JP5440690B2 - Curable resin composition, cured product and fluoropolymer - Google Patents

Description

The present invention relates to a curable resin composition, a cured product, and a fluoropolymer. More specifically, the present invention relates to a curable resin composition that can be cured by a hydrosilylation reaction, a cured product obtained by curing the curable resin composition, and a fluorine-containing polymer suitable for the curable resin composition.

As a curable resin composition using a fluorinated polymer, for example, Patent Document 1 proposes a composition comprising a curable fluorinated polymer having an ethylenic carbon-carbon double bond at the end of the side chain. . Patent Document 2 discloses a curable composition containing a specific fluorine-containing amide compound having vinyl groups at both ends, a specific fluorine-containing organohydrogensiloxane, and a catalytic amount of a platinum group compound.

International Publication No. 02/18457 Pamphlet JP-A-8-199070

However, the crosslinking reaction disclosed in Patent Document 1 is a photocuring reaction, and a curing system based on a hydrosilylation reaction is not disclosed. The curable fluorinated polymer is composed of a chain monomer having a specific structure.

The fluorine-containing amide compound described in Patent Document 2 is obtained by introducing a carbon-carbon double bond at the terminal after the production of a polymer, and thus the amount of crosslinking points cannot be easily adjusted. There was room for improvement.

An object of the present invention is to provide a curable resin composition that is easy to manufacture and that can easily adjust the crosslinking density.

The present invention is a curable resin composition comprising a fluoropolymer (A) and a hydrosilylation crosslinking agent (B), wherein the fluoropolymer (A) is a polymer unit derived from a fluoromonomer. And a fluorine-containing polymer comprising polymerized units derived from a norbornene monomer having two or more carbon-carbon double bonds, and the hydrosilylation crosslinking agent (B) has a hydrogen atom bonded directly to a silicon atom. A curable resin composition, which is a siloxane compound having two or more groups in a molecule.

The present invention is also a cured product obtained by curing the curable resin composition.

The present invention relates to tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CF ₂ ═CF—ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms. And a polymerized unit derived from at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro (alkyl vinyl ethers) represented by the following formula (a):

(In the formula, R ¹ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 10 carbon atoms. R ² is a hydrocarbon atom that may contain a hydrogen atom or an oxygen atom having 1 to 10 carbon atoms. It is also a fluorine-containing polymer comprising polymerized units derived from a norbornene monomer having two or more carbon-carbon double bonds represented by the following formula:

The present invention relates to tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CF ₂ ═CF—ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms. And a polymerized unit derived from at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro (alkyl vinyl ethers) represented by the following formula (b):

(In the formula, R ³ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 5 carbon atoms. R ⁴ is a hydrocarbon atom that may contain a hydrogen atom or an oxygen atom having 1 to 10 carbon atoms. R ⁵ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 5 carbon atoms, n is an integer of 0 to 10). It is also a fluorine-containing polymer comprising polymerized units derived from a norbornene monomer having 2 or more.

The present invention relates to tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CF ₂ ═CF—ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms. And a polymerized unit derived from at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro (alkyl vinyl ethers) represented by the following formula (c):

(In the formula, R ⁶ is a hydrogen atom or a hydrocarbon group which may contain an oxygen atom having 1 to 5 carbon atoms.) A norbornene monomer having two or more carbon-carbon double bonds represented by It is also a fluorine-containing polymer characterized by comprising polymer units derived therefrom.

Since the curable resin composition of the present invention includes a polymer in which a norbornene monomer having two or more carbon-carbon double bonds is polymerized to introduce a crosslinking site, the amount of the crosslinking site can be easily adjusted. Can be manufactured easily. Moreover, it is possible to obtain a cured product having a high crosslinking density. Furthermore, since it can prepare even if a solvent is not included, the process of removing a solvent from the hardened | cured material obtained can also be made unnecessary.

Since the cured product of the present invention is obtained by curing the curable resin composition, it has high transparency and can be easily and inexpensively produced. In addition, the crosslinking density can be increased.
The fluoropolymer of the present invention is easy to produce, the amount of cross-linking sites can be easily adjusted, and it is easy to dissolve or disperse in a hydrosilylation cross-linking agent, so it is suitably used for the curable resin composition. be able to.

It is a graph which shows the absorption spectrum of the visible band of the film obtained in Example 15. FIG. It is a graph which shows the absorption spectrum of the visible band of the film obtained in Example 15. FIG.

The curable resin composition of the present invention has (A) a polymer unit derived from a fluorine-containing monomer (hereinafter also referred to as “fluorine-containing monomer unit”) and two or more carbon-carbon double bonds. It comprises a fluorine-containing polymer comprising polymer units derived from norbornene monomers (hereinafter also referred to as “norbornene monomer units”), and (B) a hydrosilylation crosslinking agent.

Since the curable resin composition of the present invention is composed of the fluorine-containing polymer (A) containing a fluorine-containing monomer unit, the refractive index of the resulting cured product and the transparency in the ultraviolet or near infrared region. The optical properties such as light resistance, weather resistance, heat resistance, water absorption, water and oil repellency, and chemical resistance can be made excellent.

Since the crosslinking reaction of the curable resin composition of the present invention is not a reaction in which a desorbing component such as water or salt is generated but an addition reaction, it does not require a step of removing a by-product.

Further, by appropriately selecting a hydrosilylation crosslinking agent, a composition having a predetermined viscosity can be prepared without using a solvent, and crosslinking (curing) can be easily performed. Moreover, the process of removing a solvent from the hardened | cured material obtained can also be made unnecessary. Furthermore, since it can prepare without using a solvent, the transparency of the hardened | cured material obtained can also be improved more.

In the curable resin composition of the present invention, since the norbornene monomer unit has a carbon-carbon double bond (crosslinking site), a step of introducing a crosslinking site into the fluoropolymer is unnecessary. The manufacturing process can be simplified. In addition, the amount of crosslinking sites can be easily adjusted, and a molded product having a high crosslinking density can be obtained.

Furthermore, it can be manufactured at a lower cost than a fluorine-based sealing material as described in International Publication No. 2005/085303 pamphlet and International Publication No. 2009/096342 pamphlet, and is practical.

(A) Fluoropolymer The fluoropolymer (A) is composed of a polymer unit derived from a fluoromonomer and a polymer unit derived from a norbornene monomer having two or more carbon-carbon double bonds. Become. The fluorine-containing polymer (A) is a polymer having a crosslinking site, and the amount of the crosslinking site can be easily adjusted when producing the fluorine-containing polymer (A). Moreover, since the fluoropolymer (A) is surprisingly dissolved or dispersed in the hydrosilylation crosslinking agent, the curable resin composition of the present invention can dispense with a solvent.
The amount of the crosslinking site (carbon-carbon double bond) can be easily adjusted by changing the kind of norbornene monomer and the ratio of the norbornene monomer to the total monomer amount. The presence of a crosslinking site in the fluoropolymer (A) can be confirmed, for example, by ¹ H-NMR.

A norbornene monomer having two or more carbon-carbon double bonds is a monomer having a norbornene skeleton and further having one or more carbon-carbon double bonds in a portion other than the norbornene skeleton. As the norbornene monomer, a norbornene monomer having two carbon-carbon double bonds is preferable. The norbornene monomer may have a fluorine atom or may not have a fluorine atom, but preferably has no fluorine atom.

The norbornene monomer is preferably a monomer having, for example, a norbornene skeleton, a group having one or more carbon-carbon double bonds, and / or a dicyclopentadiene skeleton.

The norbornene skeleton has the following formula:

A carbon skeleton represented by

The dicyclopentadiene skeleton has the following formula:

A carbon skeleton represented by

When the norbornene monomer is a monomer having a group having one or more carbon-carbon double bonds, the norbornene monomer has one group having one or more carbon-carbon double bonds. You may have, and you may have two or more. The norbornene monomer preferably has a norbornene skeleton and one group having one or more carbon-carbon double bonds, and the norbornene skeleton and one group having one carbon-carbon double bond are 1 It is more preferable to have one.

Examples of the group having one or more carbon-carbon double bonds include an alkenyl group such as a vinyl group, an allyl group, an isopropenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group; a vinylphenyl group, Alkenyl group-containing aryl groups such as isopropenylphenyl group; alkenyl group-containing aralkyl groups such as vinylphenylmethyl group; alkylidene groups such as vinylidene group; and the like. The group having one or more carbon-carbon double bonds is preferably at least one group selected from the group consisting of an alkenyl group, an alkenyl group-containing aryl group, an alkenyl group-containing aralkyl group, and an alkylidene group. More preferably, they are an alkenyl group and / or an alkylidene group. In addition, as the group having two or more carbon-carbon double bonds, for example, two or more introduced by reacting a compound such as Karenz BEI manufactured by Showa Denko KK with a norbornene monomer having an OH group. And a group having two carbon-carbon double bonds.

Examples of the norbornene monomer include the following formula (a):

(In the formula, R ¹ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 10 carbon atoms. R ² is a hydrocarbon atom that may contain a hydrogen atom or an oxygen atom having 1 to 10 carbon atoms. And a norbornene monomer having two or more carbon-carbon double bonds represented by: R ¹ is more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ² is more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Specific examples of R ¹ include hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, t -Pentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. R ¹ is more preferably a methyl group. Examples of R ² include the same as R ¹ . R ² is preferably a hydrogen atom. In the present specification, the “hydrocarbon group which may contain an oxygen atom” is preferably, for example, an alkyl group, an alkenyl group, an alkyl ether group or an alkenyl ether group.

As the norbornene monomer represented by the above formula (a), the following formula (1):

(Wherein R ⁷ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) and is more preferably a norbornene monomer having two carbon-carbon double bonds. R ⁷ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group.

As the norbornene monomer, the following formula (b):

(In the formula, R ³ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 5 carbon atoms. R ⁴ is a hydrocarbon atom that may contain a hydrogen atom or an oxygen atom having 1 to 10 carbon atoms. R ⁵ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 5 carbon atoms, n is an integer of 0 to 10). Norbornene monomers having 2 or more are also preferred. R ³ is more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. n is preferably an integer of 0 to 5, and more preferably 0 or 1.

As the norbornene monomer represented by the above formula (b), the following formula (2):

(Wherein R ⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and is more preferably a norbornene monomer having two carbon-carbon double bonds. R ⁸ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

Examples of the norbornene monomer represented by the above formula (a) or (b) include 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 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-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -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-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexesyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2, 3-trimethyl-4-pentenyl) -2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene And -5-norbornene. These norbornene monomers can be used alone or in combination of two or more.

As the norbornene monomer, the following formula (c):

(In the formula, R ⁶ is a hydrogen atom or a hydrocarbon group which may contain an oxygen atom having 1 to 5 carbon atoms.) Norbornene monomer having two or more carbon-carbon double bonds represented by preferable.

As the norbornene monomer represented by the above formula (c), the following formula (3):

A norbornene monomer having two carbon-carbon double bonds represented by

As the norbornene monomer, the norbornene monomer represented by the formula (a), the norbornene monomer represented by the formula (b), and the norbornene monomer represented by the formula (b) from the viewpoint of being easily dissolved or dispersed in the hydrosilylation crosslinking agent (B) The monomer is preferably at least one monomer selected from the group consisting of norbornene monomers represented by the formula (c). More preferably, it is selected from the group consisting of a norbornene monomer represented by formula (1), a norbornene monomer represented by formula (2), and a norbornene monomer represented by formula (3). At least one monomer. More preferred is a norbornene monomer represented by the formula (1).

The fluorine-containing monomer in the present invention is a monomer having a fluorine atom that can be copolymerized with the norbornene monomer. The fluorine-containing monomer preferably does not have a norbornene skeleton. More preferably, it is a monomer having a carbon-carbon double bond not having a norbornene skeleton.

Examples of the fluorine-containing monomer include tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene [HFP], hexafluoroisobutene, and CH _2. = CZ ¹ (CF ₂ ) _n ¹ Z ² (wherein Z ¹ is H or F, Z ² is H, F or Cl, and n ¹ is an integer of ¹ to 10), Perfluoro (alkyl vinyl ether) [PAVE] represented by CF ₂ = CF—ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms), and CF ₂ = CF— OCH ₂ -Rf ² (wherein, Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms) little is selected from the group consisting of alkyl perfluorovinyl ether derivative represented by the Kutomo one fluorine-containing ethylenic monomer is preferable.

