Polyimide resin composition and cured product thereof

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

[Technical Field]

[0001] The present invention relates to a resin composition containing a polyimide resin and a cured product thereof. [Background technology]

[0002] Printed circuit boards (PCBs) are essential components for mobile communication devices such as smartphones and tablets, communication base station equipment, computers, and car navigation systems. Various resin materials with excellent properties such as adhesion to metal foil, heat resistance, and flexibility are used in printed circuit boards. Furthermore, in recent years, printed circuit boards for next-generation high-speed, high-capacity high-frequency wireless applications have been developed. In addition to the characteristics mentioned above, resin materials are required to have low transmission loss, that is, low dielectric and low dielectric loss tangent.

[0003] Furthermore, adhesive films used in multilayer printed circuit boards as adhesives or coverlay films are required to exhibit excellent dielectric properties, as well as to have excellent adhesive strength to copper foil and substrates (polyimide films and PPE prepregs), and to withstand soldering.

[0004] Patent Document 1 describes that a cured product of a composition containing a polyimide resin with a dimer amine skeleton and a crosslinking agent exhibits excellent dielectric properties (low dielectric loss tangent). However, the composition described in that document had insufficient adhesion to the substrate. Patent Document 2 describes that a cured product of a resin composition containing polyimide resin, modified elastomer, and epoxy resin exhibits excellent dielectric properties, adhesion to substrates, and solder heat resistance. However, the cured product of the resin composition described in the same document has insufficient heat resistance, and blistering occurs as the number of reflow cycles increases, thus there is a need for a product with higher heat resistance. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2018-168369 [Patent Document 2] WO2020 / 071154 [Overview of the project] [Problems that the invention aims to solve]

[0006] The object of the present invention is to provide a resin composition that can be suitably used in printed circuit boards, wherein the cured product exhibits excellent substrate adhesion, mechanical properties, heat resistance, and dielectric properties. [Means for solving the problem]

[0007] As a result of diligent research, the inventors of the present invention have found that a resin composition containing a copolymer of a specific structure, a polyimide resin, and a maleimide resin solves the above problems, and have completed the present invention. In other words, the present invention is (1) A resin composition comprising a copolymer of styrene and an unsaturated monomer containing maleic anhydride (A), a soluble polyimide resin (B), a maleimide resin (C), and a curing accelerator (D), wherein 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 item (1) above, wherein the soluble polyimide resin (B) contains fatty chains having 6 to 36 carbon atoms. (3) The soluble polyimide resin (B) is the resin composition described in item (2) above, which contains a dimer amine skeleton. (4) The resin composition described in item (1) above, wherein the number average molecular weight of the soluble polyimide resin (B) is 10,000 or more. (5) Maleimide resin (C) is a compound of the following formulas (1) to (5)

[0008] [ka]

[0009] (In formula (1), R , , 5 ,

[0016] , , 6 , ,

[0015] , , , , represents an alkyl group or phenyl group having 1 to 5 carbon atoms, and R 1 When there are a plurality of them, they may be the same or different from each other. k each independently represents an integer of 0 to 3. n 1 is the average value of the repeating number and represents a real number greater than 1 and less than 5.)

[0010] [Chemical formula]

[0011] (In formula (2), R 2 represents an alkyl group or phenyl group having 1 to 5 carbon atoms, and R 2 When there are a plurality of them, they may be the same or different from each other. l each independently represents an integer of 0 to 3. n 2 is the average value of the repeating number and represents a real number of 1 or more and 10 or less.)

[0012] [Chemical formula]

[0013] (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 of 0 to 3. n 3 is the average value of the repeating number and represents a real number of 1 or more and 10 or less.)

[0014] [Chemical formula]

[0015] (In formula (4), R 5 and R 6 each independently represents a hydrogen atom, a methyl group or an ethyl group.)

