WO2022138407A1 - Composition de résine durcissable, produit durci, agent adhésif et film d'adhérence - Google Patents

Composition de résine durcissable, produit durci, agent adhésif et film d'adhérence Download PDF

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Publication number
WO2022138407A1
WO2022138407A1 PCT/JP2021/046401 JP2021046401W WO2022138407A1 WO 2022138407 A1 WO2022138407 A1 WO 2022138407A1 JP 2021046401 W JP2021046401 W JP 2021046401W WO 2022138407 A1 WO2022138407 A1 WO 2022138407A1
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curable resin
meth
resin composition
acrylate
group
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PCT/JP2021/046401
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English (en)
Japanese (ja)
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さやか 脇岡
健太郎 北條
悠 中村
幸平 竹田
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積水化学工業株式会社
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Priority to JP2021578055A priority Critical patent/JPWO2022138407A1/ja
Publication of WO2022138407A1 publication Critical patent/WO2022138407A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated

Definitions

  • the present invention relates to a curable resin composition having excellent flow characteristics before curing, excellent leaching prevention property after semi-curing, and excellent heat resistance after main curing.
  • the present invention also relates to a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition.
  • Patent Documents 1 to 3 describe a thermosetting component such as an epoxy resin and a flexible component such as a thermoplastic resin such as an acrylic resin, polyamide and polyester, and an acrylonitrile butadiene rubber.
  • the curable resin composition contained is disclosed.
  • Japanese Unexamined Patent Publication No. 2006-232984 Japanese Unexamined Patent Publication No. 2009-167396 Japanese Unexamined Patent Publication No. 2008-308686 Japanese Unexamined Patent Publication No. 5-306386
  • Patent Document 4 discloses an adhesive containing a soluble polyester, a phenoxy resin, and an imidesiloxane oligomer. However, it has been difficult for the adhesive disclosed in Patent Document 4 to have both flow characteristics and leaching prevention properties at the same time.
  • the present invention contains a curable resin, a photopolymerization initiator, and a thermosetting agent, and the thermosetting agent is a curable resin composition containing an imide oligomer.
  • the thermosetting agent is a curable resin composition containing an imide oligomer.
  • the present inventors further add a photopolymerization initiator to a curable resin composition containing a curable resin and a thermosetting agent, and photocure (semi-cure) the curable resin with the photopolymerization initiator. It was examined to use a material that can be used and to use an imide oligomer as a thermosetting agent. As a result, it has been found that a curable resin composition having excellent flow characteristics before curing, excellent leaching prevention property after semi-curing, and excellent heat resistance after main curing can be obtained, and the present invention has been completed. ..
  • the curable resin composition of the present invention contains a curable resin.
  • the curable resin preferably contains a liquid at 25 ° C.
  • the curable resin is a compound that can be photocured by a photopolymerization initiator described later when irradiated with light (thermosetting resin) and a compound that can be thermally cured by a thermosetting agent described later when heated. It is preferable to contain resin).
  • the photocurable resin and the thermosetting resin may be the same compound (thermosetting resin), and even when the curable resin contains the thermosetting resin, the photocurable resin and / or the thermosetting resin may be further used. It may contain a thermosetting resin.
  • the curable resin preferably contains a radically polymerizable compound having no epoxy group, an epoxy compound having no radically polymerizable group, and / or a compound having an epoxy group and a radically polymerizable group.
  • the curable resin is a radical polymerizable compound having no radical polymerizable group, an epoxy compound having no radical polymerizable group, and an epoxy. It is more preferable to contain a compound having a radical and a radically polymerizable group.
  • a compound having an ethylenically unsaturated double bond is preferable, and a (meth) acrylic compound is more preferable.
  • the above-mentioned "(meth) acrylic” means acrylic or methacrylic
  • the above-mentioned “(meth) acrylic compound” means a compound having a (meth) acryloyl group
  • "" Means acryloyl or methacryloyl.
  • Examples of the (meth) acrylic compound include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, and (meth) acrylamide compounds.
  • (meth) acrylate means acrylate or methacrylate
  • epoxy (meth) acrylate means that all epoxy groups in the epoxy compound are reacted with (meth) acrylic acid. Represents the compound that has been made to.
  • monofunctional ones include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • bifunctional ones include, for example, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane.
  • Dimethylol dicyclopentadienyldi (meth) acrylate Dimethylol dicyclopentadienyldi (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, Examples thereof include polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate.
  • examples thereof include trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, and propylene oxide-added trimethylolpropane tri (meth) acrylate.
  • Examples of the epoxy (meth) acrylate include bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, bisphenol E type epoxy (meth) acrylate, phenol novolac type epoxy (meth) acrylate, and cresol novolak type. Examples thereof include epoxy (meth) acrylates, resorcinol-type epoxy (meth) acrylates, and modified caprolactones thereof.
  • Examples of the (meth) acrylamide compound include N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N-hydroxyethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-. Examples thereof include isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide and the like.
  • Examples of the epoxy compound having no radically polymerizable group include bisphenol A type epoxy compound, bisphenol E type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, bisphenol O type epoxy compound, 2,2'. -Diallyl bisphenol A type epoxy compound, alicyclic epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide added bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, Dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolac type epoxy compound, orthocresol novolac type epoxy compound, dicyclopentadiene novolac type epoxy compound, biphenylnovolac type epoxy compound, naphthalenephenol novolac type epoxy compound, glycidylamine type epoxy Examples thereof include compounds, alkyl polyol type epoxy compounds, rubber-modified epoxy compounds, and glycidyl ester compounds.
  • the curable resin preferably contains a compound having an epoxy group and a (meth) acryloyl group as the compound having the epoxy group and the radically polymerizable group.
