation crosslinking agents (B 6 ) and (B 7 ). a hydrogenation crosslinking agent (B 6 ) or (B 7 ), specifically, for example, a oxoxane compound represented by the formula CH3S i {OS i (CH3) 2H} 3 , wherein: ch3 (c6h5) Si {OS i (ch3) 2h} 2 represents a oxoxane compound, a formula: C3H7 S i {OS i (CH3) 2H} 3 represents a oxoxane compound, formula: C4H9S i {OS i (CH3) 2H} 3 - 26-201207029 The oxime compound represented by the formula: C6H13S i {OS i (CH3) 2H} 3 represents a oxoxane compound, and the formula: C8H17S i {OS i (CH3) 2H} 3 Alkane compound, formula: C6H5S i {OS i (CH3) 2H} 3 represents a oxoxane compound, formula: (C6H5) 2S i {OS i (ch3) 2h} 2 represents a oxoxane compound, formula: CF3C2H4Si {OSi (CH3) 2H} a represents a oxoxane compound, a formula: ch3 CH2z=C-co-(CH2)3-Si{OSi(CH3)2H}3 0 : 【化1 6】

a oxoxane compound represented by CH9~CH-CH2-0-(CH2)3-Si{OSi(CH3)2H}3, formula: [Chem. 1 7]

The alkoxylated compound represented by the formula: -27- 201207029 [Chemical 1 8]

Ch3 I ch3 CHg 二 0—C_O—(CH2)3—Si{〇Si(CH3)2H}2 〇 The alkoxylate compound represented by the formula

CH 3 ,CH-CH2-〇-(CH2)3-Si{OSi(CH3)2H}2 represents a oxoxane compound, formula: [Chemical 2 0].

CH

3 CH2-CH2-Si{OSi(CH3)2H}2 The azoxy compound represented by the formula: {(CH3) 2HSiO} 3Si-C2H4-Si {OSi (CH3) The azoxy compound represented by the formula: { (CH3) 2HS i 0} 3s i - C6H12-S i {OSi (CH3) The alkane compound represented by the formula: { (CH3) 2HSi〇} 2CH3S i-C2H4-S i CH3 {OSi «} 2 The oxirane compound represented by the formula: {(CH3) 2HSiO} 2CH3Si-C6H12-SiCH3 {OSi 2H} 2H} 3 (CH3) 2 (ch3) 2 -28- 201207029 The azoxy compound represented by the formula: { (c6H5) 2hs iO} 3s i-C2H4-S i {os i (c6h5) 2h} 3 represents a oxoxane compound, formula: { (C6H5) 2HS i O} 3s i - C6H12-S i {os i (c6h5) 2h} 3 represents a oxane compound, and, formula: { (CH3) 2HSi〇} 3Si-C3H6 (OC2H4) m2 (OC3H6) n2〇C3 H6-S i {OS i (CH3) 2H } 3 (In the formula, 'm2 is an integer of 〇 or more, n2 is an integer of 〇 or more, m2 + η2 21), and at least one selected from the group consisting of a oxoxane compound is preferably an amphoteric compound. In particular, in view of having good solubility or compatibility, a oxoxane compound represented by the formula C6H5S i {OS i (CH3) 2H} 3 , formula: (C6H5) 2S i {OS i (ch3) 2h } 2 represents a nonoxyl compound, the formula: CH3 (C6H5) Si {OSi (CH3) 2H} 2 represents the compound of the compound, formula: C3H7S i {OS i (CH3) 2H} 3 An oxane compound, a formula: C4H9S i {OS i (CH3) 2H} 3 represents a oxoxane compound, and, 。 -29- 201207029 C6H13S i {OS i (CH3) 2H} 3 represents oxygen It is preferred that at least one of the oxoxane compounds selected from the group of the alkane compounds is present. (B8) fluorine-containing rhodium hydrogenation crosslinking agent The rhodium hydrogenation crosslinking agent (B 4 ) may also be a fluorine-containing rhodium hydrogenation crosslinking agent (B 8 ). Since the fluorine-containing hydrazine hydrogenation crosslinking agent (B8) has high compatibility with the fluoropolymer (A), it is easy to obtain a uniform composition. In the case of using the fluorine-containing hydrazine hydrogenation crosslinking agent (B8), it is not necessary to use a solvent (hereinafter referred to as a solvent (D)) for dissolving or dispersing the fluoropolymer (A), and it can be used as a so-called solvent-free type of hardening. Resin composition. For the fluorine-containing ruthenium hydrogenation cross-linking agent (B 8 ), for example, JP-A-2005-3,201,075, JP-A-2006-306086, JP-A-08-003 1 78, and JP-A 08-1 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Compounds and the like described in Japanese Patent Publication No. 1 3 7 8 9 . Among them, in view of having high compatibility, it is preferable to use a fluorine-containing hydrazine hydrogenation crosslinking agent (B8) linearly, and it is preferable to use a fluorine-containing group with respect to the introduction terminal or the main chain, and the introduction side. The chain is better. Representative structures are, for example, the compounds listed below.

Rf3 is a monovalent group containing fluorine, and Rf4 is a divalent group containing fluorine. -30- 201207029 [Chem. 2 1]

1/o i-e R—XISIM

o Le HISIM

I-oe RISIM (wherein Rf3 is a monovalent group containing fluorine, Me is a methyl group, X is a divalent organic group, and R is a monovalent organic group. n11, m11 and 〇ιι are the same or different a cyclic fluorine-containing oxoxane compound represented by an integer of 0 or more, and the following formula: [Chemical 2 2]

R HR

Rf1—X++ Bu 0-fcf· and -0-1⁄2, and —x——Rf3

Me Me Me (wherein, Rf3 is a divalent group containing fluorine; Me'X'R'n1· and m11 are the same as those described above), and a linear fluorine-containing fluorene introduced with an Rf3 group at the terminal end Oxyalkane compound, the following formula: [Chemical 2 3]

Me

H

o i-e HISIM /1 1\ \--/ i-oe R1s—Μ 3ΛI lm,

X

X

o e SIM 13⁄4

/LI

ο eb RISIM RIsilMeRIsilMe ”ρ /ο

ο.Le SIM I RI&I 士e Μ e Μ Η (wherein, 1^4, ^^, 乂, 11, 1111, 11111, and 〇11 are the same as above. P11 is an integer above )) A linear fluorine-containing oxoxane compound having an Rf4 group introduced into the main chain, and the following formula: -31 - 201207029 [Chemical 2 4]

Rf* | 1 X ,, V ' | Si-o- 1 Me Me Me Me Me

Rf3

I

X R R

In the side chain represented by Me Me Me (wherein Rf3, Me, X, R, n11, m11 and o11 are the same as those described above), a linear fluorine-containing oxoxane compound having an Rf3 group or the like is introduced. In each of the fluorine-containing oxoxane compounds, R is preferably a hydrocarbon group having a monovalent number of carbon atoms of from 1 to 20, and preferably, for example, a methyl group, an ethyl group or a phenyl group which may be the same or different. More preferably, the same or a different methyl or phenyl group; X is independently -CH2-, -CH20-, -CH2OCH2-, or -Y-NR12-CO- (however, Y is -CH2- or the following Formula: [Chemical 2 5] CH, CH* represents the base; R12 is a monovalent organic group). Further, the fluorine-containing hydrazine hydrogenation crosslinking agent (B 8 ) has the following formula: -32 - 201207029 [Chem. 2 6]

Rf6—R13-S —Η R12 (wherein Rf5 is a monovalent group containing fluorine, R12 represents a monovalent organic group, and R13 represents a divalent organic group), and a terminal chain having a Rf5 group is introduced at the terminal end. The fluorine-containing oxane compound is preferred. Rf5 is preferably a trifluoromethyl group, r12 is preferably a methyl group (-CH3), and R13 is preferably a methyl group (-CH2-CH2-). The hydrogenation crosslinking agent (B4) of the present invention has the following formula: [Chem. 2 7]

The naphthene compound represented by (η12 is an integer of 1 to 10) is also preferable. Η12 is preferably 3 to 10, more preferably 3 to 5, still more preferably 4. The hydrazine hydrogenation crosslinking agent (Β 4 ) of the present invention has the following formula: -33- 201207029 [Chem. 2 8]

