WO2011065154A1

WO2011065154A1 - Curable resin composition

Info

Publication number: WO2011065154A1
Application number: PCT/JP2010/068330
Authority: WO
Inventors: 田中　義人; 崇金村
Original assignee: ダイキン工業株式会社
Priority date: 2009-11-24
Filing date: 2010-10-19
Publication date: 2011-06-03
Also published as: JP5418602B2; JPWO2011065154A1

Abstract

Disclosed is a curable resin composition, which utilizes a hydrosilylation reaction that is an addition reaction, and which can be easily cured without containing an organic solvent that does not take part in the hydrosilylation reaction. The curable resin composition contains (A) a fluorine-containing polymer that is represented by formula (1): -(M)-(A1)-(N)- (wherein M represents a structural unit that is derived from a fluoroolefin, A1 represents a vinyl ether structural unit that contains a carbon-carbon bond, and N represents a structural unit that is derived from a copolymerizable monomer) and (B) a hydrosilylation catalyst. The curable resin composition also contains, in the absence of (F) a solvent that does not take part in a hydrosilylation crosslinking reaction, one or more of (C) a liquid siloxane-based reactive solvent which is capable of dissolving or dispersing the fluorine-containing polymer (A) and has two or more groups wherein a hydrogen atom is directly bonded to a silicon atom, (D) a non-silicon reactive solvent which is capable of dissolving or dispersing the fluorine-containing polymer (A) and takes part in a hydrosilylation crosslinking reaction, and (E) a hydrosilylation crosslinking agent.

Description

Curable resin composition

The present invention relates to a solventless curable resin composition containing a fluorine-containing polymer that is cured by a hydrosilylation reaction.

Conventionally, as a curable resin composition using a fluorine-containing polymer, a composition relating to a curable fluorine-containing polymer having an ethylenic carbon-carbon double bond at a terminal (Patent Document 1) has been proposed. Further, Patent Document 2 proposes that a fluorine-containing polymer having an ethylenic carbon-carbon double bond is cured by a hydrosilylation reaction.

In addition, as a solvent-free curable resin composition, Patent Document 3 describes that a hydroxyl group-containing curable fluororesin is dissolved in an acrylic monomer and cured by adding an isocyanate curing agent.

International Publication No. 02/18457 Pamphlet International Publication No. 2008/153002 Pamphlet International Publication No. 2008/093776 Pamphlet

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 fluorine-containing polymer described in Patent Document 2 is a copolymer of a fluorinated ethylenic monomer and a non-fluorinated ethylenic monomer, and is a structural unit that provides an ethylenic carbon-carbon double bond Is a polymer derived from a non-fluorinated ethylenic monomer. When the structural unit giving an ethylenic carbon-carbon double bond is a non-fluorinated ethylenic structural unit, the fluorine content of the fluoropolymer cannot be increased, and optical properties such as light transmittance and refractive index are not obtained. There is room for further improvement in terms of characteristics, heat resistance at high temperatures, and light resistance.

The curing system described in Patent Document 3 is a condensation reaction between a hydroxyl group and an isocyanate group. Depending on the use, the influence of water that is eliminated cannot be ignored, and the formed crosslinked structure is a urethane bond. There is room for improvement in heat resistance.

If the removal of the organic solvent is insufficient, there arises a problem that the organic solvent remains in the cured product. In addition, there is a problem that the heat resistance and mechanical strength are lowered or white turbidity due to the influence of the remaining organic solvent, and voids may be generated due to volatilization of the solvent.

An object of the present invention is to provide a curable resin composition that uses a hydrosilylation reaction that is an addition reaction and can be easily cured without containing an organic solvent that does not participate in the hydrosilylation reaction.

The present invention
(A) Formula (1):
-(M)-(A1)-(N)-
Wherein M is a structural unit derived from a fluoroolefin;
A1 is the formula (I):

(Wherein X ¹ and X ² are the same or different and are a fluorine atom or a hydrogen atom; X ³ is a fluorine atom, a hydrogen atom, a chlorine atom, a methyl group, a trifluoromethyl group; R ¹ is a carbon-carbon at the terminal) C2-C29 chain or branched alkyl group, fluoroalkyl group, perfluoroalkyl group containing at least one double bond, including ether bond, ester bond, urethane bond in the chain N is a structural unit derived from a monomer copolymerizable with the monomer giving structural units M and A1), and the structural unit M is 1 to A fluorine-containing polymer comprising 80 mol%, 20 to 80 mol% of structural unit A1 and 0 to 79 mol% of structural unit N;
(B) a hydrosilylation catalyst, and (C) a liquid siloxane-based reactive solvent capable of dissolving or dispersing the fluoropolymer (A) and having two or more groups in which hydrogen atoms are directly bonded to silicon atoms. The present invention relates to a curable resin composition (first invention) that is contained in the absence of a solvent (F) that does not participate in the chemical crosslinking reaction.

The present invention also provides
(A) a fluorine-containing polymer represented by the formula (1) and comprising 1 to 80 mol% of the structural unit M, 20 to 80 mol% of the structural unit A1, and 0 to 79 mol% of the structural unit N;
(B) a hydrosilylation catalyst,
(D) a non-silicon reactive solvent capable of dissolving or dispersing the fluoropolymer (A) and participating in the hydrosilylation crosslinking reaction; and (E) a solvent not participating in the hydrosilylation crosslinking reaction (F) ) In the absence of the curable resin composition (second invention).

The present invention also relates to a cured product obtained by curing the curable resin composition of the first or second invention.

In addition, the hydrosilylation 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, and thus does not require a step of removing a by-product.

The curable resin composition of the present invention is a solvent-free type that does not contain a solvent that does not participate in the hydrosilylation crosslinking reaction, so that removal of the organic solvent is unnecessary, and the molding process and the like can be simplified. Furthermore, the solventless curable resin composition is useful even in cases where volatile components are not allowed due to molding processing conditions. For example, it is advantageous in applications such as filling and sealing in an airtight container.

The first curable resin composition of the present invention comprises (A) a fluoropolymer represented by the formula (1) containing the structural unit (I) represented by the formula (I), (B) a hydrosilylation catalyst, And (C) a liquid siloxane-based reactive solvent capable of dissolving or dispersing the fluorine-containing polymer (A) and having two or more groups in which hydrogen atoms are directly bonded to silicon atoms, and hydrosilylation crosslinking reaction It is a solventless composition that does not contain the solvent (F) that does not participate in the process.

