JP2023179860A - Polyimide resin composition and cured product thereof - Google Patents

Abstract

To provide a resin composition that yields a cured product having superior substrate adhesion, mechanical characteristics, and heat resistance and is suitable for use in a printed wiring board.SOLUTION: A resin composition includes a copolymer of an unsaturated monomer including styrene and maleic anhydride (A), a soluble polyimide resin (B), a maleimide resin (C), and a curing accelerator (D). Relative to the total of the components (A) to (C), the content of the component (A) is 1.0 to 70 mass%. Relative to the total of the components (A) to (C), the content of the component (B) is 20 to 90 mass%. There are also provided a cured product of the resin composition and an article including the cured product.SELECTED DRAWING: None

Description

The present invention relates to a resin composition containing a polyimide resin and a cured product thereof.

Printed wiring boards are an essential component of mobile communication devices such as smartphones and tablets, communication base station devices, and electronic devices such as computers and car navigation systems. Various resin materials are used for printed wiring boards, which have excellent properties such as adhesion to metal foil, heat resistance, and flexibility.
In addition, in recent years, printed wiring boards for high-speed, large-capacity, next-generation high-frequency radios have been developed. It is required to be tangent.

In addition, adhesive films used as adhesives and coverlay films for multilayer printed wiring boards have excellent dielectric properties as well as excellent adhesive strength to copper foils and substrates (polyimide films and PPE prepregs). There is a need for heat resistance that can withstand solder mounting.

Patent Document 1 describes that a cured product of a composition containing a polyimide resin containing a dimer diamine skeleton and a crosslinking agent has excellent dielectric properties (low dielectric loss tangent). However, the composition of the same document had insufficient adhesion to the substrate.
Patent Document 2 describes that a cured product of a resin composition containing a polyimide resin, a modified elastomer, and an epoxy resin has excellent dielectric properties, adhesion to a base material, and soldering heat resistance. However, the cured product of the resin composition disclosed in the same document has insufficient heat resistance and bulges when the number of reflows increases, so a product with higher heat resistance is required.

Japanese Patent Application Publication No. 2018-168369 WO2020/071154

An object of the present invention is to provide a resin composition that can be suitably used for printed wiring boards, and whose cured product has excellent substrate adhesion, mechanical properties, heat resistance, and dielectric properties.

As a result of extensive studies, the present inventors have found that a resin composition containing a copolymer with a specific structure, a polyimide resin, and a maleimide resin can solve the above problems, and have completed the present invention.
That is, the present invention
(1) A resin composition containing a copolymer of unsaturated monomers containing styrene and maleic anhydride (A), a soluble polyimide resin (B), a maleimide resin (C), and a curing accelerator (D), , the content of component (A) relative to the total of components (A) to (C) is 1.0 to 70% by mass, and the content of component (B) relative to the total of components (A) to (C) is 20 to 90% by mass,
(2) The resin composition according to the above item (1), wherein the soluble polyimide resin (B) contains a fatty chain having 6 to 36 carbon atoms,
(3) the resin composition according to the preceding clause (2), in which the soluble polyimide resin (B) contains a dimer diamine skeleton;
(4) The resin composition according to the above item (1), wherein the soluble polyimide resin (B) has a number average molecular weight of 10,000 or more,
(5) Maleimide resin (C) has the following formulas (1) to (5)

(In formula (1), R ¹ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and when there is a plurality of R ¹ s, they may be the same or different from each other. k is each independently 0 to 3 Represents an integer. ⁿ¹ is the average value of the number of repetitions and represents a real number greater than 1 and less than 5.)

(In formula (2), R ² represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and when a plurality of R ² exist, they may be the same or different from each other. l is each independently 0 to 3 represents an integer. ⁿ² is the average value of the number of repetitions and represents a real number between 1 and 10.)

(In formula (3), R ³ represents a methyl group. ^{R 4} each independently represents a hydrogen atom or a methyl group. m each independently represents an integer from 0 to 3. n ³ is the average value of the number of repetitions. and represents a real number between 1 and 10.)

(In formula (4), R ⁵ and R ⁶ each independently represent a hydrogen atom, a methyl group, or an ethyl group.)

(In formula (5), ⁿ⁴ is the average value of the number of repetitions and represents a real number from 1 to 30.)
The resin composition according to the preceding item (1), which contains one or more selected from the group consisting of compounds represented by
(6) Copolymer of unsaturated monomers containing styrene and maleic anhydride (A) is an unsaturated monomer that satisfies the relationship: number of moles of styrene/number of moles of maleic anhydride = 5.0 to 40. The resin composition according to claim 1, which is a copolymer of
(7) The resin composition according to the above item (1), wherein the curing accelerator (D) is a thermal radical initiator;
(8) a cured product of the resin composition according to any one of the preceding clauses (1) to (7);
(9) Articles comprising the cured product described in the preceding paragraph (8),
Regarding.

By using the resin composition of the present invention, it is possible to provide printed wiring boards and the like that have excellent properties such as heat resistance, low dielectricity, and adhesiveness.

The resin composition of the present invention comprises a copolymer (A) of an unsaturated monomer containing styrene and maleic anhydride (hereinafter also simply referred to as "component (A)"), a soluble polyimide resin (B) (hereinafter also referred to as "component (A)"), (also simply referred to as "component (B)"), maleimide resin (C) (hereinafter also simply referred to as "component (C)"), and curing accelerator (D) (hereinafter also simply referred to as "component (D)") ), and the content of component (A) with respect to the total of components (A) to (C) (meaning the sum of component (A), component (B), and component (C)) is 1.0 It is a resin composition in which the content of component (B) is 20 to 90% by mass with respect to the total of components (A) to (C).

Component (A) used in the resin composition of the present invention can be obtained by random copolymerization of an unsaturated monomer containing styrene and maleic anhydride, for example, by radical polymerization, but commercially available components can be obtained. may be used, and examples of commercially available products include EF30, EF40, and EF80 manufactured by Tomoe Kogyo Co., Ltd.
In addition, in the present invention, "unsaturated monomer" means a compound having an unsaturated double bond group.

