JP2024041724A - Resin composition, adhesive, coating agent, cured product, adhesive sheet, copper foil with resin, copper-clad laminate, and printed wiring board - Google Patents

Abstract

To provide a resin composition that produces a cured product with exceptional adhesion, resistance to solder heat, resistance to moist heat, and resistance to migration, wherein the cured product, when used as a resin film, also demonstrates outstanding solder heat resistance and a high storage modulus.SOLUTION: A resin composition comprises (A) a polyimide resulting from the reaction of a monomer group including an aromatic tetracarboxylic anhydride (a1) and a diamine (a2) including a dimeric diamine, (B) a crosslinker represented by the general formula (1), and (C) a curing agent other than the component (B).SELECTED DRAWING: None

Description

The present invention relates to a resin composition, an adhesive, a coating agent, a cured product, an adhesive sheet, a resin-coated copper foil, a copper-clad laminate, and a printed wiring board.

Polyimides are generally obtained by reacting tetracarboxylic anhydrides with diamines, and have a variety of properties, including heat resistance, adhesion, and mechanical properties. For this reason, they are used in a variety of applications, such as protective films and insulating sealing films for semiconductors, and adhesives for flexible printed wiring boards and printed circuit boards.

Furthermore, in recent years, high-frequency electrical signals have been used to transmit and process large amounts of information at high speed, but since high-frequency signals are extremely susceptible to attenuation, the multilayer wiring board has also been designed to reduce transmission loss as much as possible. In this respect, polyimide having low dielectric properties (low dielectric constant, low dielectric loss tangent) is useful.

As such a technique, the present applicant has developed a method using diamine derived from tetracarboxylic acid residues and dimer acid to form an adhesive layer in a copper clad laminate including an insulating film, an adhesive layer, and a copper foil. An adhesive composition containing a polyimide having a residue and a crosslinking component is disclosed (Patent Document 1). Since the polyimide has an aromatic ring, it exhibits excellent solder heat resistance.

The following three issues are listed as current issues in each application.
1. In this technique, a polyfunctional epoxy resin is blended as one of the crosslinking components in the adhesive composition. However, such epoxy resins generally contain chlorine as an impurity during the manufacturing process, and when wiring boards are made with such compositions, there is a risk of leakage between the terminals of copper circuits in a high humidity environment. When the voltage is applied, copper eluted from the anode side is precipitated, which tends to cause a phenomenon called ion migration that short-circuits the circuit.
2. In this technique, isocyanate is blended as the thermoplastic polyimide composition in the copper-clad laminate, and a high temperature of 280° C. or higher is required when producing the copper-clad laminate.
3. Casting is a typical method for producing polyimide films. In this method, a polyamic acid solution is applied onto a support base material, dried, imidized by heat treatment, and then the support base material is peeled off. However, imidization does not proceed unless the heat treatment is performed at a very high temperature of 300 to 400°C.

Japanese Patent Application Publication No. 2018-121807

The present invention provides a cured product with excellent adhesion, solder heat resistance, moist heat resistance, and migration resistance when used as an adhesive, and also provides excellent solder heat resistance when the cured product is used as a resin film. An object of the present invention is to provide a resin composition exhibiting high properties and high storage modulus.

After intensive study, the present inventor found a solution to the above problem and completed the present invention. That is, the present invention provides the following.

1. A polyimide (A) which is a reactant of a monomer group containing an aromatic tetracarboxylic anhydride (a1) and a diamine (a2) including a dimer diamine, a crosslinking agent (B) represented by the general formula (1), and ( A resin composition containing a curing agent (C) other than component B).
(In formula (1), X ¹ , X ² and X ³ each independently represent a group having one or more epoxy skeletons.)

2. 1. The resin composition according to item 1, wherein component (C) is one or more selected from the group consisting of polyamide amine, polyether polyamine, and trimer triamine.

3. The resin composition according to item 1 or 2 above, further comprising an inorganic filler.

4. An adhesive comprising the resin composition according to item 1 above.

5. A coating agent comprising the resin composition according to item 1 above.

6. A cured product containing one or more selected from the group consisting of the resin composition described in 1 above, the adhesive described in 4 above, and the coating agent described in 5 above.

7. An adhesive sheet having the cured product described in paragraph 6 above on at least one side of a support film.

8. A resin-coated copper foil comprising the cured product according to 6 above or the adhesive sheet according to 7 above, and copper foil.

9. A copper-clad laminate comprising the resin-coated copper foil according to item 8 above, and a copper foil or an insulating sheet.

10. A printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate described in paragraph 9 above.

When the resin composition of the present invention is used as an adhesive, it provides a cured product with excellent adhesion, soldering heat resistance, moist heat resistance, and migration resistance, and when the cured product is used as a resin film, Shows excellent solder heat resistance and high storage modulus. Moreover, the resin composition of the present invention can also be cured at a lower temperature than conventional ones due to the combination of polyimide and crosslinking agent.

The resin composition of the present invention comprises a monomer containing an aromatic tetracarboxylic acid anhydride (a1) (hereinafter referred to as component (a1)) and a diamine (a2) containing dimer diamine (hereinafter referred to as component (a2)). Polyimide (A) (hereinafter referred to as component (A)), which is a reactant of the group, crosslinking agent (B) represented by general formula (1) (hereinafter referred to as component (B)), and (B) It contains a curing agent (C) other than the component (hereinafter referred to as component (C)).

(In formula (1), X ¹ , X ² and X ³ each independently represent a group having one or more epoxy skeletons.)

Component (A) is polyimide, and is a component used so that the resin composition layer (hereinafter referred to as a cured material layer) exhibits a low dielectric constant and a low dielectric loss tangent.

Component (a1) includes, for example, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 2,2',3,3 '-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3' , 3,4'-diphenyl ether tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4- dicarboxyphenyl)methane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 2,2 -Bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(2,3-dicarboxyphenoxyphenyl)sulfone dianhydride , bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 2,3 , 6,7-anthracenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6 , 7-naphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2, Examples include 2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, and the like. These may be used alone or in combination of two or more.

Among these, the component (a1) is preferably one represented by the following general formula (2) from the viewpoint of flexibility and soldering heat resistance of the cured material layer.
(In formula (1), X is a single bond, -SO ₂ -, -CO-, -O-, -O-C ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -C (CH ₃ ) ₂ -, -O-C ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-, -C(CHF ₂ ) ₂ -, -C(CF ₃ ) ₂ -, -COO-(CH ₂ ) _p -OCO-, or -COO-H ₂ C-HC (-OC(=O)-CH ₃ )-CH ₂ -OCO-, p represents an integer from 1 to 20.)

Examples of those represented by the general formula (2) include 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride Acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride anhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, Examples include 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride and 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride. These may be used alone or in combination of two or more. Among them, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4'-[propane-2,2 -diylbis(1,4-phenyleneoxy)]diphthalic dianhydride is preferred.

The amount of component (a1) used in 100 mol% of the monomer group constituting component (A) is usually 10 to 90 mol%, preferably 25 to 75 mol%.

Further, the amount of the tetracarboxylic acid anhydride represented by general formula (2) in 100 mol% of the monomer group constituting component (A) is usually 10 to 90 mol%, preferably 25 to 75 mol%. %.

The amount of the tetracarboxylic acid anhydride represented by general formula (2) to be used in 100 mol% of component (a1) is usually 10 to 100 mol%, preferably 50 to 100 mol%.

Component (a2) is a diamine including dimer diamine.

Dimer diamine is a dimer acid in which all carboxyl groups are substituted with primary amino groups or primary aminomethyl groups (see, for example, JP-A-9-12712). Here, dimer acid mainly contains dibasic acids with 36 carbon atoms obtained by dimerizing unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid, and the number of carbon atoms varies depending on the degree of purification. Contains 18 monomer acids, 54 carbon trimer acids, and polymerized fatty acids with 20 to 90 carbon atoms. Note that although the dimer acid contains a double bond, the degree of unsaturation may be reduced by, for example, a hydrogenation reaction.

