Sclerotic resin composition, adhesive, and adhesive film

Abstract

A purpose of the present invention is to provide a curable resin composition having excellent adhesive properties, long term heat resistance, and reflow resistance. Another purpose of the present invention is to provide an adhesive agent and an adhesive film which use said curable resin composition. The curable resin composition according to the present invention contains a curable resin and a cyanurate.

Description

Technical Field

[0001] The present invention relates to a curable resin composition excellent in adhesiveness, long-term heat resistance, and reflow resistance. The present invention also relates to an adhesive and an adhesive film using the curable resin composition.

Background Art

[0002] In recent years, the applications of flexible printed circuit boards (FPCs) have expanded to in-vehicle applications, and adhesives used for FPCs and coverlay films for protecting FPCs are required to have long-term heat resistance. Such adhesives use curable resin compositions containing curable resins such as epoxy resins that have low shrinkage and are excellent in adhesiveness, insulation, and chemical resistance. In particular, curable resin compositions that give good results in solder reflow tests related to short-term heat resistance and thermal cycle tests related to repeated heat resistance are widely used. As curable resin compositions excellent in heat resistance, for example, Patent Documents 1 and 2 disclose curable resin compositions containing an epoxy resin and an imide oligomer as a curing agent.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a curable resin composition excellent in adhesiveness, long-term heat resistance, and reflow resistance. Another object of the present invention is to provide an adhesive and an adhesive film using the curable resin composition.

Means for Solving the Problems

[0005] The present invention is a curable resin composition containing a curable resin and a cyanurate. The present invention will be described in detail below.

[0006] In order to improve the adhesiveness of a curable resin composition used as a heat-resistant adhesive, the inventors considered blending an adhesion-imparting agent such as a silane coupling agent. However, although the obtained curable resin composition was excellent in initial adhesiveness, bubbles sometimes occurred after reflow, or sufficient adhesive strength after reflow could not be obtained. As a result of intensive studies, the inventors have found that by blending a cyanurate into a curable resin composition having excellent heat resistance, a curable resin composition excellent not only in initial adhesiveness but also in reflow resistance can be obtained, and the present invention has been completed.

[0007] The curable resin composition of the present invention contains a curable resin. Examples of the curable resin include epoxy resins, acrylic resins, phenolic resins, cyanate resins, isocyanate resins, maleimide resins, benzoxazine resins, silicone resins, fluororesins, and the like. Among them, it is preferable that the curable resin contains an epoxy resin. These curable resins may be used alone or in combination of two or more. In addition, in order to improve the tackiness at room temperature and the processability in the case of film processing or the like, the curable resin is preferably liquid or semi-solid at 25°C, more preferably liquid at 25°C, and still more preferably contains a liquid epoxy resin at 25°C.

[0008] Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallylbisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide-added bisphenol A type epoxy resin, triazine type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, naphthylene ether type epoxy resin, phenol novolac type epoxy resin, ortho-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthalene phenol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified type epoxy resin, glycidyl ester compound, and the like. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, resorcinol type epoxy resin, and triazine type epoxy resin are preferred because they have low viscosity and make it easier to adjust the processability of the resulting curable resin composition.

[0009] The curable resin composition of the present invention contains cyanurate. By containing the above cyanurate, the curable resin composition of the present invention is excellent in adhesiveness and reflow resistance.

[0010] As the above cyanurate, zinc cyanurate is preferred.

[0011] The above cyanurate is preferably in powder form. The preferable lower limit of the average particle diameter of the above cyanurate is 0.1 μm, and the preferable upper limit is 10 μm. When the average particle diameter of the above cyanurate is within this range, the dispersibility in the curable resin composition is excellent without deteriorating the coatability or the like, and the effects of improving the adhesiveness and the reflow resistance are excellent. The more preferable lower limit of the average particle diameter of the above cyanurate is 0.5 μm, and the more preferable upper limit is 5 μm. Incidentally, the average particle diameter of the above cyanurate can be measured by dispersing the above cyanurate in a solvent (such as water or an organic solvent) using a particle size distribution measuring device. Examples of the above particle size distribution measuring device include NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

[0012] The preferable lower limit of the content of the above cyanurate in a total of 100 parts by weight of the above curable resin and a curing agent (and a curing accelerator when a curing accelerator described later is contained) described later is 0.5 part by weight, and the preferable upper limit is 40 parts by weight. When the content of the above cyanurate is 0.5 part by weight or more, the cured product of the obtained curable resin composition is excellent in adhesiveness and reflow resistance. When the content of the above cyanurate is 40 parts by weight or less, the obtained curable resin composition is excellent in coatability, reflow resistance, etc. The more preferable lower limit of the content of the above cyanurate is 1 part by weight, the more preferable upper limit is 35 parts by weight, the further more preferable upper limit is 30 parts by weight, and the particularly preferable upper limit is 25 parts by weight.

[0013] The curable resin composition of the present invention preferably further contains a curing agent. Examples of the above curing agent include an imide oligomer having an imide skeleton in the main chain and a crosslinkable functional group at the terminal, an acid anhydride-based curing agent, a phenol-based curing agent, a thiol-based curing agent, an amine-based curing agent, a cyanate-based curing agent, an active ester-based curing agent, and the like. Among them, from the viewpoints of the adhesiveness and the long-term heat resistance of the cured product of the obtained curable resin composition, the above curing agent preferably contains the above imide oligomer.

