TW202233794A - Curable resin composition, cured product, adhesive agent, and adhesion film - Google Patents

Abstract

One purpose of the present invention is to provide a curable resin composition that has excellent fluid characteristics before being cured, excellent leach preventing ability when being semi-cured, and excellent heat resistance after being fully cured. Another purpose of the present invention is to provide: a cured product of said curable resin composition; and an adhesive agent and an adhesion film which are obtained by using said curable resin composition. This curable resin composition contains a curable resin, a photoinitiator, and a thermosetting agent. The thermosetting agent contains an imide oligomer.

Description

Curable resin composition, cured product, adhesive, and adhesive film

The present invention relates to a curable resin composition which is excellent in flow properties before curing, excellent in anti-bleeding properties after semi-curing, and excellent in heat resistance after full curing. Furthermore, the present invention relates to a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition.

In recent years, the use of flexible printed wiring boards (FPC) has been expanded to vehicle use, and high-temperature long-term heat resistance is required for adhesives used for FPC or coverlay films for protecting FPC. In this type of adhesive, a curable resin composition using curable resin such as epoxy resin, which has low shrinkage and is excellent in adhesiveness, insulation, and chemical resistance, is used, especially the following curable resin composition is used. Widely used, the curable resin composition can obtain good results in the reflow test for short-time heat resistance and the cooling-heat cycle test for repeated heat resistance.

For the adhesive used in the adhesive layer of the flexible printed wiring board, it is necessary to improve its fluidity to suppress the voids during component assembly and improve the followability to the unevenness, but when the fluidity is too high, There is a problem that it is easy to seep out from the end. Therefore, the adhesive is required to have both excellent flow characteristics and anti-bleeding properties. As such an adhesive, for example, Patent Documents 1 to 3 disclose a curable resin composition containing a thermosetting component such as an epoxy resin, a thermoplastic resin such as an acrylic resin, a polyamide, and a polyester, or acrylonitrile. - Flexible components such as butadiene rubber. [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2006-232984 Patent Document 2: Japanese Patent Laid-Open No. 2009-167396 Patent Document 3: Japanese Patent Laid-Open No. 2008-308686 Patent Document 4: Japanese Patent Application Laid-Open No. 5-306386

[The problem to be solved by the invention]

In recent years, as the use for vehicles and the like has been expanded, the adhesive has been required to have long-term heat resistance. However, the heat resistance of the adhesive using the curable resin composition disclosed in Patent Documents 1 to 3 is insufficient. Patent Document 4 discloses an adhesive containing a soluble polyester, a phenoxy resin, and an imidesiloxane oligomer as an adhesive excellent in heat resistance. However, it is difficult for the adhesive disclosed in Patent Document 4 to have both flow characteristics and anti-bleeding properties.

An object of the present invention is to provide a curable resin composition which is excellent in flow properties before curing, excellent in anti-bleeding properties after semi-curing, and excellent in heat resistance after main curing. Moreover, the objective of this invention is to provide the hardened|cured material of this curable resin composition, and the adhesive agent and adhesive film which use this curable resin composition. [Technical means to solve the problem]

The present invention is a curable resin composition comprising a curable resin, a photopolymerization initiator, and a thermosetting agent, wherein the thermosetting agent contains an imide oligomer. The present invention will be described in detail below.

According to the research of the present inventors, a photopolymerization initiator is further blended into a curable resin composition containing a curable resin and a thermosetting agent, and a photopolymerization initiator that can be photocured (semi-cured) is used as a A curable resin, and an imide oligomer is used as a thermosetting agent. As a result, the inventors found that a curable resin composition having excellent flow properties before curing, excellent bleed resistance after semi-curing, and excellent heat resistance after full curing can be obtained, and the present invention has been completed.

The curable resin composition of the present invention contains a curable resin. It is preferable to contain the said curable resin in the liquid state at 25 degreeC from a viewpoint of the fluidity|liquidity before hardening, etc.

The above-mentioned curable resin preferably contains: a compound (photocurable resin) that can be photohardened by a photopolymerization initiator described later when irradiated with light; and a compound that can be thermally cured by a thermosetting agent described later when heated hardening resin). The photocurable resin and the thermosetting resin may be the same compound (photothermosetting resin), and even in the case where the curable resin contains the photothermosetting resin, the photocurable resin and/or thermosetting resin may be further contained. Hardening resin.

The curable resin preferably contains a radically polymerizable compound without an epoxy group, an epoxy compound without a radically polymerizable group, and/or a compound having an epoxy group and a radically polymerizable group. From the viewpoint of making the curing more uniform and improving the mechanical strength and reliability, the curable resin preferably contains a radically polymerizable compound having no epoxy group, and an epoxy compound having no radically polymerizable group. , and compounds with epoxy groups and radical polymerizable groups.

As a radical polymerizable compound which does not have the said epoxy group, the compound which has an ethylenically unsaturated double bond is preferable, and a (meth)acrylic acid compound is more preferable. In addition, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, the above-mentioned "(meth)acrylic acid compound" means a compound having a (meth)acryloyl group, and the above-mentioned "(meth)acrylic acid compound" means a compound having a (meth)acryloyl group. group) Acryloyl" means acryl or methacryloyl.

As said (meth)acrylic compound, a (meth)acrylate compound, an epoxy (meth)acrylate, a (meth)acrylamide compound, etc. are mentioned, for example. In addition, in this specification, the above-mentioned "(meth)acrylate" means acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" means all epoxy groups in the epoxy compound. The compound obtained by reacting with (meth)acrylic acid.

As the monofunctional compound among the above-mentioned (meth)acrylate compounds, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate can be mentioned. ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylate 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate 4-Hydroxybutyl acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2 (meth)acrylate -Methoxyethyl ester, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethyl Glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate , (meth) tetrahydrofuran methyl acrylate, tetrahydrofuran methanol acrylic polyester, ethyl carbitol (meth) acrylate, (meth) 2,2,2-trifluoroethyl acrylate, (meth)acrylic acid 2,2,3,3-tetrafluoropropyl, 1H,1H,5H-octafluoropentyl (meth)acrylate, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate , Diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl hexahydrophthalate, phthalate 2-(meth)acryloyloxyethyl 2-hydroxypropyl formate, 2-(meth)acryloyloxyethyl phosphate, (3-ethyloxetane-(meth)acrylate- 3-yl)methyl ester, (meth)acrylate 2-(((butylamino)carbonyl)oxy)ethyl ester, (meth)acrylate (3-propyloxetan-3-yl) Methyl ester, (3-butyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)ethyl (meth)acrylate, ( (3-ethyloxetan-3-yl)propyl meth)acrylate, (3-ethyloxetan-3-yl)butyl (meth)acrylate, (meth)acrylic acid (3-Ethyloxetan-3-yl)pentyl ester, (3-ethyloxetan-3-yl)hexyl (meth)acrylate, γ-butyrolactone (methyl) Acrylate, (2,2-dimethyl-1,3-dioxol-4-yl)methyl (meth)acrylate, (2-methyl-2-ethyl) (meth)acrylate -1,3-dioxolane-4-yl) methyl ester, (meth)acrylic acid (2-methyl-2-isobutyl-1,3-dioxol-4-yl) ) methyl ester, (methyl ) (2-cyclohexyl-1,3-dioxolane-4-yl)methyl acrylate, cyclic trimethylolpropane formal acrylate, and the like.

Moreover, as a bifunctional compound in the said (meth)acrylate compound, 1, 3- butanediol di(meth)acrylate, 1, 4- butanediol di(meth)acrylate are mentioned, for example , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate (meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol Alcohol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol dicyclopentadiene di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylic acid 2-Hydroxy-3-(meth)acryloyloxypropyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate Acrylate, polycaprolactone glycol di(meth)acrylate, polybutadiene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and the like.

Moreover, as a compound having a trifunctional or higher function among the above-mentioned (meth)acrylate compounds, for example, trimethylolpropane tri(meth)acrylate and ethylene oxide addition trimethylolpropane tri(meth)acrylate can be mentioned. base) acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isotrimer Cyanate tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, neotaerythritol tri(meth)acrylate, phosphate tri(methyl) ) acryloxyethyl ester, di-trimethylolpropane tetra(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dipivalerythritol penta(meth)acrylate, and bis(meth)acrylate Neotaerythritol hexa(meth)acrylate, etc.