(矽13 is 3 or 4) The alkoxyalkyl compound represented by the above is also preferable. ((5) The hydrogenation crosslinking agent is a liquid or solid which does not dissolve or disperse the fluoropolymer (Α), and has two or more. A hydrogen atom compound in which a hydrogen atom is directly bonded to a base of a halogen atom. It is preferred to use a hydrogenation crosslinker (Β 5 ) to use a solvent (D) which dissolves or disperses the fluoropolymer (A), or a ruthenium hydrogenation crosslinker (B4). Specifically, for example, the hydrogenation crosslinking agent (B 5 ) can be used, for example, B3 as described in International Publication No. 2008/044765.矽 Hydrogenation crosslinking agent (B5), specifically, for example, a fluorinated compound represented by an average molecular formula: {H (CH3) 2S i 01/2} d (S i 04/2) f , average molecular formula: {H (CH3) 2S i 01/2} d (CH3S i 03/2) e (S i o4/2) f The alkane compound represented by f, the average molecular formula: {H (CH3) 2S i 01/2} d (C6H5S i 〇3/2) e (S i 04/2) f -34- 201207029 The alkoxy compound represented by the average molecular formula: {H (CH3) 2S i 〇1/2} d (CH3S i 03 /2) The alkoxy compound represented by e, the average molecular formula: {H (CH3) 2Si〇1/2} d (C6H5Si03/2) e The alkane compound represented by e, the average molecular formula: {H (CH3) ( C6H5) S i 01/2} d (S i 04/2) f at least one selected from the group consisting of a halogenated alkane compound, etc. (also, in the above formula, d, e , f is a positive number) 'Average formula: {H (CH3) 2S i 01/2} d (S i 04/2) f (wherein, d, f are positive numbers). The alkoxysilane compound represented is preferred. In the curable resin composition of the present invention, the content of the hydrazine hydrogenation crosslinking agent (B) varies depending on the type of the fluoropolymer, the type of the hydrazine hydrogenation crosslinking agent, the presence or absence of the solvent, the type, and the like. For example, it is preferably used in an amount of 5 parts by mass or more and 500 parts by mass or less based on 100 parts by mass of the fluoropolymer (A). It is preferably 10 parts by mass or more and 300 parts by mass or less, more preferably 20 parts by mass or more and 200 parts by mass or less. When the curable resin composition of the present invention contains the solvent (D), the content of the rhodium hydrogenation cross-linking agent (B) is from the viewpoint of the function as a crosslinking agent, relative to the fluoropolymer (A) 1 〇〇 by mass. It is preferable to use 5 parts by mass or more. It is preferably 1 part by mass or more, more preferably 20 parts by mass or more. Further, it is preferably 90 parts by mass or less, more preferably 7 parts by mass or less, still more preferably -35 to 201207029 is 50 parts by mass or less. Further, in the case where the curable resin composition of the present invention does not contain the solvent (D), that is, in the case where the hydrazine hydrogenation crosslinking agent (B) functions as a solvent of the fluoropolymer (A), 矽氪The crosslinking agent (B) is 30 parts by mass or more, preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and further 500 parts by mass or less based on 100 parts by mass of the fluoropolymer (A). It is preferably 300 parts by mass or less, more preferably 200 parts by mass or less. In the case where the curable resin composition of the present invention does not contain the solvent (D), the rhodium hydrogenation crosslinker (B) is preferably a rhodium hydrogenation crosslinker (B4), wherein a fluorine-containing rhodium hydrogenation crosslinker (B8) is further used. It is better. (C) Rhodium Hydrogenation Catalyst The curable resin composition of the present invention preferably comprises a rhodium hydrogenation catalyst (C). The rhodium hydrogenation catalyst (C) is a catalyst used to promote the rhodium hydrogenation reaction of the composition of the present invention. These catalysts are preferably at least one type of catalyst selected from the group consisting of a platinum-based catalyst, a palladium-based catalyst, a ruthenium-based catalyst, a ruthenium-based catalyst, and a ruthenium-based catalyst. From the viewpoint of easiness of acquisition, etc., a platinum-based catalyst is preferred. The platinum-based catalyst is exemplified by chloroplatinic acid, an alcohol modified product of uranium chloride, a carbonyl complex of platinum, an olefin complex of platinum, an alkenyl alkane complex of platinum, and the like. The ruthenium hydrogenation catalyst (C) is not limited to the above, and it is also possible to use a known compound which hydrogenation reaction is used as a catalyst. For example, International Publication No. 2008/1 53002, International Publication No. 2008/044765, International Patent Application No. PCT/JP2007/074066, National Patent No. 36-201207029, PCT/: TP2008/0<50555 The compound described in the specification and the like. In the curable resin composition of the present invention, the content of the ruthenium hydrogenation catalyst (C) may be any amount as long as it can promote the hardening of the composition of the present invention. The content of the ruthenium hydrogenation catalyst (C) is preferably 0.1 to 100 ppm by mass based on the curable resin composition of the present invention. More preferably 1 to 500 ppm. When the content of the hydrogenation catalyst (C) is too small, there is a fear that the composition may not be sufficiently promoted to be sufficiently cured, and if the cured product is too much, the coloring of the cured product may cause coloring. (D) Solvent The fluoropolymer (A) can be easily produced even if the curable resin composition of the present invention contains no solvent. Therefore, the curable resin composition of the present invention may not contain a solvent. However, if necessary, a solvent (D) may also be contained. The solvent (D) in the present invention mainly has a function of dissolving or dispersing the fluorine-containing polymer (A). However, the solvent used for dissolving or dispersing the fluoropolymer (A) may cause problems such as incomplete removal, organic solvent remaining in the cured product, etc., and may be affected by the residual organic solvent. There are problems such as reduction in heat resistance, mechanical strength, white turbidity, and volatilization of the solvent, which may cause pores and the like, and it is highly expected that the solvent can be completely removed. Therefore, for the above reasons, it is preferable to include the burden on the work, such as reducing the environmental load or reducing the cost, so as not to use as much as possible. That is, the curable resin composition of the present invention preferably contains no solvent (D). In the present invention, the compound having the ability to dissolve or disperse the fluoropolymer (A), such as hydrazine-hydrogenated crosslinking agent (B4), may be used as described later. When the solvent in the hardened material related to the hydrazine cross-linking reaction is introduced, it is not necessary to use a solvent which can only dissolve or disperse the fluoropolymer (A). In the present invention, the solvent (D) which can dissolve or disperse the fluoropolymer (A) can be distinguished from the viewpoint of whether or not it is related to the hydro-hydrogenation crosslinking reaction, and can be distinguished as a non-antimony system related to the hydrazine cross-linking reaction. Reactive solvent (D 1 ), solvent (d 2 ) unrelated to the hydrogenation crosslinking reaction. (D 1 ) a non-oxime-reactive solvent related to the hydrazine cross-linking reaction. The hydrazine-hydrogenated crosslinking agent (B4) is a compound which can dissolve or disperse the fluoropolymer (A) and is related to the hydrazine hydrogenation crosslinking reaction. It is a part of a siloxane compound and is different from the solvent (D1). The term "related to the hydrogenation crosslinking reaction of the hydrazine" in the present invention means any reaction group (carbon-carbon double bond or a carbon-carbon double bond or a carbon-carbon double bond or a hydrogenation reaction directly bonded to a hydrogen atom of a halogen atom) The group containing a halogen atom bonded to a hydrogen atom can be combined into the reactant of the hydrogenation crosslinking reaction. Further, in view of having crosslinkability, it is preferred to have a complex reactive group. Specifically, for example, ethylene glycol diallyl ester, diethylene glycol di-diallyl ester, and triethylene glycol di- a polyvalent allyl compound such as diallyl ester, 1> 4-cyclohexanedimethanol di-diallyl ester, triallyl isocyanurate (TAIC): ethylene glycol divinyl ether, Diethylene glycol divinyl ether, triethylene glycol divinyl ether, bisphenol A bis(vinyl oxyethylene) ether, bis(vinyl oxyethylene) ether, hydroquinone bis(vinyl oxyethylene) ether, 1, 4-cyclohexanedimethanol divinyl ether, -38- 201207029 [Chem. 2 9] V_0 - ch2 〇2. J v〇 Ο