Examples of the PAVE include perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], perfluoro (butyl vinyl ether), etc. Among them, PMVE PEVE or PPVE is more preferable.

As the alkyl perfluorovinyl ether derivative, those in which Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

As said fluorine-containing monomer, TFE and / or CTFE are more preferable, and TFE is still more preferable.

The fluorine-containing polymer (A) includes a fluorine-containing monomer unit, a norbornene monomer unit derived from a norbornene monomer having two or more carbon-carbon double bonds, and the fluorine monomer and It may be composed of a monomer unit derived from another monomer copolymerizable with a norbornene monomer having two or more carbon-carbon double bonds. Said other monomer is a monomer which does not contain a fluorine atom.

As said other monomer, a fluorine-free ethylenic monomer except the said norbornene monomer which has 2 or more of the said carbon-carbon double bonds is preferable. Examples of the other monomer include ethylene, propylene, 1-butene, 2-butene, vinyl chloride, vinylidene chloride, alkyl vinyl ether, hydroxyl group-containing vinyl ether monomer, vinyl ester monomer, unsaturated carboxylic acid, and carbon- Preference is given to at least one fluorine-free ethylenic monomer selected from the group consisting of norbornene monomers having one carbon double bond. Examples of the alkyl vinyl ether include methyl vinyl ether and ethyl vinyl ether. Examples of the hydroxyl group-containing vinyl ether monomer include 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether. Examples of the vinyl ester monomer include vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and vinyl acetate.
As the other monomer, a norbornene monomer having one carbon-carbon double bond is preferable.

A norbornene monomer having one carbon-carbon double bond is a monomer having a norbornene skeleton and having no carbon-carbon double bond in a portion other than the norbornene skeleton. As a norbornene monomer having one carbon-carbon double bond, the following formula (d):

(Wherein R ¹⁴ is an alkyl group having 1 to 10 carbon atoms, x is an integer of 0 to 2), and is preferably a norbornene monomer represented by the following formula:

で示されるノルボルネン単量体であることがより好ましい。

The norbornene monomer represented by is more preferable.

The unsaturated carboxylic acid has at least one carbon-carbon double bond that enables copolymerization, and one molecule of carbonyloxy group [—C (═O) —O—]. Those having at least one are preferable, and may be an aliphatic unsaturated monocarboxylic acid, or may be an aliphatic unsaturated polycarboxylic acid having two or more carboxyl groups.

Examples of the aliphatic unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and aconite More preferably, it is at least one selected from the group consisting of acids.

In the fluorinated polymer (A), the molar ratio of the fluorinated monomer unit to the norbornene monomer unit is preferably 90:10 to 10:90. More preferably, it is 70: 30-30: 70.

In the fluorinated polymer (A), the total of the fluorinated monomer units and the norbornene monomer units is preferably 30 mol% or more based on the total polymerized units. More preferably, it is 50 mol% or more.

In the fluoropolymer (A), the other monomer units are preferably 70 mol% or less based on the total monomer units. More preferably, it is 50 mol% or less.

The number average molecular weight of the fluorinated polymer (A) is not particularly limited, but is 1,000 to 1,000,000 from the viewpoint of solubility or dispersibility in the hydrosilylation crosslinking agent (B) or the solvent (D). Preferably, it is 1000-500000.
The fluoropolymer (A) preferably has a glass transition temperature of 30 to 200 ° C, more preferably 45 to 150 ° C.

The fluorinated polymer (A) is preferably an alternating copolymer of the fluorinated monomer and the norbornene monomer from the viewpoint of obtaining a cured product having a uniform crosslinking density. Such an alternating copolymer can be preferably obtained by setting the monomer composition ratio during the polymerization to about 1: 1.

The fluoropolymer (A) can be produced by solution polymerization, suspension polymerization, emulsion polymerization, or the like. In the above polymerization, a polymerization initiator, a surfactant, a chain transfer agent, and a solvent can be used, and conventionally known ones can be used.

As said 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 a known oil-soluble peroxide, such as diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, etc. Peroxyesters such as dialkyl peroxycarbonates, t-butyl peroxyisobutyrate and t-butyl peroxypivalate, dialkyl peroxides such as di-t-butyl peroxide, and the like can also be used as di (ω -Hydro-dodecafluoroheptanoyl) peroxide, di (ω-hydro-tetradecafluoroheptanoyl) peroxide, di (ω-hydro-hexadecafluorononanoyl) peroxide, di (perfluorobutyryl) peroxide , Di (Perful Pareril) -Oxide, di (perfluorohexanoyl) peroxide, di (perfluoroheptanoyl) peroxide, di (perfluorooctanoyl) peroxide, di (perfluorononanoyl) peroxide, di (ω-chloro-hexafluoro) Butyryl) peroxide, di (ω-chloro-decafluorohexanoyl) peroxide, di (ω-chloro-tetradecafluorooctanoyl) peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydrohexadecafluoro Nonanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydrododecafluoroheptanoyl-perfluorobutyryl-peroxide, di (dichloropentafluorobuta Yl) peroxide, di (trichlorooctafluorohexanoyl) peroxide, di (tetrachloroundecafluorooctanoyl) peroxide, di (pentachlorotetradecafluorodecanoyl) peroxide, di (undecachlorodotria contourer) Fluorodocosanoyl) peroxide di [perfluoro (or fluorochloro) acyl] peroxides and the like are typical examples.

The water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, ammonium salts such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonate, potassium salts, sodium salts. , T-butyl permaleate, t-butyl hydroperoxide and the like. A reducing agent such as sulfites and sulfites may be used in combination with the peroxide, and the amount used may be 0.1 to 20 times the peroxide.

As the surfactant, a known surfactant can be used. For example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, or the like can be used. Of these, fluorine-containing anionic surfactants are preferred, and may contain an ether-bonded oxygen atom (that is, an oxygen atom may be inserted between carbon atoms). More preferred are fluorine-containing anionic surfactants. The addition amount (with respect to polymerization water) is preferably 50 to 5000 ppm.

In the solution polymerization, the polymerization is performed in a solvent capable of dissolving the reactive monomer, and the resulting polymer may be dissolved or precipitated in the solvent. Examples of such a solution polymerization solvent include CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CHFCHFCF ₂ CF ₃ , and the following formula:

A compound represented by: CHF ₂ CH ₃ CF ₃ , CF ₃ CF ₂ CHCl ₂ , CClF ₂ CF ₂ CHClF, CF ₃ CF ₂ CF ₂ CF ₂ OCH ₃ , CF ₃ CF ₂ CF ₂ CF ₂ OCH ₂ CH ₃ , Fluorocarbon solvents such as CHF ₂ CF ₂ OCH ₂ CF ₃ , aliphatic hydrocarbons such as octane and hexane, ketones such as acetone and methyl isobutyl ketone, esters such as ethyl acetate, aromatic hydrocarbons such as xylene and toluene, Examples include chlorohydrocarbons such as chloroform and alcohols such as t-butanol. Of these solvents, a fluorocarbon solvent is preferred in view of the fact that chain transfer is small. A solvent can be used individually or in mixture of 2 or more types.
In suspension polymerization, a fluorine-based solvent may be used in addition to water. Examples of the fluorine-based solvent include hydrochlorofluoroalkanes such as CH ₃ CClF ₂ , CH ₃ CCl ₂ F, CF ₃ CF ₂ CCl ₂ H, and CF ₂ ClCF ₂ CFHCl; perfluorocyclobutane, CF ₃ CF ₂ CF ₂ CF ₃ Perfluoroalkanes such as CF ₃ CF ₂ CF ₂ CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF _{3, and the} like.
It does not specifically limit as polymerization temperature, It may be 0-100 degreeC. The polymerization pressure is appropriately determined according to other polymerization conditions such as the type, amount and vapor pressure of the solvent to be used, the polymerization temperature, etc., but may usually be 0 to 9.8 MPaG. For the polymerization system, if necessary, hydrocarbons such as ethane, isopentane, n-hexane and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; acetates such as ethyl acetate and butyl acetate; Chain transfer agents such as alcohols such as methanol and ethanol; mercaptans such as methyl mercaptan; and halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride may be used.

(B) Hydrosilylation crosslinking agent The hydrosilylation reaction is an addition reaction between a carbon-carbon double bond and a hydrogen atom directly bonded to a silicon atom, and the hydrosilylation crosslinking agent (B) in the present invention is a hydrogen atom. Is a siloxane compound having two or more groups directly bonded to silicon atoms in the molecule. The hydrosilylation crosslinking agent is preferably liquid.

As the hydrosilylation crosslinking agent (B), for example, those described in International Publication No. 2008/153002 pamphlet, International Publication No. 2008/044765 pamphlet, International Publication No. 2008/072716 pamphlet and the like can be used.

Specifically, for example, B1, B2 or B3 described in International Publication No. 2008/044765 pamphlet can be used.

As hydrosilylation crosslinking agent (B), the following formula:
-O-SiR ⁸ H-
A siloxane compound having two or more structures represented by the formula (wherein R ⁸ is a monovalent hydrocarbon group having 1 to 10 carbon atoms) is preferable. R ⁸ is the same or different and is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group. R ⁸ is more preferably at least one group selected from the group consisting of a methyl group, an ethyl group, and a phenyl group, and more preferably a methyl group.

As hydrosilylation crosslinking agent (B), the following formula:
-O-SiR ⁸ ₂ H
A siloxane compound having a diorganosiloxy group (b1) represented by the formula (wherein R ⁸ is the same or different and is a monovalent hydrocarbon group having 1 to 10 carbon atoms) is preferable. R ⁸ is the same or different and is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group. R ⁸ is more preferably at least one group selected from the group consisting of a methyl group, an ethyl group, and a phenyl group, and more preferably a methyl group.

As the diorganosiloxy group (b1), for example, the formula:
_{-O-Si (CH 3) 2} H
A group represented by the formula:
_{-O-Si (C 6 H 5} ) 2 H
A group represented by the formula:
_{-O-Si (CH 3) (} C 6 H 5) H
A group represented by the formula:
_{-O-Si (C 2 H 5} ) 2 H
The group represented by these can be illustrated.

In the present invention, the hydrosilylation crosslinking agent (B) is a liquid siloxane compound (hereinafter referred to as “a”) having two or more groups in which hydrogen atoms capable of dissolving or dispersing the fluoropolymer (A) are directly bonded to silicon atoms. Hydrosilylated cross-linking agent (B4) ”), or a liquid or solid state in which the fluorine-containing polymer (A) is not dissolved or dispersed, and a group in which a hydrogen atom is directly bonded to a silicon atom. It may be a siloxane compound having at least one (hereinafter also referred to as “hydrosilylation crosslinking agent (B5)”).

(B4) Hydrosilylated crosslinker The hydrosilylated crosslinker (B4) is a liquid that has two or more groups in the molecule that can dissolve or disperse the fluoropolymer (A) and in which hydrogen atoms are directly bonded to silicon atoms. It is a siloxane compound. The hydrosilylation crosslinking agent (B4) is a siloxane compound that has the ability to crosslink (cur) the fluoropolymer (A) by a hydrosilylation reaction and can dissolve or disperse the fluoropolymer (A). .

When this hydrosilylation crosslinking agent (B4) is used, a solvent for dissolving or dispersing the fluoropolymer (A) (the solvent (D) described later) is not required, and a so-called solventless curable resin composition is used. It can be.

When the solvent-free curable resin composition is used, it is not necessary to remove the organic solvent, and the molding process and the like can be simplified. Furthermore, the solventless curable resin composition is useful even in cases where the inclusion of volatile components is not allowed due to the molding process conditions. For example, it is advantageous in applications such as filling and sealing in an airtight container.

As the hydrosilylation crosslinking agent (B4), for example, B1 or B2 described in International Publication No. 2008/044765 pamphlet can be used.