Examples of the dimer diamine include those represented by the following general formula (3). In general formula (3), m+n=6 to 17 is preferable, p+q=8 to 19 is preferable, and the broken line portion means a carbon-carbon single bond or a carbon-carbon double bond.

In addition, commercial products of dimer diamine include "Versamine 551", "Versamine 552" (all manufactured by Cognix Japan Co., Ltd.), "PRIAMINE1073", "PRIAMINE1074", and "PRIAMINE1075" (all manufactured by Croda Japan Co., Ltd.). (manufactured by), etc. Among these commercially available products, "Versamine 551" and "PRIAMINE 1074" contain the compound represented by the following formula (3-1), and "Versamine 552", "PRIAMINE 1073", and "PRIAMINE 1075" contain the compound represented by the following formula (3-2). It is a dimer diamine containing the compound represented by.

Note that the dimer diamine may contain amines derived from the monomer acid, trimer acid, and/or polymerized fatty acid, and the content thereof is 10% by weight or less, preferably 5% by weight or less, in the dimer diamine. The content is more preferably 3% by weight or less, and even more preferably 2% by weight or less.

Furthermore, the dimer diamine may be used as is, or may be used after purification treatment such as distillation.

The amount of dimer diamine used in 100 mol% of the monomer group constituting component (A) is usually 5 mol% or more, preferably 25 to 75 mol%.

Further, the amount of dimer diamine used in 100 mol% of component (a2) is usually 10 mol% or more, preferably 30 to 100 mol%.

Furthermore, the component (a2) may include a diamine (a2-1) other than dimer diamine (hereinafter referred to as component (a2-1)). Component (a2-1) may include, for example, aliphatic diamine, alicyclic diamine, aromatic diamine, diamino ether, and diamino polysiloxane. Note that these amines exclude dimer diamine.

Examples of aliphatic diamines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, and 1,8-diaminohexane. Examples include octane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

Examples of alicyclic diamines include diaminodicyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, tetramethyldiaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl) ) cyclohexane, bis(4-aminocyclohexyl)methane, diaminobicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2.2.1]heptane, 3(4),8(9)-bis Examples include (aminomethyl)tricyclo[5.2.1.0(2,6)]decane and isophoronediamine.

Examples of aromatic diamines include 2,2'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, and 2,2'-diaminobiphenyl. Diaminobiphenyl such as '-diethyl-4,4'-diaminobiphenyl, 2,2'-di-n-propyl-4,4'-diaminobiphenyl;
Bisaminophenoxyphenylpropanes such as 2,2-bis[4-(3-aminophenoxy)phenyl]propane and 2,2-bis[4-(4-aminophenoxy)phenyl]propane;
Diaminodiphenyl ethers such as 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether;
Phenyl diamines such as p-phenylene diamine and m-phenylene diamine;
Diaminodiphenylsulfides such as 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide;
Diaminodiphenylsulfones such as 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone;
Diaminobenzophenones such as 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, and 4,4'-diaminobenzophenone;
Diaminodiphenylmethane such as 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis[4-(3-aminophenoxy)phenyl]methane;
Diaminophenylpropanes such as 2,2-di(3-aminophenyl)propane, 2,2-di(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane;
2,2-di(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-di(4-aminophenyl)-1,1,1,3,3, Diaminophenylhexafluoropropane such as 3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane;
1,1-di(3-aminophenyl)-1-phenylethane, 1,1-di(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl )-1-phenylethane and other diaminophenyl phenylethanes;
1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy) Bisaminophenoxybenzene such as benzene;
1,3-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4-bis(3-aminobenzoyl)benzene, 1,4-bis(4-aminobenzoyl) Bisaminobenzoylbenzene such as benzene;
1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(3-amino-α, bis-aminodimethylbenzylbenzenes such as α-dimethylbenzyl)benzene and 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene;
1,3-bis(3-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,3-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,4-bis(3- Bisaminoditrifluoromethylbenzylbenzenes such as amino-α,α-ditrifluoromethylbenzyl)benzene, 1,4-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene;
Aminophenoxybiphenyl such as 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[1-(3-aminophenoxy)]biphenyl;
Aminophenoxyphenyl ketones such as bis[4-(3-aminophenoxy)phenyl]ketone and bis[4-(4-aminophenoxy)phenyl]ketone;
Aminophenoxyphenyl sulfides such as bis[4-(3-aminophenoxy)phenyl]sulfide and bis[4-(4-aminophenoxy)phenyl]sulfide;
Aminophenoxyphenyl sulfones such as bis[4-(3-aminophenoxy)phenyl]sulfone and bis[4-(4-aminophenoxy)phenyl]sulfone;
Aminophenoxy phenyl ethers such as bis[4-(3-aminophenoxy)phenyl]ether and bis[4-(4-aminophenoxy)phenyl]ether;
2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane , 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane and other aminophenoxyphenylpropanes;
1,3-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(3-aminophenoxy) bis(aminophenoxybenzoyl)benzene such as benzoyl]benzene, 1,4-bis[4-(4-aminophenoxy)benzoyl]benzene;
1,3-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1, Bis(amino Phenoxy-α,α-dimethylbenzyl)benzene;
Bis[(aminoaryloxy)benzoyl]diphenyl ether such as 4,4'-bis[4-(4-aminophenoxy)benzoyl]diphenyl ether;
Bis(amino-α,α-dimethylbenzylphenoxy)benzophenone such as 4,4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone:
Bis[amino-α,α-dimethylbenzylphenoxy]diphenylsulfone such as 4,4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfone;
Bis[aminophenoxyphenoxy]diphenylsulfone such as 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylsulfone;
Diaminodiaryloxybenzophenones such as 3,3'-diamino-4,4'-diphenoxybenzophenone and 3,3'-diamino-4,4'-dibiphenoxybenzophenone;
Diaminoaryloxybenzophenones such as 3,3'-diamino-4-phenoxybenzophenone and 3,3'-diamino-4-biphenoxybenzophenone;
Examples include 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine and 9,9-bis(4-aminophenyl)fluorene.

Examples of diaminoether include bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether, bis[(2-aminomethoxy)ethyl]ether, bis[2- (2-aminoethoxy)ethyl]ether, bis[2-(3-aminoprotoxy)ethyl]ether, 1,2-bis(aminomethoxy)ethane, 1,2-bis(2-aminoethoxy)ethane, 1 , 2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2-aminoethoxy)ethoxy]ethane, ethylene glycol bis(3-aminopropyl)ether, diethylene glycol bis(3 -aminopropyl) ether, triethylene glycol bis(3-aminopropyl) ether, and the like.

Examples of the diaminopolysiloxane include α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, and α,ω-bis(4-aminobutyl)polydimethylsiloxane. Dimethylsiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis[3-(2-aminophenyl)propyl]polydimethylsiloxane, α,ω-bis[3-(4-amino) phenyl)propyl]polydimethylsiloxane and the like.

These (a2-1) components may be used alone or in combination of two or more. Among these, alicyclic diamines and aromatic diamines are preferred, and aromatic diamines are more preferred, since the cured material layer exhibits excellent solder heat resistance.

The amount of component (a2-1) used in 100 mol% of the monomer group constituting component (A) is usually 90 mol% or less, preferably 50 mol% or less.

Further, the amount of component (a2-1) used in 100 mol% of component (a2) is usually 90 mol% or less, preferably 70 mol% or less.