-O-J

O-CH2 ο CH2-Ο-&quot;C ~< .〉 1_〇—ch2—^ ch2—ο—丨1 ^-〇-CH2—/ \-CH2-〇—C—(CH)3—c— Ο-ch2-/ \-ch2-o-^ OO '-' and other polyvalent vinyl ether compounds; ethylene glycol diacrylate (EDA), diethylene glycol diacrylate (DiEDA), triethylene glycol II Acrylate (TriEDA), 1,4-butanediol diacrylate (1,4-BuDA), 1,3-butanediol diacrylate (l,3-BuDA), 2,2-double 4-(2-hydroxy-3-propenyloxypropoxy)phenyl]propane (Bis-GA), 2,2-bis(4-propenyloxyphenyl)propane (BPDA), 2,2-double (4-propenyloxyethoxyphenyl)propane (Bis-AEPP), 2,2-bis(4-propenyloxypolyethoxyphenyl)propane (Bis-APEPP), bis(propylene oxide) a polyvalent acrylate-based compound such as trimethyl hexamethyldicarbamate (UDA) 'trimethylolpropane triacrylate (TMP A ); ethylene glycol dimethacrylate (EDMA), Diethylene glycol dimethacrylate (DiEDMA), triethylene glycol dimethacrylate (TriEDMA), 1,4-butanediol dimethacrylate (1,4-BuDMA) , 1,3-butanediol dimethacrylate (1,3-BuDMA), 2,2-bis[4-(2-hydroxy-3-methylpropoxypropoxy)phenyl]propane (Bis-GMA), 2,2-bis(4-methylpropoxyphenyl)propane (BPDMA), 2,2-bis(4-methylpropoxyethoxyphenyl)propane (Bis- MEPP), 2,2-bis(4-methyl-39-201207029-propenyloxypolyethoxyphenyl)propane (Bis-MPEPP), bis(methylpropionyloxyethyl)trimethylhexamethyl A polyvalent methacrylic acid compound such as a dicarbamate (UDMA) or trimethylolpropane trimethacrylate (TMPT). Among them, it is preferred to use at least one compound selected from the group consisting of TAIC, EDMA, EDA, TMPT and ΤΜPA from the viewpoints of excellent solubility and compatibility. As the non-oxime-reactive solvent (D1), the fluoropolymer (A) may be used alone as a reactive solvent, or the above-mentioned hydrazine-hydrogenated crosslinking agent (B4) or a non-reactive solvent (D2) described later may also be used. can. The amount of the non-oxime-reactive solvent (D1) to be added varies depending on the type of the fluoropolymer (A), the type of the solvent (D1), the presence or absence of other solvents, or the like, and is generally relative to the fluoropolymer. (A) 100 parts by mass 'more preferably 5 parts by mass or more and 500 parts by mass or less. From the viewpoint of the hydrazine-hydrogenation reaction, the amount of the fluoropolymer (A) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, particularly preferably 20 parts by mass or more, based on 100 parts by mass of the fluoropolymer (A). 90 parts by mass or less, more preferably 70 parts by mass or less, particularly preferably 50 parts by mass or less. In addition, when the fluoropolymer (A) is used as a solvent function, it is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and particularly preferably 70% based on 100 parts by mass of the fluoropolymer (A). More than 500 parts by mass, more preferably 300 parts by mass or less, and particularly preferably 200 parts by mass or less. -40- 201207029 (D2) Solvent not related to hydrazine cross-linking reaction The solvent (D2) is used in the case where the aforementioned hydrazine-hydrogenated crosslinking agent (B 4 ) or non-lanthanide-reactive solvent (D 1 ) is not added. Or, even if it is added, the solubility or dispersibility of the fluoropolymer (A) is not sufficiently performed. Specific examples are, for example, hexane, cyclohexane, heptane, octane, decane, brothel, i-yard, twelve-yard, mineral spirit, and the like, aliphatic hydrocarbons; benzene, toluene'-xylene , naphthalene, solvent petroleum brain and other aromatic hydrocarbons: methyl acetate, ethyl acetate, propyl acetate 'acetate-η-butyl ester, isobutyl acetate, isopropyl acetate, isobutyl acetate, fibrin acetate, Propylene glycol methyl ether acetate, carbitol acetate, diethyl ester, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, Ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, etc.; acetone, methyl ethyl Ketones such as ketone, cyclohexanone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylamino ketone, heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve Acetate, ethyl cellosolve acetate propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, C Glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, ethylene glycol monoalkyl ether and other glycerol ethers; methanol, ethanol, iso-propanol, η-butanol, isobutanol, tert- Alcohols such as butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol tert-pentyl alcohol: tetrahydrofuran, tetrahydropyran, dioxane, etc. Cyclic ethers; amides such as N,N-dimethylformamide, N,N-dimethylacetamide; methyl cellosolve, cellosolve-41 - 201207029, isopropyl cellosolve Ether alcohols such as butyl lysin and diethylene glycol monomethyl ether; 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1, 2,2-tetrafluoroethane, dimethyl alum, and the like. Or a mixed solvent of two or more of these. Further, for example, a fluorine-based solvent such as CH3CC12F (HCFC-141b), CF3CF2CHC12/CC1F2CF2CHC1F mixture (HCFC-225), perfluorohexane, perfluoro(2-butyltetrahydrofuran), methoxy-nonafluorobutane, Other than 1,3-bistrifluoromethylbenzene, H(CF2CF2)n3CH2〇H (η3: an integer of 1 to 3), F(CF2)n4CH2OH (an integer of n4: 1 to 5), CF3CH(CF3)OH Fluorine-based alcohols; trifluorobenzene, perfluoro, total gas (tributylamine), C1CF2CFC1CF2CFC12, and the like. These fluorine-based solvents may be used singly or as a mixed solvent of a fluorine-based solvent and a non-fluorine-based solvent and one or more fluorine-based solvents. The curable resin composition of the present invention does not use a solvent (D 2 ) which is not related to the hydrazine cross-linking reaction, that is, the curable resin composition of the present invention preferably contains no solvent (D 2 ). When the solvent (D 2 ) is not used, the solvent (D 2 ) is not required to be removed from the curable resin composition, and the molding step and the like can be simplified, and the problem that the solvent (D2) remains in the cured product does not occur. The influence of the residual solvent (D2), for example, may lower the heat resistance, mechanical strength, and white turbidity of the cured product. Further, in the case where the volatile component is not contained, the solvent-free curable resin composition is also useful because of the relationship between the molding processing conditions. For example, -42-201207029 in a closed container for filling, sealing, etc. The curable resin composition of the present invention can be produced by mixing a fluoropolymer (A) with a hydrazine hydrogenation crosslinking agent (B) and, if necessary, a hydrogenation catalyst (c). . The crosslinking of the curable resin composition of the present invention may be appropriately determined depending on the crosslinking agent to be used, etc., and is usually carried out at room temperature (for example, at a temperature of 20 (: ) to 200 ° for 1 minute). ~24 hours of hardening treatment. Also 'crosslinking under normal pressure, pressure, reduced pressure, or air. Cross-linking reaction, for example, can be measured by infrared spectroscopy before and after hardening The method of absorbing the peak of the Si-H bond is confirmed. The crosslinking method is not particularly limited, and for example, a usual method of crosslinking reaction such as steam crosslinking, pressure molding, or heating can be employed. The curable resin of the present invention. The composition varies depending on the application. For example, for sealing and other applications, the viscosity at 30 ° C, when the viscosity is too low, will cause severe liquid drooping, and will reduce the treatment point of view, lmPa *s or more is preferable, and it is excellent in film formability, and it is preferable that it is 5 mPa*s or more, and it is preferable to reduce hardening shrinkage at the time of hardening, and it is preferable that it is 10 mPa as or more. Moreover, it is good. The viewpoint of processing, etc. Between 20000 mPa and s or less, it is preferable to achieve a hardening composition of a fine portion at the time of forming, and it is preferably 5000 mPa*s or less, and has a good smoothness (surface smoothness) at the time of forming a film, 200 0 mPa «s or less is more preferable. In addition to the above-mentioned contents, the curable resin composition of the present invention may be optionally added with -43 to 201207029, for example, a reaction inhibitor, oxygen bengala, a pigment such as graphite, or alumina. Anti-dispersive agents, tackifiers, preservatives, ultraviolet absorption, etc. Reaction inhibitors such as 1-ethynyl-1-cycloalcohol, 2-methyl-3-butan-2-ol, 3,5-dimethyl I An acetylene alcohol such as -3-butan-2-ol; an alkenyl siloxane such as a decyl oxide: a fumarate compound such as diallyl fumarate or diethyl fumarate Ester, triazole, etc. The addition of the reaction allows the resulting composition to be liquefied or to sufficiently extend the effect of the time available. The reaction inhibition is limited, and in the composition of the present invention, it is preferably in the amount of 10 - quasi-). For example, the curable resin can be used in various applications. The method of forming the film is carried out by a suitable known method. For example, a roll coating method, a gravure coating method, a dicavity method, a strip coating method, a spray coating method, a die coating dip coating method, or the like must be employed. The curable resin composition of the present invention is particularly useful as a molding material for various molded articles. Extrusion molding, injection molding, compression molding, streamer shaping, nano implantation, vacuum forming, and the like. Huaqin, 赭色赤鐡矿 (Wanhua 矽 矽 塡 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ( ( ( ( ( ( ( ( ( ( ( ( Vinyl tetramethylcyclotetracarboxylic acid ester, dimethyl fumaric acid; other products such as triallyl, the content of the service agent having a achievable composition is not particularly 50,000 ppm (the mass of the substrate is hardened to form a hardening) The film can be controlled according to the application, and the film thickness can be controlled by a plate coating method, a flow coating method, a spin coating method, or a film forming method, and the forming method can be, for example, dynamic molding or mold forming. -44-201207029 The use of the curable resin composition of the present invention can be, for example, a sealing member, an optical member, a photoelectron image tube, various inductors, a material of an antireflection material, etc. In particular, a material used as a sealing member is used. In other words, the curable resin composition of the present invention is preferably a sealing material. Further, since the cured product obtained from the curable resin composition of the present invention has excellent transparency, etc., it is extremely suitable for use as an optical for forming an optical member. material In addition, it can be used as a material for a sealing member for an electronic semiconductor, a water- and moisture-resistant adhesive, and an adhesive for an optical component or a component. The use form of the curable resin composition of the present invention, for example, a light-emitting diode For example, a light-emitting element such as a body (LED), an EL element, or a nonlinear optical element, or an optical function element such as a CCD, a CMOS, or a PD, such as a light-emitting element, is packaged (encapsulated) or assembled. For example, an optical member such as a lens of a far-ultraviolet microscope is used. A sealing member (or a filler) or the like. The curable resin composition of the present invention is particularly suitable as a sealing material for an optical element because of its excellent transparency. The sealed optical element can be used in various places. In particular, for example, a light-emitting element such as a light-emitting diode (LED), an EL element, or a nonlinear optical element, or a light-receiving element such as a CCD, a CMOS or a PD, or the like, a high-mounted stop lamp or a backlight of a display panel or a mobile phone Light-emitting elements such as light sources for remote control devices for boards and various electrical products; autofocus for cameras, and light capture for CD/DVD The optical element or the like of the curable resin composition of the present invention has a higher barrier property (i.e., low permeability) because it does not need to contain the solvent (D) and is made of a resin. -45-201207029 The curable resin composition of the present invention is very suitable as a material for forming an optical member. The curable resin composition of the present invention contains fluorine, so that the obtained cured product can form a low refractive index optical. The member is suitable for use as, for example, a medium for optical transmission. The curable resin composition of the present invention, in particular, can be used for a plastic covering material in which a core material is quartz or optical glass, a coating material for an optical fiber, and a core material is a plastic material. Coating material of all plastic optical fiber, anti-reflective coating material, lens material, optical waveguide material, germanium material, lens material, optical memory disc material, nonlinear optical element material, optical material, photolithography Materials, sealing materials for light-emitting elements, and the like. Also, it can be used as a material for optical devices. Optical devices such as known optical waveguides, OADMs, optical switches, optical filters, optical connectors, multiplexer demultiplexers, and the like, and optical devices such as optical guides are suitable materials for forming such devices. In addition, it can be used in optical devices such as modulators, wavelength conversion elements, and optical amplifiers because it contains various functional compounds (non-linear optical materials, functional properties such as fluorescent light, and photolithographic etching materials). Functional components. The sensor is particularly useful for improving the sensitivity of an optical sensor or a pressure sensor or for having a water-repellent property and having a protective sensor. The present invention is a cured product obtained by curing the above curable resin composition. The cured product of the present invention can be obtained by subjecting the above curable resin composition to hydrogenation crosslinking. Since the curable resin composition of the present invention does not need to contain a solvent, the step of removing the organic solvent can be omitted, and the step of forming the carbide can be simplified. Further, it is also suitable for use in a sealing member which cannot contain a volatile component based on the relationship of forming processing conditions. That is, the cured product of the invention of the present invention is preferably a sealing member. The cured product obtained by curing the curable resin composition has excellent transparency and is suitable for use as an optical member. The cured product of the present invention preferably has a light transmittance of 80% or more. More preferably, it is more than 85%, and the best is more than 90%. The light transmittance of the cured product can be measured at a wavelength of 550 nm using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.). The cured product of the present invention not only has excellent transparency, but also exhibits excellent performance as a sealing member as described above, and is therefore particularly suitable as a sealing member for optical elements. The present invention is characterized by being represented by tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CFfCF-ORf1 (wherein Rfi represents a perfluoroalkyl group having 1 to 8 carbon atoms) a polymerization unit formed by at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro(alkyl vinyl ether), and the following formula (a):