As hydrosilylation crosslinking agent (B4), the following formula (4):
R ⁹ _b Si (OR ¹⁰ ) _4-b (4)
(In the formula, each R ⁹ is the same or different, and a part or all of hydrogen atoms may be substituted with fluorine, an alkyl group having 1 to 10 carbon atoms, an aryl group, a (meth) acryl group-containing organic group, Or an epoxy group-containing organic group, wherein R ¹⁰ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or the following formula:
-SiR ⁸ ₂ H
(In formula, R < ⁸ > is the same or different and is a C1-C10 monovalent hydrocarbon group.) Represents the diorganosilyl group (b2) represented. However, at least two R ¹⁰ in one molecule are diorganosilyl groups (b2). b is an integer of 0-2. ) (Hereinafter also referred to as hydrosilylation crosslinking agent (B6)). R ⁸ is the same or different and is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group. R ⁸ is more preferably at least one group selected from the group consisting of a methyl group, an ethyl group, and a phenyl group, and more preferably a methyl group. R ⁹ is the same or different and is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group, in which part or all of hydrogen may be substituted with fluorine. b is preferably 1, two R ¹⁰ are the above diorganosilyl groups (b2), one R ¹⁰ is a hydrogen atom, or all three R ¹⁰ are diorganosilyl. The group (b2) is preferred.

Moreover, as hydrosilylation crosslinking agent (B4), following formula (5):
^{_{R 9 c1 (R 10 O)}} 3-c1 Si-R 11 -SiR 9 c2 (OR 10) 3-c2 (5)
(In the formula, R ⁹ is the same or different, and a part or all of hydrogen atoms may be substituted by fluorine, an alkyl group having 1 to 10 carbon atoms, an aryl group, a (meth) acryl group-containing organic group, or Represents an epoxy group-containing organic group, and R ¹⁰ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or the following formula:
-SiR ⁸ ₂ H
(In formula, R < ⁸ > is the same or different and is a C1-C10 monovalent hydrocarbon group.) Represents the diorganosilyl group (b2) represented. However, at least two R ¹⁰ in one molecule are diorganosilyl groups (b2). R ¹¹ is a divalent organic group. c1 is an integer of 0 to 3, and c2 is an integer of 0 to 3. However, c1 and c2 are not both 3. ) (Hereinafter also referred to as hydrosilylation crosslinking agent (B7)).
The (meth) acryl group-containing organic group is preferably a C 1-10 alkyl group having a (meth) acryl group, or a C 1-10 alkyl ether group having a (meth) acryl group. . The epoxy group-containing organic group is preferably an alkyl group having 1 to 10 carbon atoms or an alkyl ether group having 1 to 10 carbon atoms having an epoxy group. The hydrosilylation crosslinking agent (B) is preferably at least one compound selected from the group consisting of hydrosilylation crosslinking agents (B6) and (B7).

As hydrosilylation crosslinking agent (B6) or (B7), specifically, the formula:
CH ₃ Si {OSi (CH ₃ ) ₂ H} ₃
A siloxane compound represented by the formula:
_{CH 3 (C 6 H 5)} Si {OSi (CH 3) 2 H} 2
A siloxane compound represented by the formula:
C ₃ H ₇ Si {OSi (CH ₃ ) ₂ H} ₃
A siloxane compound represented by the formula:
_{C 4 H 9 Si {OSi (} CH 3) 2 H} 3
A siloxane compound represented by the formula:
C ₆ H ₁₃ Si {OSi (CH ₃ ) ₂ H} ₃
A siloxane compound represented by the formula:
C ₈ H ₁₇ Si {OSi (CH ₃ ) ₂ H} ₃
A siloxane compound represented by the formula:
C ₆ H ₅ Si {OSi (CH ₃ ) ₂ H} ₃
A siloxane compound represented by the formula:
(C ₆ H ₅ ) ₂ Si {OSi (CH ₃ ) ₂ H} ₂
A siloxane compound represented by the formula:
CF ₃ C ₂ H ₄ Si {OSi (CH ₃ ) ₂ H} ₃
A siloxane compound represented by the formula:

A siloxane compound represented by the formula:

A siloxane compound represented by the formula:

A siloxane compound represented by the formula:

で表されるシロキサン化合物、式：

A siloxane compound represented by the formula:

A siloxane compound represented by the formula:

A siloxane compound represented by the formula:
_{{(CH 3) 2 HSiO}} 3 Si-C 2 H 4 -Si {OSi (CH 3) 2 H} 3
A siloxane compound represented by the formula:
_{{(CH 3) 2 HSiO}} 3 Si-C 6 H 12 -Si {OSi (CH 3) 2 H} 3
A siloxane compound represented by the formula:
{(CH ₃ ) ₂ HSiO} ₂ CH ₃ Si—C ₂ H ₄ —SiCH ₃ {OSi (CH ₃ ) ₂ H} ₂
A siloxane compound represented by the formula:
_{{(CH 3) 2 HSiO}} 2 CH 3 Si-C 6 H 12 -SiCH 3 {OSi (CH 3) 2 H} 2
A siloxane compound represented by the formula:
_{{(C 6 H 5) 2} HSiO} 3 Si-C 2 H 4 -Si {OSi (C 6 H 5) 2 H} 3
A siloxane compound represented by the formula:
_{{(C 6 H 5) 2} HSiO} 3 Si-C 6 H 12 -Si {OSi (C 6 H 5) 2 H} 3
And a siloxane compound represented by the formula:
_{{(CH 3) 2 HSiO}} 3 Si-C 3 H 6 (OC 2 H 4) m 2 (OC 3 H 6) n 2 OC 3 H 6 -Si {OSi (CH 3) 2 H} 3
(Wherein m ² is an integer of 0 or more, n ² is an integer of 0 or more, and m ² + n ² ≧ 1), and at least one selected from the group consisting of siloxane compounds The siloxane compound is preferred.

In particular, because of its good solubility and compatibility, the formula:
C ₆ H ₅ Si {OSi (CH ₃ ) ₂ H} ₃
A siloxane compound represented by the formula:
(C ₆ H ₅ ) ₂ Si {OSi (CH ₃ ) ₂ H} ₂
A siloxane compound represented by the formula:
_{CH 3 (C 6 H 5)} Si {OSi (CH 3) 2 H} 2
A siloxane compound represented by the formula:
C ₃ H ₇ Si {OSi (CH ₃ ) ₂ H} ₃
A siloxane compound represented by the formula:
_{C 4 H 9 Si {OSi (} CH 3) 2 H} 3
And a siloxane compound represented by the formula:
C ₆ H ₁₃ Si {OSi (CH ₃ ) ₂ H} ₃
At least one siloxane compound selected from the group consisting of siloxane compounds represented by

(B8) Fluorine-containing hydrosilylation crosslinking agent As the hydrosilylation crosslinking agent (B4), a fluorine-containing hydrosilylation crosslinking agent (B8) is also preferable. Since the fluorine-containing hydrosilylation crosslinking agent (B8) is highly compatible with the fluorine-containing polymer (A), it is easy to obtain a uniform composition. When this fluorine-containing hydrosilylation crosslinking agent (B8) is used, a solvent for dissolving or dispersing the fluorine-containing polymer (A) (a solvent (D) described later) is not required, and so-called solventless curable resin is used. It can be a composition.
Examples of the fluorine-containing hydrosilylation crosslinking agent (B8) include, for example, JP-A No. 05-320175, JP-A No. 06-306060, JP-A No. 08-003178, JP-A No. 08-134084, and JP-A No. 08-. The compounds described in JP-A No. 157486, JP-A No. 09-2221489, JP-A No. 09-316264, JP-A No. 11-116687, and JP-A No. 2003-137891 can be used.

Among these, from the viewpoint of high compatibility, the fluorine-containing hydrosilylation crosslinking agent (B8) is preferably linear rather than cyclic, and the fluorine-containing group is preferably introduced into the side chain rather than the terminal or main chain. . Typical structural formulas include the following. Rf ³ is a monovalent group containing fluorine, and Rf ⁴ is a divalent group containing fluorine. Following formula:

(In the formula, Rf ³ is a monovalent group containing fluorine, Me is a methyl group, X is a divalent organic group, and R represents a monovalent organic group. N ¹¹ , m ¹¹ And o ¹¹ are the same or different and each represents an integer of 0 or more.) A cyclic fluorine-containing siloxane compound represented by the following formula:

(Wherein, Rf ³ is a divalent group in which ^.Me, X, R, ^{n 11} and ^{m 11} are the same. As above containing fluorine) straight chain terminated Rf ³ group was introduced which is represented by Fluorine-containing siloxane compound having the following formula:

(Wherein Rf ⁴ , Me, X, R, n ¹¹ , m ^11, and o ¹¹ are the same as described above. P ¹¹ is an integer of 0 or more) Rf ⁴ group is introduced into the main chain represented by Linear fluorinated siloxane compound having the following formula:

(Wherein, Rf ³ , Me, X, R, n ¹¹ , m ^11, and o ¹¹ are the same as above), a linear fluorine-containing siloxane compound in which an Rf ³ group is introduced into the side chain represented by Can be mentioned.
In each fluorine-containing siloxane compound, R is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms, and is preferably the same or different, for example, a methyl group, an ethyl group, or a phenyl group. More preferably, they are the same or different and are a methyl group or a phenyl group. X is ^{independently, -CH 2 -, - CH 2} O -, - CH 2 OCH 2 -, ^{or, -Y-NR} 12 -CO- (where, Y is -CH ² - or the following formula:

It is group represented by these. R ¹² is a monovalent organic group. ) Is preferable.

Moreover, as a fluorine-containing hydrosilylation crosslinking agent (B8), following formula:

(Wherein, Rf ⁵ is a monovalent group containing ^{fluorine, R 12} is a monovalent represents an organic ^{group, R 13} is a divalent represents an organic group.) Rf ⁵ group at the terminal represented by A linear fluorine-containing siloxane compound into which is introduced is also preferred. Rf ⁵ is preferably a trifluoromethyl group, R ¹² is preferably a methyl group (—CH ₃ ), and R ¹³ is preferably a methylene group (—CH ₂ —CH ₂ —).

The hydrosilylation crosslinking agent (B4) of the present invention also has the following formula:

^{(N 12} is an integer of 1 to 10.) Preferred is also a siloxane compound represented by the. n ¹² is preferably 3 to 10, more preferably 3 to 5, and still more preferably 4.

The hydrosilylation crosslinking agent (B4) of the present invention also has the following formula:

^{(N 13} is 3 or 4.) Preferred siloxane compound represented by the.

(B5) A siloxane compound having two or more groups in which a hydrogen atom is directly bonded to a silicon atom in a liquid or solid state in which the hydrosilylation crosslinking agent fluoropolymer (A) is not dissolved or dispersed.

When the hydrosilylation crosslinking agent (B5) is used, it is preferable to use a solvent (D) that dissolves or disperses the fluoropolymer (A) or to use a hydrosilylation crosslinking agent (B4) in combination.

As a specific hydrosilylation crosslinking agent (B5), for example, B3 described in International Publication No. 2008/044765 pamphlet can be used as it is.
Specific examples of the hydrosilylation crosslinking agent (B5) include an average unit formula:
{H (CH ₃ ) ₂ SiO _1/2 } _d (SiO _4/2 ) _f
A siloxane compound represented by the formula:
{H (CH ₃ ) ₂ SiO _1/2 } _d (CH ₃ SiO _3/2 ) _e (SiO _4/2 ) _f
A siloxane compound represented by the formula:
{H (CH ₃ ) ₂ SiO _1/2 } _d (C ₆ H ₅ SiO _3/2 ) _e (SiO _4/2 ) _f
A siloxane compound represented by the formula:
{H (CH ₃ ) ₂ SiO _1/2 } _d (CH ₃ SiO _3/2 ) _e
A siloxane compound represented by the formula:
{H (CH ₃ ) ₂ SiO _1/2 } _d (C ₆ H ₅ SiO _3/2 ) _e
A siloxane compound represented by the formula:
{H (CH ₃ ) (C ₆ H ₅ ) SiO _1/2 } _d (SiO _4/2 ) _f
And at least one siloxane compound selected from the group consisting of siloxane compounds (wherein, d, e and f are all positive numbers), and the average unit formula:
{H (CH ₃ ) ₂ SiO _1/2 } _d (SiO _4/2 ) _f
(In the formula, d and f are both positive numbers.)
It is preferable that it is a siloxane compound represented by these.

