KR20240099151A - Curable resin compositions, cured products, adhesives, and adhesive films - Google Patents

Abstract

The purpose of the present invention is to provide a curable resin composition excellent in heat resistance, thermal conductivity, low linear expansion, and adhesiveness. Additionally, the present invention aims to provide a cured product of the curable resin composition, and an adhesive and adhesive film made using the curable resin composition. The present invention is a curable resin composition containing a curable resin and a curing agent, wherein the curing agent includes an imide oligomer having a crosslinkable functional group capable of reacting with the curable resin, and the imide oligomer has mesogenic properties. Alternatively, the curing agent is a curable resin composition containing another curing agent having mesogenic properties in addition to the imide oligomer.

Description

Curable resin compositions, cured products, adhesives, and adhesive films

The present invention relates to a curable resin composition. Additionally, the present invention relates to a cured product of the curable resin composition, and an adhesive and adhesive film made using the curable resin composition.

As a heat dissipation method for electronic components, a method of introducing a heat dissipation material between the electronic component and a metal heat transfer plate is generally used to prevent heat generated from the electronic component from accumulating in the electronic component. As such a heat insulating material, adhesives using curable resin compositions excellent in thermal conductivity and heat resistance are being studied. As a curable resin composition excellent in thermal conductivity and heat resistance, for example, Patent Document 1 discloses an adhesive composition containing an epoxy resin and a siloxane-modified polyamideimide component, and Patent Document 2 discloses two or more adhesives per molecule. A curable resin composition containing a polyimide silicone resin having a phenolic hydroxyl group, an epoxy resin, etc. is disclosed. In addition, as a curable resin composition using a non-silicon-based material, for example, Patent Document 3 discloses an epoxy resin composition containing an epoxy compound having a mesogenic structure, etc., and Patent Document 4 discloses an epoxy resin composition containing a mesogenic group in the molecule. A thermosetting resin composition containing a non-epoxy thermosetting resin containing an epoxy group and not containing an epoxy group is disclosed.

Additionally, Patent Documents 5 and 6 disclose a resin composition containing an epoxy resin and a curing agent having a mesogenic skeleton in the molecule.

Japanese Patent Publication No. 2003-193016 Japanese Patent Publication No. 2005-113059 Japanese Patent Publication No. 2019-65126 Japanese Patent Publication No. 2019-108516 Japanese Patent Publication No. 9-302070 Japanese Patent Publication No. 2019-123834

When the curable resin composition using the silicone-based material disclosed in Patent Document 1 or Patent Document 2 is used as an adhesive for electronic components, low molecular weight siloxane compounds derived from these compositions adhere to the electronic component, causing problems such as contact defects. There was a case.

In contrast, the above problems do not occur in curable resin compositions using non-silicon-based materials, but in the curable resin composition disclosed in Patent Document 3, the synthesis of the epoxy compound is complicated, workability is difficult, heat resistance is insufficient, or There was a problem. Additionally, the curable resin compositions disclosed in Patent Documents 4, 5, and 6 had problems of insufficient adhesiveness, low linear expansion, and heat resistance.

The purpose of the present invention is to provide a curable resin composition excellent in heat resistance, thermal conductivity, low linear expansion, and adhesiveness. Additionally, the present invention aims to provide a cured product of the curable resin composition, and an adhesive and adhesive film made using the curable resin composition.

This disclosure 1 is a curable resin composition containing a curable resin and a curing agent, wherein the curing agent includes an imide oligomer having a crosslinkable functional group capable of reacting with the curable resin, and the imide oligomer has mesogenic properties. Alternatively, the curing agent is a curable resin composition containing another curing agent having mesogenic properties in addition to the imide oligomer.

This disclosure 2 is the curable resin composition of this disclosure 1 in which the crosslinkable functional group is at least one of an acid anhydride group and a phenolic hydroxyl group.

This disclosure 3 is the curable resin composition of this disclosure 1 or 2 in which the molecular weight of the imide oligomer is 5000 or less.

In this disclosure 4, the curing agent is a curable resin composition of this disclosure 1, 2, or 3, which has a structure represented by the following formula (1-1), (1-2), or (1-3).

In this disclosure 5, the curable resin is the curable resin composition of this disclosure 1, 2, 3, or 4 containing an epoxy resin.

This disclosure 6 is the curable resin composition of this disclosure 1, 2, 3, 4 or 5, which further contains a heat conductive filler.

This disclosure 7 is a cured product of the curable resin composition of this disclosure 1, 2, 3, 4, 5 or 6.

This disclosure 8 is an adhesive formed using the curable resin composition of this disclosure 1, 2, 3, 4, 5 or 6.

This disclosure 9 is an adhesive film made using the adhesive of this disclosure 8.

[Formula 1]

In formula (1-1), A ¹ and A ² each independently represent an aromatic group or a condensed aromatic group, and in formula (1-2), A ³ represents an aromatic group or a condensed aromatic group, and is represented by formula (1-1) In -3), A ⁴ and A ⁵ each independently represent an aromatic group or a condensed aromatic group. In formulas (1-1) and (1-3), X is a direct bond, -CH=CH-, -C≡C-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CH=N-, -CH=NN=CH-, -N=N-, -N ⁺ (-O ^- )=N-, -CH=C(CH ₃ ) -, -CH=C(CN)-, -CH=CH-C(=O)-, -Ph-, -Ph-Ph-, -S(=O) ₂ -, -C(=O)OROC( =O)-, -OC(=O)-RC(=O)-O-, -C(=O)O-Ph-OC(=O)-, or -OC(=O)-Ph-C (=O)-O-, Ph represents an aromatic ring that is unsubstituted or has a substituent, and R represents a straight or branched alkylene chain having 1 to 10 carbon atoms. In formulas (1-1) to (1-3), * represents the binding position.

The present invention is described in detail below.

The present inventors decided to use an imide oligomer having a crosslinkable functional group capable of reacting with the curable resin as a curing agent used in the curable resin composition, and then used an imide oligomer having mesogenic properties, or , the use of another curing agent having mesogenic properties in addition to the imide oligomer was considered as the curing agent. As a result, it was found that a curable resin composition excellent in heat resistance, thermal conductivity, low linear expansion, and adhesiveness could be obtained, leading to completion of the present invention.

The curable resin composition of the present invention further contains a curing agent.

The curing agent contains an imide oligomer (hereinafter also referred to as “imide oligomer related to the present invention”) having a crosslinkable functional group that can react with the curable resin. By using the imide oligomer according to the present invention as the curing agent, the curable resin composition of the present invention becomes excellent in heat resistance, low linear expansion, and adhesiveness.

In the curable resin composition of the present invention, the imide oligomer related to the present invention has mesogenic property, or the curing agent includes another curing agent having mesogenic property in addition to the imide oligomer related to the present invention.

The curable resin composition of the present invention has excellent thermal conductivity when the imide oligomer related to the present invention has mesogenic property, or the curing agent contains another curing agent having mesogenic property in addition to the imide oligomer related to the present invention. It becomes a thing.

In addition, in this specification, the term "having mesogenicity" refers to having a structural unit that exhibits liquid crystallinity. The expression of liquid crystallinity can be confirmed by, for example, observation under orthogonal Nicols with a polarizing microscope equipped with a hot stage while raising the temperature, and whether the optical structure originating from the liquid crystalline phase is observed. Additionally, it can also be confirmed from evaluation of the phase transition temperature by differential scanning calorimetry (DSC measurement) or the like, or evaluation of the diffraction pattern by X-ray diffraction measurement (XRD measurement).

The curing agent preferably has a structure represented by the formula (1-1), (1-2), or (1-3).

In addition, the structure represented by the above formula (1-1), (1-2), or (1-3) may be a group showing mesogenicity (mesogenic group), but in the above formula (1-1), Having a structure represented by (1-2) or (1-3) does not necessarily mean that it has mesogenicity.

The crosslinkable functional group of the imide oligomer according to the present invention may vary depending on the type of curable resin used, but when an epoxy resin is used as the curable resin, it is preferably at least one of an acid anhydride group and a phenolic hydroxyl group. do.

The imide oligomer according to the present invention preferably has the crosslinkable functional group at the end of the main chain, and more preferably has it at both ends of the main chain.

The imide oligomer related to the present invention has a structure containing the above crosslinkable functional group, and has the following formula (2-1) or the following formula (2-2), or the following formula (3-1) or the following formula (3- 2) It is desirable to have the structure represented by . By having a structure represented by the following formula (2-1) or the following formula (2-2), or the following formula (3-1) or the following formula (3-2), the imide oligomer related to the present invention has the above Reactivity and compatibility with the curable resin become more excellent.