Component (A) of the present invention can be obtained by various known production methods. As for the manufacturing method, for example, a monomer group containing components (a1) and (a2) is heated at a temperature of preferably about 30 to 120°C, more preferably about 60 to 100°C, and for a time of preferably 0.1 to 100°C. A step of performing a polyaddition reaction for about 2 hours, more preferably about 0.1 to 0.5 hours to obtain a polyadduct, and heating the obtained polyadduct to a temperature of preferably about 80 to 250°C, more preferably 100 to 250°C. Examples include a method including a step of carrying out an imidization reaction, that is, a dehydration ring-closing reaction, at a temperature of about 170° C., preferably for about 0.5 to 50 hours, more preferably for about 1 to 20 hours. Note that the method and order of mixing the components (a1) and (a2) are not particularly limited.

In the imidization reaction step, various known reaction catalysts, dehydrating agents, and organic solvents may be used, and these may be used alone or in combination of two or more.

Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline. Further, examples of the dehydrating agent include aliphatic carboxylic acid anhydrides such as acetic anhydride and aromatic carboxylic acid anhydrides such as benzoic anhydride.

Examples of organic solvents include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, diazabicycloundecene, etc. Nitrogen-based organic solvent;
Methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, n-butyl methyl ketone, isobutyl methyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, n-butyl ethyl ketone, di-n-propyl ketone, etc. Aliphatic ketones;
Alicyclic ketones such as cyclopropyl methyl ketone, cyclobutanone, cyclobutyl methyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone;
n-propyl formate, isopropyl formate, n-butyl formate, isobutyl formate, n-pentyl formate, isopentyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate , aliphatic esters such as methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate;
Alkyl carbonate esters such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate;
Alicyclic esters such as methyl cyclopropanecarboxylate, ethyl cyclopropanecarboxylate, methyl cyclobutanecarboxylate;
Ethyl-n-propyl ether, di-n-propyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,1-diethoxyethane, 1,2-diethoxyethane, 1,2-dimethoxypropane, 2,2- Aliphatic ethers such as dimethoxypropane, 1,1-diethoxypropane, 2,2-diethoxypropane;
Cyclic ethers such as tetrahydrofuran and dioxane;
Alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-methoxy-2-propyl alcohol, t-butyl alcohol;
2-Methylpentane, 3-ethylpentane, n-hexane, 2-methylhexane, 3-methylhexane, 3-ethylhexane, n-heptane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 3- Aliphatic hydrocarbons such as ethylheptane, n-octane, 2-methyloctane, 3-methyloctane, 4-methyloctane;
Methylcyclopentane, ethylcyclopentane, n-propylcyclopentane, isopropylcyclopentane, n-butylcyclopentane, isobutylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,1-dimethylcyclohexane, 1-ethyl-3-methyl Alicyclic hydrocarbons such as cyclohexane and cycloheptane;
Aromatic hydrocarbons such as benzene, toluene, and xylene; dimethyl sulfoxide, and the like. These may be used alone or in combination of two or more.

Further, the amount of the organic solvent used is adjusted so that the reaction concentration is 5 to 60% by weight, preferably 20 to 50% by weight.

The imide ring closure rate of component (A) is preferably about 90 to 100%, more preferably about 95 to 100%, from the viewpoint of obtaining component (A) with high softening point and high flexibility.
It is presumed that because the imide ring closure ratio of component (A) is within the above range, component (A) is likely to form a structure of hard segments and soft segments, and its softening point and flexibility are both high. The term "imide ring closure rate" as used herein means the content of cyclic imide bonds in the polyimide of component (A), and can be determined by various spectroscopic means such as NMR and IR analysis.

As for the physical properties of component (A), for example, the weight average molecular weight is preferably 10,000 to 100,000. Further, the number average molecular weight of component (A) is preferably 5,000 to 50,000. The weight average molecular weight and number average molecular weight are determined, for example, as polystyrene equivalent values measured by gel permeation chromatography (GPC).

The softening point of component (A) of the present invention is preferably about 50 to 250°C, more preferably about 80 to 200°C. The softening point is the temperature at which the storage modulus begins to decrease in the storage modulus profile measured using a commercially available measuring instrument (device name: "ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific). refers to

Component (B) is a crosslinking agent represented by general formula (1), and in combination with component (A) and component (C) described below, exhibits, for example, one or more of the following effects: be able to.
(1) The resin composition can be cured at low temperatures.
(2) The cured product exhibits excellent adhesion, solder heat resistance, and migration resistance.
(3) When the cured product is used as a resin film, it exhibits excellent solder heat resistance and high storage modulus.

(In formula (1), X ¹ , X ² and X ³ each independently represent a group having one or more epoxy skeletons.)

In formula (1), X ¹ , X ^{2 and} 4-epoxycyclohexyl)ethyl group, an alkyl group represented by general formula (1-1), an epoxy group, a group having a structure aligned with an alkyl group, an alkyl group represented by general formula (1-2), epoxy group, an alkyl group, an epoxy group, a group having a structure aligned with an alkyl group, and the like.

(In formula (1-1), Y ₁ and Y ₂ are each independently an integer of 1 to 15.)

(In formula (1-2), Z ₁ , Z ₂ , and Z ₃ are each independently an integer from 1 to 15.)

Commercial products of component (B) (i.e., crosslinking agent represented by general formula (1)) include, for example, "Sunsocizer E-2000H" and "Sunsocizer E-9000H" (all of which are manufactured by Shin Nippon Rika Co., Ltd.). ), "ADEKASIZER O-130P", "ADEKASIZER O-180P" (manufactured by ADEKA Co., Ltd.), "Epocizer W-100-EL" (manufactured by DIC Corporation), "Kapox S-6" " (manufactured by Kao Corporation), "Nusocizer 510R" (manufactured by NOF Corporation), etc., and "Sansocizer E-2000H" contains a compound represented by the following formula (1-3). It is an epoxy resin.

The content of component (B) is preferably 1 to 15 parts by weight, and 3.5 to 10 parts by weight, based on 100 parts by weight of component (A), in terms of non-volatile content, in order to easily exhibit the above-mentioned effects. parts by weight is more preferable, and 3.5 to 7 parts by weight is even more preferable. Note that the term "nonvolatile content" refers to components that remain after removing volatile components such as water and organic solvents.

Component (C) is a curing agent other than component (B) and can promote the reaction between components (A) and (B), so it can be cured at a relatively low temperature and the resulting cured product is also an excellent solder. Shows heat resistance. Here, the curing agent refers to a component that has the function of curing, and includes those that cure while the curing agent reacts with components other than the curing agent (non-crosslinking curing agent), and those that cure as the curing agent reacts with components other than the curing agent. It is classified as a curing agent that self-crosslinks with each other (crosslinkable curing agent, crosslinking agent).

Examples of component (C) include epoxy resins, benzoxazine, bismaleimide, cyanate esters, polyisocyanates, phosphorus compounds, acid anhydrides, amines, imidazole, guanidine, phenolic resins, and active esters. These may be used alone or in combination of two or more.

Examples of the epoxy resin include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, and hydrogenated bisphenol F type epoxy resin. Epoxy resin, stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenol Methane type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, naphthalene skeleton-containing epoxy resin, arylalkylene type epoxy resin, tetraglycidyl xylylene diamine, dimer acid modified epoxide which is a dimer acid modified product of the above epoxide, Examples include dimer acid diglycidyl ester.

Commercially available epoxy resins include "jER828", "jER834", "jER807", "jER604", "jER630", "jER871", "jER872" (manufactured by Mitsubishi Chemical Corporation), and "ST-3000". ", "YD-172-X75" (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), "Celoxide 2021P" (manufactured by Daicel Corporation), "TETRAD-X" (manufactured by Mitsubishi Gas Chemical Co., Ltd.), Examples include "NC-513", "NC-514S", and "NC-547" (all manufactured by Cardolite Corp.).