The second curable resin composition of the present invention comprises (A) a fluoropolymer represented by the formula (1) containing the structural unit (I) represented by the formula (I), (B) a hydrosilylation catalyst, And (D) a non-silicon reactive solvent capable of dissolving or dispersing the fluoropolymer (A) and participating in the hydrosilylation crosslinking reaction, and (E) a hydrosilylation crosslinking agent, It is a solventless composition that does not contain a solvent (F) that does not participate.

Hereinafter, each component will be described.

(A) Fluoropolymer represented by formula (1) containing structural unit (I) represented by formula (I) In the curable resin composition of the present invention, formula (1):
-(M)-(A1)-(N)-
Wherein M is a structural unit derived from a fluoroolefin;
A1 is the formula (I):

(Wherein X ¹ and X ² are the same or different and are a fluorine atom or a hydrogen atom; X ³ is a fluorine atom, a hydrogen atom, a chlorine atom, a methyl group, a trifluoromethyl group; R ¹ is a carbon-carbon at the terminal) C2-C29 chain or branched alkyl group, fluoroalkyl group, perfluoroalkyl group containing at least one double bond, including ether bond, ester bond, urethane bond in the chain N is a structural unit derived from a monomer copolymerizable with the monomer giving structural units M and A1), and the structural unit M is 1 to A fluorine-containing polymer containing 80 mol%, 20 to 80 mol% of the structural unit A1, and 0 to 79 mol% of the structural unit N is used.

This fluoropolymer (A) is characterized in that it contains a structural unit (I) having a chain having an ethylenic carbon-carbon double bond at the terminal, and a skeleton having high solubility, transparency and light resistance. There is a point.

Such structural unit A1 includes, among others, formula (Ia):

(Wherein X ¹ to X ³ are the same as those in formula (I); Y is a linear or branched alkylene group, a fluoroalkylene group or a perfluoroalkylene group having 1 to 27 carbon atoms, An ether bond, an ester bond, a urethane bond, or an ethylenic carbon-carbon double bond may be included; Z is preferably a structural unit represented by H or CH ₃ ) from the viewpoint of good hydrosilylation crosslinking reaction.

Y is preferably a linear alkylene group having 1 to 8 carbon atoms, and preferably contains an ether bond and / or an ester bond and / or a urethane bond in the chain, and has particularly good heat resistance and compatibility. Therefore, a chain alkylene group having 5 or less carbon atoms and containing an ether bond in the chain is preferable.

Specifically, among these, the following structural units are preferable from the viewpoint of good heat resistance, light resistance, and compatibility.

(Where h is 2 or 4)

The structural unit M of the fluoropolymer (A) is a structural unit derived from a fluoroolefin. Examples of the fluoroolefin include a perfluoroolefin such as a tetrafluoroethylene (TFE) unit, a hexafluoropropylene (HFP) unit, a perfluoromethyl vinyl ether unit, a perfluoropropyl vinyl ether unit, or two or more of these; chlorotrifluoroethylene (CTFE) ) Units, vinyl fluoride units, vinylidene fluoride (VdF) units, trifluoroethylene units and other non-perfluoroolefins.

Among these, TFE and HFP are preferable from the viewpoint of weather resistance and light resistance, and CTFE and VdF are preferable from the viewpoint of compatibility.

Examples of the structural unit N include non-fluorinated vinyl ether units and / or non-fluorinated vinyl ester units that do not contain an ethylenic carbon-carbon double bond.

Specific examples include, for example, formula (II):

(Wherein R ³ is —OR ² or —CH ₂ OR ² (where R ² is an alkyl group having a hydroxyl group)), and hydroxyalkyl vinyl ethers and hydroxyalkyl allyl ethers. R ² is, for example, one having 1 to 3, preferably 1 hydroxyl group bonded to a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of these are, for example, 2-hydroxyethyl vinyl ether unit, 3-hydroxypropyl vinyl ether unit, 2-hydroxypropyl vinyl ether unit, 2-hydroxy-2-methylpropyl vinyl ether unit, 4-hydroxybutyl vinyl ether unit, 4-hydroxy- 2-methylbutyl vinyl ether unit, 5-hydroxypentyl vinyl ether unit, 6-hydroxyhexyl vinyl ether unit, 2-hydroxyethyl allyl ether unit, 4-hydroxybutyl allyl ether unit, ethylene glycol monoallyl ether unit, diethylene glycol monoallyl ether unit, Examples include triethylene glycol monoallyl ether unit and glycerin monoallyl ether unit. Hydroxyalkyl vinyl ether of 3 to 8, these, 4-hydroxybutyl vinyl ether unit and 2-hydroxyethyl vinyl ether unit are most preferred from the viewpoint of polymerization is easy.

R ³ is an alkyl vinyl ether or an alkyl allyl ether represented by —OR ⁴ , —COOR ⁴ or —OCOR ⁴ (where R ⁴ is an alkyl group). R ⁴ is, for example, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Examples of these are, for example, cyclohexyl vinyl ether units, methyl vinyl ether units, ethyl vinyl ether units, propyl vinyl ether units, n-butyl vinyl ether units, isobutyl vinyl ether units, vinyl acetate units, vinyl propionate units, vinyl butyrate units, vinyl isobutyrate units. , Vinyl pivalate units, vinyl caproate units, vinyl versatate units, vinyl laurate units, vinyl stearate units and vinyl cyclohexylcarboxylate units are preferred. Also, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and vinyl acetate from the viewpoint of excellent weather resistance, solubility, and low cost. Among these, from the viewpoint of chemical resistance, non-aromatic carboxylic acid vinyl esters, particularly carboxylic acid vinyl esters having a carboxylic acid having 6 or more carbon atoms, more preferably carboxylic acids having 9 or more carbon atoms. Esters are preferred. The upper limit of the carbon number of the carboxylic acid in the carboxylic acid vinyl ester is preferably 20 or less, and more preferably 15 or less. As a specific example, vinyl versatate is most preferable.

The copolymerization ratio is preferably such that structural unit A / structural unit M / structural unit N is 1 to 80/20 to 80/0 to 79 (molar ratio), more preferably 5 to 65/35 to 65/0 to 60. (Mole% ratio).

The number average molecular weight of the fluorinated polymer (A) is not particularly limited, but as described later, it is 1,000 to 1,000,000, particularly 3,000 to 50,000 from the viewpoint of solubility in hydrosilylation crosslinking agents and solvents. Is preferred.

(B) Hydrosilylation catalyst 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.