[0016] [Chemical formula]<00​​​

[0017] (In formula (5), n 4 (This represents the average number of repetitions, a real number between 1 and 30.) The resin composition according to item (1) above, comprising one or more compounds selected from the group consisting of compounds represented by (6) The resin composition according to claim 1, wherein the copolymer (A) of unsaturated monomers containing styrene and maleic anhydride satisfies the relationship between the number of moles of styrene and the number of moles of maleic anhydride = 5.0 to 40. (7) The resin composition according to item (1) above, wherein the curing accelerator (D) is a thermal radical initiator. (8) A cured product of any one of the resin compositions described in item (1) to (7) above, (9) Articles equipped with the cured material described in item (8) above, Regarding. [Effects of the Invention]

[0018] By using the resin composition of the present invention, it is possible to provide printed circuit boards and the like with excellent properties such as heat resistance, low dielectric properties, and adhesive properties. [Modes for carrying out the invention]

[0019] The resin composition of the present invention comprises a copolymer of styrene and an unsaturated monomer containing maleic anhydride (A) (hereinafter also simply referred to as "component (A)"), a soluble polyimide resin (B) (hereinafter also simply referred to as "component (B)"), a maleimide resin (C) (hereinafter also simply referred to as "component (C)"), and a curing accelerator (D) (hereinafter also simply referred to as "component (D)"), wherein the content of component (A) relative to the total of components (A) to (C) (meaning the sum of components (A), (B), and (C)) is 1.0 to 50% by mass, and the content of component (B) relative to the total of components (A) to (C) is 20 to 90% by mass.

[0020] Component (A) used in the resin composition of the present invention can be obtained by random copolymerizing an unsaturated monomer containing styrene and maleic anhydride, for example by radical polymerization, but commercially available components may also be used. Examples of commercially available components include EF30, EF40, and EF80 manufactured by Tomoe Engineering Co., Ltd. In this invention, "unsaturated monomer" means a compound having an unsaturated double bond group.

[0021] When producing component (A), the content of styrene and maleic anhydride in the unsaturated monomer preferably satisfies the relationship between the number of moles of styrene and the number of moles of maleic anhydride (S / M ratio) = 5.0 to 40. By setting the S / M ratio within the above range, good dielectric properties (low dielectric properties) and high substrate adhesion are obtained in the cured product of the resin composition of the present invention containing component (A). From the above viewpoint, a more preferable S / M ratio is 7.0 to 20.

[0022] (A) In the production of 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-alkylmaleimide monomers such as N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide and N-cyclohexylmaleimide, N-arylmaleimide monomers such as N-phenylmaleimide, N-methylphenylmaleimide and N-chlorophenylmaleimide, and styrene monomers such as 2-isopropenyl-2-oxazoline and 4-tert-butylstyrene. These unsaturated monomers may be used individually or in combination of two or more types. The amount of unsaturated monomers that can be used in combination is not particularly limited as long as it does not impair the effects of the present invention. However, from the viewpoint of balancing the various physical properties of the resin composition of the present invention, the amount is preferably 50 mol% or less, more preferably 25 mol% or less, even more preferably 10 mol% or less, particularly preferably 5 mol% or less, and most preferably 0 mol% (substantially no unsaturated monomers other than styrene and maleic anhydride are used in combination) with respect to the total number of moles of all unsaturated monomers, including styrene and maleic anhydride, used in the production of component (A).

[0023] 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, the solder heat resistance of the cured resin composition is improved, as is the handling properties of component (A) obtained by copolymerization. From the above viewpoint, a more preferable number-average molecular weight is 10,000 to 70,000. Note that the number-average molecular weight in this invention is a value calculated in polystyrene equivalent based on the measurement results of gel permeation chromatography (GPC).

[0024] (A) There are no particular limitations on the polymerization method of component (A), and it can be carried out by known methods such as solution polymerization or bulk polymerization, but solution polymerization is preferred because it is less likely to produce by-products. The type of solvent used in 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 aromatic hydrocarbons such as toluene, ethylbenzene, xylene, and chlorobenzene. From the viewpoint of the solubility of the raw material components and copolymer, and the ease of solvent recovery, it is preferable to use methyl ethyl ketone or methyl isobutyl ketone. The amount of solvent used in copolymerization is preferably 10 to 100 parts by mass, and more preferably 30 to 80 parts by mass, per 100 parts by mass of the total of the raw materials styrene, maleic anhydride, and optionally used unsaturated monomers. By setting the amount of solvent used within the above range, it becomes easier to control the reaction rate and molecular weight (viscosity of the polymerization solution).