As said epoxy (meth)acrylate, bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol E type epoxy (meth)acrylate, for example ) acrylates, phenolic novolac type epoxy (meth)acrylates, cresol novolac type epoxy (meth)acrylates, resorcinol type epoxy (meth)acrylates, and the like Caprolactone modified body, etc.

As said (meth)acrylamide compound, for example, N,N- dimethyl(meth)acrylamide, N-(meth)acrylamide, N-hydroxyethyl (methyl) ) acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide Amines etc.

Examples of the epoxy compound having no radical polymerizable group include bisphenol A-type epoxy compounds, bisphenol E-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol S-type epoxy compounds, Bisphenol O type epoxy compound, 2,2'-diallyl bisphenol A type epoxy compound, alicyclic epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide addition bisphenol A type ring Oxygen compounds, resorcinol-type epoxy compounds, biphenyl-type epoxy compounds, thioether-type epoxy compounds, diphenyl ether-type epoxy compounds, dicyclopentadiene-type epoxy compounds, naphthalene-type epoxy compounds, Phenolic novolak epoxy compounds, o-cresol novolak epoxy compounds, dicyclopentadiene novolak epoxy compounds, biphenyl novolak epoxy compounds, naphthol novolak epoxy compounds, Glycidamine-type epoxy compounds, alkyl polyol-type epoxy compounds, rubber-modified epoxy compounds, and glycidyl ester compounds, etc.

It is preferable that the said curable resin contains the compound which has an epoxy group and a (meth)acryloyl group as said compound which has an epoxy group and a radically polymerizable group. As a compound which has the said epoxy group and (meth)acryloyl group, a partial (meth)acrylic acid modified epoxy compound, (meth)acrylic acid glycidyl, and 4-hydroxybutyl acrylic acid are mentioned, for example Ester glycidyl ether, etc. In addition, in this specification, the above-mentioned "partially (meth)acrylic acid-modified epoxy compound" means a compound having one or more epoxy groups and one or more (meth)acryloyl groups in one molecule. It is obtained by reacting a part of epoxy groups of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid.

Examples of the partially (meth)acrylic-modified epoxy compound include a partially (meth)acrylic-modified bisphenol A-type epoxy compound, a partially (meth)acrylic-modified bisphenol F-type epoxy compound, Partially (meth)acrylic modified bisphenol E epoxy compounds, partially (meth)acrylic modified phenolic novolak epoxy compounds, partially (meth)acrylic modified cresol novolac epoxy compounds, And some (meth)acrylic acid modified resorcinol epoxy compounds, etc.

化合物等。 作為上述光聚合起始劑，具體而言，例如可列舉：2-羥基-1-(4-異丙烯基苯基)-2-甲基-1-丙酮之低聚物、1-羥基環己基苯基酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-1-丁酮、2-(二甲基胺基)-2-((4-甲基苯基)甲基)-1-(4-(4-

啉基)苯基)-1-丁酮、2,2-二甲氧基-1,2-二苯乙烷-1-酮、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2-甲基-1-(4-甲基苯硫基)-2-

啉基丙烷-1-酮、1-(4-(2-羥基乙氧基)-苯基)-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-(苯硫基)苯基)-1,2-辛二酮2-(O-苯甲醯肟)、2,4,6-三甲基苯甲醯基二苯基氧化膦、安息香甲醚、安息香乙醚、安息香異丙醚、低聚(2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基))丙酮、2-羥基-1-(4-(4-(2-羥基-2-甲基丙醯基)苯氧基)苯基)-2-甲基丙烷-1-酮、2-羥基-1-(4-(4-(2-羥基-2-甲基丙醯基)苄基)苯基)-2-甲基丙烷-1-酮、及1-(4-(4-苯甲醯基苯基巰基)苯基)-2-甲基-2-(4-甲基苯基巰基)丙烷-1-酮等。 The curable resin composition of the present invention contains a photopolymerization initiator. Examples of the above-mentioned photopolymerization initiator include α-hydroxyketone compounds, α-hydroxybenzophenone compounds, benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, and oxime esters. Compounds, Benzoin Ether Compounds, and 9-Oxysulfur

compounds, etc. Specific examples of the above-mentioned photopolymerization initiator include oligomers of 2-hydroxy-1-(4-isopropenylphenyl)-2-methyl-1-propanone, 1-hydroxycyclohexyl Phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-

Linophenyl)-1-butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-

Lino)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzyl) Phenylphosphine oxide, 2-methyl-1-(4-methylphenylthio)-2-

Linopropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(benzene Thio)phenyl)-1,2-octanedione 2-(O-benzyl oxime), 2,4,6-trimethylbenzyldiphenylphosphine oxide, benzoin methyl ether, benzoin ether , Benzoin isopropyl ether, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl))acetone, 2-hydroxy-1-(4-(4-( 2-Hydroxy-2-methylpropionyl)phenoxy)phenyl)-2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methyl) propionyl)benzyl)phenyl)-2-methylpropan-1-one, and 1-(4-(4-benzylphenylmercapto)phenyl)-2-methyl-2- (4-methylphenylmercapto)propan-1-one and the like.

With respect to 100 parts by weight of the above-mentioned curable resin, the content of the above-mentioned photopolymerization initiator preferably has a lower limit of 0.1 part by weight, and a preferred upper limit of 20 parts by weight. By making the content of the above-mentioned photopolymerization initiator into this range, the obtained curable resin composition maintains excellent storage stability, is more excellent in photocurability, and is more excellent in bleed-out resistance after semi-curing. A more preferable lower limit of the content of the above-mentioned photopolymerization initiator is 0.5 parts by weight, and a more preferable upper limit is 10 parts by weight.

The curable resin composition of the present invention contains a thermosetting agent. The above-mentioned thermosetting agent contains an imide oligomer. By using the above-mentioned imide oligomer as the above-mentioned thermosetting agent, the curable resin composition of the present invention has excellent heat resistance after main hardening.

The above-mentioned 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 above-mentioned imide oligomer preferably has the following formula (1-1) or the following formula (1-2), or is represented by the following formula (2-1) or the following formula (2-2) structure. By having the 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 above imide is made low The polymer is more excellent in reactivity and compatibility with the above-mentioned curable resin.

In formula (1-1) and formula (1-2), A is an acid dianhydride residue, in formula (1-1), B is an aliphatic diamine residue or an aromatic diamine residue, formula (1) In -2), Ar is a divalent aromatic group which may be substituted.

In formula (2-1) and formula (2-2), A is an acid dianhydride residue, B is an aliphatic triamine residue or an aromatic triamine residue, and in formula (2-2), Ar is an optional A substituted divalent aromatic group.

The above acid dianhydride residue is preferably a tetravalent group represented by the following formula (3-1) or the following formula (3-2).

In formula (3-1) and formula (3-2), * is a bonding position, and in formula (3-1), Z is a bonding bond, oxygen atom, carbonyl group, sulfur atom, sulfonyl group, straight chain Or a branched divalent hydrocarbon group, or a divalent group having an aromatic ring. When Z is a hydrocarbon group, it may have an oxygen atom between the hydrocarbon group and each aromatic ring in formula (3-1), and when Z is a divalent group having an aromatic ring, it may also have an aromatic ring. An oxygen atom is present between the divalent group of the 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.

When 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 may be substituted. As a substituent when the above-mentioned linear or branched divalent hydrocarbon group or the above-mentioned divalent group having an aromatic ring is substituted, for example, a halogen atom, a linear or branched alkyl group can be mentioned. , linear or branched alkenyl, alicyclic, aryl, alkoxy, nitro, and cyano groups, etc.

As an acid dianhydride which the said acid dianhydride residue originates, the acid dianhydride etc. which are represented by the following formula (9) are mentioned, for example.