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

The hydrosilylation catalyst (B) is a catalyst for promoting the hydrosilylation reaction of the composition of the present invention. Examples of such catalysts include platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, ruthenium-based catalysts, and iridium-based catalysts, and platinum-based catalysts are preferred because they are relatively easily available. Examples of the platinum-based catalyst include chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum carbonyl complex, platinum olefin complex, and platinum alkenylsiloxane complex.

Specific examples of platinum complexes include platinum carbonylcyclovinylmethylsiloxane complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, etc. It can be obtained as a reagent having a platinum concentration of 1 to 5%, such as a methyl cyclic siloxane solution, a vinyl polydimethylsiloxane solution having both ends of a platinum-divinyltetramethyldisiloxane complex, and a cyclic methylvinylsiloxane solution of a platinum-cyclovinylmethylsiloxane complex.

In the composition of the present invention, the content of the hydrosilylation catalyst (B) is a catalyst amount that promotes the curing of the composition of the present invention. Specifically, the content of the catalyst metal in the composition of the present invention is The amount is preferably in the range of 0.1 to 1,000 ppm in terms of mass unit, and particularly preferably in the range of 1 to 500 ppm. If the content of the component (B) is less than the lower limit of the above range, curing of the resulting composition tends not to be sufficiently promoted. This is because problems such as coloring may occur in the cured product.

(C) Liquid siloxane-based reactive solvent capable of dissolving or dispersing the fluoropolymer (A) and having two or more groups in which hydrogen atoms are directly bonded to silicon atoms

The solvent used in the first curable resin composition of the present invention and a compound that also functions as a crosslinking agent in the hydrosilylation crosslinking reaction.

The hydrosilylation reaction is an addition reaction between an ethylenic carbon-carbon double bond and a hydrogen atom directly bonded to a silicon atom. Therefore, in the present invention, the compound that functions as a hydrosilylation crosslinking agent is a siloxane compound having two or more groups in which hydrogen atoms are directly bonded to silicon atoms.

Examples of the siloxane-based reactive solvent include, for example, International Publication No. 2008/153002, International Publication No. 2008/044765, International Patent Application PCT / JP2007 / 074066, International Patent Application PCT / JP2008 / 060555. Among the compounds described as hydrosilylation crosslinking agents in the above, liquid compounds capable of dissolving or dispersing the fluoropolymer (A) can be used.

When this siloxane-based reactive solvent (C) is used, the solvent (F) for dissolving and dispersing the fluoropolymer (A) is not required, and a so-called solventless curable composition can be obtained. it can.

When a solvent-free curable composition is used, it is not necessary to remove the organic solvent, and the molding process and the like can be simplified. In addition, if the removal of the organic solvent is insufficient, there is a problem that the organic solvent remains in the cured product, and the influence of the remaining organic solvent causes problems such as heat resistance, a decrease in mechanical strength, cloudiness, Although voids may occur due to volatilization, these problems can be solved by using a solvent-free type. Furthermore, the solventless curable resin composition is useful even in cases where volatile components are not allowed due to molding processing conditions. For example, it is advantageous in applications such as filling and sealing in an airtight container.

A hydrosilylation crosslinking agent that does not have the ability to dissolve and disperse the fluoropolymer (A) may be used in combination, or a non-silicon reactive solvent (D) involved in the hydrosilylation crosslinking reaction may be used in combination. Also good.

As the siloxane-based reactive solvent (C), for example, B1 and B2 described in International Publication No. 2008/044765 pamphlet can be used as they are.

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:

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
A siloxane compound represented by the formula:
{(CH ₃ ) ₂ HSiO} ₃ Si—C ₃ H ₆ (OC ₂ H ₄ ) _m (OC ₃ H ₆ ) _n OC ₃ H ₆ —Si {OSi (CH ₃ ) ₂ H} ₃
(In the formula, m is an integer of 0 or more, and n is an integer of 0 or more, provided that m and n are not 0.)
A siloxane compound represented by

In particular, because of its good solubility and compatibility, 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
The siloxane compound represented by these is preferable.

The compounding quantity of a siloxane type reactive solvent (C) is 5 mass parts or more with respect to 100 mass parts of fluoropolymer (A), Furthermore, 10 mass parts or more, Especially 20 mass parts or more, and 90 It is preferably at most 70 parts by mass, more preferably at most 50 parts by mass.

(D) Non-silicon reactive solvent that can dissolve or disperse the fluoropolymer (A) and participates in the hydrosilylation crosslinking reaction. This solvent is used in the second curable resin composition of the present invention.

The siloxane-based reactive solvent (C) is also a compound that dissolves and disperses the fluoropolymer (A) and participates in the hydrosilylation crosslinking reaction. However, since it is a siloxane-based compound, the non-silicon reactive solvent (D) )is not.

In the present invention, “involved in the hydrosilylation crosslinking reaction” means any reaction involved in the hydrosilylation reaction, which is an addition reaction between an ethylenic carbon-carbon double bond and a hydrogen atom directly bonded to a silicon atom. It has a group (ethylenic carbon-carbon double bond or silicon atom-bonded hydrogen atom-containing group), and as a result, is incorporated into the reaction product of the hydrosilylation crosslinking reaction.

Specifically, 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), polyvalent methacrylic compounds such as trimethylolpropane trimethacrylate (TMPT), and the like.

Of these, TAIC, EDMA, EDA, TMPT, and TMPA are preferable from the viewpoint of good solubility and compatibility.

In the second composition of the present invention, the non-silicon-based reactive solvent (D) may be used alone as the reactive solvent for the fluoropolymer (A), or the fluoropolymer (A). You may use together with the said siloxane type reactive solvent (C) which functions as a solvent.

The compounding amount of the non-silicon-based reactive solvent (D) varies depending on the type of the fluorine-containing polymer, the type of the solvent, the presence / absence of the siloxane-based reactive solvent (C), and the type, but the fluorine-containing polymer (A) The amount is 5 parts by mass or more, further 10 parts by mass or more, particularly 20 parts by mass or more, and 100 parts by mass or less, more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less.

(E) Hydrosilylation cross-linking agent A siloxane-based compound having two or more silicon-bonded hydrogen atoms, and an essential component in the second composition of the present invention.

The hydrosilylation crosslinking agent (E) may be the siloxane-based reactive solvent (C), or a liquid that does not dissolve or disperse the fluorinated polymer (A) other than the siloxane-based reactive solvent (C). Alternatively, it may be a siloxane compound (E1) that is solid and has two or more silicon-bonded hydrogen atoms (hereinafter sometimes referred to as “insoluble hydrosilylation crosslinking agent (E1)”).