Examples of the benzoxazine include 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylidene)bis (3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like. In addition, a phenyl group, a methyl group, a cyclohexyl group, etc. may be bonded to the nitrogen of the oxazine ring.

Commercial products of benzoxazine include "Benzoxazine Fa type", "Benzoxazine P-d type" (manufactured by Shikoku Kasei Kogyo Co., Ltd.), and "RLV-100" (manufactured by Air Water Co., Ltd.). ) etc.

Examples of the bismaleimide include N,N'-ethylene bismaleimide, N,N'-trimethylene bismaleimide, N,N'-tetramethylene bismaleimide, N,N'-pentamethylene bismaleimide, N,N' -Hexamethylene bismaleimide, N,N'-hexamethylenebismethylmaleimide, N,N-heptamethylenemaleimide, N,N-octamethylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl ) N,N'-alkylene bismaleimides such as hexane, 1,1'-(decane-1,10-diyl)bis(1H-pyrrole-2,5-dione);
N,N'-dicyclohexylmethane bismaleimide, 1,1'-[(4-hexyl-3-octylcyclohexane-1,2-diyl)bis(octane-1,8-diyl)]bis(1H-pyrrole-2 ,5-dione), 1,1'-(cyclohexane-1,10-diyl)bis(1H-pyrrole-2,5-dione), 1,1'-[4,4'-methylenebis(cyclohexane-1, 4-diyl)] bis(1H-pyrrole-2,5-dione) and other cycloalkane-containing bismaleimides;
N,N'-xylene bismaleimide, N,N'-tolylene bismaleimide, N,N'-xylylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide , phenylene bismaleimides such as 4-methyl-1,3-phenylenebismaleimide;
1,1'-[methylenebis(1,4-phenylene)]bis(1H-pyrrole-2,5-dione), 1,1'-[methylenebis(2-ethyl-6-methyl-1,4-phenylene) ] Bisphenylene bismaleimides such as bis(1H-pyrrole-2,5-dione, 1,1′-(1,3-phenylene)]bis(1H-pyrrole-2,5-dione, etc.);
N,N'-(4,4'-diphenylmethane)bismaleimide, N,N'-4,4'-[3,3'-dimethyldiphenylmethane]maleimide, N,N'-4,4'-[3, 3'-diethyldiphenylmethane]maleimide, N,N'-(4,4'-diphenylpropane)bismaleimide, N,N'-diphenylcyclohexanebismaleimide, 3,3'-dimethyl-5,5'-diethyl-4 ,4-diphenylmethanebismaleimide, N,N'-(4,4'-diphenylmethane)bismaleimide, N,N'-4,4'-[3,3'-dimethyldiphenylmethane]maleimide, N,N'-4 , 4'-[3,3'-diethyldiphenylmethane]maleimide, N,N'-(4,4'-diphenylpropane)bismaleimide, N,N'-diphenylcyclohexanebismaleimide, 3,3'-dimethyl-5 , 5'-diethyl-4,4'-diphenylmethane bismaleimide, N,N'-diphenyl ether bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, N,N'-3,3'-diphenylsulfone bismaleimide, N,N'-4,4'-diphenylsulfone bismaleimide, N,N'-dichlorodiphenyl bismaleimide, 1,1'-[2,2'-bis(trifluoromethyl){1,1'-biphenyl}-4,4'-diyl]bis[1H-pyrrole-2,5-dione], etc. N,N'-diphenyl bismaleimides;
2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[3-methyl-4- (4-Maleimidophenoxy)phenyl]propane, 2,2-bis[3-methyl-4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[3,5-dimethyl-4-(4 -maleimidophenoxy)phenyl]propane, 2,2-bis[3,5-dimethyl-4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[3-ethyl-4-(4-maleimide) Examples include bis(phenoxyphenyl)alkanes such as phenoxy)phenyl]propane and 2,2-bis[3-ethyl-4-(4-maleimidophenoxy)phenyl]hexafluoropropane. These may be used alone or in combination of two or more.

In addition, commercially available bismaleimide products include "BMI", "BMI-70", "BMI-80" (manufactured by K.I. Kasei Co., Ltd.), "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-2000", "BMI-2300", "BMI-3000", "BMI-3000H", "BMI-4000", "BMI-5100", "BMI -7000'', ``BMI-7000H'', and ``BMI-TMH'' (manufactured by Daiwa Kasei Co., Ltd.).

Furthermore, as the bismaleimide, bismaleimide derived from the aforementioned dimer diamine (hereinafter referred to as maleimide having a dimer diamine skeleton) may be used. Commercial products of the bismaleimide include, for example, "BMI-689", "BMI-689C", "BMI-1400", "BMI-1500", "BMI-1550", "BMI-1700", "BMI- 2500", "BMI-2560", "BMI-3000-C", "BMI-3000J", "BMI-3000 Solution", "BMI-5000P", "BMI-5000T", "BMI-6000", "BMI -6100'' (manufactured by Designer Molecule Inc.).

Examples of the cyanate ester include 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis(4-isocyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, Bisphenol A cyanate ester, diallyl bisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris(4-cyanatophenyl)ethane, 4-cumylphenol cyanate ester, 1,1-bis(4- Examples thereof include cyanatophenyl)ethane, 4,4'-bisphenol cyanate ester, and 2,2-bis(4-cyanatophenyl)propane.

Commercially available cyanate esters include "PRIMASET BTP-6020S" (manufactured by Lonza Japan Co., Ltd.).

Examples of polyisocyanates include straight chain fatty acids such as methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate. Group diisocyanates;
Branched aliphatic polyisocyanates such as trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, trimethylhexamethylene diisocyanate;
Dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, cycloheptylene diisocyanate, norbornene diisocyanate, norbornenemethane diisocyanate, adamantane diisocyanate, cyclohexane-1,4-diylbis( methylene) diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, tricyclodecylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogen Alicyclic polyisocyanates such as dimethyldiphenylmethane diisocyanate and hydrogenated naphthalene diisocyanate;
Aromatic polyisocyanates such as xylylene diisocyanate, tolylene diisocyanate, phenylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, m-tetramethylxylylene diisocyanate, naphthalene diisocyanate, and the like.

Furthermore, as the polyisocyanate, biuret, isocyanurate, allophanate, and adduct forms of the above-mentioned polyisocyanates can also be used. These polyisocyanates may be used alone or in combination of two or more.

Commercially available polyisocyanates include, for example,
The biuret bodies are "Duranate 24A-100", "Duranate 22A-75P", "Duranate 21S-75E" (all manufactured by Asahi Kasei Corporation), and "Desmodur N3200A" (all manufactured by Sumitomo Bayer Urethane Co., Ltd.). etc. are mentioned,
The isocyanurates include "Duranate TPA-100", "Duranate TKA-100", "Duranate MFA-75B", "Duranate MHG-80B" (manufactured by Asahi Kasei Corporation), and "Coronate HXR" (manufactured by Tosoh Corporation). ), "Takenate D-131N", "Takenate D204EA-1", "Takenate D-127N" (manufactured by Mitsui Chemicals Co., Ltd.), "VESTANAT T1890/100" (manufactured by Evonik Japan Co., Ltd.) etc. are mentioned,
Examples of allophanates include "Takenate D-178N" (manufactured by Mitsui Chemicals, Inc.),
Adduct bodies include "Duranate P301-75E" (manufactured by Asahi Kasei Corporation), "Takenate D110N", "Takenate D160N" (all manufactured by Mitsui Chemicals, Inc.), "Coronate L" (manufactured by Tosoh Corporation), etc. can be mentioned.