  • the compound having the epoxy group and the (meth) acryloyl group include a partially (meth) acrylic modified epoxy compound, glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether and the like.
  • the above-mentioned "partially (meth) acrylic-modified epoxy compound” is obtained by reacting an epoxy group of a part of an epoxy compound having two or more epoxy groups in one molecule with (meth) acrylic acid. 1 means a compound having one or more epoxy groups and one or more (meth) acryloyl groups in one molecule.
  • Examples of the partial (meth) acrylic-modified epoxy compound include a partial (meth) acrylic-modified bisphenol A-type epoxy compound, a partial (meth) acrylic-modified bisphenol F-type epoxy compound, and a partial (meth) acrylic-modified bisphenol E-type epoxy compound.
  • Examples thereof include a partially (meth) acrylic-modified phenol novolac-type epoxy compound, a partially (meth) acrylic-modified cresol novolac-type epoxy compound, and a partially (meth) acrylic-modified resorcinol-type epoxy compound.
  • the curable resin composition of the present invention contains a photopolymerization initiator.
  • the photopolymerization initiator include ⁇ -hydroxyketone compounds, ⁇ -hydroxyalkylphenone compounds, benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds and the like. Can be mentioned.
  • Specific examples of the photopolymerization initiator include an oligomer of 2-hydroxy-1- (4-isopropenylphenyl) -2-methyl-1-propanol, 1-hydroxycyclohexylphenylketone, and 2-benzyl-2.
  • the content of the photopolymerization initiator is preferably 0.1 part by weight and a preferable upper limit of 20 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the photopolymerization initiator is in this range, the obtained curable resin composition has excellent photocurability while maintaining excellent storage stability, and prevents leaching after semi-curing. It will be superior to the sex.
  • the more preferable lower limit of the content of the photopolymerization initiator is 0.5 parts by weight, and the more preferable upper limit is 10 parts by weight.
  • the curable resin composition of the present invention contains a thermosetting agent.
  • the thermosetting agent contains an imide oligomer.
  • the imide oligomer As the thermosetting agent, the curable resin composition of the present invention has excellent heat resistance after the main curing.
  • the imide oligomer preferably has an acid anhydride group or a phenolic hydroxyl group at the end of the main chain, and more preferably has an acid anhydride group or a phenolic hydroxyl group at both ends of the main chain.
  • the imide oligomer preferably has a structure represented by the following formula (1-1) or the following formula (1-2), or the following formula (2-1) or the following formula (2-2).
  • the imide oligomer can be cured. It becomes more excellent in reactivity and compatibility with the sex resin.
  • A is an acid dianhydride residue
  • B is an aliphatic diamine residue or an aromatic diamine residue.
  • Ar is a optionally substituted divalent aromatic group.
  • A is an acid dianhydride residue
  • B is an aliphatic triamine residue or an aromatic triamine residue
  • Ar is a divalent aromatic group which may be substituted.
  • the acid dianhydride residue is preferably a tetravalent group represented by the following formula (3-1) or the following formula (3-2).
  • Z is a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, and a direct chain. It is a chain-like or branched chain-like divalent hydrocarbon group or a divalent group having an aromatic ring.
  • Z is a hydrocarbon group
  • an oxygen atom may be contained between the hydrocarbon group and each aromatic ring in the formula (3-1)
  • Z is a divalent group having an aromatic ring.
  • an oxygen atom may be provided between the divalent group having the aromatic ring and each aromatic ring in the formula (3-1).
  • the hydrogen atom of the aromatic ring in the formula (3-1) and the formula (3-2) may be substituted.
  • Z in the above formula (3-1) is a linear or branched divalent hydrocarbon group or a divalent group having an aromatic ring
  • these groups are substituted. May be good.
  • the linear or branched divalent hydrocarbon group or the divalent group having an aromatic ring is substituted, the substituent includes, for example, a halogen atom, a linear or branched chain. Examples thereof include a linear alkyl group, a linear or branched alkenyl group, an alicyclic group, an aryl group, an alkoxy group, a nitro group, a cyano group and the like.
  • Examples of the acid dianhydride from which the acid dianhydride residue is derived include an acid dianhydride represented by the formula (9) described later.
  • B in the above formula (1-1) is the above aliphatic diamine residue
  • B in the above formula (2-1) or the above formula (2-2) is the above aliphatic triamine residue.
  • the preferable lower limit of the carbon number of the aliphatic diamine residue and the aliphatic triamine residue is 4.
  • the curable resin composition obtained by having 4 or more carbon atoms in the aliphatic diamine residue and the aliphatic triamine residue has flexibility and processability before curing and dielectric properties after curing. Will be better.
  • the more preferable lower limit of the number of carbon atoms of the aliphatic diamine residue and the aliphatic triamine residue is 5, and the more preferable lower limit is 6.
  • the practical upper limit is 60.
  • Examples of the aliphatic diamine from which the above aliphatic diamine residue is derived include an aliphatic diamine derived from dimer acid, a linear or branched aliphatic diamine, an aliphatic ether diamine, and an aliphatic alicyclic type. Examples include diamine. Examples of the aliphatic diamine derived from the dimer acid include dimer diamine, hydrogenated diamine diamine and the like.
  • linear or branched aliphatic diamine examples include 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonandiamine, 1,10-decanediamine, and 1, 11-Undecanediamine, 1,12-Dodecanediamine, 1,14-Tetradecanediamine, 1,16-Hexadecanediamine, 1,18-Octadecanediamine, 1,20-Eicosandiamine, 2-Methyl-1,8-octane Examples thereof include diamine, 2-methyl-1,9-nonanediamine, 2,7-dimethyl-1,8-octanediamine and the like.