The content of styrene and maleic anhydride in the unsaturated monomer used in producing component (A) is from 5.0 to 5.0 (mol number of styrene/number of moles of maleic anhydride (S/M ratio)) It is preferable that the relationship of 40 is satisfied. By setting the S/M ratio within the above range, the cured product of the resin composition of the present invention containing the component (A) exhibits good dielectric properties (low dielectric properties) and high substrate adhesion. From the above point of view, a more preferable S/M ratio is 7.0 to 20.

As the unsaturated monomer used in producing component (A), unsaturated monomers other than styrene and maleic anhydride may be used in combination.
Examples of unsaturated monomers that can be used in combination include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, N-methylmaleimide, N-ethylmaleimide, and - N-alkylmaleimide monomers such as butylmaleimide and N-cyclohexylmaleimide, N-arylmaleimide monomers such as N-phenylmaleimide, N-methylphenylmaleimide and N-chlorophenylmaleimide, 2-isopropenyl-2 -oxazoline and styrenic monomers such as 4-tert-butylstyrene. These unsaturated monomers may be used in combination of one type or two or more types.
The amount of the unsaturated monomer that can be used in combination is not particularly limited as long as it does not impair the effects of the present invention, but from the viewpoint of the balance of physical properties of the resin composition of the present invention, the amount of the unsaturated monomer used in combination is not particularly limited. Preferably 50 mol% or less, more preferably 25 mol% or less, even more preferably 10 mol% or less, particularly preferably is 5 mol% or less, most preferably 0 mol% (substantially no unsaturated monomers other than styrene and maleic anhydride are used together).

The number average molecular weight of component (A) is preferably 5,000 to 100,000. By setting the number average molecular weight within the above range, not only the cured product of the resin composition has good soldering heat resistance, but also the component (A) obtained by copolymerization has good handling properties. From the above point of view, a more preferable number average molecular weight is 10,000 to 70,000. The number average molecular weight in the present invention is a value calculated in terms of polystyrene based on the measurement results of gel permeation chromatography (GPC).

The polymerization mode of component (A) is not particularly limited, and may be carried out by any known method such as solution polymerization or bulk polymerization, but solution polymerization is preferred since by-products are less likely to be produced. The type of solvent used during copolymerization is not particularly limited, but examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone, ethers such as tetrahydrofuran and 1,4-dioxane, and toluene, ethylbenzene, xylene, and Examples include aromatic hydrocarbons such as chlorobenzene. It is preferable to use methyl ethyl ketone or methyl isobutyl ketone from the viewpoints of solubility of the raw material components and copolymer, ease of recovering the solvent, and the like. The amount of the solvent used during copolymerization is preferably 10 to 100 parts by mass, and 30 to 80 parts by mass, based on a total of 100 parts by mass of the raw materials styrene, maleic anhydride, and optionally used unsaturated monomer. part is more preferable. By controlling the amount of the solvent used within the above range, the reaction rate and molecular weight (viscosity of the polymerization solution) can be easily controlled.

The method for copolymerizing component (A) is not particularly limited, but a radical polymerization method is preferred from the viewpoint of a simple process and excellent productivity. The polymerization initiator is not particularly limited, but for example, dibenzoyl peroxide, t-butylperoxybenzoate, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butylperoxyisopropyl monocarbonate, -Known organic peroxides such as -butylperoxy-2-ethylhexanoate, t-butylperoxyacetate, dicumyl peroxide and ethyl-3,3-di-(t-butylperoxy)butyrate, Known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile can be used. Two or more of these polymerization initiators may be used in combination. Among these, it is preferable to use an organic peroxide having a 10-hour half-life temperature of 70 to 110°C.

After the copolymerization reaction, heat stabilizers such as hindered phenol compounds, lactone compounds, phosphorus compounds, and sulfur compounds, hindered amine compounds, and benzene are optionally added to the reaction solution containing component (A) after the copolymerization reaction. Light stabilizers such as triazole compounds, and additives such as lubricants, plasticizers, colorants, antistatic agents, and mineral oil may be added. The amount of these additives is preferably less than 0.2 parts by mass based on 100 parts by mass of the unsaturated monomer as a raw material. These additives may be used alone or in combination of two or more.

The content of component (A) in the resin composition of the present invention is preferably 1.0 to 70% by mass based on the total of components (A) to (C). By setting the content of component (A) within the above range, the substrate adhesion and heat resistance of the cured product of the resin composition are improved.
The content of component (A) is more preferably 5.0 to 50% by mass based on the total of components (A) to (C).

Component (B) used in the resin composition of the present invention can be a soluble polyimide resin obtained by imidization reaction of a diamine component and a tetracarboxylic dianhydride component, an aliphatic soluble polyimide resin and an aromatic soluble polyimide resin. The present invention is not limited to any type of soluble polyimide resin. In addition, soluble polyimide resins obtained by modifying the ends and side chains of these soluble polyimide resins can also be used. The soluble polyimide resin may be a commercially available product or a synthesized one, and one type or a combination of two or more types may be used.
In addition, the soluble polyimide in the present invention is a polyimide resin that is soluble in an organic solvent, and the term soluble in this specification means dissolving 1.0% by mass or more at 23°C. The organic solvents used here include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone, ether solvents such as 1,4-dioxane, tetrahydrofuran, and diglyme, and glycol ether solvents such as methyl cellosolve and ethyl cellosolve. , propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, benzyl alcohol, N-methylpyrrolidone, γ-butyrolactone, ethyl acetate, N,N-dimethylformamide, anisole and the like.