Examples of phosphorus compounds include tributylphosphine, phenylphosphine, diphenylphosphine, methyldiphenylphosphine, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, Examples include (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate. These may be used alone or in combination of two or more.

Examples of acid anhydrides include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride. Phthalic acid, mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2,3-dicarboxylic anhydride methylnorbornane-2,3-dicarboxylic anhydride, methylcyclohexenedicarboxylic anhydride, 3-dodecenylsuccinic anhydride, octenylsuccinic anhydride, and the like. These may be used alone or in combination of two or more.

Examples of amines include the aforementioned dimer diamine, component (a2-1), aliphatic amines such as triethylamine, tributylamine, triethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine;
Amino alcohols such as triethanolamine and dimethylaminoethanol;
Alicyclic amines such as trimer triamine;
Aromatic amines such as 1,3-aminobenzene, benzyldimethylamine, 1,3-bis(aminomethyl)benzene, 2,4,6-tris(dimethylaminomethyl)phenol;
Heterocyclic amines such as 4-dimethylaminopyridine, N-aminoethylpiperazine, 1,8-diazabicyclo[5,4,0]-undecene;
Examples include polyamide polyamine, polyether polyamine, polyester polyamine, and the like. These may be used alone or in combination of two or more.

Examples of imidazoles include 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-ethyl-4-methylimidazole tetraphenylborate, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid addition Examples of such compounds include 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline. These may be used alone or in combination of two or more.

Examples of guanidine include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5- ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, Examples include 1-phenylbiguanide and 1-(o-tolyl)biguanide. These may be used alone or in combination of two or more.

Examples of phenolic resins include phenol novolac resin, cresol novolac resin, bisphenol A type novolac resin, triazine modified phenol novolac resin, phenolic hydroxyl group-containing phosphazene, etc. These may be used alone or in combination of two or more.

Examples of the active ester include those containing a dicyclopentadienyl diphenol structure described in JP-A-2019-183071, those containing a naphthalene structure, acetylated products of phenol novolak, benzoylated products of phenol novolac, and the like. These may be used alone or in combination of two or more.

Commercially available active esters include, for example,
Those containing dicyclopentadienyl diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8150-"62T","HPC-8000H-65MT","HPC-8000L-65MT","EXB-8000L","EXB-8000L-65MT","EXB-8150-65T" (all manufactured by DIC Corporation);
Contains a naphthalene structure, “EXB9416-70BK” (manufactured by DIC Corporation);
An acetylated product of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation);
Examples of benzoylated phenol novolacs include "YLH1026", "YLH1030", and "YLH1048" (all manufactured by Mitsubishi Chemical Corporation).

Active esters produced by various known methods can also be used, such as those produced by reacting a polyfunctional phenol compound and an aromatic carboxylic acid described in Japanese Patent No. 5152445.

The above component (C) may be used alone or in combination of two or more. Among these, amines are preferred, and polyamide polyamines, polyether polyamines, and trimer triamines are more preferred, since the cured product exhibits excellent heat resistance.

Commercially available polyamide polyamine products include, for example, "VegiChem Green V115", "VegiChem Green V125", "VegiChem Green V140", "VegiChem Green V150", "VegiChem Green V1460", "VegiChem Green V1480", "VegiChem Green G250", and "VegiChem Green G747" (all manufactured by Tsuno Foods Industries Co., Ltd.), "Luckamide TD-960", "Luckamide TD-984", and "Luckamide TD-982" (all manufactured by DIC Corporation).

Commercially available polyether polyamines include, for example, "PEG #1000 diamine" (manufactured by NOF Corporation), "JEFFAMINE" series (for example, "JAFFAMINE D-230", "JAFFAMINE T-403", etc.) (HUNTSMAN) (manufactured by BASF), "Baxxodur" series (manufactured by BASF), and the like.

Trimer triamine is a trimer of unsaturated fatty acids such as oleic acid (see Japanese Patent Application Publication No. 2013-505345) in which all carboxyl groups have been replaced with primary amino groups, and it is available as a commercially available product. Examples include "PRIAMINE1071" and "PRIAMINE1073" (all manufactured by Croda Japan Co., Ltd.).

The content of component (C) is preferably from 0.5 to 10 parts by weight, and from 0.9 to 10 parts by weight, based on 100 parts by weight of component (A), in terms of non-volatile content, in order to facilitate the aforementioned effects. More preferably 7 parts by weight, and even more preferably 1 to 5 parts by weight.

The resin composition of the present invention may further contain an inorganic filler.

Examples of the inorganic filler include silica filler, phosphorus filler, fluorine filler, and inorganic ion exchange filler. Note that the silica filler may be one whose surface has been modified with a treatment agent such as a silane coupling agent. These may be used alone or in combination of two or more.

Examples of commercially available inorganic fillers include "FB-3SDC", "SFP-20M" (manufactured by Denka Corporation), "SC-2500-SPJ", "SC-2500-SXJ", and "SC-2500". -SVJ", "SC-2500-SEJ" (manufactured by Admatex Co., Ltd.), "Exolit OP935" (manufactured by Clariant Chemicals Co., Ltd.), "KTL-500F" (manufactured by Kitamura Co., Ltd.), "IXE" ” (manufactured by Toagosei Co., Ltd.).

The content of the inorganic filler is determined based on 100 parts by weight of component (A) in terms of non-volatile content, since the cured product tends to have a low dielectric loss tangent and the storage modulus tends to improve when used as a resin film. The amount is preferably 5 to 70 parts by weight, more preferably 10 to 60 parts by weight, and even more preferably 10 to 50 parts by weight.

The resin composition of the present invention may further contain a phosphorus flame retardant.

Examples of the phosphorus flame retardant include polyphosphoric acid, phosphoric acid ester, and phosphazene derivatives having no phenolic hydroxyl group. Among the phosphazene derivatives, cyclic phosphazene derivatives are preferred in terms of flame retardancy, heat resistance, bleed-out resistance, and the like. Commercially available cyclic phosphazene derivatives include "SPB-100" (manufactured by Otsuka Chemical Co., Ltd.) and "Rabitor FP-300B" (manufactured by Fushimi Pharmaceutical Co., Ltd.).

The content of the phosphorus-based flame retardant is preferably 0.01 to 5 parts by weight based on 100 parts by weight of component (A) in terms of nonvolatile content.

The resin composition of the present invention has a general formula: W-Si(R ¹ ) _a (OR ² ) _3-a (wherein, W is a group containing a functional group that reacts with an acid anhydride group, and R ¹ is a group containing a functional group that reacts with an acid anhydride group. Hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² is a hydrocarbon group having 1 to 8 carbon atoms, and a is 0, 1 or 2). good. The reactive alkoxysilyl compound allows the melt viscosity of the resin composition layer to be adjusted while maintaining low dielectric properties. As a result, the interfacial adhesion (so-called anchor effect) between the layer of the resin composition and the support can be enhanced, while the bleeding of the cured layer from the edges of the support can be suppressed.

Examples of the reactive functional group included in W in the general formula include an amino group, an epoxy group, and a thiol group.

Compounds in which W contains an amino group include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. , 3-aminopropyltriethoxysilane and 3-ureidopropyltrialkoxysilane. Examples of compounds in which W contains an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. Examples include sidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of the compound in which W contains a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. Among these, compounds in which W contains an amino group are preferred because they have good reactivity and flow control effects.

The content of the reactive alkoxysilyl compound is preferably 0.01 to 5 parts by weight based on 100 parts by weight of component (A) in terms of nonvolatile content.

Further, the resin composition of the present invention may further contain the above-mentioned organic solvent. The content of the organic solvent is preferably adjusted so that the nonvolatile content concentration of the resin composition is preferably 20 to 40% by weight, more preferably 25 to 35% by weight.