[0014] The above imide oligomer preferably has a structure containing the above crosslinkable functional group and 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). By having 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 above imide oligomer becomes excellent in reactivity and compatibility with curable resins such as epoxy resins.

[0015]

Chemical formula

[0016] In formula (1-1) and formula (1-2), A is an acid dianhydride residue, B is an aliphatic diamine residue or an aromatic diamine residue, and in formula (1-2), Ar is an optionally substituted divalent aromatic group.

[0017]

Chemical formula

[0018] 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 optionally substituted divalent aromatic group.

[0019] The above acid dianhydride residue is preferably a tetravalent group represented by the following formula (3-1) or the following formula (3-2).

[0020]

Chemical formula

[0021] In Formula (3-1) and Formula (3-2), * represents a bonding position. In Formula (3-1), Z represents a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position. The hydrogen atoms of the aromatic ring in Formula (3-1) and Formula (3-2) may be substituted.

[0022] When Z in the above Formula (3-1) is a linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position, these groups may be substituted. Examples of the substituent when the linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or the divalent group having an aromatic ring which may have an oxygen atom at the bonding position is substituted include a halogen atom, a linear or branched 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.

[0023] Examples of the acid dianhydride from which the above acid dianhydride residue is derived include the acid dianhydride represented by Formula (9) described later and the like.

[0024] When B in the above Formula (1-1), the above Formula (1-2), the above Formula (2-1), or the above Formula (2-2) is the above aliphatic diamine residue and / or 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. When the carbon number of the aliphatic diamine residue and the aliphatic triamine residue is 4 or more, the resulting curable resin composition is excellent in flexibility and processability before curing and dielectric properties after curing. The more preferable lower limit of the carbon number of the aliphatic diamine residue and the aliphatic triamine residue is 5, and the further preferable lower limit is 6. In addition, although there is no particular preferable upper limit for the carbon number of the aliphatic diamine residue and the aliphatic triamine residue, the substantial upper limit is 60.

[0025] Examples of the aliphatic diamine from which the aliphatic diamine residue is derived include aliphatic diamines derived from dimer acid, linear or branched aliphatic diamines, aliphatic ether diamines, aliphatic alicyclic diamines, and the like. Examples of the aliphatic diamine derived from the dimer acid include dimer diamine, hydrogenated dimer diamine, and the like. Examples of the linear or branched aliphatic diamine include 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-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, 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, isophoronediamine, and the like. Among them, the aliphatic diamine residue is preferably an aliphatic diamine residue derived from the dimer acid.

[0026] Examples of the aliphatic triamine from which the aliphatic triamine residue is derived include aliphatic triamines derived from trimer acid, linear or branched aliphatic triamines, aliphatic ether triamines, aliphatic alicyclic triamines, and the like. 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, 2,2'-bis(methylamino)-N-methyldiethylamine, and the like. Among them, the aliphatic triamine residue is preferably an aliphatic triamine residue derived from the trimer acid.

[0027] Moreover, a mixture of the dimer diamine and the trimer triamine can also be used as the aliphatic diamine and / or the aliphatic triamine.

[0028] Examples of commercially available aliphatic diamines and / or aliphatic triamines derived from the dimer acid and / or the trimer acid include aliphatic diamines and / or aliphatic triamines manufactured by BASF, aliphatic diamines and / or aliphatic triamines manufactured by Croda, and the like. Examples of the aliphatic diamines and / or aliphatic triamines manufactured by BASF include Versamine 551, Versamine 552, and the like. Examples of the aliphatic diamines and / or aliphatic triamines manufactured by Croda include Priamine 1071, Priamine 1073, Priamine 1074, Priamine 1075, and the like.

[0029] When B in the above formula (1-1), the above formula (1-2), the above formula (2-1), or the above formula (2-2) is the aromatic diamine residue, the aromatic diamine residue is preferably a divalent group represented by the following formula (4-1) or the following formula (4-2).

[0030]

Chemical formula

[0031] In Formula (4-1) and Formula (4-2), * represents a bonding position. In Formula (4-1), Y represents a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position. The hydrogen atoms of the aromatic ring in Formula (4-1) and Formula (4-2) may be substituted.

[0032] When Y in the above Formula (4-1) is a linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position, these groups may be substituted. Examples of the substituent when the linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or the divalent group having an aromatic ring which may have an oxygen atom at the bonding position is substituted include a halogen atom, a linear or branched 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.

[0033] Examples of the aromatic diamine from which the above aromatic diamine residue is derived include those when the diamine represented by Formula (10) described later is an aromatic diamine.

[0034] In addition, when the above imide oligomer has a siloxane skeleton in its structure, it may lower the glass transition temperature after curing or may contaminate the adherend and cause poor adhesion. Therefore, it is preferably an imide oligomer having no siloxane skeleton in its structure.