Specific examples of diamine components that can be used in the synthesis of component (B) include 9,9-bis(4-aminophenyl)fluorene, m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4' -diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 3,3'-dimethyl-4,4'-diaminodiphenyl thioether, 3,3'-diethoxy-4,4'-diaminodiphenyl thioether, 3,3'-diaminodiphenyl thioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylthioether, 2,2'-bis(3-amino phenyl)propane, 2,2'-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfone sulfone, 4,4'-diaminodiphenylsulfone sulfone, Benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, 2,2' -Bis(3-aminophenoxyphenyl)propane, 2,2'-bis(4-aminophenoxyphenyl)propane, 1,3-bis(4-aminophenoxyphenyl)benzene, 1,3'-bis(3-amino phenoxyphenyl)propane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, bis(4- Amino-3,5-diethylphenyl)methane, bis(4-amino-3-propylphenyl)methane and bis(4-amino-3,5-dipropylphenyl)methane, hexamethylenediamine, 1,3-bis( (aminomethyl) cyclohexane, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl , 3,3'-diamino-4,4'-dihydroxybenzophenone, 2,2-bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane and 9,9'-bis(3- Examples include amino-4-hydroxyphenyl)fluorene and diaminopolysiloxane having 6 to 36 carbon atoms. Particularly from the viewpoint of heat resistance, it is preferable to use a diamine containing a fluorene skeleton such as 9,9-bis(4-aminophenyl)fluorene.
These diamine components may be used alone or in combination of two or more.

Specific examples of the tetracarboxylic dianhydride component that can be used in the synthesis of component (B) include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3, 3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane Tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylene Diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenyl phthalic acid) dianhydride m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride Examples thereof include anhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic dianhydride, and the like. Among them, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride and 3,3',4,4'-benzophenone are preferred in terms of solvent solubility, adhesion to substrates, and photosensitivity. Tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride or 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is preferred. These may be used alone or in combination of two or more.

The component (B) contained in the resin composition of the present invention preferably contains a soluble polyimide resin in which a fatty chain having 6 to 36 carbon atoms is introduced into the skeleton. When synthesizing component (B), for example, 1,3-bisaminomethylcyclohexane, norbornane diamine, isophorone diamine, dimer diamine, 2-methyl-1,5-diaminopentane, 1,7-diaminoheptane, 1,8- Diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebiscyclohexylamine , Diamine H20 (manufactured by Okamura Oil Co., Ltd.), dimer diamine, trimer triamine, etc., as the diamine component, it is possible to introduce fatty chains derived from these diamine components into the skeleton of the soluble polyimide resin. In particular, from the viewpoint of improving dielectric properties and substrate adhesion, it is preferable that component (B) contains a soluble polyimide resin in which an aliphatic chain derived from dimer diamine is introduced into the skeleton.

Dimer diamine is obtained by substituting two carboxy groups of dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid, with primary amino groups (see JP-A-9-12712, etc.). Specific examples of commercial products of dimer diamine include PRIAMINE 1074 and PRIAMINE 1075 (both manufactured by Croda Japan Co., Ltd.), and Versamine 551 (manufactured by Cognis Japan Co., Ltd.). These may be used alone or in combination of two or more. The non-limiting general formula of dimer diamine is shown below (in each formula, m + n = 6 to 17 is preferred, p + q = 8 to 19 is preferred, and the dashed line indicates a carbon-carbon single bond or a carbon-carbon double bond). means).

The content of component (B) in the resin composition of the present invention is preferably 20 to 90% by mass based on the total of components (A) to (C). By setting the content of component (B) within the above range, the dielectric properties (low dielectricity) and substrate adhesion of the cured product of the resin composition are improved.
The content of component (B) is more preferably 40 to 80% by mass based on the total of components (A) to (C).

The number average molecular weight of component (B) is preferably 10,000 or more. By setting the number average molecular weight within the above range, the soldering heat resistance becomes good. From the above viewpoint, a more preferable number average molecular weight is 10,000 to 20,000. The number average molecular weight in the present invention is a value calculated in terms of polystyrene based on the measurement results of gel permeation chromatography (GPC).

Component (B) can be synthesized by a known method. For example, after dissolving the diamine and tetracarboxylic anhydride used in the synthesis in a solvent, the copolymerization reaction between the diamine and the tetracarboxylic anhydride is carried out by heating and stirring at 10 to 140°C in an inert atmosphere such as nitrogen. occurs, and a polyamic acid resin solution is obtained. In addition, by adding a dehydrating agent and a catalyst to the polyamic acid resin solution obtained above and heating and stirring at 100 to 300°C, an imidization reaction (ring-closing reaction accompanied by dehydration) occurs, and component (B) is obtained. It will be done. Toluene, xylene, etc. can be used as the dehydrating agent, and tertiary amines and dehydrating catalysts can be used as the catalyst. The tertiary amine is preferably a heterocyclic tertiary amine, such as pyridine, picoline, quinoline, and isoquinoline. Examples of the dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride. The reaction time when synthesizing polyamic acid resins and polyimide resins is greatly affected by the reaction temperature, but it is preferable to carry out the reaction until the viscosity increase as the reaction progresses reaches equilibrium and the maximum molecular weight is obtained. , usually for several minutes to 20 hours.
The above example is a method for synthesizing polyimide resin via polyamic acid, but after dissolving the diamine and tetracarboxylic acid anhydride used in the synthesis in a solvent, adding a dehydrating agent and catalyst as necessary, Component (B) may be obtained by performing the copolymerization reaction and the imidization reaction at once by heating and stirring at °C.

Solvents that can be used during the synthesis of component (B) include methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclopentanone, Cyclohexanone, methylcyclohexanone, acetylacetone, γ-butyrolactone, diacetone alcohol, cyclohexen-1-one, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, tetrahydropyran, ethylisoamyl ether, ethyl-t-butyl ether, ethylbenzyl ether, Cresyl methyl ether, anisole, phenethole, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, acetoacetic acid Methyl, ethyl acetoacetate, methyl propionate, ethyl propionate, butyl propionate, benzyl propionate, methyl butyrate, ethyl butyrate, isopropyl butyrate, butyl butyrate, isoamyl butyrate, methyl lactate, ethyl lactate, butyl lactate, ethyl isovalerate , isoamyl isovalerate, diethyl oxalate, dibutyl oxalate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide etc., but are not limited to these. These may be used alone or in combination of two or more. The preferred amount of the solvent to be used should be adjusted as appropriate depending on the viscosity of the resulting resin and the intended use, but the solid content is preferably 60 to 10% by mass, more preferably 50 to 20% by mass.