The resin composition of the present invention may contain as an additive an ingredient other than component (A), component (B), component (C), inorganic filler, phosphorus-based flame retardant, reactive alkoxysilyl compound, or organic solvent. good.

Examples of the additives include a ring-opening esterification catalyst, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a coloring agent, a conductive agent, and a mold release agent. agents, surface treatment agents, viscosity modifiers, inorganic pigments, organic pigments, etc.

The content of the additive, calculated as non-volatile matter, per 100 parts by weight of component (A), may be less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, or 0 part by weight.

The resin composition of the present invention includes component (A), component (B), and component (C), and if necessary, an inorganic filler, a phosphorus-based flame retardant, a reactive alkoxysilyl compound, an organic solvent, and an additive. It can be obtained by dissolving it while mixing.

[glue]
In the present invention, an adhesive containing the resin composition is also one of the embodiments. As a result, the cured product has excellent adhesive properties, solder heat resistance, and migration resistance.

[Coating agent]
One of the embodiments of the present invention is a coating agent containing the resin composition. As a result, it can be cured at low temperatures, and the cured product exhibits excellent adhesion, soldering heat resistance, and low dielectric properties. Furthermore, when the cured product is used as a resin film, it has excellent soldering heat resistance and a high storage modulus. This will indicate the following.

[Cured product]
The present invention also includes a cured product containing one or more selected from the group consisting of the resin composition, the adhesive, and the coating agent. The method for producing the cured product includes a method including a step of coating the resin composition on a suitable support, a step of curing by heating to volatilize the organic solvent, a step of peeling off the support, etc. Can be mentioned. Further, the thickness of the cured product is preferably 3 to 40 μm. Examples of the support include release paper, release film, and the support film described below. Furthermore, when producing a cured product, the resin composition and various known resin compositions other than the resin composition may be used in combination. Furthermore, the obtained cured product can be used as a resin film by peeling off the support.

[Adhesive sheet]
The adhesive sheet of the present invention contains the cured product of the present invention on at least one side of the support film.

The adhesive sheet can be obtained, for example, by coating the resin composition of the present invention on a support film and curing it by heating, or by laminating the cured product of the present invention onto a support film.

The support film is made of polyimide, polyester, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, ethylene terephthalate, phenol, phthalate. Aromatic polyester resins obtained from acids, hydroxynaphthoic acid, etc. and parahydroxybenzoic acid (so-called liquid crystal polymers; "Vexter" (manufactured by Kuraray Co., Ltd.), etc.), cycloolefin polymers, fluorine-based resins (polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), polyvinylidene fluoride (PVDF), etc.). Polyimide includes the polyimide film of the present invention.

When coating the resin composition of the present invention on the support film, examples of the coating method include comma, die, knife, lip, and other coaters. The thickness of the coating layer after drying is preferably about 1 to 100 μm, more preferably about 3 to 50 μm. Moreover, the cured material layer of the adhesive sheet may be protected with various protective films.

[Resin-coated copper foil]
The resin-coated copper foil of the present invention includes the cured product or adhesive sheet of the present invention and a copper foil. Specifically, the resin composition of the present invention is applied to a copper foil and cured by heating, or the cured product of the present invention is laminated to the copper foil. Examples of the copper foil include rolled copper foil and electrolytic copper foil, and those that have been subjected to various surface treatments (roughening, rust prevention, etc.) can also be used. Examples of the rust prevention treatment include so-called mirror finish treatments such as plating treatment using a plating solution containing Ni, Zn, Sn, etc., and chromate treatment.

The thickness of the copper foil is preferably about 1 to 100 μm, and more preferably about 2 to 38 μm. Coating methods include the methods described above.

Further, the resin composition layer or cured product of the resin-coated copper foil may be partially or completely cured under heating. The partially cured resin composition layer or cured product is in a so-called B stage state. Further, the thickness of the resin composition layer or cured product is preferably about 0.5 to 30 μm. Moreover, a layer of a resin composition can be further bonded to the copper foil of the resin-coated copper foil to obtain a double-sided resin-coated copper foil.

[Copper-clad laminate]
The copper-clad laminate of the present invention includes the resin-coated copper foil and the copper foil or the insulating sheet of the present invention. A copper clad laminate is also called CCL (Copper Clad Laminate). Specifically, the copper-clad laminate is made by pressing the resin-coated copper foil onto at least one or both sides of various known copper foils or insulating sheets under heat. When pasting on one side, a material different from the resin-coated copper foil may be crimped onto the other side. Further, the number of resin-coated copper foils, copper foils, and insulating sheets in the copper-clad laminate is not particularly limited.

In one embodiment, the insulating sheet is preferably a prepreg or the support film described above. Prepreg is a sheet-like material made by impregnating a reinforcing material such as glass cloth with resin and curing it to B stage (JIS C 5603). As the resin, insulating resins such as the resin composition of the present invention, phenol resins, epoxy resins, polyester resins, liquid crystal polymers, and aramid resins are used. The thickness of the insulating sheet is preferably about 20 to 500 μm. The heating/pressing conditions are preferably about 150 to 280°C (more preferably about 170 to 240°C), and preferably about 0.5 to 20 MPa (more preferably about 1 to 8 MPa).

[Printed wiring board]
The printed wiring board of the present invention has a circuit pattern on the copper foil surface of the copper-clad laminate of the present invention. The patterning means for forming a circuit pattern on the copper foil surface of the copper-clad laminate include a subtractive method and a semi-additive method. As the semi-additive method, a method in which the copper foil surface of the copper-clad laminate is patterned with a resist film, electrolytic copper plating is performed, the resist is removed, and etching is performed with an alkaline solution is exemplified. The thickness of the circuit pattern layer in the printed wiring board is not particularly limited. A multilayer board can also be obtained by laminating the same printed wiring board or other known printed wiring boards or printed circuit boards on the printed wiring board as a core. When laminating, the resin composition and other known resin compositions other than the resin composition can be used in combination. The number of layers in the multilayer board is not particularly limited. In addition, a via hole may be inserted and the inside may be plated each time the layers are laminated. The line/space ratio of the circuit pattern is preferably about 1 μm/1 μm to 100 μm/100 μm. The height of the circuit pattern is also preferably about 1 to 50 μm.

Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not particularly limited thereto. Furthermore, unless otherwise specified, all "%" are based on mass.

Manufacturing example 1
3,3',4,4'-benzophenonetetracarboxylic dianhydride (trade name: "BTDA", manufactured by EVONIK INDUSTRIES) was placed in a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube. , hereinafter referred to as BTDA), 1008.00 g of cyclohexanone, and 201.60 g of methylcyclohexane were charged and heated to 60°C. Next, 318.41 g of dimer diamine (trade name: "PRIAMINE1075", manufactured by Croda Japan Co., Ltd.) (hereinafter also referred to as PRIAMINE1075), polydimethylsiloxane (trade name: "KF-8010", manufactured by Shin-Etsu Chemical Co., Ltd.) After gradually adding 27.31 g of Polyimide (A-1), a solution of polyimide (A-1) (non-volatile content: 30%) was obtained by carrying out an imidization reaction at 120° C. for 14 hours.

Manufacturing example 2
In a reaction vessel similar to Production Example 1, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride (trade name: "BisDA-1000", SABIC Innovative Plastics BisDA (manufactured by Sujapan LLC, hereinafter referred to as BisDA), 794.64 g of cyclohexanone, and 158.93 g of methylcyclohexane were charged and heated to 70°C. Next, 71.88 g of 4,4'-diaminophenyl ether (trade name: "ODA", manufactured by Wakayama Seika Kogyo Co., Ltd.) and 83.08 g of dimer diamine (PRIAMINE1075) were gradually added, and the mixture was heated at 110°C for 12 hours. A solution of polyimide (A-2) (non-volatile content: 30%) was obtained by carrying out an imidization reaction over a period of time.