[Formula 2]

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

[Formula 3]

In formula (3-1) and formula (3-2), A is an acid dianhydride residue, B is an aliphatic triamine residue or aromatic triamine residue, and in formula (3-2), Ar is substituted It is a divalent aromatic group that may be present.

The acid dianhydride residue is preferably a tetravalent group represented by the following formula (4-1) or the following formula (4-2).

[Formula 4]

In formula (4-1), A ³ represents an aromatic group or a condensed aromatic group, and in formula (4-2), A ⁴ and A ⁵ each independently represent an aromatic group or a condensed aromatic group. In formula (4-2), -NH-, -CH=N-, -CH=NN=CH-, -N=N-, -N ⁺ (-O ^- )=N-, -CH=C(CH ₃ )-, -CH=C (CN)-, -CH=CH-C(=O)-, -Ph-, -Ph-Ph-, -S(=O) ₂ -, -C(=O)OROC(=O)-, - OC(=O)-RC(=O)-O-, -C(=O)O-Ph-OC(=O)-, or -OC(=O)-Ph-C(=O)-O - represents, Ph represents an aromatic ring that is unsubstituted or has a substituent, and R represents a straight or branched alkylene chain having 1 to 10 carbon atoms. In formulas (4-1) and (4-2), * represents the binding position.

Examples of the acid dianhydride from which the acid dianhydride residue is derived include acid dianhydride represented by formula (10) described later.

When B in the formula (2-1) is the aliphatic diamine residue, or when B in the formula (3-1) or (3-2) is the aliphatic triamine residue, the aliphatic diamine residue and the The preferred lower limit of the number of carbon atoms in 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 has superior flexibility and processability before curing and dielectric properties after curing. A more preferable lower limit of the number of carbon atoms of the aliphatic diamine residue and the aliphatic triamine residue is 5, and a more preferable lower limit is 6.

There is no particular upper limit to the preferred carbon number of the aliphatic diamine residue and the aliphatic triamine residue, but the practical upper limit is 60.

Examples of the aliphatic diamine from which the aliphatic diamine residue is derived include aliphatic diamine derived from dimer acid, straight-chain or branched-chain aliphatic diamine, aliphatic ether diamine, and aliphatic alicyclic diamine.

Examples of aliphatic diamine derived from the dimer acid include dimer diamine, hydrogenated dimer diamine, and the like.

Examples of the linear or branched chain 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- Examples include methyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, and 2,7-dimethyl-1,8-octanediamine.

Examples of the aliphatic etherdiamine include 2,2'-oxybis(ethylamine), 3,3'-oxybis(propylamine), 1,2-bis(2-aminoethoxy)ethane, etc. I can hear it.

Examples of the aliphatic alicyclic diamine include 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, cyclohexanediamine, methylcyclohexanediamine, isophoronediamine, etc. I can hear it.

Among these, the aliphatic diamine residue is preferably an aliphatic diamine residue derived from the dimer acid.

Examples of the aliphatic triamine from which the aliphatic triamine residue is derived include aliphatic triamine derived from trimeric acid, straight-chain or branched-chain aliphatic triamine, aliphatic ethertriamine, and alicyclic triamine. etc. can be mentioned.

Examples of aliphatic triamine derived from the above trimeric acid include trimertriamine, hydrogenated trimertriamine, and the like.

Examples of the linear or branched chain aliphatic triamine include 3,3'-diamino-N-methyldipropylamine, 3,3'-diaminodipropylamine, diethylenetriamine, and bis(hexamethylamine). Methylene)triamine, 2,2'-bis(methylamino)-N-methyldiethylamine, etc. are mentioned.

Among these, it is preferable that the aliphatic triamine residue is an aliphatic triamine residue derived from the above trimeric acid.

Additionally, as the aliphatic diamine and/or the aliphatic triamine, a mixture of the dimerdiamine and the trimertriamine may be used.

Commercially available products of the aliphatic diamine and/or aliphatic triamine derived from the dimer acid and/or the trimer acid include, for example, aliphatic diamine and/or aliphatic triamine manufactured by BASF, and aliphatic diamine and/or aliphatic triamine manufactured by Croda. Or an aliphatic triamine, etc. can be mentioned.

Examples of the aliphatic diamine and/or aliphatic triamine manufactured by BASF include Basamine 551 and Basamine 552.

Examples of the aliphatic diamine and/or aliphatic triamine manufactured by Croda include Priamine 1071, Priamine 1073, Priamine 1074, and Priamine 1075.

When B in the formula (2-1) is the aromatic diamine residue, the aromatic diamine residue is preferably a divalent group represented by the following formula (5-1) or the following formula (5-2).

[Formula 5]

In formula (5-1) and formula (5-2), * is a bonding position, and in formula (5-1), Y is a bond, oxygen atom, carbonyl group, sulfur atom, sulfonyl group, linear Alternatively, it is a branched divalent hydrocarbon group or a divalent group having an aromatic ring. When Y is a hydrocarbon group, it may have an oxygen atom between the hydrocarbon group and each aromatic ring in formula (5-1), and when Y is a divalent group having an aromatic ring, the divalent group having the aromatic ring and the formula ( It may have an oxygen atom between each aromatic ring in 5-1). The hydrogen atom of the aromatic ring in formulas (5-1) and (5-2) may be substituted.

When Y in the above formula (5-1) is a linear or branched divalent hydrocarbon group or a divalent group having an aromatic ring, these groups may be substituted.

When the linear or branched divalent hydrocarbon group or the divalent group having an aromatic ring is substituted, the substituent includes, for example, a halogen atom, a linear or branched alkyl group, Examples include linear or branched alkenyl groups, alicyclic groups, aryl groups, alkoxy groups, nitro groups, and cyano groups.

Moreover, Y in the above formula (5-1) may include the same group as X in the above formula (4-2).

Examples of the aromatic diamine from which the aromatic diamine residue is derived include those in which the diamine represented by formula (11) described later is an aromatic diamine.

As described later, the curing agent preferably does not contain a compound having a siloxane skeleton. In particular, when the imide oligomer related to the present invention has a siloxane skeleton in its structure, it may lower the glass transition temperature of the cured product of the curable resin composition or contaminate the adherend and cause adhesion defects. It is preferable that it is an imide oligomer that does not have a siloxane skeleton.

The molecular weight of the imide oligomer according to the present invention is preferably 5000 or less. When the molecular weight of the imide oligomer according to the present invention is 5000 or less, the cured product of the curable resin composition obtained has more excellent long-term heat resistance. The more preferable upper limit of the molecular weight of the imide oligomer according to the present invention is 4000, and the more preferable upper limit is 3000.

In particular, the molecular weight of the imide oligomer according to the present invention is preferably 900 or more and 5000 or less when it has a structure represented by the formula (2-1) or (3-1), and the molecular weight of the imide oligomer according to the present invention is preferably 900 or more and 5000 or less. , when it has the structure represented by the above formula (3-2), it is preferably 550 or more and 4000 or less. When it has the structure represented by the above formula (2-1) and the above formula (3-1), the more preferable lower limit of the molecular weight is 950, and the more preferable lower limit is 1000. When it has the structure represented by the above formula (2-2) and the above formula (3-2), the more preferable lower limit of the molecular weight is 580, and the more preferable lower limit is 600.

In addition, in this specification, the “molecular weight” refers to the molecular weight determined from the structural formula for compounds with a specified molecular structure, but for compounds with a wide distribution of polymerization degrees and compounds with an unspecified modification site, the number average molecular weight is used. There are cases where it is indicated. In addition, the above-mentioned “number average molecular weight” is a value determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converted to polystyrene. Examples of the column used when measuring the number average molecular weight in terms of polystyrene by GPC include JAIGEL-2H-A (manufactured by Japan Analytical Industry Co., Ltd.).

The imide oligomer related to the present invention is specifically, the following formula (6-1), the following formula (6-2), the following formula (6-3), the following formula (6-4), or the following formula ( 6-5), or the following formula (7-1), the following formula (7-2), the following formula (7-3), the following formula (7-4), or the following formula (7-5) ), or an imide oligomer represented by the following formula (7-6).