  • Examples of the aliphatic ether diamine include 2,2'-oxybis (ethylamine), 3,3'-oxybis (propylamine), 1,2-bis (2-aminoethoxy) ethane and the like.
  • Examples of the aliphatic alicyclic diamine include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine.
  • the aliphatic diamine residue is preferably an aliphatic diamine residue derived from the dimer acid.
  • Examples of the aliphatic triamine from which the above aliphatic triamine residue is derived include an aliphatic triamine derived from trimeric acid, a linear or branched aliphatic triamine, an aliphatic ether triamine, and an aliphatic alicyclic type. Examples thereof include triamine. Examples of the aliphatic triamine derived from the trimer acid include trimer triamine, hydrogenated trimer triamine and the like. Examples of the linear or branched aliphatic triamine include 3,3'-diamino-N-methyldipropylamine, 3,3'-diaminodipropylamine, diethylenetriamine, bis (hexamethylene) triamine, and 2,2. '-Bis (methylamino) -N-methyldiethylamine and the like can be mentioned. Among them, the aliphatic triamine residue is preferably an aliphatic triamine residue derived from the trimeric acid.
  • aliphatic diamine and / or the aliphatic triamine a mixture of the dimer diamine and the trimer triamine can also be used.
  • Examples of commercially available products of the aliphatic diamine and / or the aliphatic triamine derived from the dimer acid and / or the trimer acid include the aliphatic diamine and / or the aliphatic triamine manufactured by BASF and the fat manufactured by Croder. Examples thereof include group diamines and / or aliphatic triamines. Examples of the aliphatic diamine and / or aliphatic triamine manufactured by BASF include Versamine 551 and Versamine 552. Examples of the aliphatic diamine and / or aliphatic triamine manufactured by Croda International include preamine 1071, preamine 1073, preamine 1074, and preamine 1075.
  • the aromatic diamine residue is a divalent represented by the following formula (4-1) or the following formula (4-2). It is preferably the basis of.
  • Y is a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, and a direct chain. It is a chain-like or branched chain-like divalent hydrocarbon group or a divalent group having an aromatic ring.
  • Y is a hydrocarbon group
  • an oxygen atom may be contained between the hydrocarbon group and each aromatic ring in the formula (4-1)
  • Y is a divalent group having an aromatic ring.
  • an oxygen atom may be provided between the divalent group having the aromatic ring and each aromatic ring in the formula (4-1).
  • the hydrogen atom of the aromatic ring in the formula (4-1) and the formula (4-2) may be substituted.
  • Y in the above formula (4-1) is a linear or branched divalent hydrocarbon group or a divalent group having an aromatic ring
  • these groups are substituted. May be good.
  • the linear or branched divalent hydrocarbon group or the divalent group having an aromatic ring is substituted, the substituent includes, for example, a halogen atom, a linear or branched chain. Examples thereof include a linear alkyl group, a linear or branched alkenyl group, an alicyclic group, an aryl group, an alkoxy group, a nitro group, a cyano group and the like.
  • aromatic diamine from which the aromatic diamine residue is derived examples include those in which the diamine represented by the formula (10) described later is an aromatic diamine.
  • the imide oligomer may lower the glass transition temperature after curing or contaminate the adherend and cause poor adhesion.
  • it is an imide oligomer having no siloxane skeleton in its structure.
  • the number average molecular weight of the imide oligomer is preferably 5000 or less.
  • the number average molecular weight of the imide oligomer is 5000 or less, the cured product of the obtained curable resin composition is superior in long-term heat resistance.
  • a more preferable upper limit of the number average molecular weight of the imide oligomer is 4000, and a further preferable upper limit is 3000.
  • the number average molecular weight of the imide oligomer is preferably 900 or more and 5000 or less when it has a structure represented by the above formula (1-1) and the above formula (2-1), and the above formula (1-). 2) When having a structure represented by the above formula (2-2), it is preferably 550 or more and 4000 or less.
  • the more preferable lower limit of the number average molecular weight is 950, and the further preferable lower limit is 1000.
  • the more preferable lower limit of the number average molecular weight is 580, and the further preferable lower limit is 600.
  • the above-mentioned "number average molecular weight” is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene. Examples of the column used when measuring the number average molecular weight in terms of polystyrene by GPC include JAIGEL-2H-A (manufactured by Nippon Analytical Industry Co., Ltd.).
  • the above-mentioned imide oligomer has the following formula (5-1), the following formula (5-2), the following formula (5-3), the following formula (5-4), or the following formula (5-5). ), Or the following formula (6-1), the following formula (6-2), the following formula (6-3), the following formula (6-4), the following formula (6-5), Alternatively, it is preferably an imide oligomer represented by the following formula (6-6).
  • A is the acid dianhydride residue, and in formulas (5-1), (5-3) to (5-5), A is. Each may be the same or different.
  • B is the aliphatic diamine residue or the aromatic diamine residue, and in the formulas (5-3) and (5-4), B is. , Each may be the same or different.
  • B is the aliphatic triamine residue or the aromatic triamine residue.
  • X is a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may be substituted
  • W is a hydrogen atom, a halogen atom. , Or a monovalent hydrocarbon group which may be substituted.
  • n is a repetition number.
  • A is the acid dianhydride residue, and in formulas (6-1) to (6-6), A is the same. It may or may not be different.
  • R is a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may be substituted, and formulas (6-1) and (6). -2), in the formula (6-4), and in the formula (6-6), R may be the same or different.
  • W is a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may be substituted.
  • B is the aliphatic diamine residue or the aromatic diamine residue
  • B is.
  • Each may be the same or different.
  • B is, or the aliphatic triamine residue or the aromatic triamine residue.