(wherein R1 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 10 carbon atoms; R2 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 10 carbon atoms), and has two or more carbon-carbons The double bond of the fluorinated polymer (al) formed by the polymerization unit formed by the monomer. The norbornene monomer represented by the above formula (a) is, for example, given by the following formula (1): -47 - 201207029

(In the formula, R7 is a hydrogen atom or a carbon number of 1 to 院, the base of the group) is a freezer having two carbon-carbon double bonds! The preferred form of the fluoromonomer in the fluoropolymer (al) is the same as described above. The fluoropolymer (al) ' may contain a fluorine-containing monomer, and a monomer unit which can be formed from other monomers copolymerized with the norbornene monomer represented by the formula (a). The preferred form of the other monomer is the same as the above content. The fluoropolymer (al) has the following formula: [Chemical 3 2]

The polymerization unit represented by the formula (wherein R7 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) is preferred. The present invention is also composed of tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CF2 = CF-〇R f 1 (wherein Rf1 represents a perfluoroalkyl group having 1 to 8 carbon atoms) The polymerization unit formed by the fluorine-containing ethylenic monomer of at least one selected from the group consisting of perfluoro(alkyl vinyl ether)-48-201207029 and the following formula (b)

(wherein R3 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 5 carbon atoms; R4 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 1 carbon; R5 is a hydrogen atom or may have a carbon number a hydrocarbon group characterized by a hydrocarbon group of 1 to 5 oxygen atoms; η is an integer of 0 to 10) which is formed by a polymerization unit formed by a norbornene monomer having two or more carbon-carbon double bonds (a2). The norbornene monomer represented by the above formula (b) is represented by the following formula (2):

(wherein R8 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) is preferred. Among the above fluoropolymers (a2), preferred embodiments of the fluorinated monomers are the same as those described above. The fluoropolymer (a2) may contain a fluorine-containing monomer and a monomer unit which can be formed from another monomer copolymerized with the norbornene monomer represented by the formula (2). The preferred form of the other monomer is the same as that described above -49-201207029. The fluoropolymer (a2) is a norbornene monomer represented by the following formula: (Chemical Formula 5) X=CH-R8 (wherein R8 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) The unit is better. The present invention also contains tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CF2 = CF-〇R f 1 (wherein, Rf1 represents a perfluoroalkyl group having a carbon number of 1 to 8). a polymerization unit formed by at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro(alkyl vinyl ether), and the following formula (c)

(In the formula, R6 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom having 1 to 5 carbon atoms), and the polymerization unit of 201207029 which is formed by a norbornene monomer having two or more carbon-carbon double bonds is formed by A characteristic fluoropolymer (a3). The norbornene monomer represented by the above formula (c) has the following formula (3):

(3) Preferably, the norbornene monomer having two carbon-carbon double bonds is represented. In the fluoropolymer (a3), a preferred embodiment of the fluorinated monomer is the same as described above. The fluoropolymer (a3) may further contain a fluorine-containing monomer, and a monomer unit which can be formed from another monomer copolymerized with the norbornene monomer represented by the formula (3). The preferred form of the other monomer is the same as described above. The fluoropolymer (a3) has the following formula:

The norbornene monomer unit represented is preferred. The above (al), (a2) and (a3) may be a unit of a fluorinated monomer, and a norbornene monomer unit formed from a norbornene monomer having two or more carbon-carbon double bonds, and The monomer unit formed by the above-mentioned fluoromonomer and another monomer having a norbornene monomer having two or more carbon--51 - 201207029 carbon double bonds may be formed. The other monomer described above is a monomer having no fluorine atom, and other monomers, and a norbornene monomer having one carbon-carbon double bond is preferred. The norbornene monomer having a carbon-carbon double bond is a monomer having a norbornene skeleton and having a carbon-carbon double bond other than the norbornene skeleton. The norbornene monomer is represented by the following formula (d): [Chem. 3 9]

降 (wherein R14 is an alkyl group having 1 to 10 carbon atoms; \ is an integer of 〇~2) is preferably a norbornene monomer, and the following formula: [Chemical 4 0]

The norbornene monomer shown is preferred. The above (al), (a2) and (a3) are compounds having two or more carbon-carbon stomach compounds, which are sufficiently soluble or easily dispersed in the point of the hydrogenation crosslinking agent, and are suitable for use in the above-mentioned curable resin composition. Things. Among them, (a 1 ) is particularly good. [Embodiment] [Embodiment] -52-201207029 The following examples are given to illustrate the invention and are not to be construed as being limited by the examples. The measurement methods used in the present specification are summarized as follows, but the present invention is contained. (1) Measurement of average molecular weight The GPC HLC-8020 of the Gel Permeation Chromatography Analyzer (GPC) was used to connect with the column of Shodex (pipe column, GPC KF-802 1 column, GPC KF-806M) The solvent is the data measured by using tetrahydrofuran (THF) and stream: respectively, and the weight average molecular weight of GPC KF-801 1 2 column in-line speed 1 m 1 /min flow, number average molecule ( 2) Fluorine content The sample was burned by an oxygen flask combustion method, 〇mg, and 20 ml of deionized water was absorbed, and the result (mass%) in the absorption liquid was measured by a fluorine selective electrode method (Model 901 manufactured by Orion). (3) Refractive index (nD) The sodium D-line (589 μm) was used as the light source, and the Uber refractive decomposition gas produced by the ATAGO optical machine was used under the fluoride ion concentration of 25 t: Rate measurement (4) Glass transition temperature (Tg) -53- 201207029 Using DSC (differential scanning calorimeter: SEIKO public RTG220), the temperature range from -50 °C to 200 °C °C / min Under the conditions of the temperature rise (first curve) - a temperature drop - I two curve), and the intermediate point (r) of the endothermic curve in the second curve. (5) IR analysis Measurement was carried out at room temperature using a Fourier variable infrared meter 1 760X manufactured by Perkin Elmer Co., Ltd. (6) Film thickness J.A. Woollam JAPAN Co., Ltd. split optical ellipse EC400 was measured. The analysis software uses WVASE32. (7) Viscosity The viscosity (mPa·s) at 27 ° C was measured using a Toki Shoji (type) viscometer based on JIS K7117-2. Synthesis Example 1 (TFE/ENB copolymer) After adding a high pressure of 0.5 L stainless steel to a stirrer, 200 g of dichloropentafluoropropane (HCFC-225) and 22 g of 5-norbornene (ENB) were added. The mixture was stirred at 300 rpm for 90 g of fluoroethylene (TFE). Secondly, the temperature in the autoclave was adjusted three times, and 40 masses of di-n-propyl peroxydicarbonate were introduced: s, and 10 deg. Luminous circular polarization