In the curable resin composition of the present invention, the content of the hydrosilylation crosslinking agent (B) varies depending on the type of the fluoropolymer, the type of the hydrosilylation crosslinking agent, the presence or absence of a solvent, the type, and the like. It is preferable that they are 5 mass parts or more and 500 mass parts or less with respect to 100 mass parts of polymers (A). More preferably, they are 10 mass parts or more and 300 mass parts or less, More preferably, they are 20 mass parts or more and 200 mass parts or less.

When the curable resin composition of the present invention contains a solvent (D), the content of the hydrosilylation crosslinking agent (B) is based on 100 parts by mass of the fluoropolymer (A) from the viewpoint of the function as a crosslinking agent. And 5 parts by mass or more is preferable. More preferably, it is 10 mass parts or more, More preferably, it is 20 mass parts or more. Moreover, it is preferable that it is 90 mass parts or less, More preferably, it is 70 mass parts or less, More preferably, it is 50 mass parts or less.

Further, when the curable resin composition of the present invention does not contain a solvent (D), that is, when the hydrosilylation crosslinking agent (B) also serves as a solvent for the fluoropolymer (A), hydrosilylation The crosslinking agent (B) is 30 parts by mass or more, further 50 parts by mass or more, particularly 70 parts by mass or more, and 500 parts by mass or less, further 100 parts by mass with respect to the fluoropolymer (A). 300 parts by mass or less, particularly 200 parts by mass or less are preferable. When the curable resin composition of the present invention does not contain a solvent (D), the hydrosilylation crosslinking agent (B) is preferably a hydrosilylation crosslinking agent (B4), and among them, a fluorinated hydrosilylation crosslinking agent (B8). ) Is more preferable.

(C) Hydrosilylation catalyst The curable resin composition of the present invention preferably further comprises a hydrosilylation catalyst (C). The hydrosilylation catalyst (C) is a catalyst for promoting the hydrosilylation reaction of the composition of the present invention. Such a catalyst is preferably at least one catalyst selected from the group consisting of platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, ruthenium-based catalysts, and iridium-based catalysts. From the viewpoint of availability, a platinum-based catalyst is preferable. Examples of the platinum-based catalyst include chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum carbonyl complex, platinum olefin complex, platinum alkenylsiloxane complex, and the like.

The hydrosilylation catalyst (C) is not limited to those described above, and a compound that catalyzes a known hydrosilylation reaction can be used. For example, those described in International Publication No. 2008/153002, International Publication No. 2008/044765, International Patent Application PCT / JP2007 / 074066, International Patent Application PCT / JP2008 / 060555, etc. Can be used.

In the curable resin composition of the present invention, the content of the hydrosilylation catalyst (C) may be any catalyst amount that promotes the curing of the composition of the present invention. The content of the hydrosilylation catalyst (C) is preferably 0.1 to 1000 ppm by mass with respect to the curable resin composition of the present invention. More preferably, it is 1 to 500 ppm. If the content of the hydrosilylation catalyst (C) is too low, curing of the resulting composition may not be sufficiently promoted, and if it is too high, problems such as coloring may occur in the resulting cured product. .

(D) Solvent Since the fluorinated polymer (A) can be easily prepared even if the curable resin composition of the present invention does not contain a solvent, the curable resin composition of the present invention is a solvent. May not be included. However, the solvent (D) may be included as necessary.

The solvent (D) in the present invention mainly has a role of dissolving or dispersing the fluoropolymer (A). However, the solvent used only to dissolve or disperse the fluoropolymer (A) may cause a problem that the organic solvent remains in the cured product when the removal is insufficient, or the influence of the remaining organic solvent. Since problems such as heat resistance, a decrease in mechanical strength, and white turbidity may occur or voids may be generated due to volatilization of the solvent, it is desirable to remove the solvent as completely as possible. Therefore, it is desirable not to use it as much as possible from the viewpoint of reducing environmental load and cost, including the work burden for that purpose. That is, it is preferable that the curable resin composition of the present invention does not contain the solvent (D).

By the way, in this invention, when using the compound which has the capability to melt | dissolve or disperse | distribute a fluorine-containing polymer (A) like a hydrosilylation crosslinking agent (B4), it is concerned in hydrosilylation crosslinking reaction as mentioned later. When using a solvent incorporated in the cured product, a solvent only for dissolving or dispersing the fluoropolymer (A) is not necessary.

Therefore, in the present invention, from the viewpoint of whether or not it is involved in the hydrosilylation crosslinking reaction, a solvent (D) that can dissolve or disperse the fluoropolymer (A) is used as a non-silicon-based reaction involved in the hydrosilylation crosslinking reaction. The solvent is classified into a solvent (D1) and a solvent (D2) not involved in the hydrosilylation crosslinking reaction.

(D1) Non-silicon reactive solvent involved in hydrosilylation crosslinking reaction The hydrosilylation crosslinking agent (B4) is a compound that dissolves or disperses the fluoropolymer (A) and participates in the hydrosilylation crosslinking reaction. It differs from the solvent (D1) in that it is a siloxane compound.

In the present invention, “participating in hydrosilylation crosslinking reaction” means any reactive group participating in hydrosilylation reaction which is an addition reaction between a carbon-carbon double bond and a hydrogen atom directly bonded to a silicon atom ( Having a carbon-carbon double bond or a silicon atom-bonded hydrogen atom-containing group), and as a result, incorporated into the reaction product of the hydrosilylation crosslinking reaction. Moreover, it is preferable to have a some reactive group from a viewpoint that there exists crosslinking | crosslinked property.

Specific examples include polyvalent allyl compounds such as ethylene glycol diallyl, diethylene glycol diallyl, triethylene glycol diallyl, 1,4-cyclohexanedimethanol diallyl, triallyl isocyanurate (TAIC); ethylene glycol divinyl ether, diethylene glycol Divinyl ether, triethylene glycol divinyl ether, bisphenol A bis (vinyloxyethylene) ether, bis (vinyloxyethylene) ether, hydroquinone bis (vinyloxyethylene) ether, 1,4-cyclohexanedimethanol divinyl ether,

Polyvalent vinyl ether compounds such as ethylene glycol diacrylate (EDA), diethylene glycol diacrylate (DiEDA), triethylene glycol diacrylate (TriEDA), 1,4-butanediol diacrylate (1,4-BuDA), 1,3 -Butanediol diacrylate (1,3-BuDA), 2,2-bis [4- (2-hydroxy-3-acryloxypropoxy) phenyl] propane (Bis-GA), 2,2-bis (4-acrylic) Roxyphenyl) propane (BPDA), 2,2-bis (4-acryloxyethoxyphenyl) propane (Bis-AEPP), 2,2-bis (4-acryloxypolyethoxyphenyl) propane (Bis-APPP), di (Acryloxyethyl) trimethylhexamethyle Polyacrylic compounds such as diurethane (UDA) and trimethylolpropane triacrylate (TMPA); 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-methacryloxypropoxy) phenyl] propane (Bis -GMA), 2,2-bis (4-methacryloxyphenyl) propane (BPDMA), 2,2-bis (4-methacryloxyethoxyphenyl) propane (Bis-MEPP), 2,2-bis (4-methacryloxy) Li ethoxyphenyl) propane (Bis-MPEPP), di (methacryloxyethyl) trimethylhexamethylene diurethane (UDMA), trimethylolpropane trimethacrylate (TMPT), and the like polyvalent methacrylic compounds such.

Among these, at least one compound selected from the group consisting of TAIC, EDMA, EDA, TMPT, and TMPA is preferable from the viewpoint of good solubility and compatibility.

The non-silicon-based reactive solvent (D1) may be used alone as the reactive solvent for the fluoropolymer (A), or the hydrosilylation crosslinking agent (B4) or the non-reactive solvent (D2) described later. You may use together.

The compounding amount of the non-silicon-based reactive solvent (D1) varies depending on the type of the fluoropolymer (A), the type of the solvent (D1), the presence or type of other solvents, etc., but the fluoropolymer (A) 5 mass parts or more and 500 mass parts or less are preferable with respect to 100 mass parts. From the point of proceeding the hydrosilylation reaction smoothly, it is 5 parts by mass or more, further 10 parts by mass or more, particularly 20 parts by mass or more, and 90 parts by mass with respect to 100 parts by mass of the fluoropolymer (A). Hereinafter, it is preferably 70 parts by mass or less, particularly preferably 50 parts by mass or less.

Moreover, when the role as a solvent of a fluoropolymer (A) can also be used, it is 30 mass parts or more with respect to 100 mass parts of fluoropolymer (A), Furthermore, 50 mass parts or more, Especially 70 mass parts or more. Moreover, 500 mass parts or less, Furthermore, 300 mass parts or less, Especially 200 mass parts or less are preferable.

(D2) Solvent that does not participate in hydrosilylation crosslinking reaction This solvent (D2) is a fluorine-containing polymer in the case where the hydrosilylation crosslinking agent (B4) or the non-silicon-based reactive solvent (D1) is not blended or by itself. It may be used when the solubility or dispersibility of A) is not sufficient.

Specific examples include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; Methyl, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate Rate, ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, 2-hydroxyisobutyric acid Esters such as chill; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol Glycol ethers such as monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, ethylene glycol monoalkyl ether; methanol , Etano Alcohols such as sodium, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, tert-amyl alcohol; tetrahydrofuran, tetrahydro Cyclic ethers such as pyran and dioxane; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve and diethylene glycol monomethyl ether; 1,1, Examples include 2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, and the like. Or these 2 or more types of mixed solvents are mentioned.

Furthermore, examples of the fluorine-based solvent include CH ₃ CCl ₂ F (HCFC-141b), CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF mixture (HCFC-225), perfluorohexane, perfluoro (2- Butyltetrahydrofuran), methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene,
^{_{H (CF 2 CF 2) n}} 3 CH 2 OH (n 3: 1~3 integer),
^{_{F (CF 2) n 4 CH}} 2 OH (n 4: 1~5 integer),
Fluorinated alcohols such as CF ₃ CH (CF ₃ ) OH;
Examples thereof include benzotrifluoride, perfluorobenzene, perfluoro (tributylamine), ClCF ₂ CFClCF ₂ CFCl _{2 and the} like.

These fluorinated solvents may be used alone or as a mixed solvent of fluorinated solvents, a non-fluorinated solvent and one or more fluorinated solvents.

It is preferable that the curable resin composition of the present invention does not use the solvent (D2) that does not participate in the hydrosilylation crosslinking reaction, that is, the curable resin composition of the present invention does not contain the solvent (D2). By not using the solvent (D2), it is not necessary to remove the solvent (D2) from the curable resin composition, the molding process can be simplified, and the solvent (D2) remains in the cured product. Does not occur. As an influence of the remaining solvent (D2), there are problems such as heat resistance of the cured product, reduction in mechanical strength, and cloudiness. Furthermore, the solventless curable resin composition is useful even in cases where the inclusion of volatile components is not allowed due to the molding process conditions. For example, it is used for filling and sealing in an airtight container.

The curable resin composition of the present invention is prepared by mixing the fluorine-containing polymer (A), the hydrosilylation crosslinking agent (B), and, if necessary, the hydrosilylation catalyst (C) by a usual method. be able to.

The crosslinking of the curable resin composition of the present invention may be appropriately determined depending on the crosslinking agent to be used, but is usually cured at a temperature of room temperature (for example, 20 ° C.) to 200 ° C. for 1 minute to 24 hours. Moreover, it can bridge | crosslink under normal pressure, pressurization, pressure reduction, and also in the air.
The progress of the crosslinking reaction can be confirmed, for example, by measuring a sample before and after curing by infrared spectroscopy and observing a change in the absorption peak of the Si—H bond.

The crosslinking method is not particularly limited, and a steam crosslinking, a pressure molding method, and a usual method in which a crosslinking reaction is started by heating can be employed.