Manufacturing example 3
210.00 g of BTDA, 1006.32 g of cyclohexanone, and 201.26 g of methylcyclohexane were placed in a reaction vessel similar to Production Example 1, and heated to 60°C. Next, after gradually adding 340.02 g of dimer diamine (PRIAMINE1075), an imidization reaction was carried out at 120° C. for 14 hours to obtain a solution (non-volatile content: 30%) of polyimide resin (A-3). .

Production example 4
In a reaction vessel similar to Production Example 1, 280.00 g of BisDA-1000, 371.38 g of ethylene glycol dimethyl ether, and 866.56 g of toluene were charged and heated to 70°C. Next, after gradually adding 276.92 g of dimer diamine (PRIAMINE1075), an imidization reaction was carried out at 140° C. for 12 hours to obtain a solution (non-volatile content: 30%) of polyimide resin (A-4). .

Example 1-1
As the polyimide, 333.3 g (non-volatile content: 100.0 g) of (A-1), as the crosslinking agent of component (B), a polyfunctional epoxy resin having a glycerin triester group (trade name: "Sansocizer E-2000H", 5.3 g (non-volatile content: 5.3 g) manufactured by Shin Nippon Chemical Co., Ltd., and 1.6 g (non-volatile 1.6 g) and 87.4 g of methyl ethyl ketone as an organic solvent were mixed and stirred thoroughly to obtain a resin composition (1) with a nonvolatile content of 25%.

Examples 1-2 to 1-10, Comparative Examples 1-1 to 1-5
Resin compositions (1) were obtained in the same manner as in Example 1-1 except for changing the composition shown in Table 1.

<Preparation of adhesive sheet>
A commercially available polyimide film (trade name: "Kapton 100EN", film thickness: 25 μm, coefficient of thermal expansion: 15 ppm/°C, manufactured by DuPont-Toray Co., Ltd.) (produced by DuPont Toray Co., Ltd.) of each example and comparative example (1) was used. (hereinafter referred to as Kapton) using a gap coater so that the thickness after drying would be 25 μm, and then dried at 150° C. for 5 minutes to obtain adhesive sheets (Kapton/cured material layer).

<Production of copper-clad laminate (1)>
The cured layer side of the adhesive sheet (Kapton/cured layer) was placed on the mirror side of a commercially available electrolytic copper foil (product name: "F2-WS", manufactured by Furukawa Electric Co., Ltd.) (film thickness 18 μm). These were overlapped to produce a laminate (Kapton/cured material layer/electrolytic copper foil). Next, it was placed on a press support and heated from above through a support obtained from the same material at a pressure of 10 MPa and a temperature of 100°C for 30 seconds, and then heat-cured at a temperature of 170°C for 30 minutes. and copper-clad laminates (1) were produced.

<Adhesive strength>
Regarding the copper-clad laminate (1), the peel strength (N/mm) was measured according to JIS C 6481 (Test method for copper-clad laminates for flexible printed wiring boards). The results are shown in Table 1.

<Solder heat resistance>
After leaving the copper-clad laminate (1) in a constant temperature room with a temperature of 23 ° C. and a humidity of 50% for 24 hours, it was floated in a solder bath at 288 ° C. with the copper foil side facing down, and the presence or absence of foaming was confirmed. Evaluation was made based on the following criteria. The results are shown in Table 1.
(Evaluation criteria)
○: No change in appearance △: There is foaming, swelling, and peeling on half of the copper-clad laminate ×: There is foaming, swelling, and peeling on the entire copper-clad laminate

<Moisture heat resistance>
The copper-clad laminate (1) was placed in a constant temperature and humidity machine at a temperature of 85° C. and a humidity of 85%, and then taken out after 1000 hours had elapsed. Peel strength (N/mm) was measured according to JIS C 6481 (Test method for copper-clad laminates for flexible printed wiring boards). The results are shown in Table 1.

<Migration resistance>
A comb-shaped copper circuit with a circuit width/circuit distance (L/S) of 20 μm/40 μm was formed on a commercially available polyimide film with copper foil on one side (trade name: "Pyralux TAS124500", manufactured by DUPONT Co., Ltd.) (hereinafter referred to as a copper-clad laminate with PI). The cured layer side of the adhesive sheet (Kapton/cured layer) was overlapped on the copper circuit side of the copper-clad laminate with PI. Then, it was placed on a press support, and heat-pressed from above through a support made of the same material at a pressure of 10 MPa and a temperature of 100 ° C. for 30 seconds, and then thermally cured at a temperature of 170 ° C. for 30 minutes to prepare an evaluation board. A voltage of 30 V was applied to the obtained evaluation board for 500 hours under conditions of a temperature of 85 ° C. and a humidity of 85% (relative humidity), and the evaluation was performed according to the following criteria. The adhesive sheet having the resin composition of Comparative Example 1-1 was not evaluated.
(Evaluation criteria)
A: No short circuit was observed even after 500 hours or more. B: A short circuit was observed in less than 500 hours.

*The parts by weight of each component are expressed as non-volatile weight.

The symbols shown in Table 1 represent the following compounds.
(Polyimide)
A-1: Polyimide of Production Example 1 A-3: Polyimide of Production Example 3 A-4: Polyimide of Production Example 4 E-1: Hydrogenated styrene resin (product name: "Tuftec H1062", manufactured by Asahi Kasei Corporation)
(Crosslinking Agent)
B-1: Multifunctional epoxy resin having a glycerin ester skeleton (product name: "Sanso Cizer E-2000H", manufactured by New Japan Chemical Co., Ltd.)
F-1: Multifunctional epoxy resin (product name: "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.)
F-2: Multifunctional epoxy resin (product name: "jER604", manufactured by Mitsubishi Chemical Corporation)
(Hardening agent)
C-1: Polyamide polyamine (product name: "Vegichem Green V150", manufactured by Tsuno Foods Co., Ltd.)
C-2: Polyether polyamine (product name: "JAFFAMINE T-403", manufactured by HUNTSMAN)
C-3: Trimer triamine (product name: PRIAMINE 1071, manufactured by Croda Japan Co., Ltd.)

Example 2-1
As a polyimide, 333.3 g (non-volatile content: 100.0 g) of (A-2), as a crosslinking agent for component (B), an epoxy resin having a glycerin triester group (trade name: "Sansocizer E-2000H", Shin Nippon (manufactured by Rika Co., Ltd.) 5.9 g (nonvolatile content 5.9 g), as a curing agent, trimer triamine (trade name: "PRIAMINE 1071", manufactured by Croda Japan Co., Ltd.) 3.6 g (nonvolatile content 3.6 g), organic 204.7 g of cyclohexanone was mixed as a solvent and stirred thoroughly to obtain a resin composition (2) with a nonvolatile content of 20%.

Examples 2-2 to 2-6, Comparative Examples 2-1 to 2-5
Resin compositions (2) were obtained in the same manner as in Example 2-1 except for changing the composition shown in Table 2.

<Preparation of cured material layer (1)>
The resin compositions (2) of each example and comparative example were coated on release paper (manufactured by San-A Kaken Co., Ltd.) using a gap coater so that the thickness after drying was 4 μm, and then heated at 150°C for 5 minutes. After drying, the release paper was peeled off to obtain a cured product layer (1).