[0025] The copolymerization method for component (A) is not particularly limited, but radical polymerization is preferred from the viewpoint of simplicity of process and excellent productivity. The polymerization initiator is not particularly limited, but known organic peroxides such as dibenzoyl peroxide, t-butyl peroxybenzoate, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyacetate, dicumyl peroxide, and ethyl-3,3-di-(t-butylperoxy)butyrate, or known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonilonitrile, 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 with a 10-hour half-life temperature of 70 to 110°C.

[0026] The reaction solution containing component (A) after the copolymerization reaction may optionally contain heat stabilizers such as hindered phenol compounds, lactone compounds, phosphorus compounds, and sulfur compounds, light stabilizers such as hindered amine compounds and benzotriazole compounds, and additives such as lubricants, plasticizers, colorants, antistatic agents, and mineral oil. The amount of these additives is preferably less than 0.2 parts by mass per 100 parts by mass of the unsaturated monomer used as the raw material. These additives may be used individually or in combination of two or more types.

[0027] The content of component (A) in the resin composition of the present invention is preferably 1.0 to 70% by mass relative to 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 resin composition are improved. The content of component (A) is more preferably 5.0 to 50% by mass relative to the total of components (A) to (C).

[0028] The component (B) used in the resin composition of the present invention is not limited to aliphatic soluble polyimide resins or aromatic soluble polyimide resins, as long as it is a soluble polyimide resin obtained by the imidation reaction of a diamine component and a tetracarboxylic dianhydride component. Furthermore, soluble polyimide resins obtained by modifying the ends or side chains of these soluble polyimide resins can also be used. The soluble polyimide resin may be a commercially available product or a synthesized product, and may be used alone or in combination of multiple types. In this invention, soluble polyimide refers to a polyimide resin soluble in organic solvents, and solubility as used herein means dissolving at 23°C in an amount of 1.0% by mass or more. The organic solvents referred to 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; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and diethylene glycol methyl ethyl ether; and other solvents such as benzyl alcohol, N-methylpyrrolidone, γ-butyrolactone, ethyl acetate, N,N-dimethylformamide, and anisole.

[0029] (B)Specific examples of diamine components that can be used in the synthesis of component 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'-diaminodiphenyl thioether, 3,3'-dimethyl-4,4'-diaminodiphenyl thioether, 3,3'-diethoxy-4,4'-diaminodiphenyl thioether, and 3,3'-diaminodi Phenylthioether, 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-aminophenyl)propane, 2,2'-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl Sulfonolone, 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-aminophenoxyphenyl)propane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-di Methylphenyl)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,Examples include 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-amino-4-hydroxyphenyl)fluorene, as well as diaminopolysiloxanes having 6 to 36 carbon atoms. Particularly from the viewpoint of heat resistance, it is preferable to use diamines containing a fluorene skeleton, such as 9,9-bis(4-aminophenyl)fluorene. These diamine components may be used individually or as a mixture of two or more.

[0030] Specific examples of tetracarboxylic dianhydride components that can be used in the synthesis of component (B) include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic 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-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4' Examples include -bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, and 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic acid dianhydride. In particular, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, or 3,3',4,4'-diphenylethertetracarboxylic dianhydride are preferred in terms of solvent solubility, adhesion to the substrate, and photosensitivity. These may be used individually or in combination of two or more.

[0031] The resin composition of the present invention preferably contains a soluble polyimide resin in which fatty chains having 6 to 36 carbon atoms are introduced into the backbone. When synthesizing component (B), for example, 1,3-bisaminomethylcyclohexane, norbornanediamine, isophoronediamine, dimeramine, 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 H2O (manufactured by Okamura Oil Co., Ltd.), dimeramine, or trimertriamine can be used as a diamine component to introduce fatty chains derived from these diamine components into the backbone 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 amine is introduced into the backbone.