In the second invention, when the siloxane-based reactive solvent (C) is used as the crosslinking agent (E), it overlaps with the embodiment of the first composition of the present invention.

In the second invention, when only the non-silicon-based reactive solvent (D) is used as the solvent (when the siloxane-based reactive solvent (C) is not used in combination), the non-soluble hydrosilylation crosslinking agent (E1) is essential. is there.

As a specific non-soluble hydrosilylation crosslinking agent (E1), for example, B3 described in International Publication No. 2008/044765 pamphlet can be used as it is.

Specific examples include the 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 ′}
(Wherein, d, e ′, and f ′ are all positive numbers), and the compatibility with the component (A) is excellent. Average unit formula:
{H (CH ₃ q 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 type compound represented by these.

Moreover, the formula which is a cyclic siloxane type compound:
(—Si (CH ₃ ) HO—) _n
(Wherein n is an integer of 3 or more and 8 or less) can also be used, and among these, n is 4 in terms of good heat resistance:

Is preferred.

The blending amount of the hydrosilylation crosslinking agent (E) in the second invention varies depending on the type of the fluoropolymer, the type of the hydrosilylation crosslinking agent, the presence or absence of the siloxane-based reactive solvent (C), the type, etc. From the viewpoint of the function, it is 1 part by mass or more, further 2 parts by mass or more, particularly 5 parts by mass or more, and 50 parts by mass or less, further 100 parts by mass of the fluoropolymer (A). It is preferably 20 parts by mass or less, particularly 10 parts by mass or less.

(F) Solvent that does not participate in hydrosilylation crosslinking reaction The curable resin composition of the present invention does not use a solvent (F) that does not participate in the hydrosilylation crosslinking reaction, regardless of whether it is the first invention or the second invention. .

The solvent that is used only to dissolve or disperse the fluoropolymer (A) and does not participate in the hydrosilylation crosslinking reaction needs to be finally removed, which is undesirable from the viewpoint of environment and cost, including energy for that purpose.

Specific examples of the solvent (F) not used in the present invention include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; benzene, toluene, xylene, naphthalene, Aromatic hydrocarbons such as solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate , Ethyl-2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, 2- Esters such as ethyl droxyisobutyrate; 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 , Glycol ethers such as propylene glycol 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 Kind; Alcohols such as ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, tert-amyl alcohol; tetrahydrofuran Cyclic ethers such as tetrahydropyran 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; 1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, etc. It is. Or these 2 or more types of mixed solvents etc. are mention | raise | lifted.

Further, as the fluorine-based solvent, for example, 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, etc.
H (CF ₂ CF ₂ ) _n CH ₂ OH (n: an integer of 1 to 3),
F (CF ₂ ) _n CH ₂ OH (n: an integer of 1 to 5),
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 may be fluorinated solvents, or a mixed solvent of one or more of non-fluorinated and fluorinated solvents.

As described above, the curable resin composition of the present invention can be a so-called solventless curable resin composition that does not use the solvent (F) that does not participate in the hydrosilylation crosslinking reaction. In the present invention, the solventless type refers to the case where only the reactive solvents (C) and (D) are used, and is distinguished from the solvent type using the solvent (F) that does not participate in the hydrosilylation crosslinking reaction. By using the solvent-free type in this way, it is not necessary to remove the solvent (F), the molding process and the like can be simplified, and the problem that the solvent (F) remains in the cured product does not occur. As the influence of the remaining solvent (F), there are problems such as heat resistance, reduction in mechanical strength, and cloudiness. Furthermore, the solventless curable resin composition is useful even in cases where volatile components are not allowed due to molding processing conditions. For example, it is used for filling and sealing in an airtight container.

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 curing 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.

Hereinafter, preferred embodiments of the first and second curable resin compositions of the present invention will be described with specific combinations, but the present invention is not limited to these.

(1) First curable resin composition (A) fluorinated polymer:
In formula (1), the structural unit A1 is the formula (Ia), and the structural unit M is hydroxyethyl vinyl ether. The fluorine-containing polymer having a number average molecular weight of 2000 to 50000 (B) hydrosilylation catalyst Platinum catalyst (C) siloxane system Reactive solvent C ₆ H ₅ Si (OSi (CH ₃ ) ₂ H) ₃
(Preparation method)
After (A) is uniformly dissolved in (C), (B) is added to obtain a curable composition.

(2) First curable resin composition (A) fluorinated polymer:
In formula (1), the structural unit A1 is the formula (Ia), and the structural unit M is hydroxyethyl vinyl ether. The fluorine-containing polymer having a number average molecular weight of 2000 to 50000 (B) hydrosilylation catalyst Platinum catalyst (C) siloxane system Reactive solvent C ₆ H ₅ Si (OSi (CH ₃ ) ₂ H) ₃
(D) Non-silicon reactive solvent TAIC
(Preparation method)
(C) and (D) are mixed uniformly, then (A) is uniformly dissolved, and (B) is added to obtain a curable composition.

(3) First curable resin composition (A) fluorinated polymer:
In formula (1), the structural unit A1 is the formula (Ia), and the structural unit M is hydroxyethyl vinyl ether. The fluorine-containing polymer having a number average molecular weight of 2000 to 50000 (B) hydrosilylation catalyst Platinum catalyst (C) siloxane system Reactive solvent C ₆ H ₅ Si (OSi (CH ₃ ) ₂ H) ₃
(E) Hydrosilylation crosslinking agent

(Preparation method)
After (A) is uniformly dissolved in (C), (E) is added to make it uniform. Finally, (B) is added to obtain a curable composition.

(4) Second curable resin composition (A) fluorinated polymer:
In the formula (1), the fluorine-containing polymer (B) hydrosilylation catalyst having a number average molecular weight of 2,000 to 50,000, wherein the structural unit A1 is the formula (Ia) and the structural unit M is hydroxyethyl vinyl ether. Platinum catalyst (D) Non-silicon Reactive solvent TAIC
(E) Hydrosilylation crosslinking agent

(Preparation method)
(A) is uniformly dissolved in (D), (E) is added, and (B) is further added to obtain a curable composition.