[0035] The number average molecular weight of the above imide oligomer is preferably 5000 or less. When the number average molecular weight of the above imide oligomer is 5000 or less, the cured product of the resulting curable resin composition will be more excellent in long-term heat resistance. A more preferable upper limit of the number average molecular weight of the above imide oligomer is 4000, and a further preferable upper limit is 3000. In particular, when the imide oligomer has the structure represented by the above formula (1-1) or the above formula (2-1), the number average molecular weight is preferably 900 or more and 5000 or less, and when it has the structure represented by the above formula (1-2) or the above formula (2-2), the number average molecular weight is preferably 550 or more and 4000 or less. When the imide oligomer has the structure represented by the above formula (1-1) or the above formula (2-1), the more preferable lower limit of the number average molecular weight is 950, and the even more preferable lower limit is 1000. When the imide oligomer has the structure represented by the above formula (1-2) or the above formula (2-2), the more preferable lower limit of the number average molecular weight is 580, and the even more preferable lower limit is 600. In this specification, the above "number average molecular weight" is a value obtained by measurement using tetrahydrofuran as a solvent by gel permeation chromatography (GPC) and converted to polystyrene equivalent. Examples of the column used for measuring the number average molecular weight in terms of polystyrene by GPC include JAIGEL-2H-A (manufactured by Nippon Analytical Industry Co., Ltd.).

[0036] Specifically, the above imide oligomer is preferably an imide oligomer represented by the following formula (5-1), formula (5-2), formula (5-3), formula (5-4), or formula (5-5), or an imide oligomer represented by the following formula (6-1), formula (6-2), formula (6-3), formula (6-4), or formula (6-5).

[0037]

Chemical formula

[0038] In formulas (5-1) to (5-5), A is the above acid dianhydride residue. In formulas (5-1) to (5-5), A may be the same or different from each other. In formulas (5-1) to (5-5), B is the above aliphatic diamine residue, aromatic diamine residue, aliphatic triamine residue, or aromatic triamine residue. In formulas (5-3) and (5-4), B may be the same or different from each other. In formula (5-2), X is a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may be substituted. In formula (5-4), W is a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may be substituted. In formulas (5-3) and (5-4), n is the number of repetitions.

[0039]

Chemical formula

[0040] In formulas (6-1) to (6-5), A is the above acid dianhydride residue. In formulas (6-1) to (6-5), A may be the same or different from each other. In formulas (6-1) to (6-5), R is a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may be substituted. In formulas (6-1), (6-3), and (6-5), R may be the same or different from each other. In formulas (6-2) and (6-4), W is a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may be substituted. In formulas (6-1) to (6-5), B is the above aliphatic diamine residue, aromatic diamine residue, aliphatic triamine residue, or aromatic triamine residue. In formulas (6-3) and (6-4), B may be the same or different from each other.

[0041] In the above formulas (5-1) to (5-5) and (6-1) to (6-5), A is preferably a tetravalent group represented by the following formula (7-1) or the following formula (7-2).

[0042]

Chemical formula

[0043] In formulas (7-1) and (7-2), * represents a bonding position. In formula (7-1), Z represents a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position. The hydrogen atoms of the aromatic ring in formulas (7-1) and (7-2) may be substituted.

[0044] In the above formulas (5-1) to (5-5) and formulas (6-1) to (6-5), B is preferably a divalent group represented by the following formula (8-1) or the following formula (8-2).

[0045]

Chemical formula

[0046] In formulas (8-1) and (8-2), * represents a bonding position. In formula (8-1), Y represents a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or a divalent group having an aromatic ring which may have an oxygen atom at the bonding position. The hydrogen atoms of the aromatic ring in formulas (8-1) and (8-2) may be substituted.

[0047] As a method for producing an imide oligomer having the structure represented by the above formula (1-1), for example, a method of reacting an acid dianhydride represented by the following formula (9) with a diamine represented by the following formula (10) 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 the structure represented by the above formula (2-1) can be produced.

[0048]

Chemical formula

[0049] In formula (9), A is the same tetravalent group as A in the above formula (1-1).

[0050]

Chemical formula

[0051] In formula (10), B is the same divalent group as B in the above formula (1-1), and R 1 ~R 4 are each independently a hydrogen atom or a monovalent hydrocarbon group.

[0052] Specific examples of 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. First, the diamine represented by the above formula (10) is previously dissolved in a solvent (for example, N-methylpyrrolidone or the like) in which the amic acid oligomer obtained by the reaction is soluble, and the acid dianhydride represented by the above formula (9) is added to the obtained solution and reacted to obtain an amic acid oligomer solution. Next, methods such as removing the solvent by heating or reducing the pressure, and further heating at about 200 °C or higher for 1 hour or more to react the amic acid oligomer can be mentioned. By adjusting the molar ratio of the acid dianhydride represented by the above formula (9) to the diamine represented by the above formula (10) and the imidization conditions, an imide oligomer having a desired number average molecular weight and having the structure represented by the above formula (1-1) at both ends can be obtained. Further, by replacing a part of the acid dianhydride represented by the above formula (9) with the acid anhydride represented by the following formula (11), an imide oligomer having a desired number average molecular weight, having the structure represented by the above formula (1-1) at one end, and having the structure derived from the acid anhydride represented by the following formula (11) at the other end can be obtained. 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 replacing part of the diamine represented by the above formula (10) with the monoamine represented by the following formula (12), an imide oligomer having a desired number average molecular weight, having the structure represented by the above formula (1-1) at one end and having a structure derived from the 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 simultaneously or separately.