When B in the above formula (1-1) is the above aliphatic diamine residue, or when B in the above formula (2-1) or the above formula (2-2) is the above aliphatic triamine residue In this case, the preferable lower limit of the carbon number of the aliphatic diamine residue and the aliphatic triamine residue is 4. By making the carbon number of the above-mentioned aliphatic diamine residue and the above-mentioned aliphatic triamine residue to be 4 or more, the flexibility and workability of the obtained curable resin composition before curing, and the intermediate after curing The electrical characteristics are more excellent. A more preferable lower limit of the carbon number of the aliphatic diamine residue and the aliphatic triamine residue is 5, and a further preferable lower limit is 6. In addition, the preferable upper limit of the carbon number of the said aliphatic diamine residue and the said aliphatic triamine residue is not specifically limited, The practical upper limit is 60.

Examples of aliphatic diamines from which the above-mentioned aliphatic diamine residues are derived include aliphatic diamines derived from dimer acids, linear or branched chain aliphatic diamines, aliphatic ether diamines, and aliphatic diamines. Alicyclic diamines, etc. As aliphatic diamine derived from the said dimer acid, dimer diamine, hydrogenated dimer diamine, etc. are mentioned, for example. As said straight-chain or branched-chain aliphatic diamine, for example, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,9-diamine, 10-Decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, 1,18- octadecanediamine, 1,20-eicosanediamine, 2-methyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, and 2,7-dimethyl -1,8-Octanediamine, etc. As said aliphatic ether diamine, 2,2'- oxybis(ethylamine), 3,3'-oxybis(propylamine), and 1,2-bis(2-amine) are mentioned, for example ethoxy)ethane, etc. As said aliphatic alicyclic diamine, 1, 3- bis (aminomethyl) cyclohexane, 1, 4- bis (aminomethyl) cyclohexane, cyclohexanediamine, methyl cyclohexanediamine, isophoronediamine, etc. Among them, the above-mentioned aliphatic diamine residue is preferably the above-mentioned aliphatic diamine residue derived from a dimer acid.

Examples of aliphatic triamines from which the above-mentioned aliphatic triamine residues are derived include aliphatic triamines derived from trimer acid, linear or branched chain aliphatic triamines, aliphatic ether triamines, and aliphatic lipids. Cyclic triamines, etc. Examples of the aliphatic triamine derived from the trimer acid include trimer triamine, hydrogenated trimer triamine, and the like. As said straight-chain or branched-chain aliphatic triamine, for example, 3,3'-diamino-N-methyldipropylamine, 3,3'-diaminodipropylamine, ethylidene triamine, bis(hexamethylene)triamine, and 2,2'-bis(methylamino)-N-methyldiethylamine, and the like. Among them, the above-mentioned aliphatic triamine residue is preferably the above-mentioned aliphatic triamine residue derived from a trimer acid.

Moreover, as the said aliphatic diamine and/or the said aliphatic triamine, the mixture of the said dimer diamine and the said trimer triamine can also be used.

As a commercial item of the aliphatic diamine and/or aliphatic triamine derived from the said dimer acid and/or the said trimer acid, for example, the aliphatic diamine and/or aliphatic triamine manufactured by BASF can be mentioned. Triamine, aliphatic diamine and/or aliphatic triamine manufactured by Croda Corporation, etc. As aliphatic diamine and/or aliphatic triamine manufactured by the said BASF company, VERSAMINE 551, VERSAMINE 552 etc. are mentioned, for example. Examples of the aliphatic diamines and/or aliphatic triamines manufactured by Croda include Priamine 1071, Priamine 1073, Priamine 1074, and Priamine 1075.

When B in the above formula (1-1) is the above aromatic diamine residue, the aromatic diamine residue is preferably the following formula (4-1) or the following formula (4-2) The 2-valence base represented.

In formula (4-1) and formula (4-2), * is a bonding position, and in formula (4-1), Y is a bonding bond, oxygen atom, carbonyl group, sulfur atom, sulfonyl group, straight chain Or a branched divalent hydrocarbon group, or a divalent group having an aromatic ring. When Y is a hydrocarbon group, there may be an oxygen atom between the hydrocarbon group and each aromatic ring in the formula (4-1), and when Y is a divalent group having an aromatic ring, in the case of the aromatic ring An oxygen atom may be included between the divalent group 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.

When 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 may be substituted. Examples of the substituent when the above-mentioned linear or branched divalent hydrocarbon group or the above-mentioned divalent group having an aromatic ring is substituted include a halogen atom, a linear or branched alkyl group, Linear or branched alkenyl, alicyclic, aryl, alkoxy, nitro, cyano and the like.

As an aromatic diamine which the said aromatic diamine residue originates, the case where the diamine represented by the following formula (10) is an aromatic diamine is mentioned, for example.

In addition, with regard to the above-mentioned imide oligomer, when it has a siloxane skeleton in its structure, the glass transition temperature after hardening may be lowered, or the adherend may be contaminated, which may lead to poor adhesion. An imide oligomer without a siloxane skeleton in its structure.

The number average molecular weight of the above-mentioned imide oligomer is preferably 5,000 or less. By setting the number average molecular weight of the above-mentioned imide oligomer to be 5,000 or less, the cured product of the obtained curable resin composition is further excellent in long-term heat resistance. A more preferable upper limit of the number average molecular weight of the above-mentioned imide oligomer is 4,000, and a further preferable upper limit is 3,000. In particular, the number average molecular weight of the above-mentioned imide oligomer is preferably 900 or more and 5,000 or less when it has the structure represented by the above formula (1-1) and the above formula (2-1). (1-2) In the case of the structure represented by the above formula (2-2), 550 or more and 4000 or less are preferable. In the case of having the structure represented by the above formula (1-1) and the above formula (2-1), the more preferable lower limit of the number average molecular weight is 950, and the more preferable lower limit is 1000. In the case of having the structure represented by the above formula (1-2) and the above formula (2-2), the more preferable lower limit of the number average molecular weight is 580, and the more preferable lower limit is 600. In addition, in this specification, the said "number average molecular weight" is the value calculated|required by polystyrene conversion by measuring by gel permeation chromatography (GPC), using tetrahydrofuran as a solvent. As a column used for measuring the number average molecular weight in terms of polystyrene by GPC, for example, JAIGEL-2H-A (manufactured by Nippon Kagaku Kogyo Co., Ltd.) and the like can be mentioned.

Specifically, the above-mentioned imide oligomer is preferably the following formula (5-1), the following formula (5-2), the following formula (5-3), the following formula (5-4), or an imide oligomer represented by 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), an imide oligomer represented by the following formula (6-5), or the following formula (6-6).

In formulas (5-1) to (5-5), A is the above-mentioned acid dianhydride residue, and in formulas (5-1) and (5-3) to (5-5), A may be the same, or may be different. In formulas (5-1) to (5-4), B is the above-mentioned aliphatic diamine residue or the above-mentioned aromatic diamine residue, and in formulas (5-3) and (5-4), B may be respectively Same or different. In formula (5-5), B is the aforementioned aliphatic triamine residue or the aforementioned aromatic triamine residue. In the formula (5-2), X is a hydrogen atom, a halogen atom, or a substituted monovalent hydrocarbon group, and in the formula (5-4), W is a hydrogen atom, a halogen atom, or a substituted monovalent hydrocarbon group. In formula (5-3) and formula (5-4), n is the number of repetitions.

In formulas (6-1) to (6-6), A is the above-mentioned acid dianhydride residue, and in formulas (6-1) to (6-6), A may be the same or different, respectively. In formulas (6-1) to (6-6), R is a hydrogen atom, a halogen atom, or a substituted monovalent hydrocarbon group, formula (6-1), formula (6-2), formula (6-4) ) and formula (6-6), R may be the same or different, respectively. In formula (6-3) and formula (6-5), W is a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may be substituted. In formulas (6-2) to (6-4), B is the above-mentioned aliphatic diamine residue or the above-mentioned aromatic diamine residue, and in formulas (6-4) and (6-5), B may be respectively Same or different. In formula (6-6), B is either the aforementioned aliphatic triamine residue or the aforementioned aromatic triamine residue.

A in the above formulae (5-1) to (5-5) and the above formulae (6-1) to (6-6) is preferably the following formula (7-1) or the following formula (7-2) ) represents the 4-valent base.

In formula (7-1) and formula (7-2), * is a bonding position, and in formula (7-1), Z is a bonding bond, oxygen atom, carbonyl group, sulfur atom, sulfonyl group, straight chain Or a branched divalent hydrocarbon group, or a divalent group having an aromatic ring. When Z is a hydrocarbon group, there may be an oxygen atom between the hydrocarbon group and each aromatic ring in the formula (7-1), and when Z is a divalent group having an aromatic ring, in the case of the aromatic ring An oxygen atom may be present between the divalent group 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.

