WO2011065154A1 - Composition de résine durcissable - Google Patents

Composition de résine durcissable Download PDF

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Publication number
WO2011065154A1
WO2011065154A1 PCT/JP2010/068330 JP2010068330W WO2011065154A1 WO 2011065154 A1 WO2011065154 A1 WO 2011065154A1 JP 2010068330 W JP2010068330 W JP 2010068330W WO 2011065154 A1 WO2011065154 A1 WO 2011065154A1
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Prior art keywords
structural unit
formula
resin composition
curable resin
solvent
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PCT/JP2010/068330
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English (en)
Japanese (ja)
Inventor
田中　義人
崇 金村
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ダイキン工業株式会社
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Priority to JP2011543172A priority Critical patent/JP5418602B2/ja
Publication of WO2011065154A1 publication Critical patent/WO2011065154A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a solventless curable resin composition containing a fluorine-containing polymer that is cured by a hydrosilylation reaction.
  • Patent Document 1 a composition relating to a curable fluorine-containing polymer having an ethylenic carbon-carbon double bond at a terminal
  • Patent Document 2 proposes that a fluorine-containing polymer having an ethylenic carbon-carbon double bond is cured by a hydrosilylation reaction.
  • 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.
  • 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.
  • 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.
  • 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 A
  • 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).
  • 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
  • the present invention also relates to a cured product obtained by curing the curable resin composition of the first or second invention.
  • 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.
  • formula (1) -(M)-(A1)-(N)-
  • 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 derived from a monomer cop
  • 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.
  • the following structural units are preferable from the viewpoint of good heat resistance, light resistance, and compatibility.
  • the structural unit M of the fluoropolymer (A) is a structural unit derived from a fluoroolefin.
  • 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.
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • CTE chlorotrifluoroethylene
  • TFE and HFP are preferable from the viewpoint of weather resistance and light resistance
  • 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.
  • R 3 is —OR 2 or —CH 2 OR 2 (where R 2 is an alkyl group having a hydroxyl group)
  • 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.
  • vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and vinyl acetate from the viewpoint of excellent weather resistance, solubility, and low cost.
  • 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.
  • 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.
  • Hydrosilylation catalyst A compound that catalyzes a known hydrosilylation reaction can be used.
  • 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.
  • 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.
  • 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.
  • platinum-based catalyst include chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum carbonyl complex, platinum olefin complex, and platinum alkenylsiloxane complex.
  • 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.
  • the content of the hydrosilylation catalyst (B) is a catalyst amount that promotes the curing of the composition of the present invention.
  • 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 are 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.
  • siloxane-based reactive solvent examples 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.
  • liquid compounds capable of dissolving or dispersing the fluoropolymer (A) can be 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.
  • the solvent-free curable composition 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.
  • siloxane-based reactive solvent (C) for example, B1 and B2 described in International Publication No. 2008/044765 pamphlet can be used as they are.
  • 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.
  • 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.
  • “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.
  • 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
  • TAIC EDMA
  • EDA EDA
  • TMPT TMPA
  • TMPA TMPA
  • 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).
  • 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)”).
  • the siloxane-based reactive solvent (C) when used as the crosslinking agent (E), it overlaps with the embodiment of the first composition of the present invention.
  • the non-soluble hydrosilylation crosslinking agent (E1) is essential. is there.
  • non-soluble hydrosilylation crosslinking agent (E1) for example, B3 described in International Publication No. 2008/044765 pamphlet can be used as it is.
  • n is an integer of 3 or more and 8 or less
  • 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.
  • solvent (F) not used in the present invention examples 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-me
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • First curable resin composition (A) fluorinated polymer:
  • the structural unit A1 is the formula (Ia)
  • 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.
  • 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.
  • First or second curable resin composition (A) fluorinated polymer:
  • the structural unit A1 is the formula (Ia)
  • 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)
  • (A) is uniformly dissolved therein, (E) is added, and (B) is further added to obtain a curable composition.
  • 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.
  • reaction inhibitor examples 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.
  • 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.
  • a cured film can be formed and used for various purposes.
  • 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.
  • sealing member examples 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.
  • the optical material contains fluorine in particular, it becomes an optical material with a low refractive index.
  • it is useful as an optical transmission medium.
  • 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
  • lens material optical waveguide material
  • prism material optical window
  • 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.
  • 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.
  • the sealing member material for electronic semiconductors, a water and moisture resistant adhesive, and an adhesive for optical components and elements.
  • IR analyzer Fourier transform infrared spectrophotometer 1760X manufactured by PERKIN ELMER Conditions: Measure at room temperature.
  • Hydroxyl value (mgKOH / g) The hydroxyl value is determined according to a conventional method by an acetylation method using acetic anhydride.
  • 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.
  • 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.
  • 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.
  • Light transmittance (%) A value obtained by measuring a spectral transmittance curve of a sample (cured film) having a thickness of about 100 ⁇ m at a wavelength of 300 to 800 nm using a self-recording spectrophotometer (U-3310 (trade name) manufactured by Hitachi, Ltd.) is adopted.
  • 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.
  • 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.
  • allyl isocyanate CH 2 ⁇ CHCH 2 NCO
  • 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.
  • 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
  • CH 2 CHCOOCH 2 CH 2 NCO
  • 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.
  • Karenz MOI CH 2 ⁇ C (CH 3 ) COOCH 2 CH 2 NCO
  • the fluoropolymer (3) was fluid at room temperature and had a number average molecular weight of 5400.
  • 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.
  • 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 ⁇ L 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.
  • TAIC triallyl isocyanurate
  • 3-phenyltrisiloxane 14.5 g (theoretical equivalent of hydrosilylation reaction) was added and placed in a constant temperature bath at 40 ° C. When
  • 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.
  • NF-0100 thickness: 100 ⁇ m
  • Daikin Industries, Ltd. which is a fluororesin film for release
  • 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.
  • the evaluation criteria are as follows. ⁇ : Transparent and uniform. ⁇ : Some cloudiness is observed. X: Opaque and cloudy.
  • the evaluation criteria are as follows. ⁇ : No swelling is visually observed. ⁇ : Swelling is visually observed. X: Dissolve.
  • 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 ⁇ L 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.
  • TAIC triallyl isocyanurate
  • 3-phenyltrisiloxane 13 g
  • 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 ⁇ L 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.
  • TAIC triallyl isocyanurate
  • 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 ⁇ L 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.
  • TAIC triallyl isocyanurate
  • 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 ⁇ L 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.
  • 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 ⁇ L 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.
  • a platinum-cyclovinylmethylsiloxane complex product number SIP6832.2 manufactured by AZMAX was added as a platinum catalyst to obtain a solvent-free
  • 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: 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 ⁇ L 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.
  • TAIC triallyl isocyanurate
  • 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.
  • TMPA trimethylolpropane triacrylate
  • NF-0100 thinness: 100 ⁇ m
  • NF-0100 thinness: 100 ⁇ m
  • 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 ⁇ L 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.
  • MIBK methyl isobutyl ketone
  • 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 ⁇ m 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.
  • Example 5 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.
  • 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.