[0053]

Chemical formula

[0054] In formula (11), Ar is a divalent aromatic group which may be substituted.

[0055]

Chemical formula

[0056] 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.

[0057] As a method for producing the imide oligomer having the structure represented by the above formula (1-2), for example, a method of 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 following formula (13) can be mentioned. Further, by using an aliphatic triamine or an aromatic triamine instead of the diamine represented by the above formula (10), an imide oligomer having the structure represented by the above formula (2-2) can be produced.

[0058]

Chemical formula

[0059] In formula (13), Ar is an optionally substituted divalent aromatic group, and R 7 and R 8 are each independently a hydrogen atom or a monovalent hydrocarbon group.

[0060] 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. First, the phenolic hydroxyl group-containing monoamine represented by the above formula (13) and the diamine represented by the above formula (10) are previously dissolved in a solvent (for example, N-methylpyrrolidone, etc.) in which the amic acid oligomer obtained by the reaction is soluble, and the acid dianhydride represented by the above formula (9) is added to the obtained solution and reacted to obtain an amic acid oligomer solution. Next, the solvent is removed by heating, reduced pressure, etc., and further, heating at about 200 °C or higher for 1 hour or more to react the amic acid oligomer, etc. can be mentioned. By adjusting 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 the imidization conditions, an imide oligomer having a desired number average molecular weight and having the structure represented by the above formula (1-2) at both ends can be obtained. Also, by replacing a part of the phenolic hydroxyl group-containing monoamine represented by the above formula (13) with the monoamine represented by the above formula (12), an imide oligomer having a desired number average molecular weight, having the structure represented by the above formula (1-2) at one end, and having the structure derived from the monoamine represented by the above formula (12) at the other end can be obtained. 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.

[0061] Examples of the acid dianhydride represented by the above formula (9) include pyromellitic dianhydride, 3,3'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, the acid dianhydride of 4,4'-bis(2,3-dicarboxylphenoxy)diphenyl ether, p-phenylenebis(trimellitate anhydride), 2,3,3',4'-biphenyltetracarboxylic dianhydride, and the like. Among them, since they are particularly excellent in solubility and heat resistance, the acid dianhydride used as a raw material for the above imide oligomer is preferably an aromatic acid dianhydride having a melting point of 240°C or lower, more preferably an aromatic acid dianhydride having a melting point of 220°C or lower, still more preferably an aromatic acid dianhydride having a melting point of 200°C or lower. 3,4'-oxydiphthalic dianhydride (melting point 180°C) and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (melting point 190°C) are particularly preferred. In this specification, the above "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 EXTEAR DSC6100 (manufactured by SII NanoTechnology Inc.).

[0062] Among the diamines represented by the above formula (10), examples of the aromatic diamine include 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'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 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, bisaminophenylfluorene, bistoluidinefluorene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxyphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, and the like.Among them, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 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 are preferred because of their excellent availability. Further, 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 are more preferred because of their excellent solubility and heat resistance.

[0063] Examples of the acid anhydride represented by the above formula (11) include phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 1,2-naphthalic anhydride, 2,3-naphthalic anhydride, 1,8-naphthalic anhydride, 2,3-anthracenedicarboxylic anhydride, 4-tert-butylphthalic anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-fluorophthalic anhydride, 4-chlorophthalic anhydride, 4-bromophthalic anhydride, 3,4-dichlorophthalic anhydride, and the like.

[0064] Examples of the monoamine represented by the above formula (12) include aniline, o-toluidine, m-toluidine, p-toluidine, 2,4-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, 1-aminopyrene, 3-chloroaniline, o-anisidine, m-anisidine, p-anisidine, 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, N,N-dimethyl-1,4-phenylenediamine, and the like.

[0065] 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-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. Among them, 4-amino-o-cresol and 5-amino-o-cresol are preferred because of their excellent availability and storage stability and the high glass transition temperature obtained after curing.

[0066] When the imide oligomer is produced by the above-described production method, the imide oligomer is obtained as one contained in a mixture (imide oligomer composition) of a plurality of types of imide oligomers having the structure represented by the above formula (1-1) or a plurality of types of imide oligomers having the structure represented by the above formula (1-2) and each raw material. When an aliphatic triamine or an aromatic triamine is used instead of the diamine represented by the above formula (10), the imide oligomer is obtained as one contained in a mixture (imide oligomer composition) of a plurality of types of imide oligomers having the structure represented by the above formula (2-1) or a plurality of types of imide oligomers having the structure represented by the above formula (2-2) and each raw material. Since the imide oligomer composition has an imidization rate of 70% or more, a cured product excellent in mechanical strength at high temperature and long-term heat resistance can be obtained when used as a curing agent. The preferable lower limit of the imidization rate of the imide oligomer composition is 75%, and the more preferable lower limit is 80%. Also, there is no particular preferable upper limit for the imidization rate of the imide oligomer composition, but the substantial upper limit is 98%. Note that the above "imidization rate" is measured by the total reflection measurement method (ATR method) using a Fourier transform infrared spectrophotometer (FT-IR), and is derived from the following formula from the peak absorbance area near 1660 cm -1 near the carbonyl group of the amic acid. Examples of the Fourier transform infrared spectrophotometer include UMA600 (manufactured by Agilent Technologies). In the following formula, the "peak absorbance area of the amic acid oligomer" is the absorbance area of the amic acid oligomer obtained by reacting an acid dianhydride with a diamine or a phenolic hydroxyl group-containing monoamine and then removing the solvent by evaporation or the like without performing an imidization step. Imidization rate (%) = 100×(1 - (peak absorbance area after imidization) / (peak absorbance area of amic acid oligomer))

[0067] From the viewpoint of solubility in the curable resin composition, the imide oligomer composition preferably dissolves 3 g or more in 10 g of tetrahydrofuran at 25°C.