During the synthesis of component (B), it is preferable to use a catalyst to promote the dehydration reaction, and the amount of the catalyst used is twice the number of moles of component (B) (the number of moles of water produced by dehydration condensation). It is preferably 1 to 30%, more preferably 5 to 15%. Specific examples of catalysts that can be used include commonly known basic catalysts such as triethylamine and pyridine. Among these, triethylamine is preferred because it has a low boiling point and is difficult to remain.

Component (C) used in the resin composition of the present invention is not particularly limited as long as it has one or more maleimide groups in one molecule. Specific examples include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 4,4-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane. , bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p -Phenylenebismaleimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide , 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1, 3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, polyphenylmethanemaleimide, novolac-type maleimide compound, biphenylaralkyl-type maleimide compound, 2,2-bis(4-(4) -maleimidophenoxy)phenyl)propane, 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N'-1,3-phenylene dimaleimide , N,N'-1,4-phenylene dimaleimide, N-phenylmaleimide, and maleimide compounds represented by formulas (1) to (5). The maleimide compound (C) is in the form of a prepolymer obtained by polymerizing a maleimide compound, a prepolymer obtained by polymerizing a maleimide compound with another compound such as an amine compound, etc., in the resin composition according to the present embodiment. It can also be included. Commercially available products can also be used, and specific examples include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.), MIR-5000 (manufactured by Nippon Kayaku Co., Ltd.), BMI-70 (manufactured by K.I. Kasei Co., Ltd.), BMI-80 (manufactured by K-I Kasei Co., Ltd.), BMI-2300 (manufactured by Daiwa Kasei Co., Ltd.), BMI-3000 (manufactured by Designer Molecules inc.), BMI-5000 (manufactured by Designer Molecules inc.), BMI-6000 (manufactured by Designer Molecules inc.) (manufactured by Designer Molecules inc.), BMI-689 (manufactured by Designer Molecules inc.), BMI-1700 (manufactured by Designer Molecules inc.), BMI-1500 (manufactured by Designer Molecules inc.) Inc.), BMI-TMH (Daiwa Kasei Co., Ltd.) , MAHD (manufactured by Evonik), BMI-1000P (manufactured by K-I Kasei Co., Ltd.), BMI-650P (manufactured by K-I Kasei Co., Ltd.), BMI-250P (manufactured by K-I Kasei Co., Ltd.), CUA-4 (manufactured by K.I. Kasei Co., Ltd.). Maleimide resins having aromatic rings such as benzene rings, biphenyl rings, and naphthalene rings are preferred because the cured product of the resin composition has excellent properties such as mechanical strength and flame retardancy. Moreover, one type of component (C) may be used or a mixture of two or more types may be used.

Among these, maleimide compounds represented by the following formulas (1) to (5) are more preferred from the viewpoint of solubility in organic solvents.

In formula (1), R ¹ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and when a plurality of R ^1s exist, they may be the same or different from each other. Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, and a neopentyl group. The alkyl group having 1 to 5 carbon atoms represented by R ¹ in formula (1) is preferably a methyl group or an ethyl group.
In formula (1), k each independently represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0.
ⁿ¹ is the average value of the number of repetitions, and represents a real number greater than 1 and less than 5.
When k is larger than 3, or when R ¹ is an alkyl group having 6 or more carbon atoms, the electrical properties may deteriorate due to molecular vibration when the alkyl group is exposed to high frequency.

In formula (2), R ² represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and when a plurality of R ² exist, they may be the same or different from each other. Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, and a neopentyl group.
In formula (2), l each independently represents an integer from 0 to 3.
In formula (2), n ² is the average value of the number of repetitions and represents a real number from 1 to 10.

In formula (3), R ³ represents an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group, and more preferably a methyl group.
In formula (3), R ⁴ each independently represents a hydrogen atom or a methyl group.
In formula (3), m each independently represents an integer of 0 to 3, each independently preferably an integer of 0 to 2, each independently more preferably an integer of 0 or 1, and still more preferably 0.
In formula (3), ⁿ³ is the average value of the number of repetitions, and represents a real number from 1 to 10.
When m is larger than 3, or when R ³ is an alkyl group having 6 or more carbon atoms, the electrical properties may be deteriorated due to molecular vibration when the alkyl group is exposed to high frequency.

In formula (4), R ⁵ and R ⁶ each represent a hydrogen atom, a methyl group, or an ethyl group.

In formula (5), n ⁴ is the average value of the number of repetitions and represents a real number from 1 to 30. From the viewpoint of achieving the effects of this embodiment more effectively and reliably, ⁿ⁴ is preferably a real number of 7 or more and 30 or less, and more preferably a real number of 7 or more and 18 or less.

The content of component (C) in the resin composition of the present invention is preferably 5.0 to 40% by mass based on the total of components (A) to (C). By setting the content of component (C) within the above range, the heat resistance, substrate adhesion, low water absorption, and dielectric properties of the cured resin composition are improved.
The content of component (C) is more preferably 10 to 25% by mass based on the total of components (A) to (C).

By containing component (D), the resin composition of the present invention can adjust the curing speed of the resin composition, and also imparts appropriate moldability to the resin composition.
Component (D) contained in the resin composition of the present invention is not particularly limited as long as it is a compound that can accelerate the curing of component (C) and an optional thermosetting resin (described later). Component (D) can be used alone or in combination of two or more.

Component (D) that can be used in the resin composition of the present invention is not particularly limited, but examples thereof include thermal radical polymerization initiators, imidazole compounds, and tertiary amines such as triethylamine and tributylamine. Among these, thermal radical polymerization initiators are preferred from the viewpoint of obtaining a good curing rate.
A thermal radical polymerization initiator is a compound that releases an active substance (radical) that can polymerize the maleimide group contained in component (C) and the radically polymerizable functional group contained in the thermosetting resin described below by heating. There are no particular limitations, and any known thermal radical polymerization initiator can be used. Thermal radical polymerization initiators can be used alone or in combination of two or more.