B in the above formulae (5-1) to (5-4) and the above formulae (6-2) to (6-5) is preferably the following formula (8-1) or the following formula (8-2) ) represents the 2-valent basis.

In formula (8-1) and formula (8-2), * is a bonding position, and in formula (8-1), Y is a bonding bond, oxygen atom, carbonyl group, sulfur atom, sulfonyl group, straight chain Or a branched divalent hydrocarbon group, or a divalent group having an aromatic ring. When Y is a hydrocarbon group, there may be an oxygen atom between the hydrocarbon group and each aromatic ring in formula (8-1), and when Y is a divalent group having an aromatic ring, in the case of the aromatic ring An oxygen atom may be present between the divalent group 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.

As a method for producing 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 an acid dianhydride represented by the following formula (10) can be mentioned. The method of diamine reaction, etc. Furthermore, by using an aliphatic triamine or an aromatic triamine in place 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.

In the formula (9), A is the same tetravalent group as A in the above-mentioned formula (1-1).

In formula (10), B is the same divalent group as B in the above-mentioned formula (1-1), and R ¹ to R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group.

A specific example of the method of reacting the acid dianhydride represented by the above formula (9) and the diamine represented by the above formula (10) is shown below. The following methods can be mentioned. First, the diamine represented by the above formula (10) is previously dissolved in a solvent (for example, N-methylpyrrolidone, etc.) that can dissolve the amide acid oligomer obtained by the reaction. ), the acid dianhydride represented by the above-mentioned formula (9) was added to the obtained solution and reacted to obtain an amide acid oligomer solution. Next, the solvent is removed by heating, decompression, or the like, and the amide acid oligomer is reacted by heating at about 200° C. or higher for 1 hour or longer. By adjusting the molar ratio of the acid dianhydride represented by the above formula (9) and the diamine represented by the above formula (10), and the imidization conditions, it is possible to obtain a desired number average molecular weight in An imide oligomer having a structure represented by the above formula (1-1) at both ends. In addition, by substituting a part of the acid dianhydride represented by the above formula (9) with an acid anhydride represented by the following formula (11), the following imide oligomer having a desired number average molecular weight can be obtained , and has a structure represented by the above formula (1-1) at one end, and a structure derived from an acid anhydride represented by the following formula (11) at the other end. In this case, the acid dianhydride represented by the above formula (9) and the acid anhydride represented by the following formula (11) may be added simultaneously or separately. Furthermore, by substituting a part of the diamine represented by the above formula (10) with a monoamine represented by the following formula (12), the following imide oligomer having a desired number average molecular weight can be obtained , and has a structure represented by the above formula (1-1) at one end, and a structure derived from a monoamine represented by the following formula (12) at the other end. In this case, the diamine represented by the above formula (10) and the monoamine represented by the following formula (12) may be added simultaneously or separately.

In formula (11), Ar is a divalent aromatic group which may be substituted.

In formula (12), Ar is a monovalent aromatic group which may be substituted, and R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent hydrocarbon group.

As a method for producing an imide oligomer having a structure represented by the above formula (1-2), for example, an acid dianhydride represented by the above formula (9) and an acid dianhydride represented by the following formula (13) can be mentioned. A method of reacting a phenolic hydroxyl group-containing monoamine; or an acid dianhydride represented by the above formula (9), a diamine represented by the above formula (10), and a phenolic group represented by the following formula (13) The method for the reaction of the monoamine of the hydroxyl group, etc. Furthermore, by using an aliphatic triamine or an aromatic triamine in place of the diamine represented by the above formula (10), an imide oligomer having a structure represented by the above formula (2-2) can be produced.

In formula (13), Ar may be a substituted divalent aromatic group, and R ⁷ and R ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group.

A specific example of the method of reacting the acid dianhydride represented by the above formula (9) and the phenolic hydroxyl group-containing monoamine represented by the above formula (13) is shown below. The following methods can be mentioned. First, the phenolic hydroxyl group-containing monoamine represented by the above formula (13) is previously dissolved in a solvent (for example, N-methyl amide) that can dissolve the amide acid oligomer obtained by the reaction. pyrrolidone etc.), the acid dianhydride represented by the said formula (9) is added to the obtained solution, and it is made to react, and the amide acid oligomer solution is obtained. Then, the solvent is removed by heating, depressurization, etc., and further, the method of heating at about 200 degreeC or more for 1 hour or more, and making an amide|amid acid oligomer react, etc.. By adjusting the molar ratio of the acid dianhydride represented by the above formula (9) and the phenolic hydroxyl group-containing monoamine represented by the above formula (13), and the imidization conditions, the desired compound can be obtained. An imide oligomer having a number average molecular weight and a structure represented by the above formula (1-2) at both ends. In addition, by substituting a part of the phenolic hydroxyl group-containing monoamine represented by the above formula (13) with a monoamine represented by the above formula (12), the following imide oligomer can be obtained, which has the desired The number-average molecular weight has the structure represented by the above formula (1-2) at one end, and the structure derived from the monoamine represented by the above formula (12) at the other end. In this case, the phenolic hydroxyl group-containing monoamine represented by the above formula (13) and the monoamine represented by the above formula (12) may be added simultaneously or separately.

Specific examples of the method for reacting the acid dianhydride represented by the above formula (9), the diamine represented by the above formula (10), and the phenolic hydroxyl group-containing monoamine represented by the above formula (13) are shown below. The method, etc. can be mentioned. First, the phenolic hydroxyl group-containing monoamine represented by the above formula (13) and the diamine represented by the above formula (10) are dissolved in the amide acid low in the amide acid obtained by the reaction. In a solvent (for example, N-methylpyrrolidone, etc.) in which the polymer is dissolved, the acid dianhydride represented by the above formula (9) is added to the obtained solution and reacted to obtain an amide acid oligomer solution. Next, the solvent is removed by heating, decompression, or the like, and further, the amide acid oligomer is reacted by heating at about 200° C. or higher for 1 hour or longer. By the molar ratio of the acid dianhydride represented by the above formula (9), the diamine represented by the above formula (10), and the phenolic hydroxyl group-containing monoamine represented by the above formula (13), and imide By adjusting the chemical conditions, an imide oligomer having a desired number average molecular weight and a structure represented by the above formula (1-2) at both ends can be obtained. Further, by substituting a part of the phenolic hydroxyl group-containing monoamine represented by the above formula (13) with a monoamine represented by the above formula (12), the imide oligomer can be obtained, which has the desired The number average molecular weight has a structure represented by the above formula (1-2) at one end and a structure derived from the monoamine represented by the above formula (12) at the other end. In this case, the phenolic hydroxyl group-containing monoamine represented by the above formula (13) and the monoamine represented by the above formula (12) may be added simultaneously or separately.

Examples of the acid dianhydride represented by the above formula (9) include pyromellitic anhydride, 3,3'-oxybisphthalic anhydride, and 3,4'-oxybisphthalic anhydride , 4,4'-oxybisphthalic anhydride, 4,4'-(4,4'-isopropylidene diphenoxy)bisphthalic anhydride, 4,4'-bis(2 , 3-dicarboxyphenoxy) diphenyl ether acid dianhydride, p-phenylene bis (trimellitic anhydride), and 2,3,3',4'-biphenyltetracarboxylic dianhydride, etc. Among them, the acid dianhydride used as a raw material for the above-mentioned imide oligomer is preferably an aromatic acid dianhydride having a melting point of 240° C. or lower, from the viewpoint of making the solubility and heat resistance more excellent, and more preferably Preferably, it is an aromatic acid dianhydride having a melting point of 220°C or lower, more preferably an aromatic acid dianhydride having a melting point of 200°C or lower, and particularly preferably 3,4'-oxybisphthalic dianhydride ( Melting point 180 ℃), 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride (melting point 190 ℃). In addition, in this specification, the said "melting point" means the value measured as the temperature of an endothermic peak when raising temperature at 10 degreeC/min using a differential scanning calorimeter. As said differential scanning calorimeter, EXTEAR DSC6100 (made by SII Nanotechnologies) etc. are mentioned, for example.