  • a in the above formulas (5-1) to (5-5) and the above formulas (6-1) to (6-6) is the following formula (7-1) or the following formula (7-2). It is preferably a tetravalent group represented.
  • Z is a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, and a direct chain. It is a chain-like or branched chain-like divalent hydrocarbon group or a divalent group having an aromatic ring.
  • Z is a hydrocarbon group
  • an oxygen atom may be contained between the hydrocarbon group and each aromatic ring in the formula (7-1)
  • Z is a divalent group having an aromatic ring.
  • an oxygen atom may be provided between the divalent group having the aromatic ring and each aromatic ring in the formula (7-1).
  • the hydrogen atom of the aromatic ring in the formula (7-1) and the formula (7-2) may be substituted.
  • Y is a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, and a direct chain. It is a chain-like or branched chain-like divalent hydrocarbon group or a divalent group having an aromatic ring.
  • Y is a hydrocarbon group
  • an oxygen atom may be contained between the hydrocarbon group and each aromatic ring in the formula (8-1)
  • Y is a divalent group having an aromatic ring.
  • an oxygen atom may be provided between the divalent group having the aromatic ring and each aromatic ring in the formula (8-1).
  • the hydrogen atom of the aromatic ring in the formula (8-1) and the formula (8-2) may be substituted.
  • an imide oligomer having a structure represented by the above formula (1-1) for example, an acid dianhydride represented by the following formula (9) and a diamine represented by the following formula (10) are used. A method of reacting with the above can be mentioned. Further, by using an aliphatic triamine or an aromatic triamine instead of the diamine represented by the following formula (10), an imide oligomer having a structure represented by the above formula (2-1) can be produced.
  • A is the same tetravalent group as A in the above formula (1-1).
  • B is the same divalent group as B in the above formula (1-1), and R 1 to R 4 are independently hydrogen atoms or monovalent hydrocarbon groups, respectively. ..
  • the method for reacting the acid dianhydride represented by the above formula (9) with the diamine represented by the above formula (10) are shown below.
  • the diamine represented by the above formula (10) is previously dissolved in a solvent (for example, N-methylpyrrolidone) in which the amic acid oligomer obtained by the reaction is soluble, and the obtained solution is prepared with the above formula (9).
  • the acid dianhydride represented by is added and reacted to obtain an amic acid oligomer solution.
  • a method of removing the solvent by heating, reducing the pressure, or the like, and further heating at about 200 ° C. or higher for 1 hour or longer to react the amic acid oligomer and the like can be mentioned.
  • the desired number average molecular weight can be obtained.
  • An imide oligomer having a structure represented by the above formula (1-1) can be obtained at the end. Further, by substituting a part of the acid anhydride represented by the above formula (9) with the acid anhydride represented by the following formula (11), the acid anhydride has a desired number average molecular weight, and the above-mentioned one end is described. An imide oligomer having a structure represented by the formula (1-1) and having a structure derived from an acid anhydride represented by the following formula (11) at the other end can be obtained.
  • the acid anhydride represented by the above formula (9) and the acid anhydride represented by the following formula (11) may be added at the same time or separately. Further, by substituting a part of the diamine represented by the above formula (10) with a monoamine represented by the following formula (12), it has a desired number average molecular weight and has the above formula (1-1) at one end. ), And an imide oligomer having a structure derived from a monoamine represented by the following formula (12) at the other end can be obtained. In this case, the diamine represented by the above formula (10) and the monoamine represented by the following formula (12) may be added at the same time or separately.
  • Ar is a divalent aromatic group that may be substituted.
  • Ar is a optionally substituted monovalent aromatic group
  • R 5 and R 6 are independently hydrogen atoms or monovalent hydrocarbon groups, respectively.
  • an acid dianhydride represented by the above formula (9) and a phenolic agent represented by the following formula (13) are used as a method for producing an imide oligomer having a structure represented by the above formula (1-2).
  • a method of reacting with the above can be mentioned.
  • an imide oligomer having a structure represented by the above formula (2-2) can be produced.
  • Ar is a divalent aromatic group which may be substituted, and R 7 and R 8 are independently hydrogen atoms or monovalent hydrocarbon groups, respectively.
  • the desired number average molecular weight can be obtained. It is possible to obtain an imide oligomer having a structure represented by the above formula (1-2) at both ends. Further, by substituting a part of the phenolic hydroxyl group-containing monoamine represented by the above formula (13) with the monoamine represented by the above formula (12), it has a desired number average molecular weight and has the above formula at one end.
  • An imide oligomer having a structure represented by (1-2) and having a structure derived from a monoamine represented by the above formula (12) at the other end can be obtained.
  • the phenolic hydroxyl group-containing monoamine represented by the above formula (13) and the monoamine represented by the above formula (12) may be added at the same time or separately.
  • the phenolic hydroxyl group-containing monoamine represented by the above formula (13) by substituting a part of the phenolic hydroxyl group-containing monoamine represented by the above formula (13) with the monoamine represented by the above formula (12), it has a desired number average molecular weight and has the above formula at one end.
  • An imide oligomer having a structure represented by (1-2) and having a structure derived from a monoamine represented by the above formula (12) at the other end can be obtained.
  • the phenolic hydroxyl group-containing monoamine represented by the above formula (13) and the monoamine represented by the above formula (12) may be added at the same time or separately.
  • Examples of the acid dianhydride represented by the above formula (9) include pyromellitic acid anhydride, 3,3'-oxydiphthalic acid anhydride, 3,4'-oxydiphthalic acid anhydride, and 4,4'-oxydiphthalic acid.
  • the acid dianhydride used as the raw material of the imide oligomer is preferably an aromatic acid dianhydride having a melting point of 240 ° C. or lower, and has a melting point of 220 ° C., because it is more excellent in solubility and heat resistance.