Abstract

L'invention porte sur une composition de résine durcissable, qui utilise une réaction d'hydrosilylation qui est une réaction d'addition et qui peut être facilement durcie sans contenir un solvant organique qui ne prend pas part à la réaction d'hydrosilylation. La composition de résine durcissable contient (A) un polymère contenant du fluor qui est représenté par la formule (1) : -(M)-(A1)-(N)- (dans laquelle M représente un motif de structure qui est issu d'une oléfine fluorée, A1 représente un motif de structure éther de vinyle qui contient une liaison carbone-carbone et N représente un motif de structure qui est issu d'un monomère copolymérisable) et (B) un catalyseur d'hydrosilylation. La composition de résine durcissable contient également, en l'absence de (F) un solvant qui ne prend pas part à une réaction de réticulation par hydrosilylation, un ou plusieurs composants parmi (C) un solvant réactif à base de siloxane liquide qui peut dissoudre ou disperser le polymère contenant du fluor (A) et qui a au moins deux groupes, un atome d'hydrogène étant lié directement à un atome de silicium, (D) un solvant réactif sans silicium qui peut dissoudre ou disperser le polymère contenant du fluor (A) et qui prend part à une réaction de réticulation par hydrosilylation et (E) un agent de réticulation par hydrosilylation.
PCT/JP2010/068330 2009-11-24 2010-10-19 Composition de résine durcissable WO2011065154A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010084150A (ja) * 2002-08-13 2010-04-15 Daikin Ind Ltd 光硬化性含フッ素ポリマーを含む光学材料および光硬化性含フッ素樹脂組成物
WO2012133557A1 (fr) * 2011-03-30 2012-10-04 ダイキン工業株式会社 Composition de résine fluorée pour la soudure d'éléments optiques et produit durci
WO2016104377A1 (fr) * 2014-12-25 2016-06-30 旭硝子株式会社 Composition de résine durcissable
CN110494500A (zh) * 2017-04-14 2019-11-22 三键有限公司 固化性树脂组合物、使用该固化性树脂组合物的燃料电池和密封方法
WO2021132104A1 (fr) * 2019-12-27 2021-07-01 Ａｇｃ株式会社 Polymère fluoré, composition durcissable, et article durci