[Formula 6]

In formulas (6-1) to (6-5), A is the acid dianhydride residue, and in formulas (6-1) to (6-3) to (6-5), A may be the same. Yes, it may be different. In formulas (6-1) to (6-4), B is the aliphatic diamine residue or the aromatic diamine residue, and in formulas (6-3) and (6-4), B may be the same. , may be different. In formula (6-5), B is the aliphatic triamine residue or the aromatic triamine residue. In formula (6-2), It is an optional monovalent hydrocarbon group. In formulas (6-3) and (6-4), n is the number of repetitions.

[Formula 7]

In formulas (7-1) to (7-6), A is the acid dianhydride residue, and in formulas (7-2) to (7-6), A may be the same or different. In formulas (7-1) to (7-6), R is a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group, and is represented by formula (7-1), formula (7-2), formula In (7-4) and formula (7-6), R may be the same or different, respectively. In formulas (7-3) and (7-5), W is a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group that may be substituted. In formulas (7-2) to (7-4), B is the aliphatic diamine residue or the aromatic diamine residue, and in formulas (7-4) and (7-5), B may be the same. , may be different. In formula (7-6), B is the aliphatic triamine residue or the aromatic triamine residue.

A in the above formulas (6-1) to (6-5) and the above formulas (7-1) to (7-6) is represented by the following formula (8-1) or the following formula (8-2) It is preferable that it is a tetravalent group.

[Formula 8]

In formula (8-1), A ³ represents an aromatic group or a fused aromatic group, and in formula (8-2), A ⁴ and A ⁵ each independently represent an aromatic group or a fused aromatic group. In formula (8-2), -NH-, -CH=N-, -CH=NN=CH-, -N=N-, -N ⁺ (-O ^- )=N-, -CH=C(CH ₃ )-, -CH=C (CN)-, -CH=CH-C(=O)-, -Ph-, -Ph-Ph-, or -C(=O)O-Ph-OC(=O)-, and Ph is , represents an aromatic ring that is unsubstituted or has a substituent. In formulas (8-1) and (8-2), * represents the binding position.

B in the above formulas (6-1) to (6-4) and the above formulas (7-2) to (7-5) is represented by the following formula (9-1) or the following formula (9-2) It is preferable that it is a divalent group.

[Formula 9]

In formula (9-1) and formula (9-2), * is a bonding position, and in formula (9-1), Y is a bond, oxygen atom, carbonyl group, sulfur atom, sulfonyl group, linear Alternatively, it is a branched divalent hydrocarbon group or a divalent group having an aromatic ring. When Y is a hydrocarbon group, it may have an oxygen atom between the hydrocarbon group and each aromatic ring in formula (9-1), and when Y is a divalent group having an aromatic ring, the divalent group having the aromatic ring and the formula ( It may have an oxygen atom between each aromatic ring in 9-1). The hydrogen atom of the aromatic ring in formulas (9-1) and (9-2) may be substituted.

Methods for producing an imide oligomer having the structure represented by the formula (2-1) include, for example, reacting an acid dianhydride represented by the formula (10) below with a diamine represented by the formula (11), etc. can be mentioned. Moreover, by using aliphatic triamine or aromatic triamine instead of diamine represented by the following formula (11), an imide oligomer having a structure represented by the above formula (3-1) can be produced.

[Formula 10]

In formula (10), A is the same tetravalent group as A in formula (2-1) above.

[Formula 11]

In formula (11), B is the same divalent group as B in formula (2-1), and R ¹ to R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group.

A specific example of a method of reacting the acid dianhydride represented by the formula (10) and the diamine represented by the formula (11) is shown below.

First, the diamine represented by the above formula (11) is dissolved in advance in a solvent in which the amic acid oligomer obtained by the reaction is soluble (for example, N-methylpyrrolidone, etc.), and the obtained solution is added to the above formula (10). The indicated acid dianhydride is added and reacted to obtain an amic acid oligomer solution. Next, the solvent is removed by heating or reduced pressure, and further, the amic acid oligomer is reacted by heating at about 200° C. or higher for 1 hour or more. By adjusting the molar ratio of the acid dianhydride represented by the formula (10) and the diamine represented by the formula (11) and the imidization conditions, a compound having a desired number average molecular weight and represented by the formula (2-1) at both ends is obtained. An imide oligomer having a structure can be obtained.

Additionally, by substituting part of the acid dianhydride represented by the formula (10) with an acid anhydride represented by the formula (12) below, a structure having the desired number average molecular weight and represented by the formula (2-1) at one end is obtained. and an imide oligomer having a structure derived from an acid anhydride represented by the following formula (12) at the other terminal can be obtained. In this case, the acid dianhydride represented by the above formula (10) and the acid anhydride represented by the following formula (12) may be added simultaneously or may be added separately.

In addition, by substituting a part of the diamine represented by the formula (11) with a monoamine represented by the formula (13), it has a desired number average molecular weight and has a structure represented by the formula (2-1) at one end, An imide oligomer having a structure derived from a monoamine represented by the following formula (13) at the other terminal can be obtained. In this case, the diamine represented by the above formula (11) and the monoamine represented by the following formula (13) may be added simultaneously or may be added separately.

[Formula 12]

In formula (12), Ar is a divalent aromatic group that may be substituted.

[Formula 13]

In formula (13), Ar is a monovalent aromatic group that 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 the structure represented by the above formula (2-2), for example, an acid dianhydride represented by the above formula (10) and a phenolic hydroxyl group-containing monoamine represented by the following formula (14) A method of reacting, a method of reacting an acid dianhydride represented by the above formula (10), a diamine represented by the above formula (11), and a phenolic hydroxyl group-containing monoamine represented by the following formula (14), etc. can be mentioned. Moreover, by using aliphatic triamine or aromatic triamine instead of the diamine represented by the above formula (11), an imide oligomer having a structure represented by the above formula (3-2) can be produced.

[Formula 14]

In formula (14), Ar is a divalent aromatic group that may be substituted, and R ⁷ and R ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group.

A specific example of a method of reacting the acid dianhydride represented by the formula (10) and the phenolic hydroxyl group-containing monoamine represented by the formula (14) is shown below.

First, the phenolic hydroxyl group-containing monoamine represented by the above formula (14) is dissolved in a solvent in which the amic acid oligomer obtained by the reaction is soluble (for example, N-methylpyrrolidone, etc.), and the resulting solution is added to the above-described solution. An acid dianhydride represented by formula (10) is added and reacted to obtain an amic acid oligomer solution. Next, the solvent is removed by heating or reduced pressure, and further, the amic acid oligomer is reacted by heating at about 200° C. or higher for 1 hour or more. By adjusting the molar ratio of the acid dianhydride represented by the formula (10) and the phenolic hydroxyl group-containing monoamine represented by the formula (14) and the imidization conditions, the desired number average molecular weight is obtained, and the formula (2) is present at both ends. -2) An imide oligomer having the structure represented by can be obtained.

In addition, by substituting a part of the phenolic hydroxyl group-containing monoamine represented by the formula (14) with the monoamine represented by the formula (13), a desired number average molecular weight is obtained, and at one end, the monoamine has the formula (2-2). An imide oligomer having the structure shown and having a structure derived from a monoamine represented by the above formula (13) at the other end can be obtained. In this case, the phenolic hydroxyl group-containing monoamine represented by the formula (14) and the monoamine represented by the formula (13) may be added simultaneously or separately.

A specific example of a method of reacting the acid dianhydride represented by the formula (10), the diamine represented by the formula (11), and the phenolic hydroxyl group-containing monoamine represented by the formula (14) is shown below.

First, the phenolic hydroxyl group-containing monoamine represented by the above formula (14) and the diamine represented by the above formula (11) are mixed in a solvent in which the amic acid oligomer obtained by the reaction is soluble (for example, N-methylpyrrolidone, etc. ), and the acid dianhydride represented by the above formula (10) is added to the obtained solution and reacted to obtain an amic acid oligomer solution. Next, the solvent is removed by heating or reduced pressure, and further, the amic acid oligomer is reacted by heating at about 200° C. or higher for 1 hour or more. By adjusting the molar ratio of the acid dianhydride represented by the formula (10), the diamine represented by the formula (11), and the phenolic hydroxyl group-containing monoamine represented by the formula (14), and the imidization conditions, the desired number average molecular weight is achieved. and an imide oligomer having a structure represented by the above formula (2-2) at both ends can be obtained.