  • aromatic acid dianhydrides are more preferred, aromatic acid dianhydrides having a melting point of 200 ° C. or lower are even more preferred, and 3,4'-oxydiphthalic acid dianhydrides (melting point 180 ° C.), 4,4'. -(4,4'-isopropyridenediphenoxy) diphthalic anhydride (melting point 190 ° C.) is particularly preferred.
  • melting point means a value measured as the temperature of the endothermic peak when the temperature is raised at 10 ° C./min using a differential scanning calorimeter.
  • Examples of the differential scanning calorimeter include EXTER DSC6100 (manufactured by SII Nanotechnology).
  • examples of the aromatic diamine include 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and 3,3'-.
  • Examples of the acid anhydride represented by the above formula (11) include phthalic acid anhydride, 3-methylphthalic acid anhydride, 4-methylphthalic acid anhydride, 1,2-naphthalic acid anhydride, and 2,3-naphthal. Acid anhydride, 1,8-naphthalic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 4-tert-butylphthalic acid anhydride, 4-ethynylphthalic acid anhydride, 4-phenylethynylphthalic acid anhydride, Examples thereof include 4-fluorophthalic acid anhydride, 4-chlorophthalic acid anhydride, 4-bromophthalic acid anhydride, 3,4-dichlorophthalic acid anhydride and the like.
  • Examples of the monoamine represented by the above formula (12) include aniline, o-toluidine, m-toluidine, p-toluidine, 2,4-dimethylaniline, 3,4-dimethylaniline, and 3,5-dimethylaniline.
  • Examples of the phenolic hydroxyl group-containing monoamine represented by the above formula (13) include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, and 4-amino-2. , 3-Xylenol, 4-amino-2,5-xylenol, 4-amino-2,6-xylenol, 4-amino-1-naphthol, 5-amino-2-naphthol, 6-amino-1-naphthol, 4 -Amino-2,6-diphenylphenol and the like can be mentioned. Of these, 4-amino-o-cresol and 5-amino-o-cresol are preferable because they are excellent in availability and storage stability, and a high glass transition temperature can be obtained after curing.
  • the imide oligomer is a plurality of imide oligomers having a structure represented by the above formula (1-1) or a structure represented by the above formula (1-2). It is obtained as a mixture of a plurality of types of imide oligomers having the above and each raw material (imide oligomer composition).
  • the imide oligomer is a plurality of types of imide oligomers having a structure represented by the above formula (2-1).
  • the imide oligomer composition has an imidization ratio of 70% or more, a cured product having superior mechanical strength and long-term heat resistance at high temperatures can be obtained when used as a curing agent.
  • the preferable lower limit of the imidization ratio of the imide oligomer composition is 75%, and the more preferable lower limit is 80%. Further, although there is no particular preferable upper limit of the imidization ratio of the imide oligomer composition, the practical upper limit is 98%.
  • the above “imidization rate” was measured by a total reflection measurement method (ATR method) using a Fourier transform infrared spectrophotometer (FT-IR), and was derived from the carbonyl group of amic acid at 1660 cm -1 . It can be derived from the peak absorbance area in the vicinity by the following formula. Examples of the Fourier transform infrared spectrophotometer include UMA600 (manufactured by Agilent Technologies) and the like.
  • the imide oligomer composition is preferably dissolved in an amount of 3 g or more with respect to 10 g of tetrahydrofuran at 25 ° C.
  • the preferable lower limit of the content of the imide oligomer in 100 parts by weight of the total of the curable resin and the thermosetting agent (further curing accelerator when the curing accelerator described later is contained) is 20 parts by weight, and the preferable upper limit is 20 parts by weight. It is 80 parts by weight.
  • the content of the imide oligomer is in this range, the obtained curable resin composition becomes more excellent in flexibility and processability before curing and heat resistance after curing.
  • the more preferable lower limit of the content of the imide oligomer is 25 parts by weight, and the more preferable upper limit is 75 parts by weight.
  • the content of the imide oligomer is the imide oligomer composition (when another imide oligomer is used in combination, the imide oligomer is used). It means the content of the composition and other imide oligomers).
  • the curable resin composition of the present invention preferably contains a curing accelerator.
  • a curing accelerator By containing the above-mentioned curing accelerator, the curing time can be shortened and the productivity can be improved.
  • the curing accelerator examples include an imidazole-based curing accelerator, a tertiary amine-based curing accelerator, a phosphine-based curing accelerator, a phosphorus-based curing accelerator, a photobase generator, a sulfonium salt-based curing accelerator, and the like. .. Of these, an imidazole-based curing accelerator is preferable because it has excellent storage stability.
  • the content of the curing accelerator is preferably 0.01 part by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the total of the curable resin, the thermosetting agent and the curing accelerator. ..
  • the more preferable lower limit of the content of the curing accelerator is 0.05 parts by weight, and the more preferable upper limit is 5 parts by weight.
  • the curable resin composition of the present invention may contain an inorganic filler as long as the object of the present invention is not impaired.
  • the inorganic filler is preferably at least one of silica and barium sulfate.
  • the curable resin composition of the present invention is excellent in reflow resistance, plating resistance, and processability.
  • Examples of the inorganic filler other than the silica and the barium sulfate include alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, carbon fiber, and an inorganic ion exchanger.
  • the inorganic filler those having an average particle size of 50 nm or more and less than 4 ⁇ m are preferably used.
  • the content of the inorganic filler is preferably 200 parts by weight with respect to a total of 100 parts by weight of the curable resin and the thermosetting agent (further, if the curing accelerator is contained, the curing accelerator). Is.
  • the content of the inorganic filler is in this range, the cured product of the obtained curable resin composition is excellent in reflow resistance and plating resistance while maintaining excellent tackiness and the like.