The system E was degassed. Ethyl-2-added to 4 g 4 0 ° C 匮% -54- 201207029 1H, 1H, 3H-tetrafluoropropanol solution 10 g, polymerization was started, and the reaction was allowed to proceed for 20 hours. After the completion of the reaction, unreacted TF E was discharged at room temperature, and secondly, HCFC-225 in which the content was uniformly dissolved was introduced into ethanol. The precipitated solid was filtered off and dried under vacuum at 80 ° C for 12 hours to obtain a white powder of Mg. The white powder was dissolved in dihydrochloroform, and the results of 19F-NMR, 13C-NMR and 1H-NMR measurement revealed that the polymer was a copolymer of TFE and ENB. Further, in the 1H-NMR measurement, it was confirmed that 5.33 ppm was a peak of =CHCH3, and thus it was confirmed that a double bond formed by an ethylene group of ENB was present in the copolymer. Further, as a result of elemental analysis of the fluorine of the copolymer, it was found to be 31.8% by mass, and based on this, the composition of the copolymer was calculated to be TFE unit/ENB unit = 46/54 mol%. The copolymer was colorless and transparent, and was subjected to a thermal measurement result measured by a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments Co., Ltd.) at a temperature rising rate of 1 〇 ° C /min to 200 ° C, and it was found that no melting point was present. It is known that 80 ° C (end heat end temperature) is the glass transition temperature. Further, it was found that the mass of the copolymer which was subjected to the heating test using the differential thermal and thermal gravimetric apparatus [TG-DTA] was reduced to a temperature of 212 °C by 1% by mass. Further, the number average molecular weight measured by GPC analysis was 1582, and the weight average molecular weight was 2422. The copolymer was dissolved in a solvent such as chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone or dioxane. It may also be compatible with a hydrogenated polyoxosiloxane having a SiH group (for example, phenyltris(dimethylnonyloxy)decane). -55-201207029 Synthesis Example 2 (TFE/ENB copolymer) After degassing a stainless steel autoclave having a 300 ml internal volume of a valve, a pressure gauge, and a thermometer, dichloropentafluoropropane (HCFC-22 5 ) was added. After 5 g of 5 g of 5-ethylidene-2-norbornene (ENB), 25 g of tetrafluoroethylene (TFE) was further added, and then the temperature in the autoclave was adjusted to 40 ° C, and then di-n-propyl group was injected. 8 g of a 40% by mass peroxydicarbonate solution of 1H, 1H, 3H-tetrafluoropropanol was subjected to polymerization at 40 ° C under vibration of 80 rpm. The polymerization was started, and after returning to room temperature after 2 hours, the unreacted TFE was allowed to flow out, and the content of HCFC-225 was uniformly dissolved. Next, this solution was put into methanol. The precipitated solid was filtered off and dried under vacuum at 8 (TC) for 12 hours to give a solid. 86 g of solid. The solid was dissolved in the hydrogenated acetone to 19F-NMR, &quot The results of measurement by C-NMR and 1H-NMR showed that the polymer was a copolymer of TFE and ENB. Further, in the measurement of 1H-NMR, the peak of =CH CH3 was confirmed in the same manner as in Synthesis Example 1. It was confirmed that the double bond formed by the ethylene group of ENB was present in the copolymer. The result of elemental analysis of the fluorine of the copolymer was found to be 35.0% by mass, and the composition of the copolymer was calculated to be TFE unit/ ENB unit = 5 1/4 9 mol %. The copolymer was colorless and transparent, and was measured to 200 ° C at a temperature increase rate of 1 〇 ° C /min using a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments Co., Ltd.). As a result of the heat measurement, it was found that there was no melting point, and it was shown that 78 ° C (end heat end temperature) was the glass transition temperature. Further, a copolymer of a heating test using a differential heat and thermal weight measuring device (TG-DTA) was provided. The temperature at which the mass is reduced by 1% by mass is -56- 201207029 2 30 ° C. The number average molecular weight determined by GPC analysis was 2294, and the weight average molecular weight was 3219. The copolymer was soluble in chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone, dioxins. In addition to the solvent such as an alkane, it may be compatible with a hydrogenated polyoxosiloxane having a SiH group (for example, phenyl tris(dimethylnonyloxy)decane. Synthesis Example 3 (TFE/ENB copolymer) is provided with a valve. After the degassing of a stainless steel autoclave with a pressure gauge and a thermometer of 00 ml, after adding 105 g of dichloropentafluoropropane (HCFC-225) and 36 g of 5-ethylidene-2-norbornene (ENB), Further, tetrafluoroethylene (TFE) 25 g was added, and then the temperature in the autoclave was adjusted to 40 ° C, and then 40% by mass of 1H, 1H, 3H-tetrafluoropropene of di-n-propyl peroxydicarbonate was injected. 8 g of an alcohol solution was subjected to polymerization at 80 ° C under vibration at 80 rpm. The polymerization was started, and after 2 hours, it was returned to room temperature, and after the unreacted TFE was discharged, the content of HCFC-225 was uniformly dissolved. The solution was poured into methanol. The precipitated solid was filtered off and subjected to 12 hours at 80 °C. The mixture was vacuum dried to give 1.54 g of a solid. The solid was dissolved in a crude hydrogenated acetone, and the results of 19F-NMR, &quot;C-NMR and 1H-NMR were measured to find that the polymer was a copolymer of TFE and ENB. Further, in the 1H-NMR measurement, in the same manner as in Synthesis Example 1, the peak of =CHCH3 was confirmed, and it was confirmed that the double bond formed by the ethylene group of ENB was present in the copolymer. Further, as a result of elemental analysis of the fluorine of the copolymer, it was found to be 25.4 - 57 - 201207029% by mass, and the composition of the copolymer was calculated to be TFE unit / ENB unit = 3 8 / 62 mol%. The copolymer was colorless and transparent, and was subjected to a thermal measurement result measured by a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments Co., Ltd.) at a temperature increase rate of 1 〇 ° C /min to 200 ° C, and it was found that no melting point was present. , at 46 ° C (endothermic end temperature) shows the glass transition temperature. Further, the temperature at which the mass of the copolymer subjected to the heating test using the differential thermal/thermal weight measuring device [TG-DTA] was reduced by 1 mass% was 180 t. Further, the number average molecular weight measured by GPC analysis was 1〇71, and the weight average molecular weight was 1,753. The copolymer may be dissolved in a solvent such as chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone or dioxane, and may also be a hydrogenated polyoxosiloxane having a SiH group (for example, phenyl tris(( Dimethylnonyloxy) decane) is compatible. Synthesis Example 4 (TFE/VNB copolymer) After degassing a stainless steel autoclave having a 300 ml internal volume of a valve, a pressure gauge, and a thermometer, dichloropentafluoropropane (HCFC·22 5 ) 105 g, 5-ethylene was added. After the bis(2,2,1]hept-2-ene (VNB) llg, then add tetrafluoroethylene (TFE) 25g, and then adjust the temperature in the autoclave to 4 (TC, pressurize the di-n-propyl 8 g of a 40% by mass solution of 1H, 1H, 3H-tetrafluoropropanol based on oxydicarbonate was subjected to polymerization at 40 ° C under vibration of 80 rpm. The polymerization was started to return to room temperature after 24 hours. After the unreacted TFE was discharged, the content of the HCFC-225 was uniformly dissolved. Then the solution was poured into ethanol. -58- 201207029 The precipitated solid was filtered off and dried at 80 ° C for 12 hours under vacuum. The liquid polymer was obtained by dissolving 3 g of the polymer. The polymer was dissolved in heavy hydrogenated acetone, and the results of 19F-NMR, 13C-NMR and 1 H-NMR were measured to find that the polymer was copolymerized with TFE and VNB. Further, in the j-NMR measurement, the peak of -CH = CH2 was confirmed, and it was confirmed that the double bond formed by the allylic group of VNB was present in the copolymer. The elemental analysis of the fluorine of the copolymer was found to be 29.4% by mass, and the composition of the copolymer was calculated to be TFE unit/VNB unit = 43/5 7 mol%. The copolymer was colorless and transparent, and was used poorly. The calorimeter RDC220 (manufactured by Seiko Instruments Co., Ltd.) was measured at a temperature rise rate of 1 〇 ° C /min to a thermal measurement result of 200 ° C, and it was found that there was no melting point at 35 ° C (end of heat absorption) The temperature shows the glass transition temperature. Further, the temperature of the copolymer which is subjected to the heating test using the differential thermal and thermal gravimetric apparatus [TG-DTA] is reduced by 1% by mass and the temperature is 202 ° C. Further, it is determined by GPC analysis. The number average molecular weight is 1 805, and the weight average molecular weight is 3169. The copolymer may be dissolved in a solvent such as chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone or dioxane. The SiH-based hydrogenated polyoxo compound (for example, phenyltris(dimethylnonyloxy)decane) is compatible. Synthesis Example 5 (TFE/NB/ENB copolymer) has an internal volume of a valve, a pressure gauge, and a thermometer. 300ml stainless steel After degassing the autoclave, add dichloropentafluoropropane (HCFC-225) -59- 201207029 105g, norbornene (NB) 8.8g and 5-ethylidene-2-degraded ENB) 2.2g, then add Tetrafluoroethylene (TFE) 25g, after adjusting the temperature in the autoclave to 40 °C, injecting 40g of 1H, 1H, 3H-tetrafluoropropanol solution of di-propyl peroxygen into 8g, conditions at SOrpm The polymerization is carried out in the vibration. The polymerization was started, and the temperature was returned to room temperature, and after the unreacted TFE was discharged, a homogeneous content of HCFC-225 was obtained. This solution is then placed in ethanol. The precipitated solid was filtered off and dried at 80 ° C to give 13 g of solid polymer. The polymer was dissolved in a weight, and the results of l9F-NMR, 13C-NMR and 1H-NMR were measured, and the copolymer was a copolymer of TFE and NB and ENB. Further, the peak of CHCH3 was confirmed in 1], and the double bond formed by the ethylene group of ENB in the copolymer was confirmed. Further, the elemental analysis of the fluorine of the copolymer gave a mass %, and as a result of elemental analysis of carbon, it was found to be 56. From this, the composition of the copolymer was calculated to be TFE unit / NB unit = 4 7 / 41 / 12 mol%. The copolymer was colorless and transparent, and the calorimeter RDC220 (the temperature measured by Seiko Instruments Inc. at a temperature of 1 〇 ° C / min was measured to 200 ° C. The thermal measurement revealed that there was no melting point at 90 ° C (endothermic). End temperature) transfer temperature. Further, the mass of the copolymer subjected to the heating test using differential thermal and thermal gravimetric TTA was reduced by 1 mass% 248 t. The number average molecular weight measured by GPC analysis was the average molecular weight. 2859. Borneene (: times the high pressure dicarbonate is dissolved at 4 ° C for 24 hours and then dissolved in the vacuum, the dry hydrogenated acetone is known to have a polyH-NMR measurement of 37.7.8% by mass. ENB uses differential) to increase the result, showing glass specificity [TG- temperature is 2 1 8 1 , weight -60- 201207029. The copolymer is soluble in chloroform, tetrahydrofuran, xylene, ethyl acetate, A In addition to the solvent such as ketoethyl ketone or dioxane, it may be compatible with a hydrogenated polyoxosiloxane having a SiH group (for example, phenyl tris(dimethyl; oximeoxy) decane). (TFE/NB/ENB copolymer) except for the synthesis example 5 The initial addition amount of NB and ENB was changed according to the contents of Table 1, and the polymerization was carried out in the same manner as in Synthesis Example 5. The analysis of the polymer of 卩 得 値 and the result of Synthesis Example 5 are shown in Table 1. [Table 1] Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 NB (g) 8.8 5 5.5 3.8 ENB (g) 2.2 5 0.8 1.2 Polymerization time (hour) 24 18 6 6 Agglomeration amount (g) 13 1.3 3.5 2.5 Composition ratio (TFE/NB/ENB) 47/41/12 45/30/25 44/50/6 45/39/16 Glass transfer temperature (0C) 90 108 111 85-year-old brewing (〇C) 248 237 228 211 Average molecular weight 2181 2256 1650 1928 Weight average molecular weight 2859 3285 2200 2592 Synthesis Example 9 (TFE/NB/VNB copolymer) After degassing a stainless steel autoclave having a 300 ml internal volume of a valve, a pressure gauge, and a thermometer, 105 g of chloropentafluoropropane (HCFC-2 2 5 ), 8.8 g of norbornene (NB) and 2.2 g of 5-vinylbicyclo[2,2,1]heptane-2-diuret (VNB), then add four Fluorine B (TFE) 25g, followed by •61 - 201207029 After adjusting the temperature in the autoclave to 40 °C, press 40% by mass of 1H, 1H, 3H-four of di-n-propyl peroxydicarbonate 8 g of a fluoropropanol solution was subjected to polymerization at 40 ° C under vibration of 80 rpm. The polymerization was started, and after 24 hours, it was returned to room temperature, and after the unreacted TFE was discharged, the content of HCFC-22 5 was uniformly dissolved. Next, the solution was poured into ethanol. The precipitated solid was filtered off at 80 °. Vacuum drying was carried out for 12 hours under C to obtain llg of a solid polymer. The polymer was dissolved in heavy argonized acetone, and the polymer was found to be a copolymer of TFE and NB and ENB by measuring 19F-NMR, 13C-NMR and 1H-NMR. Further, in the j-NMR measurement, the peak of -CH = CH2 was confirmed, and it was confirmed that a double bond derived from the allylic group of VNB was present in the copolymer. Further, as a result of elemental analysis of the fluorine of the copolymer, it was found to be 36.7 mass%, and as a result of elemental analysis of carbon, it was found to be 57.7 mass%, and the composition of the copolymer was calculated to be TFE unit/NB unit. /VNB unit = 46/4 0/14 mole %. The copolymer was colorless and transparent, and was subjected to a thermal measurement result measured by a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments Co., Ltd.) at a temperature increase rate of 1 〇 ° C /min to 200 ° C, and it was found that no melting point was present. It is known that 80 ° C (end heat end temperature) is the glass transition temperature. Further, the temperature at which the mass of the copolymer which was subjected to the heating test using the differential thermal/thermal weight measuring device (TG-DTA) was reduced by 1% by mass was 207 °C. Further, the number average molecular weight measured by GPC analysis was 1,750, and the weight average molecular weight was 2,805. The copolymer may be dissolved in a solvent such as chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone or dioxane, and may have a -62-201207029