(5) First or second curable resin composition (A) fluorinated polymer:
In formula (1), the structural unit A1 is the formula (Ia), and the structural unit M is hydroxyethyl vinyl ether. The fluorine-containing polymer having a number average molecular weight of 2000 to 50000 (B) hydrosilylation catalyst Platinum catalyst (C) siloxane system Reactive solvent C ₆ H ₅ Si (OSi (CH ₃ ) ₂ H) ₃
(D) Non-silicon reactive solvent TAIC
(E) Hydrosilylation crosslinking agent

(Preparation method)
(C) and (D) are mixed uniformly. (A) is uniformly dissolved therein, (E) is added, and (B) is further added to obtain a curable composition.

In addition to those described above, the curable resin composition of the present invention optionally includes, for example, reaction inhibitors, pigments, dispersants, thickeners, preservatives, ultraviolet absorbers, antifoaming agents, leveling agents, etc. May be.

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. The content of the reaction inhibitor is not particularly limited, but is preferably such an amount that it is 10 to 50,000 ppm (mass basis) in the composition of the present invention.

The curable resin composition of the present invention is cured by hydrosilylation crosslinking, and the resulting cured product can be used in various forms for various applications.

For example, a cured film can be formed and used for various purposes. 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.

Examples of the use of the curable resin composition of the present invention include a sealing member, an optical material, an optoelectronic imaging tube, various sensors, and an antireflection material.

Examples of usage of the sealing member include packages (encapsulation) and mounting of light-emitting elements such as light-emitting diodes (LEDs), EL elements, and nonlinear optical elements, and optical functional elements such as light-receiving elements such as CCD, CMOS, and PD. Can be illustrated. Moreover, sealing materials (or fillers) for optical members such as lenses for deep ultraviolet microscopes are also included. Sealed light elements are used in various places, but non-limiting examples include light emission from high-mount stop lamps, meter panels, mobile phone backlights, and light sources for remote control devices for various electrical products. Elements: Camera autofocus, CD / DVD optical pickup light receiving element, and the like.

Since the optical material contains fluorine in particular, it becomes an optical material with a low refractive index. For example, it is useful as an optical transmission medium. In particular, cladding material of plastic clad optical fiber whose core material is quartz or optical glass, cladding material of all plastic optical fiber whose core material is plastic, anti-reflection coating material, lens material, optical waveguide material, prism material, optical window It can be used for optical materials such as materials, optical storage disk materials, nonlinear optical elements, hologram materials, photolithographic materials, and light emitting element sealing materials. 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. Furthermore, various functional compounds (non-linear optical materials, fluorescent light-emitting functional dyes, photorefractive materials, etc.) are contained and used as functional elements for optical devices such as modulators, wavelength conversion elements, and optical amplifiers. Is suitable.

As a sensor application, it is particularly useful because it has the effect of improving the sensitivity of optical sensors and pressure sensors, and protecting the sensor with water and oil repellent properties.

In addition, it can 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 use can be exemplified as described above, but are not limited thereto.

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

The measurement methods used in this specification are summarized below.

(1) NMR analyzer: manufactured by BRUKER
¹ H-NMR measurement conditions: 300 MHz (tetramethylsilane = 0 ppm)
¹⁹ F-NMR measurement conditions: 282 MHz (trichlorofluoromethane = 0 ppm)

(2) IR analyzer: Fourier transform infrared spectrophotometer 1760X manufactured by PERKIN ELMER
Conditions: Measure at room temperature.

(3) Number average molecular weight Using gel permeation chromatography (GPC), a column made by Shodex (one GPC KF-801 and one GPC KF-802) using GPC HLC-8020 manufactured by Tosoh Corporation. The number average molecular weight is 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.

(4) Hydroxyl value (mgKOH / g)
The hydroxyl value is determined according to a conventional method by an acetylation method using acetic anhydride.

(5) Fluorine content (% by mass)
By burning 10 mg of sample by the oxygen flask combustion method, absorbing the decomposition gas in 20 ml of deionized water, and measuring the fluorine ion concentration in the absorption liquid by the fluorine selective electrode method (fluorine ion meter, model 901 manufactured by Orion) Ask.

(6) Viscosity (mPa · s)
Using a cone-plate viscometer CV-1E manufactured by Tokai Yagami Co., Ltd., the viscosity at 25 ° C. is measured under the condition of 100 rpm using CP-100 cone, and a stable value is adopted for 60 seconds.

(7) 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.

(8) Thermal decomposition temperature (℃)
Using a thermogravimeter (TGA-50 manufactured by Shimadzu Corporation), the temperature is measured under a nitrogen atmosphere at a rate of temperature increase of 10 ° C./min and evaluated at a temperature of 1% mass loss.

(9) Light transmittance (%)
A value obtained by measuring a spectral transmittance curve of a sample (cured film) having a thickness of about 100 μm at a wavelength of 300 to 800 nm using a self-recording spectrophotometer (U-3310 (trade name) manufactured by Hitachi, Ltd.) is adopted.

(10) Solvent resistance A sample of 10 mm × 10 mm × 0.1 mm is immersed in 20 mL of butyl acetate, and the state after 8 hours at room temperature is visually observed.

(11) Heat resistance Each sample is held for 1 hour at a temperature of 150 ° C., and the change in appearance is visually observed.

Synthesis Example 1 (Production of hydroxyl-containing fluorine-containing polymer)
According to the method described in JP-A-2004-204205, the following hydroxyl group-containing fluorine-containing copolymer (A-1) polymers (a) to (d) were synthesized.

Polymer (a): TFE / VV9 / HBVE = 45/39/16 (mol%), number average molecular weight (Mn) = 1.2 × 10 ³ , Tg = 35 ° C., fluorine content (mass%) = 24, Hydroxyl value (mgKOH / g) = 54

Polymer (b): TFE / VV10 / HEVE / VtBz = 45/35/15/5 (mol%), Mn = 1.3 × 10 ³ , Tg = 12 ° C., fluorine content (mass%) = 24, hydroxyl group Value (mgKOH / g) = 68

Polymer (c): TFE / VV9 / HBVE / CA = 45 / 39.3 / 15 / 0.7, Mn = 1.1 × 10 ³ , Tg = 33 ° C., fluorine content (mass%) = 24, hydroxyl group Value (mgKOH / g) = 51

Polymer (d): TFE / VV9 / HEVE / VBz / CA = 45 / 34.4 / 14/6 / 0.6 (mol%), Mn = 1.2 × 10 ³ , Tg = 30 ° C., fluorine content (Mass%) = 25, hydroxyl value (mgKOH / g) = 66