The 10-hour half-life temperature of the thermal radical polymerization initiator is preferably 100°C or higher, and more preferably 110°C or higher from the viewpoint of manufacturability. By setting the 10-hour half-life temperature of the thermal radical polymerization initiator within the above-mentioned preferred range, it is possible to increase the temperature of the solvent removal step during production.

Examples of the thermal radical polymerization initiator include dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2, Ketone peroxides of 5-bis(tert-butylperoxy)hexyne-3, benzoyl peroxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, and cyclohexanone peroxide; 1,1-di(t-butylperoxy) Cyclohexane and peroxyketal of 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane; tert-butyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, cumene Hydroperoxide and hydroperoxide of t-butyl hydroperoxide; di(2-t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t - dialkyl peroxides of butylcumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, and di-t-butyl peroxide; dibenzoyl peroxide and diacyl peroxide of di(4-methylbenzoyl) peroxide; peroxydicarbonate of di-n-propyl peroxydicarbonate and diisopropyl peroxydicarbonate; 2,5-dimethyl-2, Organic peroxides such as peroxy esters of 5-di(benzoylperoxy)hexane, t-hexylperoxybenzoate, t-butylperoxybenzoate, and t-butylperoxy-2-ethylhexanonate; 2 , 2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). Examples include. In the composition of the present invention, organic peroxides are preferred from the viewpoint of obtaining a good curing rate, and organic peroxides having peroxyester, peroxyketal, dialkyl peroxide, and hydroperoxide skeletons are more preferred. Preferably, dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy) ) Hexyne-3 and tert-butyl hydroperoxide are more preferred from the viewpoint of manufacturability.

The content of component (D) in the resin composition of the present invention is from 0.05 to 100 parts by mass in total of component (C) and the thermosetting resin described below, in order to obtain a good curing speed. 10 parts by mass is preferred, and 0.05 to 8 parts by mass is more preferred.

In the resin composition of the present invention, a thermosetting compound (E) (hereinafter also referred to as "component (E)") other than component (C) is used in combination, since the curing speed can be easily adjusted. Good too.
Examples of the component (E) include epoxy resins, carbodiimide resins, benzoxazine compounds, and compounds having ethylenically unsaturated groups. These resins or compounds can be used singly or in an appropriate mixture of two or more, depending on the physical properties of the cured product of the resin composition and the intended use.

The epoxy resin as component (E) is not particularly limited as long as it has one or more epoxy groups in one molecule, but since the cured product of the resin composition has excellent properties such as mechanical strength and flame retardancy, Epoxy resins having aromatic rings such as , benzene ring, biphenyl ring, and naphthalene ring are preferable, and specific examples thereof include jER828 (manufactured by Mitsubishi Chemical Corporation), NC-3000, and XD-1000 (all manufactured by Nippon Kayaku Co., Ltd.). (manufactured by a company).
Epoxy resin is added for the purpose of reacting with the acid anhydride group of component (A), thereby increasing the crosslinking density of the cured product, improving resistance to polar solvents, and improving adhesion to substrates. and heat resistance.
The curing temperature of the resin composition containing the epoxy resin is preferably 150 to 250°C. The curing time depends on the curing temperature, but is approximately several minutes to several hours.

The content of the epoxy resin in the resin composition of the present invention containing the epoxy resin is preferably such that the epoxy equivalent of the epoxy resin is 0.1 to 500 equivalents per equivalent of the acid anhydride group of the component (A).

A curing agent can be added to the resin composition of the present invention containing an epoxy resin, if necessary, for the purpose of promoting the curing reaction of the epoxy resin. Examples of the curing agent include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. imidazoles, tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo(5,4,0)undecene-7, phosphines such as triphenylphosphine, octylic acid Examples include metal compounds such as tin.
The amount of curing agent added in the resin composition of the present invention containing an epoxy resin is 0.1 to 10% by mass based on the epoxy resin.

The carbodiimide resin (compound) as component (E) is not particularly limited as long as it has one or more carbodiimide structures in one molecule.
Specific examples of carbodiimide resins (compounds) include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane-bis(methylene-t-butylcarbodiimide); phenylene-bis(xylylcarbodiimide); Biscarbodiimides such as aromatic biscarbodiimide; aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), poly(isophoronecarbodiimide); poly(phenylenecarbodiimide) ), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylene) Polycarbodiimides such as aromatic polycarbodiimides such as poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylene diphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide] are mentioned.
These may be used in combination of two or more types.

Commercially available carbodiimide resins (compounds) include, for example, "Carbodilyte V-02B", "Carbodilyte V-03", "Carbodilyte V-04K", "Carbodilyte V-07", and "Carbodilyte V-" manufactured by Nisshinbo Chemical Co., Ltd. 09''; Examples include "Stavaxol P", "Stavaxol P400", and "Hikasil 510" manufactured by Rhein Chemie.

The content of the carbodiimide resin (compound) in the resin composition of the present invention containing the carbodiimide resin (compound) is preferably 1.0 to 40% by mass based on the total of components (A) to (C). . By setting the content of the carbodiimide resin (compound) within the above range, the heat resistance, substrate adhesion, low water absorption, and dielectric properties of the cured product of the resin composition are improved.
The content of the carbodiimide resin (compound) is more preferably 10 to 25% by mass based on the total of components (A) to (C).

The benzoxazine resin (compound) as component (E) is not particularly limited as long as it has one or more benzoxazine structures in one molecule.
Specific examples of benzoxazine resins (compounds) include bisphenol A-type benzoxazine resin, bisphenol F-type benzoxazine resin, diamine-type benzoxazine resin, phenolphthalein-type benzoxazine resin, dicyclopentadiene-type benzoxazine resin, and bisphenol. It may contain any one type or a mixture of two or more selected from fluorene-type benzoxazine resins, preferably bisphenol F-type benzoxazine resins, diamine-type benzoxazine resins, phenolphthalein-type benzoxazine resins, Or and bisphenol fluorene type benzoxazine resins are preferred.
These may be used in combination of two or more types, and include any one selected from these or a mixture of two or more types.