Although the curable resin composition of the present invention varies depending on the application, for example, for applications such as sealing, if the viscosity at 30 ° C. is too low, there is a lot of liquid dripping, and on the contrary, the handleability is lowered. It is preferably 1 mPa · s or more, more preferably 5 mPa · s or more from the viewpoint of good thin film formability, and further preferably 10 mPa · s or more from the viewpoint of small cure shrinkage during curing. Further, from the viewpoint of good handleability, 20000 mPa · s or less is preferable, and from the viewpoint that the curable composition spreads over the details during molding, 5000 mPa · s or less is more preferable, and when a thin film is formed. From the viewpoint of good leveling (surface smoothness), 2000 mPa · s or less is more preferable.

The curable resin composition of the present invention includes, in addition to those mentioned above, for example, a reaction inhibitor, a pigment such as titanium oxide, bengara, and carbon black, a filler such as alumina and silica, a dispersant, and a thickener. , Preservatives, ultraviolet absorbers, antifoaming agents, leveling agents and the like may be optionally added.

Examples of the reaction inhibitor include 1-ethynyl-1-cyclohexanol, 2-ethynylisopropanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl. Acetylenic alcohols such as -3-butyn-2-ol; alkenyl siloxanes such as 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane; malate compounds such as diallyl fumarate, dimethyl fumarate and diethyl fumarate; Other examples include triallyl cyanurate and triazole. By blending the reaction inhibitor, the effect of being able to make the obtained composition one component and the pot life (pot life) of the resulting composition to be sufficiently long is exhibited. Although content of this reaction inhibitor is not specifically limited, It is preferable that it is the quantity which will be 10-50000 ppm (mass basis) in the composition of this invention.

For example, the curable resin composition can be cured to form a cured film and used for various applications. As a method of forming the film, a known method suitable for the application can be employed. For example, when it is necessary to control the film thickness, roll coating, gravure coating, micro gravure coating, flow coating, bar coating, spray coating, die coating, spin coating, dip coating, etc. are used. it can.

The curable resin composition of the present invention may be used for film formation, but is particularly useful as a molding material for various molded products. As the molding method, extrusion molding, injection molding, compression molding, blow molding, transfer molding, stereolithography, nanoimprinting, vacuum molding and the like can be adopted.

As a use of the curable resin composition of this invention, it can use as a material of a sealing member, an optical member, a photoelectric imaging tube, various sensors, an antireflection material, for example. In particular, it is preferably used as a material for forming a sealing member. That is, the curable resin composition of the present invention is preferably a sealing material. Moreover, since the hardened | cured material obtained from the curable resin composition of this invention is excellent in transparency, it can utilize suitably as an optical material which forms an optical member. In addition, it can also be used as a sealing member material for electronic semiconductors, a water and moisture resistant adhesive, and an adhesive for optical components and elements.

Examples of usage of the curable resin composition of the present invention include light emitting elements such as light emitting diodes (LEDs), EL elements, and nonlinear optical elements, and packages of optical functional elements such as light receiving elements such as CCD, CMOS, and PD ( Encapsulation), mounting and the like. Moreover, sealing members (or fillers) for optical members such as lenses for deep ultraviolet microscopes are also included.

Since the curable resin composition of the present invention is excellent in transparency, it can be suitably used particularly as a sealing material for optical elements. The sealed optical element is used in various places. Although it does not specifically limit as an optical element, For example, in addition to light emitting elements, such as a light emitting diode (LED), EL element, and a nonlinear optical element, light receiving elements, such as CCD, CMOS, and PD, a high mount stop lamp and a meter Light emitting elements such as a panel, a backlight of a mobile phone, a light source of a remote control device of various electric products; a camera autofocus, a light receiving element for an optical pickup for CD / DVD, and the like. The curable resin composition of the present invention does not need to contain the solvent (D), and further has a higher barrier property (that is, lower permeability) than the case of using silicone or the like because it is made of a resin.

The curable resin composition of the present invention is suitable as a material for forming an optical member. Since the curable resin composition of the present invention contains fluorine, the obtained cured product becomes an optical member having a low refractive index, and is useful as an optical transmission medium, for example. The curable resin composition of the present invention includes, in particular, a plastic clad material whose core material is quartz or optical glass, an optical fiber clad material, an all plastic optical fiber clad material whose core material is plastic, an antireflection coating material, It can be used as a lens material, an optical waveguide material, a prism material, an optical window material, an optical storage disk material, a non-linear optical element material, a hologram material, a photolithographic material, a light emitting element sealing material, and the like.
It can also be used as a material for optical devices. As optical devices, optical devices such as optical waveguides, OADMs, optical switches, optical filters, optical connectors, multiplexers / demultiplexers, and other optical devices are known and useful for forming these devices. Material. In addition, various functional compounds (non-linear optical materials, fluorescent light-emitting functional dyes, photorefractive materials, etc.) are contained and used for functional devices for optical devices such as modulators, wavelength conversion elements, and optical amplifiers. Is suitable. As a sensor application, there is an effect such as an improvement in sensitivity of an optical sensor or a pressure sensor, and protection of the sensor by water / oil repellency characteristics, which is useful.

The present invention is also a cured product obtained by curing the curable resin composition. The cured product of the present invention can be obtained by hydrosilylation crosslinking the curable resin composition. Since the curable resin composition of the present invention does not need to contain a solvent, the organic solvent removing step can be omitted, and the molding step of the cured product can be simplified. Furthermore, it can be suitably used as a sealing member that does not allow the inclusion of volatile components due to the molding process conditions. That is, the cured product of the present invention is preferably a sealing member.

A cured product obtained by curing the curable resin composition can be suitably used as an optical member in terms of excellent transparency. The cured product of the present invention preferably has a light transmittance of 80% or more. More preferably, it is 85% or more, and still more preferably 90% or more. 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 is not only excellent in transparency but also exhibits special performance as a sealing member as described above, and is particularly suitable as a sealing member for optical elements. .

The present invention relates to tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CF ₂ ═CF—ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms. And a polymerized unit derived from at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro (alkyl vinyl ethers) represented by the following formula (a):

(In the formula, R ¹ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 10 carbon atoms. R ² is a hydrocarbon atom that may contain a hydrogen atom or an oxygen atom having 1 to 10 carbon atoms. It is also a fluorine-containing polymer (a1) characterized by comprising polymerized units derived from a norbornene monomer having two or more carbon-carbon double bonds represented by: As the norbornene monomer represented by the above formula (a), the following formula (1):

(Wherein R ⁷ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) and is preferably a norbornene monomer having two carbon-carbon double bonds.

In the fluoropolymer (a1), the preferred form of the fluoromonomer is the same as described above. The fluorinated polymer (a1) contains a monomer unit derived from a fluorinated monomer and another monomer copolymerizable with the norbornene monomer represented by the formula (a). Also good. Preferred forms of other monomers are the same as those described above.

The fluorine-containing polymer (a1) has the following formula:

(In the formula, R ⁷ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).

The present invention relates to tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CF ₂ ═CF—ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms. And a polymerized unit derived from at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro (alkyl vinyl ethers) represented by the following formula (b):

(In the formula, R ³ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 5 carbon atoms. R ⁴ is a hydrocarbon atom that may contain a hydrogen atom or an oxygen atom having 1 to 10 carbon atoms. R ⁵ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 5 carbon atoms, n is an integer of 0 to 10). It is also a fluorinated polymer (a2) comprising polymerized units derived from a norbornene monomer having 2 or more. As the norbornene monomer represented by the above formula (b), the following formula (2):

(Wherein R ⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). In the fluoropolymer (a2), the preferred form of the fluoromonomer is the same as described above. The fluorine-containing polymer (a2) contains a monomer unit derived from a fluorine-containing monomer and another monomer copolymerizable with the norbornene monomer represented by the formula (2). Also good. Preferred forms of other monomers are the same as those described above.

The fluoropolymer (a2) has the following formula:

(In the formula, R ⁸ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).

The present invention relates to tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CF ₂ ═CF—ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms. And a polymerized unit derived from at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro (alkyl vinyl ethers) represented by the following formula (c):

(In the formula, R ⁶ is a hydrogen atom or a hydrocarbon group which may contain an oxygen atom having 1 to 5 carbon atoms.) A norbornene monomer having two or more carbon-carbon double bonds represented by It is also a fluorine-containing polymer (a3) characterized by comprising derived polymer units. As the norbornene monomer represented by the above formula (c), the following formula (3):

A norbornene monomer having two carbon-carbon double bonds represented by In the fluoropolymer (a3), the preferred form of the fluoromonomer is the same as described above. The fluorine-containing polymer (a3) contains a monomer unit derived from a fluorine-containing monomer and another monomer copolymerizable with the norbornene monomer represented by the formula (3). Also good. Preferred forms of other monomers are the same as those described above.

The fluoropolymer (a3) has the following formula:

It is preferable to have a norbornene monomer unit represented by:

(A1), (a2) and (a3) are fluorine-containing monomer units, norbornene monomer units derived from norbornene monomers having two or more carbon-carbon double bonds, and the above It may be composed of a monomer unit derived from another monomer copolymerizable with a fluorine monomer and a norbornene monomer having two or more carbon-carbon double bonds. Said other monomer is a monomer which does not contain a fluorine atom.

As the other monomer, a norbornene monomer having one carbon-carbon double bond is preferable. A norbornene monomer having one carbon-carbon double bond is a monomer having a norbornene skeleton and having no carbon-carbon double bond in a portion other than the norbornene skeleton. As the norbornene monomer, the following formula (d):

(Wherein R ¹⁴ is an alkyl group having 1 to 10 carbon atoms, x is an integer of 0 to 2), and is preferably a norbornene monomer represented by the following formula:

で示されるノルボルネン単量体であることがより好ましい。

The norbornene monomer represented by is more preferable.

The above (a1), (a2) and (a3) have two or more carbon-carbon double bonds, and the above-mentioned curable resin composition is more easily dissolved or dispersed in the hydrosilylation crosslinking agent. Can be suitably used. Among these, (a1) is particularly preferable.

EXAMPLES Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited only to these examples.

The measurement methods employed in this specification are summarized below.

(1) Measurement of average molecular weight Using gel permeation chromatography (GPC), GPC HLC-8020 manufactured by Tosoh Corporation was used, one column manufactured by Shodex (one GPC KF-801 and one GPC KF-802). The weight average molecular weight and the number average molecular weight are calculated from the data measured by flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min using two GPC KF-806M in series.

(2) Fluorine content 10 mg of sample was burned by the oxygen flask combustion method, the decomposition gas was absorbed in 20 ml of deionized water, and the fluorine ion concentration in the absorption liquid was determined by the fluorine selective electrode method (fluorine ion meter, model 901 manufactured by Orion). ) To obtain (mass%).

(3) Refractive index (n _D )
Measurement is performed using an Abbe refractometer manufactured by Atago Optical Instruments Co., Ltd. at 25 ° C. using sodium D line (589 nm) as a light source.

(4) Glass transition temperature (Tg)
Using DSC (Differential Scanning Calorimeter: RTG220, manufactured by SEIKO), the temperature range from −50 ° C. to 200 ° C. was raised at a rate of 10 ° C./min (first run) -temperature fall-temperature rise (second run) The intermediate point of the endothermic curve in the second run was defined as Tg (° C.).

(5) IR analysis Measured at room temperature with a Fourier transform infrared spectrophotometer 1760X manufactured by Perkin Elmer.

(6) Film thickness Measured with a spectroscopic ellipsometer EC400 manufactured by JA Woollam Japan. WVASE32 was used as analysis software.

(7) Viscosity Using an E-type viscometer manufactured by Toki Sangyo Co., Ltd. conforming to JIS K7117-2, the viscosity is measured at 27 ° C. (mPa · sec).

Synthesis Example 1 (TFE / ENB copolymer)
After degassing an autoclave with a stainless steel stirrer with an internal volume of 0.5 L, 200 g of dichloropentafluoropropane (HCFC-225) and 22 g of 5-ethylidene-2-norbornene (ENB) were charged, and then stirred while stirring at 300 rpm. First, 58 g of fluoroethylene (TFE) was charged, and after adjusting the temperature in the autoclave to 40 ° C., 10 g of a 1H, 1H, 3H-tetrafluoropropanol solution of 40% by mass of dinormalpropyl peroxydicarbonate was injected to perform polymerization. Initiated and allowed to react for 20 hours. After completion of the reaction, unreacted TFE was blown at room temperature, and then the content uniformly dissolved in HCFC-225 was put into ethanol.