The SiH-based hydrogenated polyoxo compound (e.g., phenyltris(dimethylnonanyloxy)decane) is compatible. Synthesis Example 10 (TFE/NB/CPD copolymer) After degassing a stainless steel autoclave having a volume of 300 ml of a valve, a pressure gauge, and a thermometer, dichloropentafluoropropane (HCFC-22 5 ) was added to 105 g. After borneol (NB) 8.8g and cyclopentadiene (CPD) 2.2g, add tetrafluoroethylene (TFE) 25g, and then adjust the temperature in the autoclave to 4〇t, press the di-n-propyl group 8 g of a 40% by mass solution of 1H, 1H, 3H-tetrafluoropropanol of oxydicarbonate was subjected to polymerization at 40 ° C under vibration of 80 rpm. The polymerization was started, and after 24 hours, it was returned to the room temperature, and after the unreacted TFE was discharged, the content of HCFC-225 was uniformly dissolved. This solution is then placed in ethanol.

The precipitated solid was filtered off and dried under vacuum at 80 ° C for 12 hours to give a solid polymer. The polymer was dissolved in dihydroacetone, and the polymer was found to be a copolymer of TFE and NB and ENB by measurement of &quot;F-NMR, 13C-NMR and 1H-NMR. Further, in the 1H-NMR measurement, the peak of -CH = CH- was confirmed, and it was confirmed that the double bond formed by the olefin of CPD was present in the copolymer. Further, as a result of elemental analysis of the fluorine of the copolymer, it was found to be 35.3 mass%, and as a result of elemental analysis of carbon, it was found to be 59.1% by mass, and the composition of the copolymer was calculated to be TFE unit/NB unit/ CPD unit = 4 5 Μ 1/14 mole %. The copolymer was colorless and transparent, and was measured using a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments Co., Ltd.) at a temperature of 1 〇 ° C /min at a temperature of -63 to 201207029 to 200 ° C. There is no melting point and the glass transition temperature is shown at 10.05 °c (endothermic end temperature). Further, the temperature at which the mass of the copolymer which was subjected to the heating test using the differential heat and thermal weight measuring device [TG-DTA] was reduced by 1 mass% was 232 °C. Further, the number average molecular weight measured by GPC analysis was 1,505, and the weight average molecular weight was 2,408. The copolymer was dissolved in a solvent such as chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone or dioxane. In addition, it may be compatible with a hydrogenated polyoxosiloxane having a SiH group (for example, phenyltris(dimethylnonyloxy)decane). Example 1 (Curable resin composition: solvent xylene) A hydrogenated polyoxonium compound (a siloxane compound) having three hydrogen atoms bonded directly to a ruthenium atom in a glass bottle of 10 cc Phenyl tris(dimethyl decyloxy) decane (C6H5Si{OSi(CH3)2H}3) 〇.54g, the TFE/ENB copolymer obtained in Synthesis Example 1.Og and the dilute solvent of xylene. Mix well, dissolve at 60 ° C, and cool to room temperature. Next, 50 ppm of a cyclic methyl ethyl sulfoxide solution containing 2% of uranium as a platinum catalyst was added, and after uniformly mixing, the mixed solution was poured into a fluororesin FEP film in an oven at 125 ° C. The hydrazine hydrogenation reaction was carried out while evaporating xylene in 8 hours to obtain a film-like cured product. Before placing the mixture into the oven, a part of the mixed solution was analyzed by an infrared spectrometer to confirm the phenyl tris(dimethyl decane oxide). The absorption peak of the SiH group formed by decane is 2134 cm·1. The peak is at 125. The underarms disappeared after 8 hours -64 - 201207029 hardening. Further, the cured product could not be redissolved in xylene, and it was confirmed that cross-linking occurred. The light transmittance of the film was measured by a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.), and was 95.2% at 550 nm and 9.28 at 405 nm. Further, the refractive index was measured by using a spectroscopic ellipsometer (M-2000D, manufactured by A. Woollam JAPAN Co., Ltd.) for a film (having a film thickness of 150 nm) formed by spin coating on a tantalum wafer, and was 1.4795 (5 9 8 nm). ). Example 2 (Solvent-free curable resin composition) In a glass bottle of l〇cc, a benzene having a hydrogenated polyoxo compound (a siloxane compound) having three hydrogen atoms directly bonded to a ruthenium atom was added. Tris(dimethyl decyloxy)decane (C6H5Si{OSi(CH3)2H}3) 0.29g, TFE/ENB copolymer obtained in Synthesis Example 2, 25g, and triallyl isocyanate as a reactive diluent solvent (TAIC) After 0_125g, it was uniformly mixed, and after being dissolved at 6 (TC, it was cooled to room temperature. Secondly, 20 ppm of a cyclic methylvinyl fluorene solution containing 2% of uranium as a platinum catalyst was added, and uniformly mixed. Thereafter, the mixed solution was poured into a fluororesin FEP film, and subjected to a hydrogenation reaction in an oven at 1.25 ° C for 8 hours to obtain a film-like cured product. A part of the solvent-free composition before being placed in the oven The results of the analysis by an infrared spectrometer 'confirmed the absorption peak 2 1 3 4 cnT 1 of the S i fluorenyl group formed by phenyl tris(dimethylnonyloxy)decane. The peak was at 1 2 5 ° C. After hardening for an hour, it disappears on the obtained hardened material. The hardened material cannot be dissolved in -65- 2012 07029 Xylene was confirmed to be crosslinked. The light transmittance of the film was measured by using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.), which was 94.8% at 550 nm and 9 1.2% at 405 nm. The film (film thickness: 150 nm) obtained by spin coating on a ruthenium wafer was measured by a spectroscopic ellipsometer (M-2000D, manufactured by J. A. Woollam JAPAN Co., Ltd.) to be 1.4845 (5 9 8 nm) °. 3 (solvent-free curable resin composition) In a 10 cc glass bottle, a phenyl tris(2) having a hydrogenated polyoxo compound (a siloxane compound) having three hydrogen atoms directly bonded to a ruthenium atom Methyl nonyloxy) decane (C6H5Si{OSi(CH3)2H}3) 61.61g, the TFE/ENB copolymer lg obtained in Synthesis Example 3 was uniformly mixed, dissolved at 60 ° C, and then cooled to room temperature. Add 5 〇ppm of a cyclic methylvinyl fluorene solution containing 2% of platinum as a platinum catalyst. After uniformly mixing, the mixed solution was poured into a fluororesin FEP film at an oven at 1.25 °C. In the case of hydrazine hydrogenation reaction for 8 hours, a film-like cured product is obtained. The solvent-free composition of one part of the front of the box was analyzed by an infrared spectrometer, and the absorption peak of the SiH group formed by phenyl tris(dimethylnonyloxy)decane was confirmed to be 213401^1°. The peak was at 125 ° C. After hardening for 8 hours, it disappeared on the obtained cured product. The cured product could not be dissolved in xylene, and it was confirmed to be crosslinked. The light transmittance of the film was measured by using a spectrophotometer (Hitachi, Ltd. -66-201207029) 4100) The measurement results were 94.6% at 550 nm and 98.8% at 405 nm. Further, the refractive index was measured by a spectroscopic ellipsometer (M-2000D manufactured by J. A. Woollam JAPAN Co., Ltd.), which was obtained by a spin coating method on a tantalum wafer (having a film thickness of 150 μm), and was 1.4763 (598 nm). Example 4 (Solventless Curable Resin Composition) In a glass bottle of 10 cc, a benzene having a hydrogenated polyoxonium compound (a siloxane compound) having three hydrogen atoms directly bonded to a ruthenium atom Tris(dimethyl decyloxy) decane (C6H5Si{OSi(CH3)2H}3) 〇.79g 'The TFE/NB/ENB ternary copolymer obtained in Synthesis Example 5 is uniformly mixed and dissolved at 6 (TC) Thereafter, the mixture was cooled to room temperature. Next, 50 ppm of a cyclic methylvinyloxirane solution containing 2% of platinum as a platinum catalyst was added, and after uniformly mixing, the mixed solution was poured onto a fluororesin FEP film. The film was cured by a hydrogenation reaction in an oven at 1.25 ° C for 8 hours. A portion of the solvent-free composition placed before the oven was analyzed by an infrared spectrometer to confirm the phenyl tris(II). The absorption peak of the SiH group formed by methyl decyloxy) decane is 2134 (^1-1. The peak 125. (: After 8 hours of hardening, it disappeared on the obtained cured product. Further, the cured product could not be dissolved in xylene, and it was confirmed that cross-linking occurred. The light transmittance and refractive index of the film were the same as in Example 1. The results are shown in Table 2. -67-201207029 Examples 5 to 7 (solvent-free curable resin composition) The TFE/NB/ENB 3-membered copolymer obtained in Synthesis Example 5 was used. The