In addition, by substituting a part of the phenolic hydroxyl group-containing monoamine represented by the formula (14) with the monoamine represented by the formula (13), a desired number average molecular weight is obtained, and at one end, the monoamine has the formula (2-2). An imide oligomer having the structure shown and having a structure derived from a monoamine represented by the above formula (13) at the other end can be obtained. In this case, the phenolic hydroxyl group-containing monoamine represented by the formula (14) and the monoamine represented by the formula (13) may be added simultaneously or separately.

Examples of the acid dianhydride represented by the formula (10) include pyromellitic dianhydride, 3,3'-oxydiphthalic dianhydride, 3,4'-oxydiphthalic dianhydride, and 4,4'- Oxydiphthalic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic dianhydride, 4,4'-bis(2,3-dicarboxylphenoxy)diphenyl ether Acid dianhydride, p-phenylenebis(trimellitate anhydride), 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid Boxylic dianhydride, 4,4'-biphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran- 5-carboxylate), 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-bi Phenyltetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, perylene-3,4,9,10-tetracarboxylic acid dianhydride, bis(1,3 -dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)ethylene, 5-isobenzofurancarboxylic acid dianhydride, bis((3,4-dicarboxylic acid anhydride)phenyl)terephthalate , 4,4'-bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy)biphenyl, etc.

Among them, when the imide oligomer related to the present invention is mesogenic, the acid dianhydride represented by the above formula (10) is pyromellitic dianhydride, 4,4'-(4,4'-iso Propylidenediphenoxy)diphthalic acid dianhydride, p-phenylenebis(trimellitate anhydride), 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 4,4'-biphthalic anhydride , 4,4'-carbonyldiphthalic anhydride, 1,4-phenylenebis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate), 2,3,6, 7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-Biphenyltetracarboxylic acid dianhydride, perylene-3,4,9,10-tetracarboxylic acid dianhydride, bis(1,3-dioxo-1,3-dihydroisobenzofuran -5-carboxylic acid)ethylene, 5-isobenzofurancarboxylic acid dianhydride, bis((3,4-dicarboxylic acid anhydride)phenyl)terephthalate, 4,4'-bis(1,3-di) Oxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy)biphenyl and the like are preferred.

These acid dianhydrides may be used individually, or two or more types may be used in combination.

Among the diamines represented by the above formula (11), examples of aromatic diamines include 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl. Methane, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, o-phenylenediamine, m-phenylenediamine, p-phenyl Lendiamine, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 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, 1,5-diaminonaphthalene , 3,3'-diamino-4,4'-dihydroxyphenylmethane, 4,4'-diamino-3,3'-dihydroxyphenylmethane, 3,3'-diamino-4,4 '-dihydroxyphenyl ether, bisaminophenylfluorene, bistoluidine fluorene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihyde Roxyphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 2-(4-aminophenyl) -1H-benzoimidazol-5-amine, 4-aminobenzoic acid 4-aminophenyl, 4,4'-diaminobenzophenone, benzidine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3, 3',5,5'-tetramethylbenzidine, 3,3'-dimethoxybenzidine, 1,3-bis(4-aminobenzoyloxy)propane, (4-(4-aminobenzoyl)oxyphenyl)4-amino Benzoate, etc. can be mentioned.

Among them, because of their excellent availability, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, and 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, 1,4-bis(4-aminophenoxy)benzene, 1,5-diaminonaphthalene, 4,4'-bis(4-aminophenoxy)biphenyl , 2-(4-aminophenyl)-1H-benzoimidazol-5-amine, 4-aminobenzoic acid 4-aminophenyl, 4,4'-diaminobenzophenone, benzidine, 3,3'-dimethylbenzidine, 2 ,2'-dimethylbenzidine, 3,3',5,5'-tetramethylbenzidine, 3,3'-dimethoxybenzidine, 1,3-bis(4-aminobenzoyloxy)propane, (4-(4- Aminobenzoyl)oxyphenyl)4-aminobenzoate is preferred, and furthermore, because of its excellent solubility and heat resistance, 4,4'-diaminodiphenylsulfone, 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-amino) Phenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,5-diaminonaphthalene, 4,4'-bis(4-aminophenoxy)biphenyl, 2-(4-aminophenyl) )-1H-benzoimidazol-5-amine, 4-aminobenzoic acid 4-aminophenyl, 4,4'-diaminobenzophenone, benzidine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3 ,3',5,5'-Tetramethylbenzidine, 3,3'-dimethoxybenzidine, 1,3-bis(4-aminobenzoyloxy)propane, (4-(4-aminobenzoyl)oxyphenyl)4- Aminobenzoate is more preferred.

These aromatic diamines may be used individually, or two or more types may be used in combination.

Examples of the acid anhydride represented by the formula (12) include phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 1,2-naphthalic anhydride, 2,3-naphthalic anhydride, 1,8 -Naphthalic anhydride, 2,3-anthracenedicarboxylic acid anhydride, 4-tert-butylphthalic anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-fluorophthalic anhydride, 4-chlorophthalic acid Anhydride, 4-bromophthalic anhydride, 3,4-dichlorophthalic anhydride, etc. can be mentioned.

Monoamines represented by the formula (13) include, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 2,4-dimethylaniline, 3,4-dimethylaniline, and 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, 1-naphthylamine, 2-naphthylamine, N-phenylnaphthalen-2-amine, N-allylnaphthalen-1-amine, etc.

Examples of the phenolic hydroxyl group-containing monoamine represented by the formula (14) include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, and 4-amino- 2,3-xylenol, 4-amino-2,5-xylenol, 4-amino-2,6-xylenol, 4-amino-1-naphthol, 5-amino-2-naphthol, 6- Amino-1-naphthol, 4-amino-2,6-diphenylphenol, etc. can be mentioned. Among them, 4-amino-o-cresol and 5-amino-o-cresol are preferred because they are excellent in availability and storage stability, and a high glass transition temperature is obtained after curing.

When the imide oligomer according to the present invention is produced by the above-described production method, the imide oligomer according to the present invention is a plurality of types of imide oligomers having the structure represented by the above formula (2-1) or the above formula (2-1) -2) It is obtained by being contained in a mixture (imide oligomer composition) of multiple types of imide oligomers having the structure shown in and each raw material. When an aliphatic triamine or an aromatic triamine is used instead of the diamine represented by the formula (11), the imide oligomer according to the present invention is a plurality of types of imide oligomers having the structure represented by the formula (3-1), or It is obtained by being contained in a mixture (imide oligomer composition) of multiple types of imide oligomers having the structure represented by the above formula (3-2) and each raw material. The imide oligomer composition has an imidization ratio of 70% or more, so that when used as a curing agent, a cured product with superior mechanical strength at high temperatures and long-term heat resistance can be obtained.

The preferable lower limit of the imidization ratio of the imide oligomer composition according to the present invention is 75%, and the more preferable lower limit is 80%. Additionally, there is no particular preferable upper limit for the imidization ratio of the imide oligomer composition according to the present invention, but the practical upper limit is 98%.

In addition, the above-mentioned “imidation rate” was measured by total reflection measurement (ATR method) using a Fourier transform infrared spectrophotometer (FT-IR), and the peak absorbance around 1660 cm ^-1 derived from the carbonyl group of amic acid was measured. It can be derived from the area by the following equation. Examples of the Fourier transform infrared spectrophotometer include UMA600 (manufactured by Agilent Technologies). In addition, the “peak absorbance area of the amic acid oligomer” in the formula below is obtained by reacting acid dianhydride with diamine or phenolic hydroxyl group-containing monoamine, then removing the solvent by evaporation or the like without performing an imidization step. This is the absorbance area of the amic acid oligomer obtained by doing this.

Imidization rate (%) = 100 × (1 - (peak absorbance area after imidization)/(peak absorbance area of amic acid oligomer))

From the viewpoint of solubility in the curable resin composition, the imide oligomer composition according to the present invention preferably dissolves 3 g or more per 10 g of tetrahydrofuran at 25°C.

The lower limit of the content of the imide oligomer according to the present invention in a total of 100 parts by weight of the curable resin and the curing agent (if it contains a curing accelerator described later, an additional curing accelerator) is preferably 20 parts by weight, and the upper limit is 80 parts by weight. It is a weight part. When the content of the imide oligomer according to the present invention is within this range, the resulting curable resin composition becomes superior in thermal conductivity, low linear expansion, and heat resistance after curing. The more preferable lower limit of the content of the imide oligomer according to the present invention is 25 parts by weight, and the more preferable upper limit is 75 parts by weight.