The precipitated solid was separated by filtration and vacuum dried at 80 ° C. for 12 hours to obtain 14 g of white powder. When this white powder was dissolved in deuterated chloroform and ¹⁹ F-NMR, ¹³ C-NMR and ¹ H-NMR were measured, it was found that the polymer was a copolymer of TFE and ENB. In ¹ H-NMR measurement, a peak of = CHCH ₃ was confirmed at 5.33 ppm, and it was confirmed that a double bond derived from ethylidene of ENB was present in the copolymer.

When the elemental analysis of fluorine of this copolymer was conducted, it was 31.8% by mass, and the composition of the copolymer was calculated as TFE units / ENB units = 46/54 mol%. This copolymer is colorless and transparent, and when a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments) is used to measure the heat up to 200 ° C. at a temperature rising rate of 10 ° C./min, there is no melting point and 80 ° C. The glass transition temperature is shown in (Endothermic end temperature). The temperature at which the mass of the copolymer subjected to the heating test using a differential heat / thermogravimetry apparatus [TG-DTA] decreased by 1 mass% was 212 ° C. The number average molecular weight measured by GPC analysis was 1,582, and the weight average molecular weight was 2,422.

This copolymer was soluble in a solvent such as chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone, and dioxane, and was also compatible with a hydrosilicone compound having an SiH group (for example, phenyltris (dimethylsiloxy) silane).

Synthesis Example 2 (TFE / ENB copolymer)
After degassing a 300 ml stainless steel autoclave equipped with a valve, pressure gauge and thermometer, after charging 105 g of dichloropentafluoropropane (HCFC-225) and 4 g of 5-ethylidene-2-norbornene (ENB) After charging 25 g of tetrafluoroethylene (TFE) and then adjusting the temperature in the autoclave to 40 ° C., 8 g of a 1 mass% 1H, 1H, 3H-tetrafluoropropanol solution of dinormalpropyl peroxydicarbonate was injected, and 40 The polymerization reaction was performed while shaking at 80 ° C. at 80 ° C. When the polymerization was started and the temperature was returned to room temperature after 2 hours and unreacted TFE was blown, a content uniformly dissolved in HCFC-225 was obtained. This solution was then poured into methanol.

The precipitated solid was separated by filtration and vacuum dried at 80 ° C. for 12 hours to obtain 0.86 g of a solid. This solid was dissolved in deuterated acetone, and ¹⁹ F-NMR, ¹³ C-NMR and ¹ H-NMR were measured, and it was found that the polymer was a copolymer of TFE and ENB. In ¹ H-NMR measurement, a peak of = CHCH ₃ could be confirmed as in Synthesis Example 1, and it was confirmed that a double bond derived from ethylidene of ENB was present in the copolymer.

When the elemental analysis of fluorine of this copolymer was conducted, it was 35.0% by mass, and the composition of the copolymer was calculated as TFE units / ENB units = 51/49 mol%. This copolymer was colorless and transparent, and when a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments) was used to measure the heat up to 200 ° C. at a heating rate of 10 ° C./min, there was no melting point and 78 ° C. The glass transition temperature is shown in (Endothermic end temperature). The temperature at which the mass of the copolymer subjected to the heating test using a differential heat / thermogravimetry apparatus [TG-DTA] decreased by 1 mass% was 230 ° C. The number average molecular weight measured by GPC analysis was 2294, and the weight average molecular weight was 3219.

This copolymer was soluble in a solvent such as chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone, and dioxane, and was also compatible with a hydrosilicone compound having an SiH group (for example, phenyltris (dimethylsiloxy) silane).

Synthesis Example 3 (TFE / ENB copolymer)
After degassing a 300 ml stainless steel autoclave equipped with a valve, pressure gauge and thermometer, after charging 105 g of dichloropentafluoropropane (HCFC-225) and 36 g of 5-ethylidene-2-norbornene (ENB) After charging 25 g of tetrafluoroethylene (TFE) and then adjusting the temperature in the autoclave to 40 ° C., 8 g of a 1 mass% 1H, 1H, 3H-tetrafluoropropanol solution of dinormalpropyl peroxydicarbonate was injected, and 40 The polymerization reaction was performed while shaking at 80 ° C. at 80 ° C. When the polymerization was started and the temperature was returned to room temperature after 2 hours and unreacted TFE was blown, a content uniformly dissolved in HCFC-225 was obtained. This solution was then poured into methanol.

The precipitated solid was separated by filtration and vacuum dried at 80 ° C. for 12 hours to obtain 1.54 g of a solid. This solid was dissolved in deuterated acetone, and ¹⁹ F-NMR, ¹³ C-NMR and ¹ H-NMR were measured, and it was found that the polymer was a copolymer of TFE and ENB. In ¹ H-NMR measurement, a peak of = CHCH ₃ could be confirmed as in Synthesis Example 1, and it was confirmed that a double bond derived from ethylidene of ENB was present in the copolymer.

When the elemental analysis of fluorine of this copolymer was conducted, it was 25.4% by mass, and the composition of the copolymer was calculated as TFE units / ENB units = 38/62 mol%. This copolymer is colorless and transparent. When a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments) was used and the heat measurement was carried out up to 200 ° C. at a temperature rising rate of 10 ° C./min, there was no melting point at 46 ° C. The glass transition temperature is shown in (Endothermic end temperature). Further, the temperature at which the mass of the copolymer subjected to the heating test using a differential heat / thermogravimetry apparatus [TG-DTA] was reduced by 1 mass% was 180 ° C. The number average molecular weight measured by GPC analysis was 1071, and the weight average molecular weight was 1753.

This copolymer was soluble in a solvent such as chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone, and dioxane, and was also compatible with a hydrosilicone compound having an SiH group (for example, phenyltris (dimethylsiloxy) silane).

Synthesis Example 4 (TFE / VNB copolymer)
A 300 ml stainless steel autoclave equipped with a valve, a pressure gauge and a thermometer was degassed, and then 105 g of dichloropentafluoropropane (HCFC-225), 5-vinylbicyclo [2,2,1] hept-2- After charging 11 g of ene (VNB), 25 g of tetrafluoroethylene (TFE) was charged, the temperature in the autoclave was adjusted to 40 ° C., and then 40% by mass of 1H, 1H, 3H-tetra of dinormalpropyl peroxydicarbonate. A polymerization reaction was carried out while 8 g of a fluoropropanol solution was injected and shaken at 40 ° C. under the condition of 80 rpm. Polymerization was started, and after 24 hours, the temperature was returned to room temperature, and unreacted TFE was blown. As a result, a content uniformly dissolved in HCFC-225 was obtained. This solution was then poured into ethanol.

The precipitated solid was separated by filtration and vacuum dried at 80 ° C. for 12 hours to obtain 1.03 g of a liquid polymer. When this polymer was dissolved in deuterated acetone and ¹⁹ F-NMR, ¹³ C-NMR and ¹ H-NMR were measured, it was found that the polymer was a copolymer of TFE and VNB. In ¹ H-NMR measurement, a peak of —CH═CH ₂ was confirmed, and it was confirmed that a double bond derived from allyl of VNB was present in the copolymer.

When the elemental analysis of fluorine of this copolymer was conducted, it was 29.4% by mass, whereby the composition of the copolymer was calculated as TFE units / VNB units = 43/57 mol%. This copolymer was colorless and transparent. When a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments Inc.) was used and the heat measurement was performed at a temperature rising rate of 10 ° C./min up to 200 ° C., there was no melting point, and 35 ° C. The glass transition temperature is shown in (Endothermic end temperature). The temperature at which the mass of the copolymer subjected to the heating test using a differential heat / thermogravimetry apparatus [TG-DTA] decreased by 1 mass% was 202 ° C. The number average molecular weight measured by GPC analysis was 1805, and the weight average molecular weight was 3169.

This copolymer was soluble in a solvent such as chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone, and dioxane, and was also compatible with a hydrosilicone compound having an SiH group (for example, phenyltris (dimethylsiloxy) silane).

Synthesis Example 5 (TFE / NB / ENB copolymer)
After degassing a 300 ml stainless steel autoclave equipped with a valve, pressure gauge and thermometer, 105 g of dichloropentafluoropropane (HCFC-225), 8.8 g of norbornene (NB) and 5-ethylidene-2-norbornene (ENB) After charging 2.2 g, tetrafluoroethylene (TFE) 25 g was charged, and then the temperature in the autoclave was adjusted to 40 ° C., and then 40% by mass of 1H, 1H, 3H— 8 g of a tetrafluoropropanol solution was injected and a polymerization reaction was performed while shaking at 40 ° C. under the condition of 80 rpm. Polymerization was started, and after 24 hours, the temperature was returned to room temperature, and unreacted TFE was blown. As a result, a content uniformly dissolved in HCFC-225 was obtained. This solution was then poured into ethanol.

The precipitated solid was separated by filtration and vacuum dried at 80 ° C. for 12 hours to obtain 13 g of a solid polymer. When this polymer was dissolved in deuterated acetone and ¹⁹ F-NMR, ¹³ C-NMR and ¹ H-NMR were measured, it was found that the polymer was a copolymer of TFE, NB and ENB. . In ¹ H-NMR measurement, a peak of ═CHCH ₃ was confirmed, and it was confirmed that double bonds derived from ENB ethylidene were present in the copolymer.

Further, the elemental analysis of fluorine of this copolymer was 37.7% by mass, and the elemental analysis of carbon was 56.8% by mass. Thereby, the composition of the copolymer was calculated as TFE units / NB units / ENB units = 47/41/12 mol%. This copolymer was colorless and transparent, and when a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments) was used to measure heat up to 200 ° C. at a rate of temperature increase of 10 ° C./min, there was no melting point and 90 ° C. The glass transition temperature is shown in (Endothermic end temperature). Further, the temperature at which the mass of the copolymer subjected to the heating test using a differential heat / thermogravimetry apparatus [TG-DTA] decreased by 1 mass% was 248 ° C. The number average molecular weight measured by GPC analysis was 2181, and the weight average molecular weight was 2859.

This copolymer was soluble in a solvent such as chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone, and dioxane, and was also compatible with a hydrosilicone compound having an SiH group (for example, phenyltris (dimethylsiloxy) silane).

Synthesis Examples 6 to 8 (TFE / NB / ENB copolymer)
Polymerization was conducted in the same manner as in Synthesis Example 5 except that the initial charge amounts of NB and ENB were changed as shown in Table 1 in Synthesis Example 5. The analytical values of the obtained polymer are summarized in Table 1 together with the results of Synthesis Example 5.

Synthesis Example 9 (TFE / NB / VNB copolymer)
After degassing a 300 ml stainless steel autoclave equipped with a valve, pressure gauge and thermometer, 105 g of dichloropentafluoropropane (HCFC-225), 8.8 g of norbornene (NB) and 5-vinylbicyclo [2, 2,1] hept-2-ene (VNB) (2.2 g), tetrafluoroethylene (TFE) (25 g), and the temperature in the autoclave was adjusted to 40 ° C. 8 g of a 1% by mass 1H, 1H, 3H-tetrafluoropropanol solution was injected and polymerization reaction was carried out while shaking at 40 ° C. and 80 rpm. Polymerization was started, and after 24 hours, the temperature was returned to room temperature, and unreacted TFE was blown. As a result, a content uniformly dissolved in HCFC-225 was obtained. This solution was then poured into ethanol.

The precipitated solid was separated by filtration and vacuum dried at 80 ° C. for 12 hours to obtain 11 g of a solid polymer. When this polymer was dissolved in deuterated acetone and ¹⁹ F-NMR, ¹³ C-NMR and ¹ H-NMR were measured, it was found that the polymer was a copolymer of TFE, NB and ENB. . In ¹ H-NMR measurement, a peak of —CH═CH ₂ was confirmed, and it was confirmed that a double bond derived from allyl of VNB was present in the copolymer.