As the aromatic diamine among the diamines represented by the above formula (10), for example, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4' -Diaminodiphenylmethane, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, o-phenylenediamine, m- Phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylene, 4,4'-diaminodiphenylene, 1,3-bis(3-aminophenoxy)benzene , 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis(4-(4-aminophenoxy)phenyl)methane , 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, 1,4 -Bis(2-(4-aminophenyl)-2-propyl)benzene, 3,3'-diamino-4,4'-dihydroxyphenylmethane, 4,4'-diamino- 3,3'-dihydroxyphenylmethane, 3,3'-diamino-4,4'-dihydroxyphenyl ether, bisaminophenyl fluoride, bistoluidine fluoride, 4,4'-bis( 4-aminophenoxy) biphenyl, 4,4'-diamino-3,3'-dihydroxyphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl, And 4,4'-diamino-2,2'-dihydroxybiphenyl, etc. Among them, from the viewpoint of being excellent in availability, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, and 1,3-bis(2-(4-amine) are preferred. phenyl)-2-propyl)benzene, 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene, 1,3-bis(3-aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, and 1,4-bis(4-aminophenoxy)benzene, and more preferably from the viewpoint of being excellent in solubility and heat resistance is 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene, 1 , 3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, and 1,4-bis(4-aminophenoxy)benzene.

Examples of the acid anhydride represented by the above formula (11) include phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-Naphthalenedicarboxylic anhydride, 1,8-Naphthalenedicarboxylic anhydride, 2,3-Anthracenedicarboxylic anhydride, 4-tert-butylphthalic anhydride, 4-ethynylphthalic anhydride, 4 - Phenylethynylphthalic anhydride, 4-fluorophthalic anhydride, 4-chlorophthalic anhydride, 4-bromophthalic anhydride, and 3,4-dichlorophthalic anhydride Wait.

Examples of the monoamine represented by the above formula (12) include aniline, o-toluidine, m-toluidine, p-toluidine, 2,4-dimethylaniline, 3,4-dimethylaniline, 3,4-dimethylaniline, 5-dimethylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-amine Anthracene, 9-aminoanthracene, 1-aminopyrene, 3-chloroaniline, o-methoxyaniline, m-methoxyaniline, p-methoxyaniline, 1-amino-2-methylnaphthalene, 2,3- Dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 3,4-dimethylaniline, 4-ethylaniline, 4-ethynylaniline, 4-isopropylaniline , 4-(methylthio)aniline, and N,N-dimethyl-1,4-phenylenediamine, etc.

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, 4-amino-o-cresol, and 4-amino-o-cresol. -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, and 4-amino-2,6-diphenylphenol, etc. Among them, 4-amino-o-cresol and 5-amino-o-cresol are preferred from the viewpoint of being excellent in availability and storage stability and obtaining a high glass transition temperature after curing.

When the above-mentioned imide oligomer is produced by the above-mentioned production method, a plurality of kinds of imide oligomers having the structure represented by the above-mentioned formula (1-1) or having the above-mentioned formula (1- 2) The above-mentioned imide oligomer in a mixture (imide oligomer composition) of a plurality of imide oligomers having the indicated structure and respective raw materials. When an aliphatic triamine or an aromatic triamine is used in place of the diamine represented by the above formula (10), a plurality of imide oligomers having the structure represented by the above formula (2-1) can be obtained The above-mentioned imide oligomer in a mixture (imide oligomer composition) of a compound or a plurality of kinds of imide oligomers having the structure represented by the above formula (2-2) and each raw material (imide oligomer composition). With regard to the imide oligomer composition, by making the imidization rate of 70% or more, when used as a curing agent, a cured product having more excellent mechanical strength at high temperature and long-term heat resistance can be obtained. The preferred lower limit of the imidization rate of the above imide oligomer composition is 75%, and a more preferred lower limit is 80%. In addition, the preferable upper limit of the imidization ratio of the above-mentioned imide oligomer composition is not particularly limited, but the practical upper limit is 98%. In addition, the above-mentioned "imidization rate" can be measured by a total reflection measurement method (ATR method) using a Fourier transform infrared spectrophotometer (FT-IR), and is based on 1660 of the carbonyl group derived from the amide acid. The peak absorbance area in the vicinity of cm ⁻¹ was derived by the following formula. As said Fourier transform infrared spectrophotometer, UMA600 (made by Agilent Technologies) etc. are mentioned, for example. In addition, the "peak absorbance area of amide acid oligomer" in the following formula is obtained by reacting acid dianhydride with diamine or phenolic hydroxyl group-containing monoamine without carrying out the amide imidization step. The absorbance area of the amide acid oligomer obtained by removing the solvent by evaporation or the like. Rate of imidization (%) = 100×(1-(area of peak absorbance after imidization)/(area of peak absorbance of imidized oligomer))

From the viewpoint of solubility in the curable resin composition, it is preferable that the above-mentioned imide oligomer composition dissolves 3 g or more in 10 g of tetrahydrofuran at 25°C.

The preferable lower limit of the content of the above-mentioned imide oligomer is 20 parts by weight in a total of 100 parts by weight of the above-mentioned curable resin and the above-mentioned thermosetting agent (in the case of containing a hardening accelerator described later, further a hardening accelerator) , the preferred upper limit is 80 parts by weight. By making content of the said imide oligomer into this range, the flexibility and workability before hardening of the curable resin composition obtained, and the heat resistance after hardening are more excellent. A more preferable lower limit of the content of the above imide oligomer is 25 parts by weight, and a more preferable upper limit is 75 parts by weight. Furthermore, when the imide oligomer of the present invention is contained in the above-mentioned imine oligomer composition, the content of the above-mentioned imine oligomer means the imine oligomer composition ( In the case where other imine oligomers are used in combination, it is the content of the total of the imine oligomer composition and other imine oligomers).

The curable resin composition of the present invention preferably contains a curing accelerator. By containing the above-mentioned hardening accelerator, hardening time can be shortened and productivity can be improved.

As said hardening accelerator, an imidazole type hardening accelerator, a tertiary amine type hardening accelerator, a phosphine type hardening accelerator, a phosphorus type hardening accelerator, a photobase generator, a perylene salt type hardening accelerator etc. are mentioned, for example. Among them, an imidazole-based hardening accelerator is preferred from the viewpoint of excellent storage stability.

The content of the above-mentioned hardening accelerator is preferably 0.01 parts by weight and a preferable upper limit is 10 parts by weight relative to 100 parts by weight of the total of the above-mentioned curable resin, the above-mentioned thermosetting agent and the above-mentioned hardening accelerator. By making content of the said hardening accelerator into this range, the effect of shortening hardening time in the state which maintains excellent adhesiveness etc. is more excellent. A more preferable lower limit of the content of the above hardening accelerator is 0.05 parts by weight, and a more preferable upper limit is 5 parts by weight.

The curable resin composition of this invention may contain an inorganic filler in the range which does not inhibit the objective of this invention.

The above-mentioned inorganic filler is preferably at least one of silicon dioxide and barium sulfate. By containing at least one of silica and barium sulfate as the above-mentioned inorganic filler, the curable resin composition of the present invention is further excellent in reflow resistance, plating resistance, and workability.

Examples of inorganic fillers other than the above-mentioned silica and the above-mentioned barium sulfate include alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, carbon fiber, and inorganic ions Swap, etc.

As the above-mentioned inorganic filler, those having an average particle diameter of 50 nm or more and less than 4 μm can be suitably used.

The content of the above-mentioned inorganic filler corresponds to 100 parts by weight in total of the above-mentioned curable resin and the above-mentioned thermosetting agent (in the case of containing the above-mentioned hardening accelerator, furthermore, the above-mentioned hardening accelerator), and a preferable upper limit is 200 parts by weight. By making the content of the above-mentioned inorganic filler into this range, the cured product of the obtained curable resin composition is more excellent in reflow resistance and plating resistance while maintaining a state of excellent touch adhesion and the like. The more preferable upper limit of the content of the above-mentioned inorganic filler is 150 parts by weight.

The curable resin composition of the present invention preferably contains a flow control agent in order to improve coatability, shape retention, etc. applied to an adherend in a short time. As said flow control agent, fumed silica (fumed silica), such as Aerosil, a layered silicate, etc. are mentioned, for example. In addition, as the above-mentioned flow conditioner, those having an average particle diameter of less than 100 nm can be suitably used.