[0068] In the total of 100 parts by weight of the above-mentioned curable resin and the above-mentioned curing agent (when containing a curing accelerator described later, further including a curing accelerator), the preferable lower limit of the content of the above-mentioned imide oligomer is 20 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the above-mentioned imide oligomer is within this range, the resulting curable resin composition becomes excellent in flexibility and processability before curing, and heat resistance after curing. The more preferable lower limit of the content of the above-mentioned imide oligomer is 25 parts by weight, and the more preferable upper limit is 75 parts by weight. In addition, when the imide oligomer according to the present invention is included in the above-mentioned imide oligomer composition, the content of the above-mentioned imide oligomer means the content of the imide oligomer composition (when further using other imide oligomers in combination, the total of the imide oligomer composition and other imide oligomers).

[0069] The curable resin composition of the present invention preferably contains a curing accelerator. By containing the above-mentioned curing accelerator, the curing time can be shortened and the productivity can be improved.

[0070] Examples of the above-mentioned curing accelerator include imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphine-based curing accelerators, phosphorus-based curing accelerators, photo base generators, sulfonium salt-based curing accelerators, and the like. Among them, imidazole-based curing accelerators are preferable because of their excellent storage stability.

[0071] The content of the above-mentioned curing accelerator is preferably 0.01 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight in total of the above-mentioned curable resin, the above-mentioned curing agent, and the above-mentioned curing accelerator. When the content of the above-mentioned curing accelerator is within this range, the effect of shortening the curing time is excellent while maintaining excellent adhesiveness and the like. The more preferable lower limit of the content of the above-mentioned curing accelerator is 0.05 part by weight, and the more preferable upper limit is 5 parts by weight.

[0072] The curable resin composition of the present invention may contain an inorganic filler as long as it does not inhibit the object of the present invention.

[0073] The above inorganic filler is preferably at least one of silica and barium sulfate. By containing at least one of silica and barium sulfate as the above inorganic filler, the curable resin composition of the present invention becomes excellent in reflow resistance, plating resistance, and processability.

[0074] Examples of other inorganic fillers other than the above silica and barium sulfate include alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, carbon fiber, inorganic ion exchanger, and the like.

[0075] As the above inorganic filler, those having an average particle diameter of 50 nm or more and less than 4 μm are preferably used.

[0076] The content of the above inorganic filler preferably has an upper limit of 200 parts by weight with respect to a total of 100 parts by weight of the above curable resin and the above curing agent (and further the above curing accelerator when the above curing accelerator is contained). When the content of the above inorganic filler is within this range, the cured product of the resulting curable resin composition becomes excellent in reflow resistance and plating resistance while maintaining excellent tackiness and the like. A more preferable upper limit of the content of the above inorganic filler is 150 parts by weight.

[0077] The curable resin composition of the present invention preferably contains a flow regulator for the purpose of improving the coatability and shape retention on the adherend in a short time. Examples of the above flow regulator include fumed silica such as Aerosil and layered silicate. Further, as the above flow regulator, those having an average particle diameter of less than 100 nm are preferably used.

[0078] The content of the above flow regulator is preferably at least 0.1 part by weight and preferably at most 50 parts by weight with respect to a total of 100 parts by weight of the above curable resin and the above curing agent (and further the above curing accelerator when the above curing accelerator is contained). When the content of the above flow regulator is within this range, effects such as improving the coatability to the adherend in a short time and the shape retention are excellent. A more preferable lower limit of the content of the above flow regulator is 0.5 part by weight, and a more preferable upper limit is 30 parts by weight.

[0079] The curable resin composition of the present invention may contain an organic filler for the purpose of stress relaxation, toughness imparting, etc. Examples of the above organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanamine particles, and core-shell particles thereof. Among them, polyamide particles, polyamideimide particles, and polyimide particles are preferable.

[0080] The content of the above organic filler is preferably at most 300 parts by weight with respect to a total of 100 parts by weight of the above curable resin and the above curing agent (and further the above curing accelerator when the above curing accelerator is contained). When the content of the above organic filler is within this range, the obtained cured product is excellent in toughness and the like while maintaining excellent adhesiveness and the like. A more preferable upper limit of the content of the above organic filler is 200 parts by weight.

[0081] The curable resin composition of the present invention may contain a polymer compound as long as the object of the present invention is not impaired. The above polymer compound serves as a film-forming component.