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WO2008044765A1 (fr) * 2006-10-12 2008-04-17 Daikin Industries, Ltd. Composition de polymère fluoré durcissable
WO2008153002A1 (fr) * 2007-06-15 2008-12-18 Dow Corning Toray Co., Ltd. Composition polymère durcissable contenant du fluor
JP2009203475A (ja) * 2008-02-28 2009-09-10 Mitsubishi Chemicals Corp 封止樹脂及びその製造方法

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Publication number Priority date Publication date Assignee Title
WO2008044765A1 (fr) * 2006-10-12 2008-04-17 Daikin Industries, Ltd. Composition de polymère fluoré durcissable
WO2008153002A1 (fr) * 2007-06-15 2008-12-18 Dow Corning Toray Co., Ltd. Composition polymère durcissable contenant du fluor
JP2009203475A (ja) * 2008-02-28 2009-09-10 Mitsubishi Chemicals Corp 封止樹脂及びその製造方法

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010084150A (ja) * 2002-08-13 2010-04-15 Daikin Ind Ltd 光硬化性含フッ素ポリマーを含む光学材料および光硬化性含フッ素樹脂組成物
WO2012133557A1 (fr) * 2011-03-30 2012-10-04 ダイキン工業株式会社 Composition de résine fluorée pour la soudure d'éléments optiques et produit durci
JP2012214754A (ja) * 2011-03-30 2012-11-08 Daikin Industries Ltd 光学素子封止用含フッ素樹脂組成物、及び、硬化物
WO2016104377A1 (fr) * 2014-12-25 2016-06-30 旭硝子株式会社 Composition de résine durcissable
JPWO2016104377A1 (ja) * 2014-12-25 2017-10-05 旭硝子株式会社 硬化性樹脂組成物
US10457815B2 (en) 2014-12-25 2019-10-29 AGC Inc. Curable resin composition
CN110494500A (zh) * 2017-04-14 2019-11-22 三键有限公司 固化性树脂组合物、使用该固化性树脂组合物的燃料电池和密封方法
JPWO2018190417A1 (ja) * 2017-04-14 2020-05-21 株式会社スリーボンド 硬化性樹脂組成物、それを用いた燃料電池およびシール方法
EP3611227A4 (fr) * 2017-04-14 2021-01-06 ThreeBond Co., Ltd. Composition de résine polymérisable, pile à combustible l'utilisant et procédé d'étanchéité
US11114679B2 (en) 2017-04-14 2021-09-07 Threebond Co., Ltd. Curable resin composition, and fuel cell and sealing method using the same
CN110494500B (zh) * 2017-04-14 2022-02-08 三键有限公司 固化性树脂组合物、使用该固化性树脂组合物的燃料电池和密封方法
JP7125651B2 (ja) 2017-04-14 2022-08-25 株式会社スリーボンド 硬化性樹脂組成物、それを用いた燃料電池およびシール方法
WO2021132104A1 (fr) * 2019-12-27 2021-07-01 Ａｇｃ株式会社 Polymère fluoré, composition durcissable, et article durci

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