The content of the above-mentioned flow control agent is based on 100 parts by weight of the total of the above-mentioned curable resin and the above-mentioned thermosetting agent (in the case of containing the above-mentioned hardening accelerator, furthermore, the above-mentioned hardening accelerator), the lower limit is preferably 0.1 parts by weight, and A preferable upper limit is 50 parts by weight. By making content of the said flow regulator into this range, it becomes more excellent in the effect of improving coatability, shape retention, etc. to a to-be-adhered body in a short time. A more preferable lower limit of the content of the above flow regulator is 0.5 parts by weight, and a more preferable upper limit is 30 parts by weight.

The curable resin composition of the present invention may contain an organic filler to relieve stress, impart toughness, and the like. Examples of the organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, and benzoguanidine. Amine particles, and these core-shell particles, etc. Among them, polyamide particles, polyamideimide particles, and polyimide particles are preferred.

The content of the organic filler is preferably 300 parts by weight based on the total of 100 parts by weight of the above curable resin and the above thermosetting agent (in the case of containing the above hardening accelerator, furthermore the above hardening accelerator). By making content of the said organic filler into this range, the toughness etc. of the hardened|cured material obtained are more excellent in the state which maintains excellent adhesiveness etc.. The more preferable upper limit of the content of the above-mentioned organic filler is 200 parts by weight.

It is preferable that the curable resin composition of this invention contains a polymer compound in the range which does not inhibit the objective of this invention. The above-mentioned polymer compound functions as a film-forming component, and by containing the above-mentioned polymer compound, the obtained curable resin composition has more excellent anti-bleeding properties.

The preferable lower limit of the number average molecular weight of the above-mentioned polymer compound is 3,000, and the preferable upper limit is 100,000. By making the number average molecular weight of the above-mentioned polymer compound into this range, the obtained curable resin composition is more excellent in flexibility and workability before curing and heat resistance after curing. A more preferable lower limit of the number-average molecular weight of the above-mentioned polymer compound is 5,000, and a more preferable upper limit is 80,000.

樹脂、丙烯酸樹脂、胺酯樹脂、及聚酯等。其中，就耐熱性之觀點而言，較佳為聚醯亞胺、聚醯胺、聚醯胺醯亞胺、及聚順丁烯二醯亞胺，更佳為聚醯亞胺。上述高分子化合物可單獨使用，亦可將2種以上組合而使用。Examples of the above-mentioned polymer compound include polyimide, phenoxy resin, polyimide, polyimide, polymaleimide, cyanate resin, benzoyl

Resin, acrylic resin, urethane resin, polyester, etc. Among them, from the viewpoint of heat resistance, polyimide, polyimide, polyimide, and polymaleimide are preferred, and polyimide is more preferred. The above-mentioned polymer compounds may be used alone or in combination of two or more.

The content of the above-mentioned polymer compound is 100 parts by weight in total relative to 100 parts by weight of the total of the above-mentioned curable resin and the above-mentioned thermosetting agent (in the case of containing the above-mentioned hardening accelerator, furthermore, the above-mentioned hardening accelerator), and the lower limit is preferably 1 part by weight, preferably 100 parts by weight. A preferable upper limit is 40 parts by weight. By making content of the said polymer compound into this range, the heat resistance of the hardened|cured material of the curable resin composition obtained is more excellent. A more preferable lower limit of the content of the above-mentioned polymer compound is 5 parts by weight, and a more preferable upper limit is 30 parts by weight.

The curable resin composition of the present invention may contain a flame retardant in a range that does not inhibit the object of the present invention. Examples of the flame retardant include boehmite-type aluminum hydroxide, metal hydrates such as aluminum hydroxide, and magnesium hydroxide, halogen-based compounds, phosphorus-based compounds, and nitrogen compounds. Among them, boehmite-type aluminum hydroxide is preferred.

The content of the flame retardant is preferably 200 parts by weight based on the total of 100 parts by weight of the above curable resin and the above thermosetting agent (and when the above hardening accelerator is contained). By making content of the said flame retardant into this range, the obtained curable resin composition maintains the state which is excellent in adhesiveness etc., and is excellent in flame retardance. The more preferable upper limit of the content of the above flame retardant is 150 parts by weight.

烷、1,3-二氧雜環戊烷、二異丙醚、乙二醇單甲醚、乙二醇單乙醚、乙二醇單丁醚、丙二醇單甲醚乙酸酯、丙二醇單甲醚、3-甲氧基-3-甲基-1-丁醇、乙二醇單第三丁醚、丙二醇單甲醚丙酸酯、3-甲氧基丁醇、二乙二醇二甲醚、苯甲醚、及4-甲基苯甲醚等。 作為上述含氮系溶劑，例如可列舉：乙腈、N,N-二甲基甲醯胺、及N,N-二甲基乙醯胺等。 其中，就操作性、醯亞胺低聚物之溶解性等觀點而言，較佳為選自由沸點為60℃以上且未達200℃之酮系溶劑、沸點為60℃以上且未達200℃之酯系溶劑、及沸點為60℃以上且未達200℃之醚系溶劑所組成之群中之至少1種。作為此種溶劑，例如可列舉：甲基乙基酮、甲基異丁基酮、乙酸乙酯、乙酸異丁酯、1,4-二

烷、1,3-二氧雜環戊烷、四氫呋喃、環己酮、甲基環己酮、二乙二醇二甲醚、及苯甲醚等。 再者，上述「沸點」意指於101 kPa之條件測定所得之值、或利用沸點換算圖表等而換算為101 kPa之值。 The said curable resin composition may contain a solvent from viewpoints, such as coatability. As the above-mentioned solvent, from the viewpoints of coatability, storage stability, and the like, a solvent having a boiling point of less than 200°C is preferable. Examples of the solvent whose boiling point is less than 200°C include alcohol-based solvents, ketone-based solvents, ester-based solvents, hydrocarbon-based solvents, halogen-based solvents, ether-based solvents, and nitrogen-containing solvents. As said alcoholic solvent, methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, 3rd butanol, 2-ethylhexanol, etc. are mentioned, for example. Examples of the ketone-based solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, and diacetone Alcohol etc. Examples of the ester-based solvent include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, isopropyl acetate, and methyl lactate. ester, ethyl lactate, and butyl lactate, etc. Examples of the hydrocarbon-based solvent include benzene, toluene, xylene, n-hexane, isohexane, cyclohexane, methylcyclohexane, ethylcyclohexane, isooctane, n-decane, and n-heptane alkane etc. As said halogen type solvent, methylene chloride, chloroform, trichloroethylene, etc. are mentioned, for example. As said ether solvent, diethyl ether, tetrahydrofuran, 1, 4- diethyl ether, tetrahydrofuran, 1, 4- diethyl ether, 1, 4- di-

Alkane, 1,3-dioxolane, diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether , 3-methoxy-3-methyl-1-butanol, ethylene glycol monotertiary butyl ether, propylene glycol monomethyl ether propionate, 3-methoxybutanol, diethylene glycol dimethyl ether, Anisole, and 4-methylanisole, etc. As said nitrogen-containing solvent, acetonitrile, N,N- dimethylformamide, N,N- dimethylacetamide, etc. are mentioned, for example. Among them, from the viewpoints of workability, solubility of the imide oligomer, etc., those selected from ketone-based solvents having a boiling point of 60°C or more and less than 200°C, and those having a boiling point of 60°C or more and less than 200°C are preferred. At least one of the group consisting of the ester-based solvent and the ether-based solvent with a boiling point of 60°C or higher and less than 200°C. As such a solvent, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, 1,4-di

alkane, 1,3-dioxolane, tetrahydrofuran, cyclohexanone, methylcyclohexanone, diethylene glycol dimethyl ether, and anisole, etc. In addition, the above-mentioned "boiling point" means a value measured under the conditions of 101 kPa, or a value converted to 101 kPa using a boiling point conversion chart or the like.

The preferable lower limit of the content of the above-mentioned solvent in 100 parts by weight of the curable resin composition containing the above-mentioned solvent is 20 parts by weight, and the preferable upper limit is 90 parts by weight. By making content of the said solvent into this range, the coatability etc. of the curable resin composition obtained are more excellent. A more preferable lower limit of the content of the above-mentioned solvent is 30 parts by weight, and a more preferable upper limit is 80 parts by weight.