  • a more preferable upper limit of the content of the inorganic filler is 150 parts by weight.
  • the curable resin composition of the present invention preferably contains a flow conditioner for the purpose of improving the applicability to the adherend in a short time and the shape retention property.
  • a flow conditioner for the purpose of improving the applicability to the adherend in a short time and the shape retention property.
  • the flow adjusting agent include fumed silica such as Aerosil and layered silicate. Further, as the flow adjusting agent, one having an average particle size of less than 100 nm is preferably used.
  • the content of the flow modifier is preferably 0.1 with respect to 100 parts by weight in total of the curable resin and the thermosetting agent (in the case of further containing the curing accelerator, the curing accelerator).
  • the preferred upper limit is 50 parts by weight.
  • the more preferable lower limit of the content of the flow adjusting agent is 0.5 parts by weight, and the more preferable upper limit is 30 parts by weight.
  • the curable resin composition of the present invention may contain an organic filler for the purpose of stress relaxation, toughness imparting and the like.
  • organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamide-imide particles, polyimide particles, benzoguanamine particles, and core-shell particles thereof. Of these, polyamide particles, polyamide-imide particles, and polyimide particles are preferable.
  • the content of the organic filler is preferably 300 parts by weight with respect to a total of 100 parts by weight of the curable resin and the thermosetting agent (further, if the curing accelerator is contained, the curing accelerator). Is. When the content of the organic filler is in this range, the obtained cured product becomes more excellent in toughness and the like while maintaining excellent adhesiveness and the like. A more preferable upper limit of the content of the organic filler is 200 parts by weight.
  • the curable resin composition of the present invention preferably contains a polymer compound within a range that does not impair the object of the present invention.
  • the polymer compound plays a role as a film-forming component, and by containing the polymer compound, the obtained curable resin composition becomes more excellent in leaching prevention property.
  • the preferable lower limit of the number average molecular weight of the polymer compound is 3000, and the preferable upper limit is 100,000.
  • the obtained curable resin composition is superior in flexibility and processability before curing and heat resistance after curing.
  • the more preferable lower limit of the number average molecular weight of the polymer compound is 5000, and the more preferable upper limit is 80,000.
  • polymer compound examples include polyimide, phenoxy resin, polyamide, polyamideimide, polymaleimide, cyanate resin, benzoxazine resin, acrylic resin, urethane resin, polyester and the like.
  • polyimide, polyamide, polyamideimide, and polymaleimide are preferable, and polyimide is more preferable, from the viewpoint of heat resistance.
  • the polymer compound may be used alone or in combination of two or more.
  • the content of the polymer compound is preferably 1 part by weight with respect to a total of 100 parts by weight of the curable resin and the thermosetting agent (in the case of further containing the curing accelerator, the curing accelerator).
  • the preferred upper limit is 40 parts by weight.
  • the more preferable lower limit of the content of the polymer compound is 5 parts by weight, and the more preferable upper limit is 30 parts by weight.
  • the curable resin composition of the present invention may contain a flame retardant as long as the object of the present invention is not impaired.
  • the flame retardant include metal hydrates such as boehmite type aluminum hydroxide, aluminum hydroxide and magnesium hydroxide, halogen-based compounds, phosphorus-based compounds and nitrogen compounds. Of these, boehmite-type aluminum hydroxide is preferable.
  • the content of the flame retardant is preferably 200 parts by weight with respect to a total of 100 parts by weight of the curable resin and the thermosetting agent (in the case of further containing the curing accelerator, the curing accelerator). be.
  • the content of the flame retardant is in this range, the obtained curable resin composition has excellent flame retardancy while maintaining excellent adhesiveness and the like.
  • a more preferable upper limit of the content of the flame retardant is 150 parts by weight.
  • the curable resin composition may contain a solvent from the viewpoint of coatability and the like.
  • a solvent having a boiling point of less than 200 ° C. is preferable from the viewpoint of coatability, storage stability and the like.
  • the solvent having a boiling point of less than 200 ° C. include alcohol-based solvents, ketone-based solvents, ester-based solvents, hydrocarbon-based solvents, halogen-based solvents, ether-based solvents, nitrogen-containing solvents and the like.
  • the alcohol-based solvent include methanol, ethanol, isopropyl alcohol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol, tertiary butyl alcohol, 2-ethielhexanol and the like.
  • Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, diacetone alcohol and the like.
  • Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, methoxybutyl acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, butyl lactate and the like.
  • hydrocarbon solvent examples include benzene, toluene, xylene, normal hexane, isohexane, cyclohexane, methylcyclohexane, ethylcyclohexane, isooctane, normal decane, normal heptane and the like.
  • halogen-based solvent examples include dichloromethane, chloroform, trichlorethylene and the like.
  • ether-based solvent examples include diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether acetate.
  • nitrogen-containing solvent examples include acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and the like.
  • a ketone solvent having a boiling point of 60 ° C. or higher and lower than 200 ° C. an ester solvent having a boiling point of 60 ° C. or higher and lower than 200 ° C., and a boiling point of 60 ° C. or higher and 200 ° C.
  • At least one selected from the group consisting of ether solvents below ° C is preferred.
  • solvents examples include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, cyclohexanone, methylcyclohexanone, diethylene glycol dimethyl ether, anisole and the like.
  • the above "boiling point” means a value measured under the condition of 101 kPa or a value converted to 101 kPa in a boiling point conversion chart or the like.
  • the preferable lower limit of the content of the solvent in 100 parts by weight of the curable resin composition containing the solvent is 20 parts by weight, and the preferable upper limit is 90 parts by weight.
  • the content of the solvent is in this range, the obtained curable resin composition is excellent in coatability and the like.