In addition, the symbol of each monomer in said polymer is the following compound.
TFE: tetrafluoroethylene VV9: vinyl versatate (Veoba 9 (trade name of aliphatic carboxylic acid vinyl ester of 9 carbon atoms manufactured by Shell Chemical Co., Ltd.))
VV10: vinyl versatate (Veoba 10 (trade name of aliphatic carboxylic acid vinyl ester having 10 carbon atoms manufactured by Shell Chemical Co., Ltd.))
HBVE: hydroxybutyl vinyl ether HEVE: hydroxyethyl vinyl ether VtBz: tert-butyl vinyl benzoate VBz: vinyl benzoate CA: crotonic acid

Synthesis example 2
20 g of polymer (a) was weighed and dissolved in 20 g of n-butyl acetate previously dehydrated with Molecular Sieves 4A, and charged into a 100 ml glass four-necked flask equipped with a stirrer and a thermometer. From the dropping funnel, 1.6 g of allyl isocyanate (CH ₂ ═CHCH ₂ NCO) was added dropwise at room temperature, and the mixture was sufficiently stirred and homogenized. Thereafter, it was placed in an oil bath, and the internal temperature was kept at 70 ± 5 ° C. and stirred for 5 hours. By measuring the IR of the reaction solution, it was confirmed that the raw material allyl isocyanate was not present in the system. Thereafter, the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone. The polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated three times in total, and the obtained polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis.

It was found that the polymer was a fluorine-containing polymer containing 16 mol% in the molecule.

Synthesis example 3
20 g of polymer (b) was weighed and dissolved in 20 g of n-butyl acetate previously dehydrated with Molecular Sieves 4A, and charged into a 100 ml glass four-necked flask equipped with a stirrer and a thermometer. From the dropping funnel, 2.0 g of allyl isocyanate (CH ₂ = CHCH ₂ NCO) was added dropwise at room temperature, and the mixture was sufficiently stirred to make it uniform. Thereafter, it was placed in an oil bath, and the internal temperature was kept at 70 ± 5 ° C. and stirred for 5 hours. By measuring the IR of the reaction solution, it was confirmed that the raw material allyl isocyanate was not present in the system. Thereafter, the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone. The polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated three times in total, and the obtained polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis.

It was found to be a fluorine-containing polymer containing 15 mol% of the unit represented by

Synthesis example 4
20 g of polymer (c) was weighed and dissolved in 20 g of n-butyl acetate previously dehydrated with Molecular Sieves 4A, and charged into a 100 ml glass four-necked flask equipped with a stirrer and a thermometer. From a dropping funnel, 2.6 g of Karenz AOI (CH ₂ = CHCOOCH ₂ CH ₂ NCO) manufactured by Showa Denko Co., Ltd. was dropped at room temperature, and the mixture was sufficiently stirred and homogenized. Thereafter, it was placed in an oil bath, and the internal temperature was kept at 80 ± 5 ° C. and stirred for 5 hours. By measuring the IR of the reaction solution, it was confirmed that the raw material allyl isocyanate was not present in the system. Thereafter, the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone. The polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated three times in total, and the obtained polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis.

Synthesis example 5
20 g of the polymer (d) was weighed and dissolved in 20 g of n-butyl acetate previously dehydrated with Molecular Sieves 4A, and charged into a 100 ml glass four-necked flask equipped with a stirrer and a thermometer. From a dropping funnel, 1.55 g of Karenz MOI (CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ NCO) manufactured by Showa Denko KK was added dropwise at room temperature, and the mixture was sufficiently stirred and homogenized. Thereafter, it was placed in an oil bath, and the internal temperature was kept at 80 ± 5 ° C. and stirred for 5 hours. By measuring the IR of the reaction solution, it was confirmed that the raw material allyl isocyanate was not present in the system. Thereafter, the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone. The polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated three times in total, and the obtained polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis.

It was found to be a fluorine-containing polymer containing 6 mol% of the unit represented by

Comparative Synthesis Example 1
In a 100 ml three-necked flask, 50 g of a 20% by mass aqueous NaCl solution was added and cooled to −15 ° C. When 1.05 g of Na ₂ O ₂ was added, the temperature rose to −10 ° C. Cool again to −15 ° C., the formula:
(CH ₃ ) ₃ C—OCH ₂ CF ₂ COCl
4.91 g of a compound represented by the formula was added dropwise. After completion of the dropwise addition, the mixture was stirred for 30 minutes while cooling to -15 ° C. 5.0 ml of 1,1,2-trichloro-1,2,2-trifluoroethane cooled to −15 ° C. was added, and the mixture was further stirred for 30 minutes. Since it separated into two layers as soon as it was allowed to stand, a white suspension containing the lower layer peroxide was collected (6.0 ml). When the concentration of peroxide in this suspension was determined by an iodometric titration method, the concentration was 134 mg / ml.

After adding 4.6 ml of 1,1,2-trichloro-1,2,2-trifluoroethane solution of the obtained peroxide to a 100 ml stainless steel reaction vessel cooled to −50 ° C., and replacing with nitrogen gas, Hexafluoropropylene (HFP) 10.9 g and vinylidene fluoride (VdF) 6.5 g were charged. Polymerization was carried out by shaking the reaction vessel at 20 ° C. for 2.5 hours. The internal pressure of the reaction vessel decreased from 1.28 MPa · G to 1.17 MPa · G. After the completion of the polymerization, the unreacted monomer and 1,1,2-trichloro-1,2,2-trifluoroethane were evaporated to obtain 4.2 g of a liquid polymer (1). As a result of MNR analysis, it was a copolymer of 76.5 mol% VdF units and 23.5 mol% HFP units.

The same amount of trifluoroacetic acid was added to the obtained liquid polymer (1) and heated at 70 ° C. for 2 hours. After the reaction, it was washed with water and then dried to obtain a liquid polymer (2). NMR analysis and IR analysis of this polymer (2) revealed that the terminal t-butoxy group of the liquid polymer (1) was converted to a hydroxyl group.

1.0 g of allyl isocyanate (CH ₂ = CHCH ₂ NCO) was mixed with 3.5 g of the obtained liquid polymer (2), reacted at room temperature for 24 hours, and then heated to 100 ° C. to complete the reaction. Furthermore, it heated at 100 degreeC under pressure reduction, volatilized and removed excess allyl isocyanate, and obtained the fluorine-containing polymer (3). When this fluoropolymer (3) was subjected to NMR analysis and IR analysis, it was found to be a polymer having an allyl group at the polymer terminal.

The fluoropolymer (3) was fluid at room temperature and had a number average molecular weight of 5400.