[0082] The preferable lower limit of the number average molecular weight of the above polymer compound is 3,000, and the preferable upper limit is 100,000. When the number average molecular weight of the above polymer compound is within this range, the obtained curable resin composition is excellent in flexibility and processability before curing, and heat resistance after curing. A more preferable lower limit of the number average molecular weight of the above polymer compound is 5,000, and a more preferable upper limit is 80,000.

[0083] Examples of the above-mentioned polymer compound include polyimide, phenoxy resin, polyamide, polyamideimide, polymaleimide, cyanate resin, benzoxazine resin, acrylic resin, urethane resin, polyester, etc. Among them, from the viewpoint of heat resistance, polyimide, polyamide, polyamideimide, and polymaleimide are preferable, and polyimide is more preferable.

[0084] The content of the above-mentioned polymer compound is preferably at least 0.5 part by weight and preferably at most 20 parts by weight with respect to 100 parts by weight in total of the above-mentioned curable resin and the above-mentioned curing agent (and further the above-mentioned curing accelerator when the above-mentioned curing accelerator is contained). When the content of the above-mentioned polymer compound is within this range, the cured product of the obtained curable resin composition will be more excellent in heat resistance. A more preferable lower limit of the content of the above-mentioned polymer compound is 1 part by weight, and a more preferable upper limit is 10 parts by weight.

[0085] The curable resin composition of the present invention may contain a flame retardant as long as it does not inhibit the object of the present invention. Examples of the above-mentioned flame retardant include metal hydrates such as boehmite-type aluminum hydroxide, aluminum hydroxide, and magnesium hydroxide, halogen-based compounds, phosphorus-based compounds, nitrogen compounds, etc. Among them, boehmite-type aluminum hydroxide is preferable.

[0086] The content of the above-mentioned flame retardant is preferably at most 200 parts by weight with respect to 100 parts by weight in total of the above-mentioned curable resin and the above-mentioned curing agent (and further the above-mentioned curing accelerator when the above-mentioned curing accelerator is contained). When the content of the above-mentioned flame retardant is within this range, the obtained curable resin composition will be excellent in flame retardancy while maintaining excellent adhesiveness and the like. A more preferable upper limit of the content of the above-mentioned flame retardant is 150 parts by weight.

[0087] The curable resin composition may contain a solvent from the viewpoint of coatability and the like. As the above-mentioned solvent, from the viewpoints of coatability, storage stability, etc., a solvent having a boiling point of less than 200°C is preferable. Examples of the solvent having a boiling point of less than 200°C include alcohol solvents, ketone solvents, ester solvents, hydrocarbon solvents, halogen solvents, ether solvents, nitrogen-containing solvents, and the like. Examples of the alcohol solvents include methanol, ethanol, isopropyl alcohol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol, tertiary butyl alcohol, 2-ethylhexanol, and the like. Examples of the ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, diacetone alcohol, and the like. Examples of the ester solvents 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. Examples of the hydrocarbon solvents include benzene, toluene, xylene, normal hexane, isohexane, cyclohexane, methyl cyclohexane, ethyl cyclohexane, isooctane, normal decane, normal heptane, and the like. Examples of the halogen solvents include dichloromethane, chloroform, trichloroethylene, and the like. Examples of the ether solvents include diethyl ether, tetrahydrofuran, 1,4-dioxane, 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, 4-methylanisole, and the like. Examples of the nitrogen-containing solvent include acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and the like. Among them, from the viewpoints of handleability and solubility of the imide oligomer, etc., at least one selected from the group consisting of a ketone solvent having a boiling point of 60°C or higher and less than 200°C, an ester solvent having a boiling point of 60°C or higher and less than 200°C, and an ether solvent having a boiling point of 60°C or higher and less than 200°C is preferable. Examples of such solvents 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 "boiling point" means a value measured under the condition of 101 kPa, or a value converted to 101 kPa using a boiling point conversion chart or the like.

[0088] 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. When the content of the solvent is within this range, the resulting 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.

[0089] The curable resin composition of the present invention may contain a reactive diluent as long as it does not inhibit the object of the present invention. As the reactive diluent, from the viewpoint of adhesion reliability, a reactive diluent having two or more reactive functional groups in one molecule is preferable.

[0090] The curable resin composition of the present invention may further contain additives such as a coupling agent, a dispersant, a storage stabilizer, a bleeding inhibitor, a flux agent, a leveling agent, and the like.

[0091] As a method for producing the curable resin composition of the present invention, for example, a method of mixing a curable resin, a curing agent, a curing accelerator, a polymer component, etc. using a mixer can be mentioned. Examples of the above mixer include a homodisper, a universal mixer, a Banbury mixer, a kneader, etc.