<Measurement of relative permittivity and dielectric loss tangent>
The above-mentioned cured material layer (1) is placed on a press support, and the same press support is placed on the side of the cured material layer (1), and the layer is cured by heating at a pressure of 6 MPa and 220° C. for 30 seconds. In this way, a heat-cured adhesive sheet (support/cured material layer/support) was prepared. The press support was removed from the cured material layer (1), and the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured material layer (1) were calculated by the following method.
Using a network analyzer (manufactured by Keysight Technologies, device name: "P5003A") and a split post dielectric resonator (manufactured by QWED) with a measurement frequency of 10.124 GHz, the resonant frequency of a single resonator with nothing inserted and the The Q value of the peak was measured.
Next, the adhesive layer was cut into 4 cm x 5 cm to prepare a test piece, and after stacking multiple test pieces so that the total thickness was 100 μm or more and inserting them into the resonator, the test pieces were tested. The resonance frequency and Q value when the piece was inserted were measured.
The dielectric constant (Dk) is calculated from the difference in resonance frequency between the resonator alone and when a test piece is inserted, and the dielectric loss tangent (Df) is calculated from the difference in Q value between the resonator alone and when a test piece is inserted. Calculated from the difference in resonance frequency. Table 2 shows the results.

<Preparation of adhesive sheet>
A commercially available polyimide film (trade name: "Kapton 100EN", film thickness: 25 μm, coefficient of thermal expansion: 15 ppm/°C, manufactured by DuPont-Toray Co., Ltd.) (produced by DuPont Toray Co., Ltd.) of each example and comparative example (2) was used. (hereinafter referred to as Kapton) using a gap coater so that the thickness after drying would be 4 μm, and then dried at 150° C. for 5 minutes to obtain adhesive sheets (Kapton/cured material layer).

<Production of copper-clad laminate (2)>
The cured layer side of the adhesive sheet (Kapton/cured layer) was placed on the mirror side of a commercially available electrolytic copper foil (product name: "F2-WS", manufactured by Furukawa Electric Co., Ltd.) (film thickness 18 μm). These were overlapped to produce a laminate (Kapton/cured material layer/electrolytic copper foil). Next, it was placed on a press support and heated from above through a support obtained from the same material at a pressure of 6 MPa and a temperature of 220° C. for 30 seconds to produce a copper-clad laminate (2).

<Passing>
The appearance of the copper-clad laminate (2) was checked and evaluated based on the following criteria. The results are shown in Table 2.
〇: There are no gaps or bulges on the copper-clad laminate ×: There are gaps or bulges on the copper-clad laminate

<Adhesive strength>
The peel strength (N/mm) of the copper-clad laminate (2) was measured in the same manner as described above. The results are shown in Table 2.

<Solder heat resistance>
The solder heat resistance of the copper clad laminate (2) was evaluated in the same manner as described above. The results are shown in Table 2.

*The weight parts of each component are expressed as non-volatile weight.

The symbols shown in Table 2 represent the following compounds, respectively.
(polyimide)
・A-2: Polyimide (crosslinking agent) of Production Example 2
・B-1: Multifunctional epoxy resin having a glycerin ester skeleton (product name: "Sansocizer E-2000H", manufactured by Shin Nippon Chemical Co., Ltd.)
・F-1: Multifunctional epoxy resin (product name: "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.)
・F-2: Multifunctional epoxy resin (product name: "jER604", manufactured by Mitsubishi Chemical Corporation)
(hardening agent)
・C-2: Polyether polyamine (product name: "JAFFAMINE T-403", manufactured by HUNTSMAN)
・C-3: Trimer triamine (product name: "PRIAMINE1071", manufactured by Croda Japan Co., Ltd.)
(Inorganic filler)
・D-1: Phenyl-modified silica (product name: "Adma Fine SC2500-SPJ", manufactured by Admatex Co., Ltd.)

Example 3-1
As a polyimide, 333.3 g (non-volatile content: 100.0 g) of (A-2), as a crosslinking agent for component (B), an epoxy resin having a glycerin triester group (trade name: "Sansocizer E-2000H", Shin Nippon 3.0 g (nonvolatile content 3.0 g) manufactured by Rika Co., Ltd., and 1.6 g (nonvolatile content 1 .6 g) and 185.1 g of cyclohexanone as an organic solvent were mixed and thoroughly stirred to obtain a resin composition (3) with a nonvolatile content of 20%.

Examples 3-2 to 3-9, Comparative Examples 3-1 to 3-2
Resin compositions (3) were obtained by changing the compositions shown in Table 3 and carrying out the same method as in Example 3-1.

<Preparation of cured material layer (2)>
The resin compositions (3) of each example and comparative example were coated on release paper (manufactured by San-A Kaken Co., Ltd.) using a gap coater so that the thickness after drying was 12 μm, and then heated at 150°C for 5 minutes. Subsequently, after drying at 170° C. for 30 minutes, the release paper was peeled off to obtain a cured material layer (2).

<Solder heat resistance>
The above-mentioned cured material layer (2) was layered on the mirror surface side of a commercially available electrolytic copper foil (product name: "F2-WS", manufactured by Furukawa Electric Co., Ltd.) (film thickness 18 μm), with the copper foil side facing downward. The cured product layer was floated in a solder bath at 288° C., and the shape of the cured product layer and adhesion to copper foil were confirmed and evaluated based on the following criteria. The results are shown in Table 3.
(Evaluation criteria)
○: No change in shape and no bonding to copper foil △: No change in shape, but bonding to copper foil ×: Change in shape and bonding to copper foil

<Storage modulus>
A resin-coated copper foil cut to 20 mm x 40 mm was set in a dynamic viscoelasticity measurement device (device name: "DMA7100", manufactured by Hitachi High-Tech Science Co., Ltd.), and the temperature was set at a spacing of 20 mm, a heating rate of 10 mm/min, and a frequency of 1 Hz. The storage modulus (E') was calculated by testing under the following conditions. The higher the value, the better the result. The results are shown in Table 3. A value of 1.0×10 ⁵ Pa or more was considered good.

*The parts by weight of each component are expressed as non-volatile weight.

The symbols shown in Table 3 represent the following compounds, respectively.
(Polyimide)
A-2: Polyimide of Production Example 2 (crosslinking agent)
B-1: Multifunctional epoxy resin having a glycerin ester skeleton (product name: "Sanso Cizer E-2000H", manufactured by New Japan Chemical Co., Ltd.)
(Hardening agent)
C-1: Polyamide polyamine (product name: "Vegichem Green V150", manufactured by Tsuno Food Industry Co., Ltd.)
C-2: Polyether polyamine (product name: "JAFFAMINE T-403", manufactured by HUNTSMAN)
C-3: Trimer triamine (product name: PRIAMINE 1071, manufactured by Croda Japan Co., Ltd.)
C-4: Activated ester (product name: "EPICLON HPC-8000L", manufactured by DIC Corporation)
(Inorganic filler)
D-2: Fused silica (product name: "FB-3SDC", manufactured by Denka Co., Ltd.)

Claims (10)

A resin composition comprising: a polyimide (A) which is a reaction product of a monomer group including an aromatic tetracarboxylic anhydride (a1) and a diamine (a2) including a dimer diamine; a crosslinking agent (B) represented by general formula (1); and a curing agent (C) other than the component (B).
(In formula (1), X ¹ , X ² and X ³ each independently represent a group having one or more epoxy skeletons.) The resin composition according to claim 1, wherein component (C) is one or more selected from the group consisting of polyamide polyamine, polyether polyamine, and trimer triamine. The resin composition according to claim 1 or 2, further comprising an inorganic filler. An adhesive comprising the resin composition according to claim 1. A coating agent comprising the resin composition according to claim 1. A cured product comprising one or more selected from the group consisting of the resin composition according to claim 1, the adhesive according to claim 4, and the coating agent according to claim 5. An adhesive sheet having the cured product according to claim 6 on at least one side of a support film. A resin-coated copper foil comprising the cured product according to claim 6 or the adhesive sheet according to claim 7, and copper foil. A copper-clad laminate comprising the resin-coated copper foil according to claim 8 and a copper foil or an insulating sheet. A printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate according to claim 9.