[0032] Dimer amines are obtained by substituting two carboxyl groups of dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid, with primary amino groups (see Japanese Patent Publication No. 9-12712, etc.). Specific examples of commercially available dimer amines include PRIAMINE 1074 and PRIAMINE 1075 (both manufactured by Croda Japan Co., Ltd.), and Versamin 551 (manufactured by Cognis Japan Co., Ltd.). These may be used individually or in combination of two or more. The following are non-restrictive general formulas for dimer amines (in each formula, m+n=6 to 17 is preferred, p+q=8 to 19 is preferred, and the dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds).

[0033] [ka]

[0034] The content of component (B) in the resin composition of the present invention is preferably 20 to 90% by mass relative to the total of components (A) to (C). By setting the content of component (B) within the above range, the dielectric properties (low dielectric properties) and substrate adhesion of the cured resin composition are improved. The content of component (B) is more preferably 40 to 80% by mass relative to the total of components (A) to (C).

[0035] 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, good solder heat resistance is achieved. From the above viewpoint, a more preferable number-average molecular weight is 10,000 to 20,000. Note that the number-average molecular weight in this invention is a value calculated in polystyrene equivalent based on the measurement results of gel permeation chromatography (GPC).

[0036] Component (B) can be synthesized by known methods. For example, after dissolving the diamine and tetracarboxylic anhydride used in the synthesis in a solvent, a copolymerization reaction between the diamine and the tetracarboxylic anhydride occurs by heating and stirring at 10 to 140°C under an inert atmosphere such as nitrogen, yielding a polyamic acid resin solution. Alternatively, a dehydrating agent and catalyst may be added to the polyamic acid resin solution obtained above, and an imidation reaction (ring-closing reaction with dehydration) occurs by heating and stirring at 100 to 300°C, yielding component (B). Toluene and xylene can be used as dehydrating agents, and tertiary amines and dehydration catalysts can be used as catalysts. Heterocyclic tertiary amines are preferred as tertiary amines, such as pyridine, picoline, quinoline, and isoquinoline. Examples of dehydration catalysts include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride. Furthermore, the reaction time when synthesizing polyamic acid resin and polyimide resin is greatly affected by the reaction temperature, but it is preferable to continue the reaction until the viscosity increase accompanying the progress of the reaction reaches equilibrium and the maximum molecular weight is obtained, which is usually several minutes to 20 hours. The above example is a method for synthesizing polyimide resin via polyamic acid, but component (B) may also be obtained by dissolving the diamine and tetracarboxylic anhydride used in the synthesis in a solvent, adding a dehydrating agent or catalyst as needed, and then heating and stirring at 100 to 300°C to carry out the copolymerization and imidization reactions simultaneously.

[0037] (B) Solvents that can be used in the synthesis of component 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, ethyl isoamyl ether, ethyl-t-butyl ether, ethyl benzyl ether, cresyl methyl ether, anisole, phenethole, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate Examples include, but are not limited to, pyryl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, methyl acetoacetate, 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, dimethyl sulfoxide, etc. These may be used individually or in combination of two or more. The preferred amount of solvent used should be adjusted as appropriate depending on the viscosity and intended use of the resulting resin, but preferably the solids content is 60 to 10% by mass, more preferably 50 to 20% by mass.

[0038] (B) When synthesizing component (B), it is preferable to use a catalyst to promote the dehydration reaction, and the amount of catalyst used is preferably 1 to 30% of twice the number of moles of component (B) (the number of moles of water produced by dehydration condensation), more preferably 5 to 15%. Specific examples of catalysts that can be used include triethylamine, pyridine, and other known basic catalysts. Among these, triethylamine is preferred because it has a low boiling point and does not leave residue.