[0092] The curable resin composition of the present invention preferably has an initial adhesive strength to a metal film of the cured product of 4 N / cm or more. By the initial adhesive strength to the metal film of the cured product being 4 N / cm or more, the curable resin composition of the present invention can be suitably used as a heat-resistant adhesive with a metal as an adherend. More preferably, the initial adhesive strength to the metal film of the cured product is 6 N / cm or more. Incidentally, the initial adhesive strength to the above metal film can be measured as the peel strength when a 90° peel test is performed at 25°C under the condition of a peel rate of 50 mm / min using a tensile tester for a test piece cut out to a width of 1 cm. As the above test piece, a polyimide base material is laminated on one side of a curable resin composition film having a thickness of 25 μm, and a metal foil, or a silicon base material or a ceramic base material having a metal film is laminated on the other side so that the curable resin composition surface side becomes the metal surface, and it is obtained by heating at 190°C for 1 hour. The above initial adhesive strength means a value measured within 24 hours after the production of the test piece. The curable resin composition film can be obtained by coating the curable resin composition on a base film and drying it. Examples of the above tensile tester include UCT-500 (manufactured by ORIENTEC). Moreover, examples of the metal constituting the above metal film include copper, titanium, gold, silver, aluminum, magnesium, tungsten, nickel, etc. Among them, it is more preferable that the curable resin composition of the present invention has an initial adhesive strength to both the copper film and the titanium film of the cured product of 4 N / cm or more.

[0093] The curable resin composition of the present invention preferably has an adhesive strength of 4 N / cm or more with respect to the metal film of the cured product after being stored in an environment of 40°C and 90% RH for 96 hours. By having an adhesive strength of 4 N / cm or more with respect to the metal film of the cured product after being stored in the environment of 40°C and 90% RH for 96 hours, the curable resin composition of the present invention can be suitably used as a heat-resistant adhesive even in applications that require a reflow process. More preferably, the adhesive strength of the cured product with respect to the metal film after being stored in the environment of 40°C and 90% RH for 96 hours is 6 N / cm or more. Note that the adhesive strength of the cured product with respect to the metal film after being stored in the environment of 40°C and 90% RH for 96 hours means the value measured by the same method as the above-described method for measuring the initial adhesive strength after a test piece prepared in the same manner is stored in the environment of 40°C and 90% RH for 96 hours and then allowed to cool to 25°C, and within 24 hours after the cooling. Among them, it is more preferable that the curable resin composition of the present invention has an initial adhesive strength of 4 N / cm or more with respect to both the copper film and the titanium film of the cured product after being stored in an environment of 40°C and 90% RH for 96 hours.

[0094] The curable resin composition of the present invention can be used in a wide range of applications, and is particularly preferably used in electronic material applications that require high long-term heat resistance. For example, it can be used as a die attach agent in applications such as aerospace and in-vehicle electric control unit applications, and power device applications using SiC and GaN. Also, for example, it can be used as an adhesive for printed wiring boards, an adhesive for cover layers of flexible printed circuit boards, copper-clad laminates, adhesives for semiconductor bonding, interlayer insulating materials, prepregs, encapsulants for LEDs, adhesives for structural materials, adhesives for power overlay packages, and the like. The adhesive using the curable resin composition of the present invention is also one of the present inventions. After coating the adhesive of the present invention on a base film and drying it, an adhesive film can be obtained on the base film by a method such as drying. The adhesive film using the adhesive of the present invention is also one of the present inventions.

Effects of the Invention

[0095] According to the present invention, a curable resin composition excellent in adhesiveness, long-term heat resistance, and reflow resistance can be provided. Further, according to the present invention, an adhesive and an adhesive film using the curable resin composition can be provided.

Mode for Carrying Out the Invention

[0096] Examples are shown below to explain the present invention in more detail, but the present invention is not limited only to these examples.

[0097] (Preparation of Imide Oligomer Composition A) 104 parts by weight of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 300 parts by weight of N-methylpyrrolidone (manufactured by Fujifilm Wako Pure Chemical Corporation, "NMP"). A solution obtained by diluting 29.2 parts by weight of 1,3-bis(4-aminophenoxy)benzene (manufactured by Seika Corporation, "TPE-R") with 100 parts by weight of N-methylpyrrolidone was added to the obtained solution, and the mixture was stirred at 25°C for 2 hours to react to obtain an amic acid oligomer solution. After removing N-methylpyrrolidone from the obtained amic acid oligomer solution under reduced pressure, heating at 300°C for 2 hours gave an imide oligomer composition A (imidation rate 93%). In addition, 1 By 1H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer composition A contains an imide oligomer represented by the above formula (5-1) or (5-3) (A is a 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride residue, B is a 1,3-bis(4-aminophenoxy)benzene residue). Further, the number average molecular weight of the imide oligomer composition A was 2010.

[0098] (Examples 1 to 7, Comparative Examples 1 to 4) Methyl ethyl ketone was added as a solvent to each material in the blending ratio described in Table 1, and the mixture was stirred and mixed to prepare each curable resin composition of Examples 1 to 7 and Comparative Examples 1 to 4. In addition, the composition in Table 1 describes the solid content excluding the solvent.

[0099] (Adhesive strength of the cured product to the copper film) Each curable resin composition obtained in the examples and comparative examples was applied onto a polyimide substrate (manufactured by Toray DuPont Co., Ltd., "Kapton 100H", thickness 25 μm) so as to have a thickness of about 25 μm and dried to obtain an adhesive film laminate. A copper foil (manufactured by Fukuda Metal Foil & Powder Co., Ltd., "CF-T8G-UN-35", thickness 35 μm) was laminated onto the obtained adhesive film laminate such that the curable resin composition surface side became the copper film surface. The curable resin composition layer was cured by performing hot pressing on the obtained laminate under the conditions of 190°C, 3 MPa, and 1 hour, and then cut into 1 cm widths to obtain test pieces. For the test pieces within 24 hours after production, a 90° peel test was performed at a peel rate of 50 mm / min at 25°C using a tensile testing machine (manufactured by ORIENTEC Co., Ltd., "UCT-500") to measure the peel strength, and the obtained peel strength was taken as the initial adhesive strength. Further, the test pieces prepared in the same manner were stored in an environment of 40°C and 90% RH for 96 hours, then allowed to cool to 25°C, and the adhesive strength of the test pieces within 24 hours after cooling was measured in the same manner as the above initial adhesive strength. The results are shown in Table 1.