  • the more preferable lower limit of the content of the solvent is 30 parts by weight, and the more preferable upper limit is 80 parts by weight.
  • the curable resin composition of the present invention may contain a reactive diluent as long as the object of the present invention is not impaired.
  • a reactive diluent a reactive diluent having two or more reactive functional groups in one molecule is preferable from the viewpoint of adhesive reliability.
  • the curable resin composition of the present invention may further contain additives such as a coupling agent, a dispersant, a storage stabilizer, an antibleeding agent, a flux agent, and a leveling agent.
  • additives such as a coupling agent, a dispersant, a storage stabilizer, an antibleeding agent, a flux agent, and a leveling agent.
  • a method for producing the curable resin composition of the present invention for example, using a mixer, a curable resin, a photopolymerization initiator, a thermosetting agent, a curing accelerator added as necessary, and the like can be used.
  • examples include a method of mixing.
  • the mixer include a homodisper, a universal mixer, a Banbury mixer, a kneader and the like.
  • the curable resin composition of the present invention preferably has a gel fraction of 5% or more and less than 90% after irradiation with ultraviolet rays of 2000 mJ / cm 2 .
  • the gel fraction after irradiation with the above-mentioned 2000 mJ / cm 2 ultraviolet rays is within this range, the leaching prevention property after semi-curing is more excellent.
  • the more preferable lower limit of the gel fraction after irradiation with the above 2000 mJ / cm 2 ultraviolet rays is 8%, and the more preferable upper limit is 80%.
  • the curable resin composition of the present invention preferably has a gel fraction of 90% or more after being heated at 190 ° C. for 1 hour.
  • the gel fraction after heating at 190 ° C. for 1 hour is 90% or more, the heat resistance and adhesiveness after curing are excellent.
  • a more preferable lower limit of the gel fraction after heating at 190 ° C. for 1 hour is 92%. After heating at 190 ° C.
  • the above-mentioned "gel fraction” means that the composition after semi-curing or heat-curing is impregnated into a solvent having a solubility capable of sufficiently dissolving the curable resin composition, and the mixture is stirred for 24 hours or more. It is a value expressed as a percentage of the ratio of the weight of the undissolved material obtained by drying to the initial weight of the curable resin composition when it is filtered into a mesh and then dried at 110 ° C. for 1 hour.
  • the solvent for example, tetrahydrofuran or the like can be used.
  • Gel fraction (%) 100 x W 2 / W 1 (W 1 : Initial weight of curable resin composition, W 2 : Weight of undissolved material obtained by drying)
  • the preferable lower limit of the 5% weight loss temperature of the cured product obtained by heating at 190 ° C. for 1 hour is 350 ° C. or higher.
  • the curable resin composition of the present invention has excellent heat resistance after curing and can be suitably used as a heat-resistant adhesive for automobiles and the like. ..
  • a more preferable lower limit of the 5% weight loss temperature of the cured product is 360 ° C., and a further preferable lower limit is 370 ° C.
  • the practical upper limit is 450 ° C.
  • the 5% weight reduction temperature can be derived by thermogravimetric measurement using a thermogravimetric measuring device at a heating rate of 10 ° C./min under heating conditions of 30 ° C. to 500 ° C.
  • thermogravimetric measuring device examples include TG / DTA6200 (manufactured by Hitachi High-Tech Science Corporation).
  • the curable resin composition of the present invention can be used for a wide range of applications, but can be suitably used for electronic material applications in which high heat resistance is particularly required.
  • it can be used as a diagnostic agent in aeronautical and in-vehicle electric control unit (ECU) applications, power device applications using SiC and GaN, and the like.
  • an adhesive for a power overlay package an adhesive, an adhesive for a flexible printed substrate or a coverlay film, a copper-clad laminate, an adhesive for semiconductor bonding, an interlayer insulating film, a prepreg, an adhesive for an LED, and a structure.
  • It can also be used as an adhesive for materials. Among them, it is suitably used for adhering a flexible printed substrate or a coverlay film.
  • a cured product of the curable resin composition of the present invention is also one of the present inventions.
  • An adhesive made by using the curable resin composition of the present invention is also one of the present inventions.
  • An adhesive film can be obtained by applying the adhesive of the present invention onto a film and then drying the film.
  • An adhesive film using the adhesive of the present invention is also one of the present inventions.
  • the present invention it is possible to provide a curable resin composition having excellent flow characteristics before curing, excellent leaching prevention property after semi-curing, and excellent heat resistance after main curing. Further, according to the present invention, it is possible to provide a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition.
  • the imide oligomer composition A has a structure represented by the above formula (5-1) or (5-3) (A is 4, 4). It was confirmed that'-(4,4'-isopropyridenediphenoxy) diphthalic acid anhydride residue and B contained 1,3-bis (3-aminophenoxy) benzene residue). The number average molecular weight of the imide oligomer composition A was 2100.
  • the imide oligomer composition B After removing N-methylpyrrolidone from the obtained amic acid oligomer solution under reduced pressure, the mixture was heated at 300 ° C. for 2 hours to obtain an imide oligomer composition B (imidization ratio 95%).
  • the imide oligomer composition B has an imide oligomer having a structure represented by the above formula (6-1) (A is 4,4'-(4,4). ''-Isopropyridenediphenoxy) Diphthalic acid anhydride residue, R is a hydrogen atom) was confirmed to be contained.
  • the number average molecular weight of the imide oligomer composition B was 700.
  • Examples 1 to 6 Comparative Examples 1 and 2
  • Each material was stirred and mixed according to the compounding ratio shown in Table 1 to prepare each curable resin composition of Examples 1 to 6 and Comparative Examples 1 and 2.