Further, the elemental analysis of fluorine of this copolymer was 36.7% by mass, and the elemental analysis of carbon was 57.7% by mass, whereby the composition of the copolymer was TFE. Unit / NB unit / VNB unit = 46/40/14 mol% was calculated. This copolymer is colorless and transparent, and when a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments) is used to measure the heat up to 200 ° C. at a temperature rising rate of 10 ° C./min, there is no melting point and 80 ° C. The glass transition temperature is shown in (Endothermic end temperature). The temperature at which the mass of the copolymer subjected to the heating test using a differential heat / thermogravimetry apparatus [TG-DTA] decreased by 1% by mass was 207 ° C. The number average molecular weight measured by GPC analysis was 1750, and the weight average molecular weight was 2805.

This copolymer was soluble in a solvent such as chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone, and dioxane, and was also compatible with a hydrosilicone compound having an SiH group (for example, phenyltris (dimethylsiloxy) silane).

Synthesis Example 10 (TFE / NB / CPD copolymer)
After degassing a 300 ml stainless steel autoclave equipped with a valve, pressure gauge and thermometer, 105 g of dichloropentafluoropropane (HCFC-225), 8.8 g of norbornene (NB) and cyclopentadiene (CPD) 2. After charging 2 g, tetrafluoroethylene (TFE) 25 g was charged, then the temperature in the autoclave was adjusted to 40 ° C., and then 40 g% 1H, 1H, 3H-tetrafluoropropanol solution of dinormalpropyl peroxydicarbonate was added. The polymerization reaction was carried out while shaking at 40 ° C. under the condition of 80 rpm. Polymerization was started, and after 24 hours, the temperature was returned to room temperature, and unreacted TFE was blown. As a result, a content uniformly dissolved in HCFC-225 was obtained. This solution was then poured into ethanol.

The precipitated solid was separated by filtration and vacuum dried at 80 ° C. for 12 hours to obtain 10 g of a solid polymer. When this polymer was dissolved in deuterated acetone and ¹⁹ F-NMR, ¹³ C-NMR and ¹ H-NMR were measured, it was found that the polymer was a copolymer of TFE, NB and ENB. . In ¹ H-NMR measurement, a peak of —CH═CH— was confirmed, and it was confirmed that a double bond derived from an olefin of CPD was present in the copolymer.

Further, the elemental analysis of fluorine of this copolymer was 35.3% by mass, and the elemental analysis of carbon was 59.1% by mass. Thus, the composition of the copolymer was TFE. Unit / NB unit / CPD unit = 45/41/14 mol%. This copolymer is colorless and transparent. When a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments Inc.) was used and the heat measurement was carried out up to 200 ° C. at a heating rate of 10 ° C./min, there was no melting point and 105 ° C. The glass transition temperature is shown in (Endothermic end temperature). Further, the temperature at which the mass of the copolymer subjected to the heating test using a differential heat / thermogravimetry apparatus [TG-DTA] decreased by 1 mass% was 232 ° C. The number average molecular weight measured by GPC analysis was 1505, and the weight average molecular weight was 2408.

This copolymer was soluble in a solvent such as chloroform, tetrahydrofuran, xylene, ethyl acetate, methyl ethyl ketone, and dioxane, and was also compatible with a hydrosilicone compound having an SiH group (for example, phenyltris (dimethylsiloxy) silane).

Example 1 (curable resin composition: solvent xylene)
Phenyltris (dimethylsiloxy) silane (C ₆ H ₅ Si {OSi (CH ₃ ) ₂ H} as a hydrosilicone compound (siloxane compound) having three groups in which hydrogen atoms are directly bonded to silicon atoms in a 10 cc glass bottle ₃ ) 0.54 g, 1.0 g of the TFE / ENB copolymer obtained in Synthesis Example 1 and 1.0 g of xylene as a diluent solvent were uniformly mixed and dissolved at 60 ° C., and then cooled to room temperature. Next, 50 ppm of a cyclic methylvinylsiloxane solution containing 2% platinum as a platinum catalyst was added and mixed uniformly, and then the mixed solution was poured onto the fluororesin FEP film while evaporating xylene in an oven at 125 ° C. for 8 hours. Hydrosilylation reaction was performed to obtain a film-like cured product.

When a part of the mixed solution before being put in the oven was analyzed with an infrared spectrometer, an absorption peak at 2134 cm ⁻¹ , which is a SiH group derived from phenyltris (dimethylsiloxy) silane, was confirmed. The peak disappeared in the cured product after curing at 125 ° C. for 8 hours. Further, it was confirmed that the cured product was not dissolved again in xylene and was crosslinked.
When the light transmittance of this film was measured with a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), it was 95.2% at 550 nm and 92.8% at 405 nm. Further, the refractive index was measured by using a spectroscopic ellipsometer (M-2000D, manufactured by JA Woollam Japan) of a thin film (film thickness: 150 nm) formed on a silicon wafer by a spin coat method. As a result, 1.4795 (598 nm) Met.

Example 2 (Solvent-free curable resin composition)
Phenyltris (dimethylsiloxy) silane (C ₆ H ₅ Si {OSi (CH ₃ ) ₂ H} as a hydrosilicone compound (siloxane compound) having three groups in which hydrogen atoms are directly bonded to silicon atoms in a 10 cc glass bottle ₃ ) After 0.29 g, 0.25 g of the TFE / ENB copolymer obtained in Synthesis Example 2 and 0.125 g of triallyl isocyanate (TAIC) as a reactive diluent were uniformly mixed and dissolved at 60 ° C. Cooled to room temperature. Next, 20 ppm of a cyclic methylvinylsiloxane solution containing 2% platinum as a platinum catalyst was added and mixed uniformly, then the mixed solution was poured onto the fluororesin FEP film, and a hydrosilylation reaction was performed in an oven at 125 ° C. for 8 hours. A film-like cured product was obtained.

When a part of the solventless composition before being put in the oven was analyzed with an infrared spectrometer, an absorption peak at 2134 cm ⁻¹ , which is a SiH group derived from phenyltris (dimethylsiloxy) silane, was confirmed. The peak disappeared in the cured product after curing at 125 ° C. for 8 hours. Further, it was confirmed that the cured product was not dissolved in xylene and was crosslinked.
When the light transmittance of this film was measured with a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), it was 94.8% at 550 nm and 91.2% at 405 nm. In addition, the refractive index was measured by using a spectroscopic ellipsometer (M-2000D manufactured by JAE Woollam Japan) of a thin film (film thickness 150 nm) formed on a silicon wafer by a spin coat method, resulting in 1.4845 (598 nm). Met.

Example 3 (Solvent-free curable resin composition)
Phenyltris (dimethylsiloxy) silane (C ₆ H ₅ Si {OSi (CH ₃ ) ₂ H} as a hydrosilicone compound (siloxane compound) having three groups in which hydrogen atoms are directly bonded to silicon atoms in a 10 cc glass bottle ₃ ) 0.61 g and 1 g of the TFE / ENB copolymer obtained in Synthesis Example 3 were uniformly mixed and dissolved at 60 ° C., and then cooled to room temperature. Next, 50 ppm of a cyclic methylvinylsiloxane solution containing 2% platinum as a platinum catalyst was added and mixed uniformly. Then, the mixed solution was poured onto the fluororesin FEP film, and a hydrosilylation reaction was performed in an oven at 125 ° C. for 8 hours. A film-like cured product was obtained.

When a part of the solventless composition before being put in the oven was analyzed with an infrared spectrometer, an absorption peak at 2134 cm ⁻¹ , which is a SiH group derived from phenyltris (dimethylsiloxy) silane, was confirmed. The peak disappeared in the cured product after curing at 125 ° C. for 8 hours. Further, it was confirmed that the cured product was not dissolved in xylene and was crosslinked.
When the light transmittance of this film was measured with a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.), it was 94.6% at 550 nm and 90.8% at 405 nm. The refractive index was 1.4763 (598 nm) as a result of measuring a thin film (thickness 150 nm) formed on a silicon wafer by a spin coat method using a spectroscopic ellipsometer (M-2000D, manufactured by JA Woollam Japan). Met.

Example 4 (Solvent-free curable resin composition)
Phenyltris (dimethylsiloxy) silane (C ₆ H ₅ Si {OSi (CH ₃ ) ₂ H} as a hydrosilicone compound (siloxane compound) having three groups in which hydrogen atoms are directly bonded to silicon atoms in a 10 cc glass bottle ₃ ) 0.79 g and 1 g of the TFE / NB / ENB terpolymer obtained in Synthesis Example 5 were uniformly mixed and dissolved at 60 ° C., and then cooled to room temperature. Next, 50 ppm of a cyclic methylvinylsiloxane solution containing 2% platinum as a platinum catalyst was added and mixed uniformly. Then, the mixed solution was poured onto the fluororesin FEP film, and a hydrosilylation reaction was performed in an oven at 125 ° C. for 8 hours. A film-like cured product was obtained.

When a part of the solventless composition before being put in the oven was analyzed with an infrared spectrometer, an absorption peak at 2134 cm ⁻¹ , which is a SiH group derived from phenyltris (dimethylsiloxy) silane, was confirmed. The peak disappeared in the cured product after curing at 125 ° C. for 8 hours. Further, it was confirmed that the cured product was not dissolved in xylene and was crosslinked.
The light transmittance and refractive index of this film were measured in the same manner as in Example 1. The results are shown in Table 2.

Examples 5 to 7 (solvent-free curable resin composition)
Instead of using the TFE / NB / ENB ternary copolymer obtained in Synthesis Examples 6 to 8 instead of the TFE / NB / ENB ternary copolymer obtained in Synthesis Example 5 used in Example 4, In the same manner as in Example 4, after preparing a solventless composition, it was cured under the same conditions to obtain a cured film.
The results of the formulation of the solventless cured resin and the measurement of film properties are summarized in Table 2 together with the results of Example 4.

Example 8 (solvent-free curable resin composition)
Phenyltris (dimethylsiloxy) silane (C ₆ H ₅ Si {OSi (CH ₃ ) ₂ H} as a hydrosilicone compound (siloxane compound) having three groups in which hydrogen atoms are directly bonded to silicon atoms in a 10 cc glass bottle ₃ ) 0.31 g, 0.25 g of TFE / VNB copolymer obtained in Synthesis Example 4 and 0.125 g of TAIC as a reactive diluent were uniformly mixed and dissolved at 60 ° C. and then cooled to room temperature. . Next, 20 ppm of a cyclic methylvinylsiloxane solution containing 2% platinum as a platinum catalyst was added and mixed uniformly, then the mixed solution was poured onto the fluororesin FEP film, and a hydrosilylation reaction was performed in an oven at 125 ° C. for 8 hours. A film-like transparent cured product was obtained.

When a part of the solventless composition before being put in the oven was analyzed with an infrared spectrometer, an absorption peak at 2134 cm ⁻¹ , which is a SiH group derived from phenyltris (dimethylsiloxy) silane, was confirmed. The peak disappeared in the cured product after curing at 125 ° C. for 8 hours. Further, it was confirmed that the cured product was not dissolved in xylene and was crosslinked.

Examples 9 to 11 (solvent-free curable resin composition)
Instead of phenyltris (dimethylsiloxy) silane used in Example 4, tetrakis (dimethylsilyloxy) silane (Example 9), phenylhydrocyclosiloxane (including straight chain) (Example 10), tri A solventless composition was prepared in the same manner as in Example 4 except that fluoropropyltetrakis (dimethylsilyloxy) silane (Example 11) was used, and then cured under the same conditions to obtain a film-like cured product.
Table 3 summarizes the results of the formulation of the solventless cured resin and the measurement of film properties.

Example 12 (Solvent-free curable resin composition)
Phenyltris (dimethylsiloxy) silane (C ₆ H ₅ Si {OSi (CH ₃ ) ₂ H} as a hydrosilicone compound (siloxane compound) having three groups in which hydrogen atoms are directly bonded to silicon atoms in a 10 cc glass bottle ₃ ) 0.76 g, 1 g of the TFE / NB / VNB terpolymer obtained in Synthesis Example 9 and 0.5 g of TAIC as a reactive diluent were uniformly mixed and dissolved at 60 ° C., and then to room temperature. Cooled down. Next, 50 ppm of a cyclic methylvinylsiloxane solution containing 2% platinum as a platinum catalyst was added and mixed uniformly. Then, the mixed solution was poured onto the fluororesin FEP film, and a hydrosilylation reaction was performed in an oven at 125 ° C. for 8 hours. A film-like transparent cured product was obtained.