In addition, when the imide oligomer related to the present invention is contained in the above-described imide oligomer composition, the content of the imide oligomer related to the present invention is determined by the imide oligomer composition (additionally, if other imide oligomers are used in combination) In this case, it means the content of the imide oligomer composition and the total of other imide oligomers).

When using other curing agents having mesogenic properties in addition to the imide oligomer related to the present invention as the curing agent, the other curing agents include, for example, phenolic hydroxyl groups, amino groups, carboxyl groups, acid anhydride groups, and activated ester groups. Compounds having reactive functional groups can be used. In addition, the other curing agent preferably has a structure represented by the formula (1-1), (1-2), or (1-3).

In addition, the structure represented by the above formula (1-1), (1-2), or (1-3) may be a group showing mesogenicity (mesogenic group), but in the above formula (1-1), Having a structure represented by (1-2) or (1-3) does not necessarily mean that it has mesogenicity.

Examples of the other curing agents include those described in Patent Documents 5 and 6.

When using the other curing agent in addition to the imide oligomer related to the present invention as the curing agent, the curing agent in the total of 100 parts by weight of the curing resin and the curing agent (if it contains a curing accelerator described later, an additional curing accelerator) The preferable lower limit of the total content of the imide oligomer according to the invention and the other curing agents mentioned above is 20 parts by weight, and the preferable upper limit is 80 parts by weight. When the total content of the imide oligomer according to the present invention and the other curing agents described above is within this range, the resulting curable resin composition becomes superior in adhesion and heat resistance after curing.

The curable resin composition of the present invention contains a curable resin.

Examples of the curable resin include epoxy resin, cyanate resin, phenol resin, polyimide resin, maleimide resin, benzoxazine resin, silicone resin, acrylic resin, and fluorine resin. Among these, it is preferable that the curable resin contains an epoxy resin.

In addition, the curable resin may not have mesogenic properties or may have mesogenic properties.

The said curable resin may be used individually, and 2 or more types may be used in combination.

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, and hydrogenated bisphenol. type epoxy resin, propylene oxide added bisphenol A 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 novolak type epoxy resin, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol epoxy resin. Examples include rockfish-type epoxy resins, glycidylamine-type epoxy resins, alkyl polyol-type epoxy resins, rubber-modified epoxy resins, and glycidyl ester compounds. Among them, when a mesogenic epoxy resin having a biphenyl skeleton, naphthalene skeleton, etc. in the molecule is used, the thermal conductivity is more excellent. Moreover, since the viscosity is low, the processability of the obtained curable resin composition is easy to adjust, and high adhesive strength is obtained, it is preferable to contain a non-mesogenic epoxy resin that is liquid at 25°C. The said epoxy resin may be used individually, and 2 or more types may be used in combination.

As will be described later, the curable resin preferably does not contain a compound having a siloxane skeleton.

It is preferable that the curable resin and the curing agent do not contain a compound having a siloxane skeleton. Since the curable resin and the curing agent do not contain a compound having a siloxane skeleton, it is possible to prevent contact defects caused by low molecular weight siloxane compounds derived from the curable resin composition.

The curable resin composition of the present invention may contain a heat conductive filler. By containing the heat conductive filler, the curable resin composition of the present invention has particularly excellent heat conductivity.

In addition, in this specification, the above-mentioned “thermal conductive filler” means a filler with a thermal conductivity of 10 W/m·K or more.

From the viewpoint of thermal conductivity, the thermally conductive filler is at least selected from the group consisting of alumina, aluminum nitride, silicon carbide, boron nitride, silicon nitride, magnesium oxide, zinc oxide, boron carbide, titanium carbide, zirconia, aluminum, and diamond. It is preferable to include one type.

The shape of the thermally conductive filler includes, for example, a plate shape, a spherical shape, an irregular shape, a crushed shape, a polygonal shape, etc. Additionally, the thermally conductive filler may be an agglomerated particle in which primary particles such as a plate-shaped filler are aggregated.

The thermally conductive filler has a preferred lower limit of average particle diameter of 0.1 µm and a preferred upper limit of 300 µm. When the average particle diameter of the heat conductive filler is within this range, the resulting curable resin composition has superior applicability and thermal conductivity. The more preferable lower limit of the average particle diameter of the heat conductive filler is 0.2 μm, and the more preferable upper limit is 200 μm.

In addition, the average particle diameter of the thermally conductive filler can be measured by dispersing the thermally conductive filler in a solvent (water, organic solvent, etc.) using a particle size distribution measuring device such as NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS). .

The preferable lower limit of the content ratio of the heat conductive filler in the curable resin composition of the present invention (the solvent is removed) is 50% by volume. When the content ratio of the heat conductive filler is 50% by volume or more, the resulting curable resin composition has more excellent heat conductivity. A more preferable lower limit of the content ratio of the heat conductive filler is 60% by volume.

Moreover, from the viewpoint of applicability and adhesiveness, the preferable upper limit of the content ratio of the above-mentioned heat conductive filler is 95 volume%, and the more preferable upper limit is 90 volume%.

The curable resin composition of the present invention may contain other fillers having a thermal conductivity of less than 10 W/m·K in addition to the above-described thermally conductive filler, as long as the purpose of the present invention is not impaired.

As the other fillers, inorganic fillers and organic fillers can be used.

Examples of the inorganic filler include silica, barium sulfate, glass powder, glass frit, glass fiber, and inorganic ion exchanger. Among them, silica and barium sulfate are preferable.

Examples of the organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamidoimide particles, polyimide particles, benzoguanamine particles, and core shell particles thereof. You can. Among them, polyamide particles, polyamidoimide particles, and polyimide particles are preferable.

The other fillers mentioned above may be used individually, or two or more types may be used in combination.

When the curable resin composition of the present invention contains the heat conductive filler, it is preferable that the curable resin composition of the present invention contains a dispersant.

By containing the dispersant, the curable resin composition of the present invention can easily uniformly disperse the heat conductive filler.

Examples of the dispersant include modified polyester compounds, modified polyether compounds, phosphoric acid esters of modified polyether compounds, fatty acid derivatives, fatty acid polycarboxylic acid amine salts, cationic group-containing acrylic polymers, polyurethane compounds, etc. I can hear it. The said dispersing agent may be used individually, and 2 or more types may be used in combination.

The preferable lower limit of the content of the dispersant in 100 parts by weight of the curable resin composition of the present invention is 0.05 parts by weight, and the preferable upper limit is 4 parts by weight. When the content of the dispersant is within this range, it becomes easier to make the dispersion state of the heat conductive filler uniform. The more preferable lower limit of the content of the dispersant is 0.1 parts by weight, and the more preferable upper limit is 3 parts by weight.

It is preferable that the curable resin composition of the present invention contains a curing accelerator. By containing the curing accelerator, curing time can be shortened and productivity can be improved.

Examples of the curing accelerator include imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphine-based curing accelerators, phosphorus-based curing accelerators, photobase generators, and sulfonium salt-based curing accelerators. Among them, an imidazole-based curing accelerator is preferable because it has excellent storage stability. The said hardening accelerator may be used individually, and 2 or more types may be used in combination.

The content of the curing accelerator has a preferable lower limit of 0.01 parts by weight and a preferable upper limit of 10 parts by weight, based on a total of 100 parts by weight of the curable resin, the curing agent, and the curing accelerator. When the content of the curing accelerator is within this range, the effect of shortening the curing time is more excellent while maintaining excellent adhesiveness, etc. The more preferable lower limit of the content of the curing accelerator is 0.05 parts by weight, and the more preferable upper limit is 5 parts by weight.

The curable resin composition of the present invention may contain a polymer component in a range that does not impair the purpose of the present invention. The polymer component serves as a film-forming component.

The preferred lower limit of the number average molecular weight of the polymer component is 3,000, and the preferred upper limit is 100,000. When the number average molecular weight of the polymer component is within this range, the resulting curable resin composition becomes superior in flexibility and processability before curing and in heat resistance after curing. The more preferable lower limit of the number average molecular weight of the polymer component is 5,000, and the more preferable upper limit is 80,000.

Examples of the polymer component include polyimide, phenoxy resin, polyamide, polyamidoimide, polymaleimide, cyanate resin, benzoxazine resin, acrylic resin, urethane resin, polyester, etc. . Among them, from the viewpoint of heat resistance, polyimide, polyamide, polyamidoimide, and polymaleimide are preferable, and polyimide is more preferable. The polymer component may be used individually, or two or more types may be used in combination.