  • a cured product was infiltrated into tetrahydrofuran, stirred for 24 hours or more, filtered through a mesh, and then dried at 110 ° C. for 1 hour to derive a gel fraction by the above formula.
  • Each of the curable resin compositions obtained in Examples and Comparative Examples was coated on a base material PET film so as to have a thickness of about 20 ⁇ m, and dried to obtain a curable resin composition on the base material PET film.
  • a film was made.
  • a cured product was prepared by irradiating each of the obtained curable resin composition films with ultraviolet rays of 2000 mJ / cm 2 and then heating at 190 ° C. for 1 hour.
  • the obtained cured product was subjected to a 5% weight under a temperature range of 30 ° C to 500 ° C and a temperature rise condition of 10 ° C / min using a thermogravimetric measuring device (“TG / DTA6200” manufactured by Hitachi High-Tech Science Co., Ltd.). The reduced temperature was measured.
  • TG / DTA6200 thermogravimetric measuring device manufactured by Hitachi High-Tech Science Co., Ltd.
  • the curable resin composition around the opening was semi-cured by irradiating ultraviolet rays of 2000 mJ / cm 2 from the polyimide film side. Then, it was heat-cured at 160 ° C. and 1.0 MPa for 1 hour using a hot press machine. The resin length exuded inside the hole was measured as the amount of exudation. " ⁇ " when there was no leaching (the amount of leaching was less than 0.2 mm), “ ⁇ " when the amount of leaching was 0.2 mm or more and 0.5 mm or less, and the amount of leaching exceeded 0.5 mm. The case of leaching was evaluated as "x".
  • the present invention it is possible to provide a curable resin composition having excellent flow characteristics before curing, excellent leaching prevention property after semi-curing, and excellent heat resistance after main curing. Further, according to the present invention, it is possible to provide a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition.

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Abstract

Un objet de la présente invention est de fournir une composition de résine durcissable qui présente d'excellentes caractéristiques fluidiques avant d'être durcie, une excellente capacité de prévention de lixiviation lorsqu'elle est semi-durcie, et une excellente résistance à la chaleur après avoir été complètement durcie. Un autre objet la présente invention est de fournir : un produit durci de ladite composition de résine durcissable ; et un agent adhésif et un film d'adhérence qui sont obtenus en faisant appel à ladite composition de résine durcissable. Cette composition de résine durcissable contient une résine durcissable, un photoinitiateur et un agent thermodurcissable. L'agent thermodurcissable contient un oligomère imide.
PCT/JP2021/046401 2020-12-23 2021-12-16 Composition de résine durcissable, produit durci, agent adhésif et film d'adhérence WO2022138407A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61270852A (ja) * 1985-05-24 1986-12-01 Nitto Electric Ind Co Ltd 半導体装置
JP2002006490A (ja) * 2000-06-26 2002-01-09 Ube Ind Ltd イミド系感光性樹脂組成物、絶縁膜およびその形成法
JP2003162055A (ja) * 2001-11-26 2003-06-06 Ube Ind Ltd 感光性樹脂組成物、感光性フィルム、絶縁膜およびその形成法
JP2004502859A (ja) * 2000-07-06 2004-01-29 スリーエム　イノベイティブ　プロパティズ　カンパニー ポリイミドハイブリッド接着剤
JP2007091799A (ja) * 2005-09-27 2007-04-12 Kaneka Corp 熱硬化性樹脂組成物、及びその利用
US20160177018A1 (en) * 2014-12-19 2016-06-23 Mark D. Soucek Synthesis and characterization of uv-curable maleimide-terminated imide oligomers
WO2018139558A1 (fr) * 2017-01-27 2018-08-02 積水化学工業株式会社 Composition de résine durcissable, adhésif, oligomère d'imide, composition d'oligomère d'imide et agent de durcissement
WO2018193983A1 (fr) * 2017-04-21 2018-10-25 積水化学工業株式会社 Oligomère d'imide, agent de durcissement, adhésif et procédé de production d'oligomère d'imide
WO2021241548A1 (fr) * 2020-05-28 2021-12-02 積水化学工業株式会社 Composition de résine durcissable, adhésif, vernis adhésif, film adhésif, et objet durci

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61270852A (ja) * 1985-05-24 1986-12-01 Nitto Electric Ind Co Ltd 半導体装置
JP2002006490A (ja) * 2000-06-26 2002-01-09 Ube Ind Ltd イミド系感光性樹脂組成物、絶縁膜およびその形成法
JP2004502859A (ja) * 2000-07-06 2004-01-29 スリーエム　イノベイティブ　プロパティズ　カンパニー ポリイミドハイブリッド接着剤
JP2003162055A (ja) * 2001-11-26 2003-06-06 Ube Ind Ltd 感光性樹脂組成物、感光性フィルム、絶縁膜およびその形成法
JP2007091799A (ja) * 2005-09-27 2007-04-12 Kaneka Corp 熱硬化性樹脂組成物、及びその利用
US20160177018A1 (en) * 2014-12-19 2016-06-23 Mark D. Soucek Synthesis and characterization of uv-curable maleimide-terminated imide oligomers
WO2018139558A1 (fr) * 2017-01-27 2018-08-02 積水化学工業株式会社 Composition de résine durcissable, adhésif, oligomère d'imide, composition d'oligomère d'imide et agent de durcissement
WO2018193983A1 (fr) * 2017-04-21 2018-10-25 積水化学工業株式会社 Oligomère d'imide, agent de durcissement, adhésif et procédé de production d'oligomère d'imide
WO2021241548A1 (fr) * 2020-05-28 2021-12-02 積水化学工業株式会社 Composition de résine durcissable, adhésif, vernis adhésif, film adhésif, et objet durci

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