Comparative Synthesis Example 2
In a 500 ml glass four-necked flask equipped with a stirrer and a thermometer, 80 g of methyl methacrylate (MMA), 20 g of hydroxyethyl methacrylate (HEMA), 1.5 g of azobisisobutyronitrile (AIBN), solvent As a starting material, 300 g of butyl acetate was added, stirred well at room temperature, and polymerized under a nitrogen stream at a temperature of 70 ° C. for 16 hours. The obtained polymer was reprecipitated in n-hexane to obtain 91 g of polymer. Its number average molecular weight was 33,000. When this polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, it was confirmed to be a copolymer of MMA and HEMA. The composition ratio was determined by NMR as MMA: HEMA = 83: 17 (molar ratio).

10 g of the obtained polymer was weighed and dissolved in 40 g of methyl isobutyl ketone (MIBK) previously dehydrated with molecular sieves 4A, and charged into a 100 ml glass four-necked flask equipped with a stirrer and a thermometer. From the dropping funnel, 0.74 g of allyl isocyanate was added dropwise at room temperature, and the mixture was sufficiently stirred to homogenize. Thereafter, it was placed in an oil bath, and the internal temperature was kept at 80 ± 5 ° C. and stirred for 5 hours. By measuring the IR of the reaction solution, it was confirmed that the raw material allyl isocyanate was not present in the system. Thereafter, the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone. The polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated a total of three times, and the obtained polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis.

The polymer was (m: n: o = 10: 6: 84).

Example 1
10 g of the polymer obtained in Synthesis Example 2, 10 g of triallyl isocyanurate (TAIC) as a non-silicon reactive solvent, and 3- (dimethylsilyloxy) -1,1,5,5-tetramethyl- as a siloxane reactive solvent 3-phenyltrisiloxane:

14.5 g (theoretical equivalent of hydrosilylation reaction) was added and placed in a constant temperature bath at 40 ° C. When taken out after 12 hours, it became a uniform, transparent and viscous composition. To this composition, 5 μL of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-free curable composition.

The appearance of the liquid composition at 25 ° C. of the composition before curing was visually evaluated. The results are shown in Table 1. The evaluation criteria are as follows.
○: Transparent and uniform, and the transmittance of light at 550 nm is 80% or more.
Δ: Partly cloudy (gel-like material) is observed.
X: Opaque and cloudy.

Table 1 shows the evaluation results of the viscosity of the liquid composition at 25 ° C. and the appearance of the liquid composition before curing.

Next, NF-0100 (thickness: 100 μm) made by Daikin Industries, Ltd., which is a fluororesin film for release, is spread on the glass plate, and applied using an applicator so that the film thickness becomes about 100 μm. A NF-0100 (thickness: 100 μm) made by Daikin Industries, Ltd., which is a fluororesin film for mold release, was placed on the top, and a slide glass with a thickness of 1 mm was placed thereon, followed by 150 hours at 100 ° C. for 2 hours. Cured for 1 hour at ° C. After curing, the release fluororesin film was peeled off to obtain a cured film.

The fluorine content, refractive index (n), thermal decomposition temperature (Td), and light transmittance visible (550 nm) (T) of the sample film (after curing) were measured.

Moreover, the external appearance was evaluated visually. The evaluation criteria are as follows.
○: Transparent and uniform.
Δ: Some cloudiness is observed.
X: Opaque and cloudy.

Moreover, the solvent resistance was evaluated. The evaluation criteria are as follows.
○: No swelling is visually observed.
Δ: Swelling is visually observed.
X: Dissolve.

Furthermore, heat resistance was evaluated. The evaluation criteria are as follows.
○: No change is visually observed.
Δ: Slight discoloration and turbidity are observed visually.
X: Discoloration, white turbidity, deformation, etc. that are clearly visible are observed.

The results are shown in Table 1.

Example 2
10 g of the polymer obtained in Synthesis Example 3, 10 g of triallyl isocyanurate (TAIC) as a non-silicon reactive solvent, and 3- (dimethylsilyloxy) -1,1,5,5-tetramethyl- as a siloxane reactive solvent 3-phenyltrisiloxane:

13 g and 1,3,5,7-tetramethyl-cyclo-tetrasiloxane as hydrosilylation crosslinker:

3.1 g was put into a 50 degreeC thermostat. When taken out after 12 hours, it became a uniform, transparent and viscous composition. To this composition, 5 μL of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-free curable composition.

This curable composition was cured in the same manner as in Example 1, and various physical properties were measured. The results are shown in Table 1.

Example 3
10 g of the polymer obtained in Synthesis Example 4, 3 g of triallyl isocyanurate (TAIC) as a non-silicon reactive solvent, and 3- (dimethylsilyloxy) -1,1,5,5-tetramethyl- as a siloxane reactive solvent 3-phenyltrisiloxane:

5.2g was put into a 40 degreeC thermostat. When taken out after 12 hours, it became a uniform, transparent and viscous composition. To this composition, 5 μL of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-free curable composition.

Example 4
10 g of the polymer obtained in Synthesis Example 5, 3 g of triallyl isocyanurate (TAIC) as a non-silicon reactive solvent, and 3- (dimethylsilyloxy) -1,1,5,5-tetramethyl- as a siloxane reactive solvent 3-phenyltrisiloxane:

4.5g was put into a 40 degreeC thermostat. When taken out after 12 hours, it became a uniform, transparent and viscous composition. To this composition, 5 μL of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-free curable composition.

Example 5
10 g of the polymer obtained in Synthesis Example 1 and tetrakis (dimethylsilyloxy) silane as a siloxane-based reactive solvent:

0.5g was put into a 40 degreeC thermostat. When taken out after 12 hours, it became a uniform, transparent and viscous composition. To this composition, 5 μL of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-free curable composition.

Example 6
10 g of the polymer obtained in Synthesis Example 1 and 1.0 g, 1,1,3 of 3- (dimethylsilyloxy) -1,1,5,5-tetramethyl-3-phenyltrisiloxane as a siloxane-based reactive solvent , 3-tetramethyldisiloxane 0.2 g, 1,3,5,7-tetramethyl-cyclo-tetrasiloxane as hydrosilylation crosslinking agent:

3.1 g was put into a 40 degreeC thermostat. When taken out after 12 hours, it became a uniform, transparent and viscous composition. To this composition, 5 μL of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-free curable composition.