The content of the polymer component has a preferable lower limit of 0.5 parts by weight and a preferable upper limit of 100 parts by weight of the total of the curable resin, the curing agent (if it contains the curing accelerator, the curing accelerator in addition) and the polymer component. It is 40 parts by weight. When the content of the polymer component is within this range, the cured product of the curable resin composition obtained has more excellent heat resistance. The more preferable lower limit of the content of the polymer component is 1 part by weight, and the more preferable upper limit is 30 parts by weight.

The curable resin composition may contain a solvent or a reactive diluent from the viewpoint of coating properties, handling properties, etc.

As the solvent, a solvent with a boiling point of less than 200°C is preferable from the viewpoint of coatability, storage stability, etc.

Examples of the solvent having a boiling point of less than 200°C include alcohol-based solvents, ketone-based solvents, ester-based solvents, hydrocarbon-based solvents, halogen-based solvents, ether-based solvents, and nitrogen-containing solvents.

Examples of the alcohol-based solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, tertiary-butyl alcohol, and 2-ethylhexanol.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, and diacetone alcohol.

Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, methoxybutyl acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, butyl lactate, etc. I can hear it.

Examples of the hydrocarbon-based solvent include benzene, toluene, xylene, n-hexane, isohexane, cyclohexane, methylcyclohexane, ethylcyclohexane, isooctane, n-decane, and n-heptane.

Examples of the halogen-based solvent include dichloromethane, chloroform, and trichlorethylene.

Examples of the ether-based solvent 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 monomethyl ether, propylene glycol monomethyl ether propionate, 3 -Methoxybutanol, diethylene glycol dimethyl ether, anisole, 4-methylanisole, etc. are mentioned.

Examples of the nitrogen-containing solvent include acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

Among them, from the viewpoint of handling and imide oligomer solubility, ketone-based solvents with a boiling point of 60°C or more and less than 200°C, ester-based solvents with a boiling point of 60°C or more and less than 200°C, and boiling points of 60°C or more and less than 200°C At least one type selected from the group consisting of ether-based solvents 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, and methylcyclo. Hexanone, diethylene glycol dimethyl ether, anisole, etc. can be mentioned.

In addition, the above “boiling point” means a value measured under conditions of 101 kPa, or a value converted to 101 kPa in a boiling point conversion chart, etc.

As the reactive diluent, a reactive diluent having one or more crosslinkable functional groups in one molecule is preferable.

Examples of the reactive diluent having one or more crosslinkable functional groups in one molecule include monofunctional epoxy resins.

Examples of the monofunctional epoxy resin include monoglycidyl compounds and monoalicyclic epoxy compounds.

Examples of the monoglycidyl compounds include tert-butylphenylglycidyl ether, 2-ethylhexylglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, and 3-glycidoxypropyltri. Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 1-(3-glycidoxypropyl)1,1,3,3,3-pentamethyldisiloxane, N-glycidyl-N,N- and bis[3-(trimethoxysilyl)propyl]amine.

Examples of the mono-alicyclic epoxy compound include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

These reactive diluents may be used individually, or two or more types may be used in combination.

The preferable lower limit of the content of the solvent or reactive diluent in 100 parts by weight of the curable resin composition of the present invention is 0.5 parts by weight, and the preferable upper limit is 30 parts by weight. When the content of the solvent or reactive diluent is within this range, the resulting curable resin composition becomes more excellent in coatability, etc. The more preferable lower limit of the content of the solvent or reactive diluent is 1 part by weight, and the more preferable upper limit is 20 parts by weight.

The curable resin composition of the present invention may further contain additives such as a coupling agent, a storage stabilizer, a bleed preventer, a flux agent, and a leveling agent, as long as they do not impair the purpose of the present invention.

Methods for producing the curable resin composition of the present invention include, for example, a method of mixing curable resin, a curing agent, a curing accelerator, etc. using a mixer. Examples of the mixer include Homo Disper, universal mixer, Banbury mixer, kneader, etc.

When the curable resin composition of the present invention does not contain the above-described heat conductive filler, the preferable lower limit of the thermal conductivity of the curable resin composition of the present invention after curing is 0.15 W/m·K. Since the heat conductivity of the curable resin composition of the present invention in the case of not containing the above-mentioned heat conductive filler after curing is 0.15 W/m·K or more, the curable resin composition of the present invention can be suitably used as a heat dissipation adhesive. A more preferable lower limit of the thermal conductivity after curing is 0.2 W/m·K, and a more preferable lower limit is 0.3 W/m·K. In addition, there is no particular upper limit of the preferable heat conductivity after curing of the curable resin composition of the present invention when it does not contain the above-mentioned heat conductive filler, but the practical upper limit is 0.5 W/m·K.

When the curable resin composition of the present invention contains the above-mentioned heat conductive filler, the preferable lower limit of the thermal conductivity of the curable resin composition of the present invention after curing is 1 W/m·K. When the curable resin composition of the present invention contains the heat conductive filler, the thermal conductivity after curing is 1 W/m·K or more, so that the curable resin composition of the present invention can be suitably used as a heat dissipation adhesive. The more preferable lower limit of the heat conductivity after curing of the curable resin composition of the present invention when containing the above-mentioned heat conductive filler is 1.5 W/m·K, and the more preferable lower limit is 2 W/m·K. Moreover, there is no particular upper limit of the preferable heat conductivity after curing of the curable resin composition of the present invention when containing the above-mentioned heat conductive filler, but the practical upper limit is 20 W/m·K.

Additionally, the thermal conductivity can be measured at 23°C according to ASTM D5470. Examples of the measuring device used to measure the thermal conductivity include the “T3Ster DynTIM Tester” manufactured by Mentor, a Siemens Business. In addition, as the cured product for measuring the thermal conductivity, a curable resin composition is dried and then cured by heating at 190°C for 1 hour.

The curable resin composition of the present invention has a preferable lower limit of viscosity at 25°C of 10 mPa·s and a preferable upper limit of 600 mPa·s. When the viscosity at 25°C is within this range, the curable resin composition of the present invention has excellent applicability. The more preferable lower limit of the viscosity at 25°C is 20 mPa·s, and the more preferable upper limit is 500 mPa·s.

In addition, in this specification, the "viscosity" means a value measured under conditions of 10 rpm using an E-type viscometer. Examples of the E-type viscometer include TPE-100 (manufactured by Toki Sangyo Co., Ltd.).

The curable resin composition of the present invention has a preferable lower limit of the shear adhesive force of the cured product to aluminum of 4 MPa. When the shear adhesive force of the cured product to aluminum is 4 MPa or more, the curable resin composition of the present invention can be suitably used as a heat conductive adhesive. A more preferable lower limit of the shear adhesion of the cured product to aluminum is 5 MPa.

Additionally, there is no particular upper limit to the shear adhesion of the cured product to aluminum, but the practical upper limit is 20 MPa.

In addition, the shear adhesion of the cured product to aluminum was measured at 25°C at a tensile speed of 1 mm/min using a Tensilon universal material tester (“RTC-1350A” manufactured by A&D) on a test piece. It can be measured by calculating the stress when tensed and peeled. For the test piece, the curable resin composition was applied so that the thickness after drying was 100 μm, dried to remove the solvent, and then an aluminum substrate with a thickness of 25 mm was bonded to both sides of the curable resin composition and heated at 190° C. for 1 hour. What is obtained is used. As the aluminum substrate, for example, A-1050P or the like can be used.

The curable resin composition of the present invention has a preferable lower limit of the 5% weight loss temperature after curing of 350°C. Since the 5% weight loss temperature after curing is 350°C or higher, the curable resin composition of the present invention can be particularly preferably used in a heat conductive adhesive (heat dissipation adhesive) that requires heat resistance. In addition, there is no particularly preferable upper limit of the 5% weight loss temperature after curing, but the practical upper limit is 450°C.

In addition, the above 5% weight loss temperature can be derived by performing thermogravimetric measurement using a thermogravimetric measurement device under temperature increasing conditions from 30°C to 500°C at a temperature increase rate of 10°C/min. Examples of the thermogravimetric measurement device include TG/DTA6200 (manufactured by Hitachi High-Tech Science). In addition, the cured product for measuring the above-mentioned 5% weight loss temperature is a curable resin composition coated on a base PET film so that the thickness after drying is 100 μm, dried, and then cured by heating at 190° C. for 1 hour. It is used.