The curable resin composition of this invention may contain a reactive diluent in the range which does not inhibit the objective of this invention. As said reactive diluent, the reactive diluent which has two or more reactive functional groups in 1 molecule is preferable from the viewpoint of reliability of adhesion.

The curable resin composition of the present invention may further contain additives such as a coupling agent, a dispersant, a storage stabilizer, an escape inhibitor, a flux, and a leveling agent.

As a method of manufacturing the curable resin composition of this invention, the method of mixing a curable resin, a photopolymerization initiator, a thermosetting agent, and a hardening accelerator etc. which are added as needed using a mixer, etc. are mentioned, for example. As said mixer, a homo disperser (homo disper), a universal mixer, a Banbury mixer, a kneader, etc. are mentioned, for example.

The curable resin composition of the present invention preferably has a gel fraction of 5% or more and less than 90% after being irradiated with ultraviolet rays of 2000 mJ/cm ² . By setting the gel fraction after irradiation with ultraviolet rays of 2000 mJ/cm ² to this range, the anti-bleeding property after semi-hardening is more excellent. A more preferable lower limit of the gel fraction after irradiating 2000 mJ/cm ² of ultraviolet rays is 8%, and a more preferable upper limit is 80%. By adjusting the type or content of the photocurable resin and photothermosetting resin contained in the curable resin, or the type or content of the photopolymerization initiator, the gel after irradiating 2000 mJ/cm ² of ultraviolet rays can be easily The fraction is adjusted to the above range. In addition, 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. By setting the gel fraction after heating at 190° C. for 1 hour to 90% or more, the heat resistance and adhesiveness after curing are more excellent. The more preferable lower limit of the gel fraction after heating at 190° C. for 1 hour is 92%. By adjusting the type or content of thermosetting resin and photothermosetting resin contained in the curable resin, or the type or content of thermosetting agent and curing accelerator, it is easy to gel after heating at 190°C for 1 hour The fraction is adjusted to the above range. In addition, the above-mentioned "gel fraction", as shown in the following formula, means a value obtained by impregnating the semi-cured or thermally cured composition with a solvent having a solubility sufficient to dissolve the curable resin composition. The value expressed as a percentage of the weight of the undissolved matter obtained after drying with respect to the initial weight of the curable resin composition, after stirring for more than 24 hours, filtering through a mesh, and drying at 110°C for 1 hour. As said solvent, tetrahydrofuran etc. can be used, for example. Gel fraction (%)=100×W ₂ /W ₁ (W ₁ : initial weight of curable resin composition, W ₂ : weight of undissolved matter obtained after drying)

About the curable resin composition of this invention, the preferable lower limit of the 5% weight reduction temperature of the hardened|cured material obtained by heating at 190 degreeC for 1 hour is 350 degreeC or more. The curable resin composition of the present invention has excellent heat resistance after curing by making the 5% weight reduction temperature of the cured product to be 350°C or higher, and can be suitably used as a heat-resistant adhesive for vehicles and the like. A more preferable lower limit of the 5% weight reduction temperature of the hardened product is 360°C, and a further preferable lower limit is 370°C. Moreover, the preferable upper limit of the 5% weight reduction temperature of the said hardened|cured material is not specifically limited, The upper limit is substantially 450 degreeC. In addition, the said 5% weight reduction temperature can be derived by thermogravimetric measurement using the thermogravimetric measuring apparatus under the heating conditions of raising temperature from 30 degreeC to 500 degreeC at a temperature increase rate of 10 degreeC/min. As said thermogravimetric measuring apparatus, TG/DTA6200 (made by Hitachi High-Tech Science Corporation) etc. are mentioned, for example.

The curable resin composition of the present invention can be used for a wide range of applications, and can be suitably used for electronic material applications requiring high heat resistance in particular. For example, it can be used as a die adhesive in aerospace, vehicle electrical control unit (ECU) applications, or power device applications using SiC and GaN. Also, for example, it can also be used in adhesives for power encapsulation, sealants, adhesives for flexible printed circuit boards or coverlay films, copper-clad laminates, adhesives for semiconductor bonding, interlayer insulating films, prepregs, and LEDs. Sealants, adhesives for structural materials, etc. Among them, it can be suitably used for bonding of flexible printed circuit boards or coverlay films.

The cured product of the curable resin composition of the present invention is also one of the present invention. The adhesive which uses the curable resin composition of this invention is also one of this invention. The adhesive film can be obtained by a method such as drying after applying the adhesive of the present invention on a film. An adhesive film formed using the adhesive of the present invention is also one of the present invention. [Effect of invention]

According to the present invention, it is possible to provide a curable resin composition which is excellent in flow properties before curing, excellent in anti-bleeding properties after semi-curing, and excellent in heat resistance after main curing. Moreover, according to this invention, the hardened|cured material of this curable resin composition, and the adhesive agent and adhesive film which use this curable resin composition can be provided.

Embodiments are disclosed below to further describe the present invention in detail, but the present invention is not limited to these embodiments.

(Synthesis example 1 (preparation of imide oligomer composition A)) 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic anhydride (Tokyo Chemical Industry Co., Ltd. Production) 104 parts by weight were dissolved in 300 parts by weight of N-methylpyrrolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "NMP"). To the obtained solution, 29.2 parts by weight of 1,3-bis(3-aminophenoxy)benzene (manufactured by Mitsui Fine Chemicals Co., Ltd., "APB-N") diluted with 100 parts by weight of N-methylpyrrolidone was added. The obtained solution was stirred at 25° C. for 2 hours and reacted to obtain an amide acid oligomer solution. After removing N-methylpyrrolidone under reduced pressure from the obtained amide acid oligomer solution, it was heated at 300°C for 2 hours to obtain amide oligomer composition A (imidization rate 95%) ). According to ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer composition A contains: an imine oligomer having a structure represented by the above formula (5-1) or (5-3) Polymer (A is 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride residue, B is 1,3-bis(3-aminophenoxy) benzene residues). In addition, the number average molecular weight of the imide oligomer composition A was 2,100.

(Synthesis example 2 (preparation of imide oligomer composition B)) 43.6 parts by weight of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in N-methylpyrrolidone (Fujifilm Wako Pure Chemical Industries, Ltd. manufacture, "NMP") 400 parts by weight. To the obtained solution, 34.4 parts by weight of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was added, stirred at 25°C for 2 hours, and reacted to obtain amide Acid oligomer solution. After removing N-methylpyrrolidone under reduced pressure from the obtained amide acid oligomer solution, it was heated at 300° C. for 2 hours to obtain amide oligomer composition B (imidization rate 95%) ). According to ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer composition B contains: an imide oligomer having a structure represented by the above formula (6-1) (A is 4 ,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride residue, R is a hydrogen atom). In addition, the number average molecular weight of the imide oligomer composition B was 700.

(Production of Synthesis Example 3 (Polyimide Resin Solution A)) 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a reaction vessel equipped with a stirrer, a water separator, and a nitrogen gas introduction tube. 54.6 parts by weight and 200 parts by weight of cyclohexanone were dissolved. To the obtained solution, a mixed solution of 56.1 parts by weight of Priamine 1074 (manufactured by Croda Co., Ltd.) and 55.0 parts by weight of cyclohexanone, a dimer diamine, was added dropwise, followed by imidization reaction at 150° C. for 8 hours to obtain a polymer. Imide resin solution A. Furthermore, the solid content concentration of the obtained polyimide resin solution A was 30% by weight, and the number average molecular weight of the polyimide resin was 25,000.

(Examples 1 to 6, Comparative Examples 1 and 2) According to the blending ratio described in Table 1, each material was stirred and mixed, and each curable resin composition of Examples 1-6 and Comparative Examples 1 and 2 was produced.

＜Evaluation＞ The following evaluation was performed about each curable resin composition obtained by the Example and the comparative example. The results are shown in Table 1.