The content of the benzoxazine resin (compound) in the resin composition of the present invention containing the benzoxazine resin (compound) is 1.0 to 40% by mass based on the total of components (A) to (C). is preferred. By setting the content of the benzoxazine resin (compound) within the above range, the heat resistance, substrate adhesion, low water absorption, and dielectric properties of the cured product of the resin composition are improved.
The content of the benzoxazine resin (compound) is more preferably 10 to 25% by mass based on the total of components (A) to (C).

The compound having an ethylenically unsaturated group as component (E) is not particularly limited as long as it has an ethylenically unsaturated group in one molecule.
Specific examples of compounds having ethylenically unsaturated groups include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, and polyethylene glycol (meth)acrylate. Acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, ) acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, glycol di(meth)acrylate, diethylene di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate , polypropylene glycol di(meth)acrylate, adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone modified hydroxypivalic acid Neopene glycol di(meth)acrylate, ε-caprolactone modified dipentaerythritol hexa(meth)acrylate, ε-caprolactone modified dipentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate ) acrylate, triethylolpropane tri(meth)acrylate, and its ethylene oxide adduct; pentaerythritol tri(meth)acrylate, and its ethylene oxide adduct; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate , and its ethylene oxide adduct.

In addition, there are also urethane (meth)acrylates that have both a (meth)acryloyl group and a urethane bond in the same molecule; polyester (meth)acrylates that have both a (meth)acryloyl group and an ester bond in the same molecule; and epoxy Epoxy (meth)acrylates derived from resins and having (meth)acryloyl groups; reactive oligomers in which these bonds are used in combination are also mentioned as specific examples of compounds having ethylenically unsaturated groups.

Examples of urethane (meth)acrylates include reaction products of hydroxyl group-containing (meth)acrylates, polyisocyanates, and other alcohols used as necessary. For example, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; ) Acrylates; sugar alcohol (meth)acrylates such as pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and toluene diisocyanate , hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexane methylene diisocyanate, isocyanurates thereof, polyisocyanates such as buret reaction products, etc. are reacted, urethane ( Examples include meth)acrylates.

Polyester (meth)acrylates include, for example, caprolactone-modified 2-hydroxyethyl (meth)acrylate, ethylene oxide and/or propylene oxide-modified phthalic acid (meth)acrylate, ethylene oxide-modified succinic acid (meth)acrylate, caprolactone-modified tetrahydrocarbon Monofunctional (poly)ester (meth)acrylates such as furfuryl (meth)acrylate; hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, epichlorohydrin-modified Di(poly)ester (meth)acrylates such as phthalic acid di(meth)acrylate; 1 mol or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. per 1 mol of trimethylolpropane or glycerin. Examples include mono-, di-, or tri(meth)acrylates of triols obtained by addition.

Also, triols obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. to 1 mole of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane. Mono, di, tri, or tetra(meth)acrylate; Triol mono or mono, obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. to 1 mole of dipentaerythritol; Mono(meth)acrylates or poly(meth)acrylates of polyhydric alcohols such as triols, tetraols, pentaols, or hexaols of poly(meth)acrylates are mentioned.

Furthermore, diol components such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butylene glycol, 3-methyl-1,5-pentanediol, hexanediol, maleic acid, fumaric acid, etc. Acids, polybasic acids such as succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, and their anhydrides. (meth)acrylate of polyester polyol which is a reaction product; (meth)acrylate of cyclic lactone-modified polyester diol consisting of a diol component, polybasic acid, anhydride thereof, ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. Examples include polyfunctional (poly)ester (meth)acrylates such as.

Epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. For example, phenol novolak type epoxy (meth)acrylate, cresol novolac type epoxy (meth)acrylate, trishydroxyphenylmethane type epoxy (meth)acrylate, dicyclopentadienephenol type epoxy (meth)acrylate, bisphenol A type epoxy (meth)acrylate , bisphenol F type epoxy (meth)acrylate, biphenol type epoxy (meth)acrylate, bisphenol A novolac type epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal type epoxy (meth)acrylate, heterocyclic epoxy ( Examples include meth)acrylates, and acid anhydride-modified epoxy acrylates thereof.

For example, vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrenes such as styrene, methylstyrene, ethylstyrene, and divinylbenzene, triallylisocyanurate, trimetaallylisocyanurate, and bisali A compound having a vinyl group such as lunadiimide is also mentioned as a specific example of a compound having an ethylenically unsaturated group.

As the compound having an ethylenically unsaturated group, commercially available products can be used, such as KAYARADZCA (registered trademark)-601H (trade name, manufactured by Nippon Kayaku Co., Ltd.), TrisP-PA epoxy acrylate compound propylene, etc. Glycol monomethyl ether acetate (Nippon Kayaku Co., Ltd. KAYARAD (registered trademark) ZCR-6007H (trade name) KAYARAD (registered trademark) ZCR-6001H (trade name), KAYARAD (registered trademark) ZCR-6002H (trade name), and KAYARAD (registered trademark) ZCR-6006H (trade name).These compounds having an ethylenically unsaturated group can be used alone or in an appropriate mixture of two or more.

The content of the compound having an ethylenically unsaturated group in the resin composition of the present invention containing the compound having an ethylenically unsaturated group is 0. An amount of 1 to 500 equivalents is preferred.

The resin composition of the present invention can be a varnish-like composition (hereinafter simply referred to as varnish) dissolved in an organic solvent.
Examples of solvents that can be used include amide solvents such as γ-butyrolactones, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and N,N-dimethylimidazolidinone, and tetramethylene sulfone. Sulfones, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate and propylene glycol monobutyl ether, anisole, ether solvents such as tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone Examples include ketone solvents such as , aromatic solvents such as toluene and xylene, and the like.
The organic solvent is used in such a range that the solid content concentration excluding the organic solvent in the varnish is preferably 10 to 80% by mass, more preferably 20 to 70% by mass.