material was changed to the TFE/NB/ENB ternary copolymer obtained in Synthesis Examples 6 to 8, and the solvent-free composition was produced in the same manner as in Example 4, and then cured under the same conditions to obtain a film-like cured product. The results of the addition of the solventless curing resin and the measurement results of the film properties and the results of Example 4 are shown in Table 2 [Table 2] Polymer polymer S (g) TAIC (g) SH crosslinking agent (g) Platinum Catalyst (ppm) Transmittance % Refractive Index (589 nm) 550 nm 405 nm Example 4 Synthesis Example 5 1 0.5 0.79 50 95 90 1.4822 K Example 5 Synthesis Example 6 1 0.5 0.93 50 95 91 1.4832 Example 6 Synthesis Example 7 1 0.5 0.73 50 95 90 1.4812 Hungry Example 7 Synthesis Example 8 1 0.5 0.83 50 96 91 1.4827 Example 8 (Solvent-free curable resin composition) In a glass bottle of l〇cc, a benzene having a hydrogenated polyoxo compound (a siloxane compound) having three hydrogen atoms directly bonded to a ruthenium atom Tris(dimethyl decyloxy)decane (C6H5Si{〇Si(CH3)2H}3) 〇.31g, TFE/VNB copolymer 合成.25g obtained in Synthesis Example 4, TAIC 0.125g of reactive diluent After mixing, after dissolving at 60 ° C, it was cooled to room temperature. Next, 20 ppm of a cyclic methylvinyl fluorene solution containing 2% of platinum as a platinum catalyst was added, and after uniformly mixing, the mixed solution was poured into a fluororesin FEP film, and dried in an oven at 125 ° C. Hour time -68 - 201207029 The hydrazine hydrogenation reaction was carried out to obtain a film-like transparent cured product. The solvent-free composition which was placed in the front of the oven was analyzed by an infrared spectrometer, and the absorption peak 2 1 3 4cnT 1 of the S i fluorenyl group formed by phenyl tris(dimethylnonyloxy)decane was confirmed. The peak was hardened at 1 2 5 ° C for 8 hours and disappeared on the resulting cured product. Further, the cured product could not be dissolved in xylene, and it was confirmed that cross-linking occurred. Example 9 to 1 1 (solvent-free curable resin composition) In addition to the phenyl tris(dimethylnonyloxy)decane used in Example 4, tetrakis(dimethylammonioalkyl) as a SiH crosslinking agent Oxy) decane (Example 9), phenyl hydrogenated cyclodecane (including linear) (Example 10), trifluoropropyl tetrakis(dimethyl decyloxy) decane (Example 11) The solvent-free composition was prepared in the same manner as in Example 4, and the film was cured under the same conditions to obtain a film-like cured product. The results of the measurement of the state of the solvent-free hardening resin and the physical properties of the film were added, and the results are shown in Table 3. [Table 3] Amount of Polymer Polymer (g) TAIC (g) SiH Crosslinking Agent (g) Platinum Catalyst (ppm) Transmittance % Refractive Index (589 nm) 550 nm 405 nm Example 9 Synthesis Example 5 1 0.5 0.59 50 96 90 1.4635 Example 1 〇 Synthesis Example 5 1 0.5 0.88 50 95 91 1.4885 Example 11 Synthesis Example 5 1 0.5 0.84 50 95 90 1.4321 Example 1 2 (solvent-free curable resin composition) In a glass bottle of l〇cc, Phenyltris(dimethylnonyloxy)decane (C6H5Si{OSi(CH3) having a hydrogen atom of three hydrogen atoms directly bonded to -69-201207029 at a ruthenium atom 2H}3) 〇.76g, 1 g of TFE/NB/VNB 3 copolymer obtained in Synthesis Example 9, and TAIC 〇.5g of reactive diluent are uniformly mixed, and after being dissolved at 6 (TC), it is cooled to room temperature. Next, 50 ppm of a cyclic methylvinyloxane solution containing 2% of platinum as a platinum catalyst was added, and after uniformly mixing, the mixed solution was poured into a fluororesin FEP film in an oven at 125 ° C. The hydrazine hydrogenation reaction was carried out for 8 hours to obtain a film-like transparent cured product. One part before being placed in the oven was solvent-free. The composition was analyzed by an infrared spectrometer, and the absorption peak 213^1^1 of the SiH group formed by phenyltris(dimethylnonyloxy)decane was confirmed. The peak was hardened at 125 t for 8 hours. The hardened material disappeared. Further, the cured product could not be dissolved in xylene, and it was confirmed that cross-linking occurred. Example 1 3 (solvent-free curable resin composition) In a 10 cc glass bottle, there will be three direct hydrogen atoms. Phenyl tris(dimethylnonyloxy)decane (C6H5Si{OSi(CH3)2H}3) 〇-75 g of a hydrogenated polyoxosiloxane (a siloxane compound) bonded to a ruthenium atom, obtained in Synthesis Example 10. The TFE/NB/CPD copolymer lg, the TAIC 〇.5g as a reactive diluent is uniformly mixed, and after being dissolved at 6 (TC, it is cooled to room temperature. Secondly, the uranium containing 2% as a platinum catalyst is added. The solution of the cyclic methyl vinyl siloxane was 5 〇 PPm, and after uniformly mixing, the mixed solution was poured into a fluororesin FEP film, and the hydrazine hydrogenation reaction was carried out in an oven of 1251 for 8 hours to obtain a film-like transparent film. Hardened. -70- 201207029 One part of the oven will be placed before the oven without solvent The product was analyzed by an infrared spectrometer to confirm the absorption peak 2134CHT1 of the SiH group formed by phenyltris(dimethylnonyloxy)decane. The peak was hardened at 125 ° C for 8 hours. Disappeared. Further, the cured product could not be dissolved in xylene, and it was confirmed that cross-linking occurred. Example 14 (Water vapor transmission data): 5 g of TFE/NB/ENB terpolymer obtained in Synthesis Example 5 and phenyl tris(dimethylnonyloxy)decane 〇.65 g, uranium as a platinum catalyst The divinyltetramethyldioxane complex xylene solution (2.1-2.4% platinum) 5//L was dissolved in a butyl acetate solvent to make the whole 14 g. Subsequently, after filtering using a 0.45 // m PTFE filter, a film of thickness 1 〇〇 #m was applied on a PET film (lumiler manufactured by Toray Industries, Inc.) using a strip coating (#24). After pre-drying for 1 hour at room temperature, it was hardened by 3 Torr in a forced air dryer under conditions of 6 (TC. The film thickness after hardening was determined by micrometer measurement) was 2 4 · 4 &quot; m. The prepared laminated film was cut to a size of 100 mm x 100 mm, and the water vapor transmission rate was measured using a water vapor permeability meter L80-5000' manufactured by Dr. Lyssy Co., Ltd. based on JIS K7129 (method A). The surface of the direct contact is PET' and the dry air side is the cured film of the present invention. First, only the PET film of the substrate is measured for water vapor transmission degree', and the water vapor transmission degree of the cured film layer is calculated according to the following formula. 71 - 201207029 [Equation 1] J=A + ll + ll + ...An Ρ Ρχ Pi P3 Pn (In general, the thickness of the nth layer and the gas permeability coefficient of the multilayer film (thickness 1) formed by the n layer, respectively In the case of 丨η and Pn, the transmission coefficient P of the entire film can be calculated by the above formula. References: Polymers and Moistures Chapter 7, Polymer Society, Kosuke (1 973). Water vapor obtained by the above method The transmittance was 7.5 g/m2*day. Comparative Example 1 LED sealing resin was used commercially. KJR9022E-2 manufactured by Kyosho Corporation, the water vapor transmission rate was measured by the cup method based on JIS Z0208, and was found to be 314 g/m2*day. Example 15 (viscosity, transmittance) The synthesis example 1 was obtained. The TFE/ENB copolymer was mixed with phenyl tris(dimethylnonyloxy)decane as a SiH crosslinking agent, and TAIC was mixed at a ratio shown in Table 4, and the viscosity was measured at 27 ° C. [Table 4] Polymer fl TAIC SiH crosslinker viscosity (g) (g) (g) (mPa.s) 1 0.033 0.58 25000 1 0.061 0.62 15800 1 0.107 0.68 3000 1 0.172 0.76 380 -72- 201207029 For the sample for viscosity measurement Adding 50 ppm of a cyclic methyl ethyl sulphate solution containing 2% uranium as a uranium catalyst, after uniformly mixing, the mixed solution is poured into a fluororesin FEP film, in an oven of 2 5 t The hydrazine hydrogenation reaction was carried out for 8 hours to obtain a film-like transparent cured product. The absorption spectrum of the visible region of the obtained film (25 μm) was measured, and the results are shown in Fig. 1 and Fig. 2. Usability] The curable resin composition of the present invention is suitable for use in a sealing member, optical Materials, photoelectron camera tubes, various sensors, anti-reflective materials, etc. [Simplified illustration of the drawings] [Fig. 1] Absorption map of the visible region of the film obtained in Example 15. [Fig. 2] The film obtained in Example 15 Absorption map of the visible region 0 - 73-