From the viewpoint of reducing warpage and improving adhesion reliability, the curable resin composition of the present invention preferably has an average coefficient of linear expansion of 80 ppm or less in a temperature range of 25°C to 80°C after curing, and is more preferably 70 ppm or less. The smaller the average coefficient of linear expansion, the more preferable it is.

In addition, the average coefficient of linear expansion can be measured using a thermomechanical analysis device for a cured product with a thickness of 400 μm. Specifically, under the conditions of a load of 5 g and a temperature increase rate of 10 °C/min, a cured product with a sample length of 1 cm was heated from 0 °C to 300 °C, then cooled, and again heated from 0 °C to 300 °C under the same conditions. Then, based on the data of temperature and dimensional change obtained in the second measurement, the average coefficient of linear expansion in the temperature range of 25°C to 80°C can be determined.

As a cured product for measuring the average linear expansion coefficient, a curable resin composition is coated on a base PET film so that the thickness after drying is 100 μm, dried, and then laminated to have a thickness of 400 μm, and incubated at 190° C. for 1 hour. Those that have been hardened by heating are used.

Examples of the thermomechanical analysis device include TMA/SS-6000 (manufactured by Hitachi High-Tech Science).

The cured product of the curable resin composition of the present invention is also one of the present invention.

An adhesive formed using the curable resin composition of the present invention is also one of the present invention.

An adhesive film can be obtained by a method such as coating the adhesive of the present invention on a base film and then drying it. An adhesive film made using the adhesive of the present invention is also one of the present invention.

The adhesive of the present invention can be preferably used as a heat conductive adhesive (heat dissipation adhesive), and the adhesive film of the present invention can be preferably used as a heat conductive adhesive film (heat dissipation adhesive film).

According to the present invention, a curable resin composition excellent in heat resistance, thermal conductivity, low linear expansion, and adhesiveness can be provided. Moreover, according to the present invention, a cured product of the curable resin composition, and an adhesive and adhesive film made using the curable resin composition can be provided.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1 (Preparation of imide oligomer composition A))

68.7 parts by weight of 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) (manufactured by Tokyo Chemical Industry Co., Ltd.) N-methylpyrrolidone (Fuji Film Wako) It was dissolved in 300 parts by weight (“NMP”, manufactured by Sun Yaksha). To the obtained solution was added a solution of 42.1 parts by weight of Priamine 1074 (manufactured by Croda), a dimer diamine, diluted with 100 parts by weight of N-methylpyrrolidone, and stirred at 25°C for 2 hours to react, thereby obtaining an amic acid oligomer solution. After N-methylpyrrolidone was removed under reduced pressure from the obtained amic acid oligomer solution, it was heated at 300°C for 2 hours to obtain imide oligomer composition A (imidation rate: 95%).

The obtained imide oligomer composition A was subjected to ¹ H-NMR, GPC, and FT-IR analysis. As a result, the imide oligomer composition A is an imide oligomer having a structure represented by the above formula (6-1) or (6-3) (A is 1,4-phenylenebis(1,3-dioxo-1) , 3-dihydroisobenzofuran-5-carboxylate) residue, and B is a dimerdiamine residue). Additionally, the number average molecular weight of the imide oligomer composition A was 1500. In addition, observation was performed under orthogonal Nicols while raising the temperature from room temperature to 200°C using a polarizing microscope equipped with a hot stage, and the optical structure derived from the liquid crystal phase was observed, so the imide oligomer composition A was mesogenic. It was confirmed that it has.

(Synthesis Example 2 (Preparation of imide oligomer composition B))

Imide oligomer composition B (imidation rate 96%) was prepared in the same manner as in Synthesis Example 1 except that 11.1 parts by weight of 1,2-bis(2-aminoethoxy)ethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of Priamine 1074. got it

The obtained imide oligomer composition B was subjected to ¹ H-NMR, GPC, and FT-IR analysis. As a result, imide oligomer composition B is an imide oligomer having a structure represented by the above formula (6-1) or (6-3) (A is 1,4-phenylenebis(1,3-dioxo-1) , 3-dihydroisobenzofuran-5-carboxylate) residue, and B was confirmed to contain a 1,2-bis(2-aminoethoxy)ethane residue). Additionally, the number average molecular weight of the imide oligomer composition B was 1100. In addition, through the same polarizing microscope observation as in Synthesis Example 1, it was confirmed that the imide oligomer composition B had mesogenic properties.

(Synthesis Example 3 (Preparation of imide oligomer composition C))

Instead of 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate), 4,4'-biphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used at 44.1 parts by weight. Imide oligomer composition C (imidation rate: 95%) was obtained in the same manner as in Synthesis Example 1 except for what was used.

The obtained imide oligomer composition C was subjected to ¹ H-NMR, GPC, and FT-IR analysis. As a result, the imide oligomer composition C is an imide oligomer having a structure represented by the above formula (6-1) or (6-3) (A is a 4,4'-biphthalic anhydride residue, B is a dimerdiamine residue) It was confirmed that it contains. Additionally, the number average molecular weight of the imide oligomer composition C was 1200. In addition, through the same polarizing microscope observation as in Synthesis Example 1, it was confirmed that the imide oligomer composition C had mesogenic properties.

(Synthesis Example 4 (Preparation of imide oligomer composition D))

16.3 parts by weight of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 300 parts by weight of N-methylpyrrolidone (“NMP” by Fujifilm Wako Pure Chemical Industries, Ltd.). To the obtained solution, 108.1 parts by weight of the imide oligomer composition A obtained in Synthesis Example 1 was added, and the mixture was stirred and reacted at 25°C for 2 hours to obtain an amic acid oligomer solution. After N-methylpyrrolidone was removed under reduced pressure from the obtained amic acid oligomer solution, it was heated at 300°C for 2 hours to obtain imide oligomer composition D (imidation rate: 95%).

The obtained imide oligomer composition D was subjected to ¹ H-NMR, GPC, and FT-IR analysis. As a result, the imide oligomer composition D is an imide oligomer having a structure represented by the above formula (7-2) or (7-4) (A is 1,4-phenylenebis(1,3-dioxo-1) , 3-dihydroisobenzofuran-5-carboxylate) residue, and B is a dimerdiamine residue). Additionally, the number average molecular weight of the imide oligomer composition D was 1600. In addition, through the same polarizing microscope observation as in Synthesis Example 1, it was confirmed that the imide oligomer composition D had mesogenic properties.

(Synthesis Example 5 (Preparation of imide oligomer composition E))

78.0 parts by weight of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 parts by weight of N-methylpyrrolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "NMP") dissolved in water. A solution of 42.0 parts by weight of Priamine 1074 (manufactured by Croda), a dimer diamine, diluted with 100 parts by weight of N-methylpyrrolidone was added to the obtained solution, and stirred at 25°C for 2 hours to react, thereby obtaining an amic acid oligomer solution. After N-methylpyrrolidone was removed under reduced pressure from the obtained amic acid oligomer solution, it was heated at 300°C for 2 hours to obtain imide oligomer composition E (imidation rate: 93%).

The obtained imide oligomer composition E was subjected to ¹ H-NMR, GPC, and FT-IR analysis. As a result, the imide oligomer composition E is an imide oligomer having a structure represented by the above formula (6-1) or (6-3) (A is 4,4'-(4,4'-isopropylidenediphenol C) It was confirmed that it contains a diphthalic anhydride residue and B is a dimerdiamine residue. Additionally, the number average molecular weight of the imide oligomer composition E was 1600. In addition, through the same polarizing microscope observation as in Synthesis Example 1, it was confirmed that the imide oligomer composition E did not have mesogenic properties.

(Synthesis Example 6 (Preparation of imide oligomer composition F))

Imide oligomer composition F (imidation rate 95%) was obtained in the same manner as in Synthesis Example 5, except that 27.6 parts by weight of 4,4'-bis(4-aminophenoxy)biphenyl was used instead of Priamine 1074.

¹ H-NMR, GPC, and FT-IR analysis were performed on the obtained imide oligomer composition F. As a result, the imide oligomer composition F is an imide oligomer having a structure represented by the above formula (6-1) or (6-3) (A is 4,4'-(4,4'-isopropylidenediphenol c) Diphthalic anhydride residue, B was confirmed to contain a 4,4'-bis(4-aminophenoxy)biphenyl residue). Additionally, the number average molecular weight of the imide oligomer composition F was 1400. In addition, through the same polarizing microscope observation as in Synthesis Example 1, it was confirmed that the imide oligomer composition F had mesogenic properties.