The resin composition of the present invention may contain known additives, if necessary. Specific examples of additives that can be used in combination include polybutadiene or a modified product thereof, a modified product of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, cyanate ester compound, silicone gel, silicone oil, and silica. , inorganic fillers such as alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, and fillers such as silane coupling agents. Processing agents, mold release agents, coloring agents such as carbon black, phthalocyanine blue, and phthalocyanine green, thixotropy agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents, hydroquinone, hydroquinone monomethyl ether, and phenol polymerization inhibition. agents, stabilizers, antioxidants, photopolymerization initiators, photobase generators, photoacid generators, and the like. The blending amount of these additives is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, based on 100 parts by mass of the resin composition. As the additive, a silane coupling agent having an acrylic group or a methacrylic group is particularly preferable from the viewpoint of heat resistance.

The curing temperature and curing time of the resin composition of the present invention may be selected in consideration of the combination of functional groups (reactive groups) possessed by the components (A) to (C). The curing temperature of a resin composition containing no component or a resin composition containing an optional epoxy resin is preferably 120 to 250°C, and the curing time is approximately several tens of minutes to several hours.

A prepreg can be obtained by heating and melting the resin composition of the present invention, reducing the viscosity, and impregnating it into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers. Further, a prepreg can also be obtained by impregnating reinforcing fibers with the varnish and drying the impregnated fibers by heating.
After cutting the above prepreg into a desired shape and laminating it with copper foil etc. as necessary, the resin composition is heated and cured by applying pressure to the laminate using a press molding method, an autoclave molding method, a sheet winding molding method, etc. Base materials (articles) including the cured product of the present invention, such as electronic laminates (printed wiring boards) and carbon fiber reinforced materials, can be obtained.

Alternatively, after coating a copper foil with varnish and drying the solvent medium, a polyimide film or LCP (liquid crystal polymer) is laminated, followed by heat pressing and heat curing to produce a base material equipped with the cured product of the present invention. You can also get it. Depending on the case, a base material provided with the cured product of the present invention can also be obtained by coating the polyimide film or LCP side and laminating it with copper foil.
In addition, after applying varnish to copper foil and drying the solvent, prepregs made by impregnating reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers with resin are laminated, and after heat pressing, A base material provided with the cured product of the present invention can also be obtained by heat curing.
A base material having a thin film made of the resin composition described above can be used for a copper clad laminate (CCL), or a printed wiring board or multilayer wiring board having a circuit pattern on the copper foil of the CCL.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that the present invention is not limited to these examples. In the examples, "part" means part by mass, and "%" means % by mass. Incidentally, the measurement conditions of GPC in the examples are as follows.
Model: TOSOH ECOSEC Elite HLC-8420GPC
Column: TSKgel Super AWM-H
Eluent: NMP (N-methylpyrrolidone); 0.5ml/min, 40°C
Detector: UV (differential refractometer)
Molecular weight standard: polystyrene

Synthesis Example 1 (Synthesis of soluble polyimide resin (B-1))
10.640 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g/mol) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark device, powder inlet, nitrogen introduction device, and stirring device. , 7.066 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Co., Ltd., molecular weight 348.16 g/mol), and 67.254 parts of anisole were added and heated to 70°C. Next, 13.029 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g/mol), 0.850 parts of triethylamine, and 15.000 parts of toluene were added, and the water generated due to ring closure of the amic acid was dissolved. The soluble polyimide resin (B-1) (molecular weight 81,300) solution was reacted with toluene at 130°C for 8 hours while removing it azeotropically, and then the remaining triethylamine and toluene were removed at 130°C. Obtained.

Synthesis Example 2 (Synthesis of soluble polyimide resin (B-2))
DAPBAF2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane ( Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g/mol) 0.782 parts, PRIAMINE 1075 (Crodda Japan Co., Ltd., molecular weight 534.38 g/mol) 11.784 parts, BAFL (9,9-bis(4- 5.723 parts of (aminophenyl)fluorene (manufactured by JFE Chemical Co., Ltd., molecular weight: 348.16 g/mol), and 68.238 parts of anisole were added and heated to 70°C. Next, 12.409 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g/mol), 0.810 parts of triethylamine, and 14.987 parts of toluene were added, and the water generated due to ring closure of the amic acid was dissolved. The mixture was reacted at 130° C. for 8 hours while being removed azeotropically with toluene to obtain an intermediate polyimide resin (phenolic OH equivalent, 6780 g/eq., molecular weight 78,600) solution. Subsequently, 0.663 parts of Karenz MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g/mol) and 0.088 parts of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor were added. After reacting at 130°C for 4 hours, remaining triethylamine and toluene were removed at 130°C to obtain a soluble polyimide resin (B-2) solution.

Synthesis Example 3 (Synthesis of soluble polyimide resin (B-3))
BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation) was placed in a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark device, raw material inlet, nitrogen introduction device, and stirring device. , molecular weight 348.45 g/mol) 5.37 parts, PRIAMINE 1075 (C36 dimer diamine, manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g/mol) 13.14 parts, ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g/mol), 74.35 parts of anisole, 0.97 parts of triethylamine, and 19.79 parts of toluene were added and heated to 120° C. to dissolve the raw materials. The reaction was carried out at 135° C. for 4 hours while removing water produced by ring closure of the amic acid by azeotropy with toluene. Next, 1.19 parts of HDI (hexamethylene diisocyanate, manufactured by Asahi Kasei Corporation, molecular weight 168.20 g/mol) and 2.64 parts of anisole were added and heated at 130°C for 3 hours to obtain a soluble polyimide resin (B-3). (molecular weight 65,900) solution was obtained.