Claims (1)

201207029 VII. Patent application scope: 1. A curable resin composition which is a curable resin composition formed of a fluoropolymer (A) and a hydrosilylation crosslinking agent (B), which is characterized by The fluoropolymer (A) is a fluoropolymer formed from a polymerization unit formed of a fluorinated monomer and a polymerization unit formed by a norbornene monomer having two or more carbon-carbon double bonds. The hydrazine hydrogenation crosslinking agent (B) is a siloxane compound having two or more hydrogen atoms in the molecule directly bonded to a ruthenium atom. 2. The sclerosing resin composition of the first aspect of the patent application, Wherein the norbornene monomer having two or more carbon-carbon double bonds is represented by the following formula (a): (wherein R1 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 10 carbon atoms; R2 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 10 carbon atoms), and has two or more carbon-carbons Double-bonded norbornene monomer, the following formula (b): -74- 201207029 [Chemical 2] =CH——R (wherein R3 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 5 carbon atoms; R4 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 1 carbon; R5 is a hydrogen atom Or a norbornene monomer having two or more carbon-carbon double bonds represented by a hydrocarbon group having an oxygen atom of 1 to 5 carbon atoms; η is an integer of 0 to 10, and the following formula (c): [化3] (wherein R6 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 5 carbon atoms), at least one selected from the group consisting of norbornene monomers having two or more carbon-carbon double bonds Monomer. 3. The curable resin composition according to claim 1 or 2, wherein the norbornene monomer having two or more carbon-carbon double bonds is represented by the following formula (1): -75 - 201207029 [ 4] (wherein 'R7 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), a norbornene monomer having two carbon-carbon double bonds, and the following formula (2); (wherein R8 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), and a norbornene monomer having two carbon-carbon double bonds, and the following formula (3): A norbornene monomer having two carbon-carbon double bonds and at least one monomer selected from the group. 4. The curable resin composition as claimed in claim 1, 2 or 3 wherein the hydrazine hydrogenation crosslinker (B) has two or more of the following formulas - Ο-si r8h--76-201207029 ( In the formula, 'R8 is a hydrocarbyl group having a structure represented by a hydrocarbon group having 1 to 10 carbon atoms. 5. The curable resin composition of claim 1, 2, 3 or 4, wherein the hydrazine hydrogenation crosslinking agent (B) is the following formula (4): R9bS i (OR10) 4_b (4) (wherein R9 is the same or different, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group or a (meth)acrylic group-containing organic group in which a part or all of hydrogen may be substituted by fluorine, or An organic group containing an epoxy group; R1() is the same or different ', and represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a formula: -si R82H (wherein R8 is the same or different, a diorganofluorenyl group (b2) represented by a hydrocarbon group having 1 to 10 carbon atoms; however, at least two of R1() in one molecule are diorganofluorenyl groups (b2); b is an integer of 0 to 2) The oxirane compound represented. 6. The curable resin composition of claim 1, 2, 3, 4 or 5, wherein the fluorine-containing monomer is tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethane Rare, fluoroethylene (vinyl f 1 u 〇ride ), hexafluoro (propylene, hexafluoroisobutylene, C Η 2 = CZ 1 (CF 2) n Z2 (where Ζ1 is Η or F, Ζ2 is H, F or Cl, η is an integer represented by an integer of 1 to 10), and CFfCF-ORf1 (wherein, Rf1 represents a perfluoroalkyl group having 1 to 8 carbon atoms) is represented by perfluoroalkyl group.及)' and 'CF2 = CF-OCH2-Rf2 (wherein, Rf2 represents a perfluoroalkyl group having 1 to 5 carbon atoms), at least one selected from the group consisting of alkyl perfluorovinyl ether derivatives Fluorinated ethylenic monomer -77- sex tree 丨 ethylene &gt; Rf1 olefin ether: ί 彳 (d) 201207029 If the patent application scope 1, 2, 3, 4, 5 or 6 The fluorine-containing monomer is a perfluoro group represented by tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and CFpCF-ORf1 and a perfluoroalkyl group having a carbon number of 1 to 8 (&gt; At least one fluorine-containing ethylene selected in the group Single I. As claimed in claim 1, the second, third, fourth, fifth, sixth or seventh sealing composition, wherein the fluoropolymer (A) can be further hardened by difluorination (in the formula The hard of the item is as follows: (Formula 丨 丨 丨 之 之 之 成 成 中 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Formed by the resulting polymerization unit. &gt;. As claimed in the patent scope 1, 2, 3, 4 '5, 6, 7: fc resin composition, which contains and (C) hydrogenated contact lens. The curable resin composition of the ninth aspect of the present invention is a hydrogenation catalyst (C) selected from the group consisting of a platinum-based catalyst, a palladium-based catalyst, a ruthenium-based catalyst, and a ruthenium-based catalyst. The curable resin composition of the first, second, third, fourth, fifth, sixth, and seventh aspects of the patent is a sealing material. 2 · a hardened material characterized by being as poor as the patented norm 8 a sclerosing resin composition of the first, the first, the second, the third, the third, the fifth, the fifth, the seventh, the eighth, the ninth Those who have been hardened. 1 3 . The cured product of the item 1 of the patent application has a light transmission rate of 80% or more. 1 4. A cured product as claimed in claim 12 or 13 which is a sealing member for an optical element. 15. A fluoropolymer characterized by 'tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and 'CFpCF-ORf1 (wherein Rf1 represents the total number of carbons 1 to 8) a polymerization unit formed of at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro(alkyl vinyl ether) represented by a fluoroalkyl group, and the following formula (a): 】 (wherein R1 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 1 carbon atom; and R2 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 1 carbon atom) has two or more carbons - a polymerization unit formed by a norbornene monomer having a carbon double bond. 16. The fluoropolymer according to claim 15, wherein the norbornene monomer having two or more carbon-carbon double bonds is the following formula (1 - 79 - 201207029) (l) (wherein, R7 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) and a norbornene monomer having two carbon-carbon double bonds. 17. A fluoropolymer characterized by tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CFpCF-ORf1 (wherein Rf1 represents a total carbon number of 1 to 8) a polymerization unit formed of at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro(alkyl vinyl ether) represented by a fluoroalkyl group, and the following formula (b): 〇】 (wherein R3 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 5 carbon atoms; R4 is a hydrogen atom or a hydrocarbon group which may have an oxygen atom of 1 to 1 carbon; R5 is a hydrogen atom or may have a carbon number A hydrocarbon unit formed by a norbornene monomer having two or more carbon-carbon double bonds represented by a hydrocarbon group of 1 to 5 oxygen atoms; η is an integer of 0 to 10). 1 8 . The fluoropolymer according to claim 17 of the patent application, wherein the norbornene monomer having two or more carbon-carbon double bonds is the following formula (2 - 80 - 201207029) A norbornene monomer having two carbon-carbon double bonds represented by (wherein R8 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). A fluoropolymer characterized by comprising tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CFfCF-ORf1 (wherein Rf1 represents a perfluoro group having a carbon number of 1 to 8) a polymerization unit formed of at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro(alkyl vinyl ether) represented by an alkyl group, and the following formula (c): 】 (In the formula, R6 is a hydrogen atom or a hydrocarbon group which may contain an oxygen atom having 1 to 5 carbon atoms), and is formed by a polymerization unit formed of a norbornene monomer having two or more carbon-carbon double bonds. 20. The fluoropolymer according to claim 19, wherein -81 - 201207029 is a norbornene monomer having two or more carbon-carbon double bonds, and the following formula (3): [Chemical Formula 1] (3) A norbornene monomer having two carbon-carbon double bonds. 2 1 · A fluoropolymer as claimed in claim 15, 5, 17, 7, 18, 19 or 20, wherein the fluoropolymer (A) is represented by the following formula (d): [化1 4] (wherein R14 is an alkyl group having 1 to 10 carbon atoms; and X is an integer of 〇2 to 2) is formed by a polymerization unit formed by a norbornene monomer. -82-