(Synthesis Example 7 (Preparation of imide oligomer composition G))

Imide oligomer composition G (imidation rate: 94%) was obtained in the same manner as in Synthesis Example 5, except that 17.1 parts by weight of 4-aminophenyl 4-aminobenzoic acid was used instead of Priamine 1074.

The obtained imide oligomer composition G was subjected to ¹ H-NMR, GPC, and FT-IR analysis. As a result, the imide oligomer composition G is an imide oligomer having a structure represented by the above formula (6-1) or (6-3) (A is 4,4'-(4,4'-isopropylidenediphenol C) It was confirmed that B contains a diphthalic anhydride residue, and B is a 4-aminobenzoic acid 4-aminophenyl residue. Additionally, the number average molecular weight of the imide oligomer composition G was 1300. In addition, through the same polarizing microscope observation as in Synthesis Example 1, it was confirmed that the imide oligomer composition G had mesogenic properties.

(Synthesis Example 8 (Preparation of cyclohexanone solution of polyimide resin))

54.6 parts by weight of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) in a reaction vessel equipped with a stirrer, a fountain, and a nitrogen gas introduction pipe, and, 150 parts by weight of cyclohexanone was injected and dissolved. To the obtained solution, a mixed solution of 56.1 parts by weight of dimer diamine Priamine 1074 (manufactured by Croda) and 55.0 parts by weight of cyclohexanone was added dropwise, and then an imidization reaction was performed at 150°C for 8 hours to form a polyimide resin solution. got it Additionally, the solid content concentration of the obtained polyimide resin solution was 35% by weight, and the number average molecular weight of the polyimide resin was 27000.

(Examples 1 to 20, Comparative Examples 1 to 6)

According to the mixing ratios shown in Tables 1 and 2, each material was stirred and mixed to produce each curable resin composition of Examples 1 to 20 and Comparative Examples 1 to 6.

＜Evaluation＞

The following evaluation was performed on each curable resin composition obtained in the examples and comparative examples. The results are shown in Tables 1 and 2.

(heat resistance)

Each curable resin composition obtained in the examples and comparative examples was coated on a base PET film so that the thickness after drying was 100 μm, dried, and then cured by heating at 190°C for 1 hour to produce a cured product. The obtained cured product was measured using a thermogravimetric measuring device (“TG/DTA6200” manufactured by Hitachi High-Tech Science Co., Ltd.) under a temperature range of 30°C to 500°C and a temperature increase of 10°C/min, and 5% by weight was obtained. The reduction temperature was measured.

The case where the 5% weight loss temperature was 380°C or higher is marked as “◎”, the case where it was between 350°C and below 380°C is marked as “○”, the case where it is between 330°C and below 350°C is marked as “△”, and the case where it is below 330°C is marked as “×”. 」, heat resistance was evaluated.

(adhesiveness)

An adhesive film was obtained by coating and drying each curable resin composition obtained in the Examples and Comparative Examples on a base PET film so that the thickness after drying was 100 μm. A test piece was produced by bonding an aluminum substrate "A-1050P" with a thickness of 25 mm to both sides of the obtained adhesive film and heating it at 190°C for 1 hour. For the obtained test piece, the shear adhesion of the cured product to aluminum was measured under the conditions of 25°C and a tensile speed of 1 mm/min using a Tensilon universal material tester (“RTC-1350A” manufactured by A&D). .

The case where the shear adhesion was 8 MPa or more was designated as “◎”, the case where it was 5 MPa or more but less than 8 MPa was designated as “○”, the case where it was 4 MPa or more but less than 5 MPa was designated as “△”, and the case where it was less than 4 MPa was designated as “×”. , adhesion was evaluated.

(thermal conductivity)

Each curable resin composition obtained in the examples and comparative examples was coated on a base PET film so that the thickness after drying was 100 μm, dried, and then cured by heating at 190°C for 1 hour to produce a cured product. The heat conductivity of the obtained cured product was measured at 23°C using a measuring device (“T3Ster DynTIM Tester” manufactured by Mentor, a Siemens Business).

For curable resin compositions that do not contain a thermally conductive filler, the case where the thermal conductivity is 0.3 W/m·K or more is indicated as “◎”, and the case where the thermal conductivity is 0.2 W/m·K or more but less than 0.3 W/m·K is indicated as “○”. Thermal conductivity was evaluated by setting the case of 0.15 W/m·K or more but less than 0.2 W/m·K as “△”, and the case of less than 0.15 W/m·K as “×”.

For the curable resin composition containing a heat conductive filler, the case where the thermal conductivity was 2 W/m·K or more was “◎”, and the case where the heat conductivity was 1.5 W/m·K or more but less than 2 W/m·K was “○”, 1 Thermal conductivity was evaluated by setting the case where it was more than W/m·K but less than 1.5 W/m·K as “△” and the case where it was less than 1 W/m·K as “×”.

(low linear expansion)

An adhesive film was obtained by coating and drying each curable resin composition obtained in the Examples and Comparative Examples on a base PET film so that the thickness after drying was 100 μm. A PET film was peeled from the obtained adhesive film, laminated, and cured by heating at 190°C for 1 hour to produce a cured product with a thickness of 400 μm.

The obtained cured product was analyzed from 0°C to 300°C using a thermomechanical analysis device (“TMA/SS-6000” manufactured by Hitachi High-Tech Science, Inc.) with a load of 5 g, a temperature increase rate of 10°C/min, and a sample length of 1 cm. After raising the temperature to , it was once cooled, and the temperature was again raised from 0°C to 300°C under the same conditions. Based on the data of temperature and dimensional change obtained in the second measurement, the average coefficient of linear expansion in the temperature range of 25°C to 80°C was determined.

The low linear expansion property was evaluated by setting the case where the average linear expansion coefficient was 80 ppm or less as “○”, the case where it was more than 80 ppm and 100 ppm or less as “△”, and the case where it exceeded 100 ppm as “×”.

Industrial applicability

According to the present invention, a curable resin composition excellent in heat resistance, thermal conductivity, low linear expansion, and adhesiveness can be provided. Moreover, according to the present invention, a cured product of the curable resin composition, and an adhesive and adhesive film made using the curable resin composition can be provided.

Claims (9)

A curable resin composition containing a curable resin and a curing agent,
The curing agent includes an imide oligomer having a crosslinkable functional group capable of reacting with the curable resin,
A curable resin composition in which the imide oligomer has mesogenic properties, or the curing agent contains another curing agent that has mesogenic properties in addition to the imide oligomer. According to claim 1,
A curable resin composition in which the crosslinkable functional group is at least one of an acid anhydride group and a phenolic hydroxyl group. The method of claim 1 or 2,
A curable resin composition wherein the molecular weight of the imide oligomer is 5000 or less. The method of claim 1, 2 or 3,
A curable resin composition in which the curing agent has a structure represented by the following formula (1-1), (1-2), or (1-3).

In formula (1-1), A ¹ and A ² each independently represent an aromatic group or a condensed aromatic group, and in formula (1-2), A ³ represents an aromatic group or a condensed aromatic group, and is represented by formula (1-1) In -3), A ⁴ and A ⁵ each independently represent an aromatic group or a condensed aromatic group. In formulas (1-1) and (1-3), X is a direct bond, -CH=CH-, -C≡C-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CH=N-, -CH=NN=CH-, -N=N-, -N ⁺ (-O ^- )=N-, -CH=C(CH ₃ ) -, -CH=C(CN)-, -CH=CH-C(=O)-, -Ph-, -Ph-Ph-, -S(=O) ₂ -, -C(=O)OROC( =O)-, -OC(=O)-RC(=O)-O-, -C(=O)O-Ph-OC(=O)-, or -OC(=O)-Ph-C (=O)-O-, Ph represents an aromatic ring that is unsubstituted or has a substituent, and R represents a straight or branched alkylene chain having 1 to 10 carbon atoms. In formulas (1-1) to (1-3), * represents the binding position. The method of claim 1, 2, 3 or 4,
The curable resin composition includes an epoxy resin. The method of claim 1, 2, 3, 4 or 5,
Additionally, a curable resin composition containing a thermally conductive filler. A cured product of the curable resin composition according to claim 1, 2, 3, 4, 5 or 6. An adhesive comprising the curable resin composition according to claim 1, 2, 3, 4, 5, or 6. An adhesive film formed using the adhesive according to claim 8.