When a part of the solventless composition before being put in the oven was analyzed with an infrared spectrometer, an absorption peak at 2134 cm ⁻¹ , which is a SiH group derived from phenyltris (dimethylsiloxy) silane, was confirmed. The peak disappeared in the cured product after curing at 125 ° C. for 8 hours. Further, it was confirmed that the cured product was not dissolved in xylene and was crosslinked.

Example 13 (solvent-free curable resin composition)
Phenyltris (dimethylsiloxy) silane (C ₆ H ₅ Si {OSi (CH ₃ ) ₂ H} as a hydrosilicone compound (siloxane compound) having three groups in which hydrogen atoms are directly bonded to silicon atoms in a 10 cc glass bottle ₃ ) 0.75 g, 1 g of the TFE / NB / CPD copolymer obtained in Synthesis Example 10 and 0.5 g of TAIC as a reactive diluent were uniformly mixed and dissolved at 60 ° C. and then cooled to room temperature. . Next, 50 ppm of a cyclic methylvinylsiloxane solution containing 2% platinum as a platinum catalyst was added and mixed uniformly. Then, the mixed solution was poured onto the fluororesin FEP film, and a hydrosilylation reaction was performed in an oven at 125 ° C. for 8 hours. A film-like transparent cured product was obtained.

When a part of the solventless composition before being put in the oven was analyzed with an infrared spectrometer, an absorption peak at 2134 cm ⁻¹ , which is a SiH group derived from phenyltris (dimethylsiloxy) silane, was confirmed. The peak disappeared in the cured product after curing at 125 ° C. for 8 hours. Further, it was confirmed that the cured product was not dissolved in xylene and was crosslinked.

Example 14 (water vapor transmission data)
5 g of TFE / NB / ENB terpolymer obtained in Synthesis Example 5, 0.65 g of phenyltris (dimethylsiloxy) silane, platinum-divinyltetramethyldisiloxane complex as a platinum catalyst, xylene solution (2.1-2. 4% platinum) 5 μL was dissolved in a butyl acetate solvent to make a total of 14 g. Then, after filtering using a 0.45 μm PTFE filter, it was applied onto a 100 μm thick PET film (Lumirror manufactured by Toray Industries, Inc.) using a bar coat (# 24). After pre-drying at room temperature for 1 hour, it was cured for 3 days in a blower dryer at 60 ° C.
It was 24.4 micrometers as a result of measuring the film thickness after hardening with a micrometer.

The produced laminated film was cut into a size of 100 mm × 100 mm, and Dr. based on JISK7129 (Method A). The water vapor transmission rate was measured using a water vapor transmission meter L80-5000 manufactured by Lyssy. Note that the surface side in direct contact with water vapor is PET, and the dry air side is the cured film of the present invention.

The water vapor permeability of only the PET film of the substrate was measured in advance, and the water vapor permeability of the cured film layer was calculated by the following formula.

(Generally, in a multi-layer film (thickness l) composed of n layers, the transmission coefficient P of the entire film when the thickness of the nth layer and the gas permeability coefficient are respectively ln and Pn can be calculated by the above formula: High Molecules and moisture Chapter 7: The Society of Polymer Science, Koshobo (1973).)
The water vapor permeability determined by the above method was 7.5 g / m ² · day.

Comparative Example 1
It was 314 g / m < ² > * day as a result of measuring the water vapor transmission rate of KJR9022E-2 by Shin-Etsu Silicone marketed as LED sealing resin with the cup method based on JISZ0208.

Example 15 (viscosity, transmittance)
The TFE / ENB copolymer obtained in Synthesis Example 1 and phenyltris (dimethylsiloxy) silane as a SiH crosslinking agent and TAIC were mixed in the proportions shown in Table 4, and the viscosity at 27 ° C. was measured.

After adding 50 ppm of a cyclic methylvinylsiloxane solution containing 2% platinum as a platinum catalyst to the sample for which the viscosity was measured, and uniformly mixing the mixture, the mixed solution was poured onto the fluororesin FEP film in an oven at 125 ° C. for 8 hours. Hydrosilylation reaction was performed to obtain a film-like transparent cured product. The absorption spectrum in the visible band of the obtained film (25 μm) was measured, and the results are shown in FIGS.

The curable resin composition of the present invention is suitably used for a sealing member, an optical material, a photoelectronic imaging tube, various sensors, an antireflection material, and the like.

Claims (21)

A curable resin composition comprising a fluoropolymer (A) and a hydrosilylation crosslinking agent (B),
The fluorinated polymer (A) is a fluorinated polymer comprising polymerized units derived from a fluorinated monomer and polymerized units derived from a norbornene monomer having two or more carbon-carbon double bonds. ,
The curable resin composition, wherein the hydrosilylation crosslinking agent (B) is a siloxane compound having two or more groups in which hydrogen atoms are directly bonded to silicon atoms. The norbornene monomer having two or more carbon-carbon double bonds is represented by the following formula (a):

(In the formula, R ¹ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 10 carbon atoms. R ² is a hydrocarbon atom that may contain a hydrogen atom or an oxygen atom having 1 to 10 carbon atoms. A norbornene monomer having two or more carbon-carbon double bonds represented by the following formula (b):

(In the formula, R ³ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 5 carbon atoms. R ⁴ is a hydrocarbon atom that may contain a hydrogen atom or an oxygen atom having 1 to 10 carbon atoms. R ⁵ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 5 carbon atoms, n is an integer of 0 to 10). And a norbornene monomer having two or more of the following formula (c):

(In the formula, R ⁶ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 5 carbon atoms.) From a norbornene monomer having two or more carbon-carbon double bonds represented by The curable resin composition according to claim 1, wherein the curable resin composition is at least one monomer selected from the group consisting of: The norbornene monomer having two or more carbon-carbon double bonds is represented by the following formula (1):

(Wherein R ⁷ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), a norbornene monomer having two carbon-carbon double bonds represented by the following formula (2):

(Wherein R ⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and a norbornene monomer having two carbon-carbon double bonds represented by the following formula (3):

The curable resin composition according to claim 1 or 2, which is at least one monomer selected from the group consisting of norbornene monomers having two carbon-carbon double bonds represented by the formula: The hydrosilylation crosslinking agent (B) has the following formula:
-O-SiR ⁸ H-
The curable resin according to claim 1, 2 or 3, which is a siloxane compound having two or more structures represented by the formula: wherein R ⁸ is a monovalent hydrocarbon group having 1 to 10 carbon atoms. Composition. The hydrosilylation crosslinking agent (B) has the following formula (4):
R ⁹ _b Si (OR ¹⁰ ) _4-b (4)
(In the formula, R ⁹ is the same or different, and a part or all of hydrogen atoms may be substituted by fluorine, an alkyl group having 1 to 10 carbon atoms, an aryl group, a (meth) acryl group-containing organic group, or Represents an epoxy group-containing organic group, and R ¹⁰ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or the following formula:
-SiR ⁸ ₂ H
(Wherein R ⁸ is the same or different and is a hydrocarbon group having 1 to 10 carbon atoms), and represents a diorganosilyl group (b2). However, at least two R ¹⁰ in one molecule are diorganosilyl groups (b2). b is an integer of 0-2. The curable resin composition according to claim 1, 2, 3, or 4. The fluorine-containing monomer includes tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, vinyl fluoride, hexafluoropropylene, hexafluoroisobutene, CH ₂ = CZ ¹ (CF ₂ ) _n Z ² (wherein Z ¹ is H or F, Z ² is H, F or Cl, and n is an integer of 1 to 10, and CF ₂ = CF-ORf ¹ (wherein Rf ¹ is carbon Perfluoro (alkyl vinyl ether) represented by the formula 1-8, and CF ₂ = CF—OCH ₂ —Rf ² (wherein Rf ² is a C 1-5 carbon atom) 6. A perfluoroalkyl group), which is at least one fluorine-containing ethylenic monomer selected from the group consisting of alkyl perfluorovinyl ether derivatives represented by: Curable resin composition of the mounting. The fluorine-containing monomer is tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, and CF ₂ = CF-ORf ¹ (wherein Rf ¹ is a perfluoro having 1 to 8 carbon atoms. 7. An at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro (alkyl vinyl ethers) represented by: Curable resin composition. The fluoropolymer (A) is further represented by the following formula (d):

(Wherein R ¹⁴ is an alkyl group having 1 to 10 carbon atoms, x is an integer of 0 to 2), and the polymer unit is derived from a norbornene monomer represented by claim 1, 2, 3 The curable resin composition according to 4, 5, 6, or 7. And (C) a hydrosilylation catalyst;
The curable resin composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8. The curable resin composition according to claim 9, wherein the hydrosilylation catalyst (C) is at least one catalyst selected from the group consisting of platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, ruthenium-based catalysts, and iridium-based catalysts. object. 11. The curable resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, which is a sealing material. A cured product obtained by curing the curable resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. The hardened | cured material of Claim 12 whose light transmittance is 80% or more. The cured product according to claim 12, which is a sealing member for an optical element. Tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, ^{_{and, CF 2 = CF-ORf 1}} ( wherein, Rf ¹ represents. A perfluoroalkyl group having 1 to 8 carbon atoms) in A polymerized unit derived from at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro (alkyl vinyl ethers) represented by the following formula (a):

(In the formula, R ¹ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 10 carbon atoms. R ² is a hydrocarbon atom that may contain a hydrogen atom or an oxygen atom having 1 to 10 carbon atoms. . a group having a carbon represented by) - Ri Do from polymerized units derived from the carbon-carbon double bond in the norbornene monomer having two or more,
A fluorine-containing polymer having a glass transition temperature of 30 to 200C . The norbornene monomer having two or more carbon-carbon double bonds is represented by the following formula (1):

The fluorine-containing compound according to claim 15, which is a norbornene monomer having two carbon-carbon double bonds represented by the formula (wherein R ⁷ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). Polymer. Tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, ^{_{and, CF 2 = CF-ORf 1}} ( wherein, Rf ¹ represents. A perfluoroalkyl group having 1 to 8 carbon atoms) in A polymerized unit derived from at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro (alkyl vinyl ethers) represented by the following formula (b):

(In the formula, R ³ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 5 carbon atoms. R ⁴ is a hydrocarbon atom that may contain a hydrogen atom or an oxygen atom having 1 to 10 carbon atoms. R ⁵ is a hydrogen atom or a hydrocarbon group that may contain an oxygen atom having 1 to 5 carbon atoms, n is an integer of 0 to 10). Ri Do from having two or more polymerizable units derived from norbornene monomer,
A fluorine-containing polymer having a glass transition temperature of 30 to 200C . A norbornene monomer having two or more carbon-carbon double bonds is represented by the following formula (2):

The fluorine-containing heavy of Claim 17 which is a norbornene monomer which has two carbon-carbon double bonds represented by (In formula, R < ⁸ > is a hydrogen atom or a C1-C5 alkyl group.). Coalescence. Tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene, ^{_{and, CF 2 = CF-ORf 1}} ( wherein, Rf ¹ represents. A perfluoroalkyl group having 1 to 8 carbon atoms) in A polymerized unit derived from at least one fluorine-containing ethylenic monomer selected from the group consisting of perfluoro (alkyl vinyl ethers) represented by the following formula (c):

(In the formula, R ⁶ is a hydrogen atom or a hydrocarbon group which may contain an oxygen atom having 1 to 5 carbon atoms.) A norbornene monomer having two or more carbon-carbon double bonds represented by Ri Do from derived from polymerized units,
A fluorine-containing polymer having a glass transition temperature of 30 to 200C . The norbornene monomer having two or more carbon-carbon double bonds has the following formula (3):

The fluorine-containing polymer according to claim 19, which is a norbornene monomer having two carbon-carbon double bonds represented by the formula: Furthermore, the fluorine-containing polymer (A) is further represented by the following formula (d):

(Wherein, R ¹⁴ is an alkyl group having 1 to 10 carbon atoms, x is an integer of 0 to 2), and is composed of a polymer unit derived from a norbornene monomer. , 18, 19 or 20.

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