Examples 1 to 11, Comparative Examples 1 and 2 (Preparation of resin compositions for the present invention and comparison)
After blending each component in the amounts shown in Table 1 (unit: parts; parts of component (B) and component (C) are equivalent to solid content, not including solvent), the solid content concentration Resin compositions of the present invention and comparative resin compositions were prepared by adding anisole as a solvent in an amount of 20% by mass and mixing uniformly.

In addition, each component in Table 1 is as follows.
<(A) component>
(A-1); EF30 (styrene-maleic anhydride copolymer, maleic anhydride ratio 25 mol%, number average molecular weight 10,000, manufactured by Tomoe Kogyo Co., Ltd.)
(A-2); RL-44 (styrene-maleic anhydride copolymer, maleic anhydride ratio 6.0 mol%, number average molecular weight 27,000, manufactured by Gifu Shellac Co., Ltd.)
(A-3); RL-07 (styrene-maleic anhydride copolymer, maleic anhydride ratio 31.2 mol%, number average molecular weight 121,000, manufactured by Gifu Shellac Co., Ltd.)
<(B) component>
(B-1) to (B-3); Soluble polyimide resins (B-1) to (B-3) obtained in Synthesis Examples 1 to 3
<(C) component>
(C-1); MIR-3000-70MT; maleimide resin, manufactured by Nippon Kayaku Co., Ltd. (C-2); BMI-70; maleimide resin, manufactured by K.I. Kasei Co., Ltd. (C-3); BMI -80; Maleimide resin, manufactured by K.I. Kasei Co., Ltd. <(E) component>
(E-1); XD-1000; Epoxy resin, Nippon Kayaku Co., Ltd. (E-2); ZXR-1889H; Epoxy acrylate resin, Nippon Kayaku Co., Ltd.
DCP; dicumyl peroxide, manufactured by Kayaku Nourion Co., Ltd.

Using each of the resin compositions obtained in Examples 1 to 11 and Comparative Examples 1 and 2, the adhesive strength and thermal properties of the cured resin composition to copper foil were evaluated in the following manner.

(Evaluation of adhesive strength)
A resin composition was applied to the rough surface of ultra-low roughness non-roughening treated electrolytic copper foil CF-T9DA-SV (hereinafter referred to as "T9DA") manufactured by Fukuda Metal Foil and Powder Industry Co., Ltd. using an automatic applicator. Each coating was applied and dried by heating at 120°C for 10 minutes. The thickness of the coating film after drying was 30 μm. A PPE prepreg (Meteorwave 4000, manufactured by AGC Nelco Co., Ltd.) was superimposed on the coating film on the copper foil obtained above, and vacuum pressed at 200° C. for 60 minutes at 3 MPa. The obtained test piece was cut to a width of 10 mm, and the 90° peel strength (peel speed was 50 mm/min) was measured using Autograph AGS-X-500N (manufactured by Shimadzu Corporation). and evaluated the adhesive strength of PPE prepreg. The results are shown in Table 1.

(Evaluation of thermal characteristics)
A test piece prepared in the same manner as in the above "Evaluation of adhesive strength" was floated in a solder bath heated to 288°C using POT-200C (manufactured by Taiyo Electric Industry Co., Ltd.), and the thermal characteristics were determined by the time until blisters appeared. was evaluated.
〇...No blistering for 600 seconds or more △...No blistering for 60 seconds or more for less than 600 seconds x...Blistering occurred in less than 60 seconds The results are shown in Table 1.

From the results in Table 1, the resin composition of the present invention was excellent in adhesive strength and heat resistance, whereas the resin composition of the comparative example was inferior in adhesive strength and heat resistance.

By using the polyimide resin having a specific structure of the present invention, it is possible to provide printed wiring boards and the like having excellent properties such as heat resistance, mechanical properties, low dielectric properties, adhesive properties, and flame retardance.

Claims (9)

A resin composition comprising a copolymer (A) of an unsaturated monomer containing styrene and maleic anhydride, a soluble polyimide resin (B), a maleimide resin (C), and a curing accelerator (D), The content of component (A) with respect to the total of components (A) to (C) is 1.0 to 70% by mass, and the content of component (B) with respect to the total of components (A) to (C) is 20 to 70% by mass. 90% by mass of the resin composition. The resin composition according to claim 1, wherein the soluble polyimide resin (B) contains a fatty chain having 6 to 36 carbon atoms. The resin composition according to claim 2, wherein the soluble polyimide resin (B) contains a dimer diamine skeleton. The resin composition according to claim 1, wherein the soluble polyimide resin (B) has a number average molecular weight of 10,000 or more. The maleimide resin (C) has the following formulas (1) to (5).

(In formula (1), R ¹ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and when there is a plurality of R ¹ s, they may be the same or different from each other. k is each independently 0 to 3 Represents an integer. ⁿ¹ is the average value of the number of repetitions and represents a real number greater than 1 and less than 5.)

(In formula (2), R ² represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and when a plurality of R ² exist, they may be the same or different from each other. l is each independently 0 to 3 represents an integer. ⁿ² is the average value of the number of repetitions and represents a real number between 1 and 10.)

(In formula (3), R ³ represents a methyl group. ^{R 4} each independently represents a hydrogen atom or a methyl group. m each independently represents an integer from 0 to 3. n ³ is the average value of the number of repetitions. and represents a real number between 1 and 10.)

(In formula (4), R ⁵ and R ⁶ each independently represent a hydrogen atom, a methyl group, or an ethyl group.)

(In formula (5), ⁿ⁴ is the average value of the number of repetitions and represents a real number from 1 to 30.)
The resin composition according to claim 1, containing one or more selected from the group consisting of compounds represented by: The copolymer (A) of unsaturated monomers containing styrene and maleic anhydride is a copolymer of unsaturated monomers that satisfies the relationship: number of moles of styrene/number of moles of maleic anhydride = 5.0 to 40. The resin composition according to claim 1, which is a combination. The resin composition according to claim 1, wherein the curing accelerator (D) is a thermal radical initiator. A cured product of the resin composition according to any one of claims 1 to 7. An article comprising the cured product according to claim 8.