Example 7
10 g of the polymer obtained in Synthesis Example 5, 3 g of triallyl isocyanurate (TAIC) as a non-silicon reactive solvent, and 1,3,5,7-tetramethyl-cyclo-tetrasiloxane as a hydrosilylation crosslinking agent:

Example 8
As a hydrosilylation crosslinker in Example 7, HPM-502 from Gelest:

A curable composition was prepared and various physical properties were measured in the same manner as in Example 7 except that was used. The results are shown in Table 1.

Comparative Example 1
5 g of the polymer obtained in Synthesis Example 4, 1 g of methyl methacrylate and 4 g of 1H, 1H, 5H-octafluoropentyl acrylate (CH ₂ ═CHCOOCH ₂ C ₄ F ₈ H) are dissolved in 1 g of trimethylolpropane triacrylate (TMPA). A uniform composition was obtained. 0.1 g of 2-hydroxy-2-methylpropiophenone was added as a UV initiator to obtain a curable composition. Next, NF-0100 (thickness: 100 μm) made by Daikin Industries, Ltd., which is a fluororesin film for release, is spread on the glass plate, and applied using an applicator so that the film thickness becomes about 100 μm. Cover with NF-0100 (thickness 100 μm) made by Daikin Industries, Ltd., which is a fluororesin film for mold release, and then place a slide glass with a thickness of 1 mm, and then use a high-pressure mercury lamp from the top to 1500 mJ / After irradiating ultraviolet rays with the intensity of cm ² U, the fluororesin film for release was peeled off to obtain a cured film.

Various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1. As is clear from Table 1, the heat resistance was clearly inferior.

Comparative Example 2
To 2.5 g of the polymer obtained in Comparative Synthesis Example 1, 3- (dimethylsilyloxy) -1,1,5,5-tetramethyl-3-phenyltrisiloxane as a siloxane-based reactive solvent:

Was added to a constant temperature bath at 40 ° C. Even when taken out after 24 hours, a non-uniform and cloudy composition was obtained. Further, the temperature was raised to 70 ° C., but the non-uniform state did not change.

Comparative Example 3
To 2.0 g of the polymer obtained in Comparative Synthesis Example 2, 3- (dimethylsilyloxy) -1,1,5,5-tetramethyl-3-phenyltrisiloxane as a siloxane-based reactive solvent:

0.21 g and 2.5 g of methyl isobutyl ketone (MIBK) as a non-silicon reactive solvent were added and placed in a constant temperature bath at 40 ° C. When taken out after 12 hours, it became a uniform, transparent and viscous composition. To this composition, 5 μL of a platinum-cyclovinylmethylsiloxane complex (product number SIP6832.2) manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-type curable composition.

A cured product was prepared in the same manner as in Example 1 except that after the solvent was volatilized and coated so that the thickness became about 100 μm and dried at 100 ° C. for 20 minutes, various physical properties were measured. The results are shown in Table 1. As is clear from Table 1, the heat resistance was clearly inferior.

Comparative Example 4
In Example 1, the same amount (weight) of butyl acetate was added to the prepared curable composition to obtain a solvent-type curable composition.

When this composition was cured by the same process as in Example 1, many bubbles were generated and a uniform coating surface could not be obtained. Table 1 shows the measurement results of various physical properties.

Comparative Example 5
In Example 1, only the platinum catalyst was not added. The initial appearance and the like were not different from those of Example 1 but were not cured at all at 100 ° C. for 2 hours and then at 150 ° C. for 1 hour. The temperature was further raised to 200 ° C., but it was not cured.

From Table 1, it can be seen that the curable composition of the present invention gives a transparent cured product having excellent heat resistance. Further, since the refractive index can be controlled by controlling the fluorine content, it can be seen that application to various optical devices is possible.

Claims

(A) Formula (1):
-(M)-(A1)-(N)-
Wherein M is a structural unit derived from a fluoroolefin;
A1 is the formula (I):

(Wherein X 1 and X 2 are the same or different and are a fluorine atom or a hydrogen atom; X 3 is a fluorine atom, a hydrogen atom, a chlorine atom, a methyl group, a trifluoromethyl group; R 1 is a carbon-carbon at the terminal) C2-C29 chain or branched alkyl group, fluoroalkyl group, perfluoroalkyl group containing at least one double bond, including ether bond, ester bond, urethane bond in the chain N is a structural unit derived from a monomer copolymerizable with the monomer giving structural units M and A1), and the structural unit M is 1 to A fluorine-containing polymer comprising 80 mol%, 20 to 80 mol% of structural unit A1 and 0 to 79 mol% of structural unit N;
(B) a hydrosilylation catalyst, and (C) a liquid siloxane-based reactive solvent capable of dissolving or dispersing the fluoropolymer (A) and having two or more groups in which hydrogen atoms are directly bonded to silicon atoms. A curable resin composition contained in the absence of a solvent (F) that does not participate in the chemical crosslinking reaction.
(A) Formula (1):
-(M)-(A1)-(N)-
Wherein M is a structural unit derived from a fluoroolefin;
A1 is the formula (I):

(Wherein X 1 and X 2 are the same or different and are a fluorine atom or a hydrogen atom; X 3 is a fluorine atom, a hydrogen atom, a chlorine atom, a methyl group, a trifluoromethyl group; R 1 is a carbon-carbon at the terminal) C2-C29 chain or branched alkyl group, fluoroalkyl group, perfluoroalkyl group containing at least one double bond, including ether bond, ester bond, urethane bond in the chain N is a structural unit derived from a monomer copolymerizable with the monomer giving structural units M and A1), and the structural unit M is 1 to A fluorine-containing polymer comprising 80 mol%, 20 to 80 mol% of structural unit A1 and 0 to 79 mol% of structural unit N;
(B) a hydrosilylation catalyst,
(D) a non-silicon reactive solvent capable of dissolving or dispersing the fluoropolymer (A) and participating in the hydrosilylation crosslinking reaction; and (E) a solvent not participating in the hydrosilylation crosslinking reaction (F) ) In the absence of curable resin composition.
In formula (I), structural unit A1 is represented by formula (Ia):

(Wherein X 1 to X 3 are the same as those in formula (I); Y is a linear or branched alkylene group, a fluoroalkylene group or a perfluoroalkylene group having 1 to 27 carbon atoms, The curable resin composition according to claim 1 or 2, which may contain an ether bond, an ester bond, a urethane bond, or an ethylenic carbon-carbon double bond; Z is a structural unit represented by H or CH 3 ). .
The curable resin composition according to any one of claims 1 to 3, wherein the curable resin composition has a viscosity of 1 to 20000 mPa · s at 30 ° C.
The curable resin composition according to any one of claims 1 to 4, which is used as an LED sealant.
A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5.