(Gel Fraction) Each curable resin composition obtained in the Examples and Comparative Examples was coated on the base PET film so as to have a thickness of about 20 μm, and was dried on the base PET film. A curable resin composition film was produced. A semi-cured film was obtained by irradiating ultraviolet rays of 2000 mJ/cm ² to each of the obtained curable resin composition films. The obtained semi-cured film was soaked in tetrahydrofuran, stirred for 24 hours or more, filtered through a mesh, and then dried at 110° C. for 1 hour, and the gel fraction was derived from the above formula. Moreover, hardened|cured material was produced by heating the obtained semi-cured film at 190 degreeC for 1 hour. The obtained cured product was soaked in tetrahydrofuran, stirred for 24 hours or more, filtered through a mesh, and then dried at 110° C. for 1 hour, and the gel fraction was derived from the above formula.

(5% weight reduction temperature) The respective curable resin compositions obtained in the examples and comparative examples were coated on the base PET film so as to have a thickness of about 20 μm, and were dried to form the base PET film. A curable resin composition film was produced on the above. Each obtained curable resin composition film was irradiated with ultraviolet rays of 2000 mJ/cm ² , and then heated at 190° C. for 1 hour to prepare a cured product. The obtained cured product was measured for 5% weight loss at a temperature range of 30°C to 500°C and a temperature rise condition of 10°C/min using a thermogravimetric measuring device (manufactured by Hitachi High-Tech Science, "TG/DTA6200"). temperature.

(Buildability (Bleed-Out Prevention and Embedding)) Each of the curable resin compositions obtained in the Examples and Comparative Examples was coated on a polyimide film with a thickness of 25 μm ( Made by Toray DuPont, "Kapton 100H"), a polyimide film with a curable resin composition was produced. After opening a hole of 5 mmϕ in the obtained curable resin composition film, a flexible copper-clad laminate with a copper wiring pattern of L/S=100 μm/100 μm was temporarily attached by a laminating machine set at 80°C. . UV rays of 2000 mJ/cm ² were irradiated from the side of the polyimide film to semi-harden the curable resin composition around the opening. Then, thermosetting was performed for 1 hour under the conditions of 160° C. and 1.0 MPa using a hot press. The resin length that bleeds out to the inside of the pores was measured as the bleed amount. The case of no exudation (the amount of exudation was less than 0.2 mm) was evaluated as "○", the case of the exudation amount of 0.2 mm or more and 0.5 mm or less was evaluated as "△", and the case of the exudation amount exceeding 0.5 mm was evaluated as "×" ” to evaluate the anti-bleeding property. In addition, after the cross-section of the sample after hot pressing was polished, it was observed with an optical microscope, and the case where no void was recognized between the copper wiring patterns was evaluated as "○", and the case where a void was recognized was evaluated as "x" to evaluate the embeddedness. Buried.

（四國化成工業公司製造，「2MZ-A」） 0.30 0.30 0.30 0.30 0.30 0.32 0.30 0.10 流動調整劑 疏水性發煙二氧化矽 （德山公司製造，「MT-10」，平均粒徑15 nm） 2.01 2.01 2.01 1.76 2.01 2.10 2.01 1.00 溶劑 乙酸乙酯與1,4-二

烷之混合溶劑 （重量比1：1） 43.1 43.1 43.1 37.6 43.1 44.9 42.6 31.2 評價 照射2000 mJ/cm ²之紫外線後之凝膠分率 （%） 11 4 20 18 8 10 0 10 照射2000 mJ/cm ²之紫外線後且於190℃加熱1小時後之凝膠分率 （%） 超過95 超過95 超過95 超過95 超過95 超過95 超過95 超過95 硬化物之5%重量減少溫度 （℃） 375 352 355 385 370 380 376 320 構裝性 防滲出性 ○ △ ○ ○ ○ ○ × ○ 嵌埋性 ○ ○ ○ ○ ○ ○ ○ ○ [產業上之可利用性] [Table 1] Example Comparative example 1 2 3 4 5 6 1 2 Composition (parts by weight) hardening resin Thermosetting resin Bisphenol F-type epoxy resin (manufactured by DIC Corporation, "EPICLON EXA-830CRP", liquid at 25°C) 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Photothermosetting resin Partially acrylic modified cresol novolak epoxy resin (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "EA-7310", solid at 25°C) 10.0 - - - 5.0 10.0 10.0 10.0 Partially acrylic modified bisphenol A epoxy resin (manufactured by DAICEL-ALLNEX, "UVACURE1561", liquid at 25°C) - 10.0 - - - - - - photocurable resin Trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "A-TMPT", liquid at 25°C) - - 10.0 - 5.0 - - - Dipiverythritol hexaacrylate (manufactured by Kyōeisha Chemical Co., Ltd., "Light acrylate DPE-6A", liquid at 25°C) - - - 5.0 - - - - photopolymerization initiator α-Hydroxyketone compound (manufactured by IGM Resins, "Esacure ONE") 0.5 0.5 0.5 0.25 0.5 0.5 - 0.5 Thermal hardener Imide oligomer composition A (acid anhydride groups at both ends) 20.3 20.3 20.3 20.3 20.3 - 20.3 - Imide oligomer composition B (phenolic hydroxyl groups at both ends) - - - - - 22.0 - - 1,2,3,6-Tetrahydrophthalic anhydride (manufactured by Nippon Rika Corporation, "RIKACID TH") - - - - - - - 9.6 polymer compound Polyimide resin solution A (solid content concentration 30% by weight, number average molecular weight 25,000) 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 hardening accelerator 2,4-Diamino-6-(2'-methylimidazolyl-(1'))-ethylsymmetric tris

(manufactured by Shikoku Chemical Industry Co., Ltd., "2MZ-A") 0.30 0.30 0.30 0.30 0.30 0.32 0.30 0.10 flow conditioner Hydrophobic fumed silica (manufactured by Tokuyama Corporation, "MT-10", average particle size 15 nm) 2.01 2.01 2.01 1.76 2.01 2.10 2.01 1.00 solvent Ethyl acetate with 1,4-di

Mixed solvent of alkane (weight ratio 1:1) 43.1 43.1 43.1 37.6 43.1 44.9 42.6 31.2 Evaluation Gel fraction (%) after irradiating 2000 mJ/ ^cm2 of UV light 11 4 20 18 8 10 0 10 Gel fraction (%) after being irradiated with 2000 mJ/cm ² of ultraviolet rays and heated at 190°C for 1 hour over 95 over 95 over 95 over 95 over 95 over 95 over 95 over 95 5% weight reduction temperature of hardened product (℃) 375 352 355 385 370 380 376 320 Constructability Exudation resistance ○ △ ○ ○ ○ ○ × ○ embeddedness ○ ○ ○ ○ ○ ○ ○ ○ [Industrial Availability]

According to the present invention, it is possible to provide a curable resin composition which is excellent in flow properties before curing, excellent in anti-bleeding properties after semi-curing, and excellent in heat resistance after main curing. Moreover, according to this invention, the hardened|cured material of this curable resin composition, and the adhesive agent and adhesive film which use this curable resin composition can be provided.

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Claims (9)

A curable resin composition, characterized in that it contains a curable resin, a photopolymerization initiator, and a thermosetting agent, and The above-mentioned thermosetting agent contains an imide oligomer. The curable resin composition according to claim 1, wherein the curable resin contains a radically polymerizable compound without an epoxy group, an epoxy compound without a radically polymerizable group, and/or an epoxy group Compounds with radically polymerizable groups. The curable resin composition according to claim 2, wherein the curable resin contains a compound having an epoxy group and a (meth)acryloyl group. The curable resin composition according to claim 1, 2 or 3, wherein the above-mentioned imide oligomer has an acid anhydride group or a phenolic hydroxyl group at the end of the main chain. As claimed in claim 1, 2, 3 or 4, the curable resin composition has a gel fraction of 5% or more and less than 90% after being irradiated with ultraviolet rays of 2000 mJ/ ^cm2 , and is heated at 190°C for 1 hour. The gel fraction is above 90%. According to the curable resin composition of claim 1, 2, 3, 4 or 5, the 5% weight reduction temperature of the cured product obtained by heating at 190°C for 1 hour is 350°C or more. A hardened product, which is a hardened product of the curable resin composition of claim 1, 2, 3, 4, 5 or 6. An adhesive prepared by using the curable resin composition of claim 1, 2, 3, 4, 5 or 6. An adhesive film produced by using the adhesive of claim 8.