[0100] (Adhesive strength of the cured product to the titanium film) Each curable resin composition obtained in the examples and comparative examples was applied onto a polyimide substrate (manufactured by Toray DuPont, "Kapton 100H", thickness 25 μm) so that the thickness became about 20 μm, and dried to obtain an adhesive film laminate. The obtained adhesive film laminate was cut out into a width of 1 cm. The cut adhesive film laminate was laminated with a silicon substrate with a titanium film (manufactured by Aites Co., thickness of titanium film 100 Å, total thickness 525 μm) in such a form that the ends partially protruded, while heating at 80 °C using a laminator with the curable resin composition side facing the titanium film surface to obtain a laminate. The obtained laminate was heated under the conditions of 190 °C for 1 hour to cure the curable resin composition layer, and test pieces were obtained. For the test pieces within 24 hours after production, the end of the adhesive film was pulled, and a 90° peel test was performed at a peel rate of 50 mm / min at 25 °C using a tensile tester (manufactured by ORIENTEC, "UCT-500") to measure the peel strength, and the obtained peel strength was taken as the initial adhesive strength. Also, the test pieces prepared in the same manner were stored in an environment of 40 °C and 90% RH for 96 hours, then allowed to cool to 25 °C, and the adhesive strength of the test pieces within 24 hours after cooling was measured in the same manner as the above initial adhesive strength. The results are shown in Table 1.

[0101] <Evaluation> The following evaluations were performed on each curable resin composition obtained in the examples and comparative examples. The results are shown in Table 1.

[0102] (Reflow resistance) Each curable resin composition obtained in the examples and comparative examples was applied onto a polyimide film (manufactured by Toray DuPont Co., Ltd., "Kapton 100H", thickness 25 μm) so as to have a thickness of about 25 μm, and dried to obtain an adhesive film laminate. A copper foil (manufactured by Fukuda Metal Foil & Powder Co., Ltd., "CF-T8G-UN-35", thickness 35 μm) was laminated on the obtained adhesive film laminate such that the curable resin composition side faced the copper film side. The obtained laminate was subjected to hot pressing at 190 °C, 3 MPa for 1 hour to cure the curable resin composition layer, and then cut into 1 cm widths to obtain test pieces. The obtained test pieces were left in an environment of 40 °C and 90% RH for 96 hours, and then a reflow test of heating at 260 °C for 20 seconds was performed. For 10 test pieces after the reflow test, the presence or absence of bubbles was visually confirmed. When no bubbles were confirmed in all the test pieces, it was rated as "◎"; when 1 or more and less than 5 bubbles less than 200 μm were confirmed in the test pieces, it was rated as "○"; when 5 or more bubbles less than 200 μm or 1 or more bubbles of 200 μm or more were confirmed in the test pieces, it was rated as "×", and the reflow resistance was evaluated. Also, the reflow resistance of test pieces prepared using a titanium-coated silicon substrate (manufactured by AITEX Co., Ltd., titanium film thickness 100 Å, total thickness 525 μm) was evaluated in the same manner.

[0103]

Table 1

Industrial Applicability

[0104] According to the present invention, a curable resin composition excellent in adhesiveness, long-term heat resistance, and reflow resistance can be provided. Further, according to the present invention, an adhesive and an adhesive film using the curable resin composition can be provided.

Claims

1. A curable resin composition comprising a curable resin, a cyanurate, and a curing agent, wherein the curable resin includes an epoxy resin, the curing agent includes an imide oligomer, when no curing accelerator is contained, the content of the imide oligomer in a total of 100 parts by weight of the curable resin and the curing agent is 20 parts by weight or more and 80 parts by weight or less, and when a curing accelerator is contained, the content of the imide oligomer in a total of 100 parts by weight of the curable resin, the curing agent, and the curing accelerator is 20 parts by weight or more and 80 parts by weight or less. The curable resin composition is characterized by the above.

2. The curable resin composition according to Claim 1, wherein the cyanurate is zinc cyanurate.

3. The curable resin composition according to Claim 1 or 2, wherein the content of the cyanurate in a total of 100 parts by weight of the curable resin and the curing agent is 0.5 parts by weight or more and 40 parts by weight or less.

4. The curable resin composition according to Claim 1, 2, or 3, wherein the initial adhesive strength of the cured product to a metal film is 4 N / cm or more, and the adhesive strength of the cured product to the metal film after storage in an environment of 40°C and 90% RH for 96 hours is 4 N / cm or more.

5. An adhesive using the curable resin composition according to Claim 1, 2, 3, or 4.

6. An adhesive film using the adhesive according to Claim 5.

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