[0039] The (C) component 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, for example, 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 Examples include 6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, polyphenylmethanemaleimide, novolac-type maleimide compounds, biphenylaralkyl-type maleimide compounds, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 1,2-bis(maleimide)ethane, 1,4-bis(maleimide)butane, 1,6-bis(maleimide)hexane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-phenylmaleimide, and maleimide compounds represented by formulas (1) to (5). The maleimide compound (C) can also be included in the resin composition according to this embodiment in the form of a prepolymer obtained by polymerizing the maleimide compound, or a prepolymer obtained by polymerizing the maleimide compound with other compounds such as amine compounds.Commercially available products can also be used, specifically: 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 Yamato Kasei Co., Ltd.), BMI-3000 (manufactured by Designer Molecules inc.), BMI-5000 (manufactured by Designer Molecules inc.), BMI-6000 (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 Examples include BMI-TMH (manufactured by Yamato 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.), etc. 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. In addition, component (C) may be used alone or as a mixture of two or more types.

[0040] Among these, maleimide compounds represented by the following formulas (1) to (5) are more preferred from the viewpoint of solubility in organic solvents.

[0041] [ka]

[0042] In formula (1), R 1 R represents an alkyl group or phenyl group having 1 to 5 carbon atoms. 1 If multiple elements exist, they may be the same or different from one another. Examples of alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and neopentyl groups. R in formula (1)1 The alkyl group having 1 to 5 carbon atoms represented is preferably a methyl group or an ethyl group. In equation (1), each k independently represents an integer from 0 to 3, preferably an integer from 0 to 2, and more preferably 0. n 1 This represents the average number of repetitions, a real number greater than 1 and less than 5. If k is greater than 3, or R 1 If the alkyl group has six or more carbon atoms, the electrical properties may deteriorate due to molecular vibrations when the alkyl group is exposed to high frequencies.

[0043] [ka]

[0044] In formula (2), R 2 R represents an alkyl group or phenyl group having 1 to 5 carbon atoms. 2 If multiple C1-C5 alkyl groups are present, they may be the same or different from one another. Examples of C1-C5 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and neopentyl groups. In equation (2), each l represents an independent integer from 0 to 3. In formula (2), n 2 This represents the average value of the number of repetitions, and is a real number between 1 and 10 (inclusive).

[0045] [ka]

[0046] 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 of these independently represents either a hydrogen atom or a methyl group. In formula (3), each m independently represents an integer from 0 to 3, preferably an integer from 0 to 2, more preferably an integer of 0 or 1, and even more preferably 0. In formula (3), n 3 This represents the average value of the number of repetitions, and is a real number between 1 and 10 (inclusive). If m is greater than 3, or R 3 If the alkyl group has six or more carbon atoms, the electrical properties may deteriorate due to molecular vibrations when the alkyl group is exposed to high frequencies.

[0047] [ka]

[0048] In formula (4), R 5 and R 6 Each of these represents a hydrogen atom, a methyl group, or an ethyl group.

[0049] [ka]

[0050] In formula (5), n 4 n is the average value of the number of repetitions and represents a real number between 1 and 30. From the viewpoint of more effectively and reliably achieving the effects of this embodiment, 4 It is preferable that it is a real number between 7 and 30, and more preferably a real number between 7 and 18.

[0051] The content of component (C) in the resin composition of the present invention is preferably 5.0 to 40% by mass relative to 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 relative to the total of components (A) to (C).

[0052] The resin composition of the present invention allows for adjustment of the curing rate of the resin composition by including component (D), and also imparts appropriate moldability to the resin composition. The component (D) contained in the resin composition of the present invention is not particularly limited as long as it is a compound that can promote the curing of component (C) and an optional thermosetting resin (described later). Component (D) can be used by mixing one or more types.

[0053] The component (D) that can be used in the resin composition of the present invention is not particularly limited, but examples include thermal radical polymerization initiators, imidazole compounds, and tertiary amines such as triethylamine and tributylamine. Among these, thermal radical polymerization initiators are preferred because they provide a good curing rate. The thermal radical polymerization initiator is not particularly limited as long as it is a compound that releases an active substance (radical) upon heating that can polymerize the maleimide group contained in component (C) and the radical polymerizable functional group contained in the thermosetting resin described later, and known thermal radical polymerization initiators can be used. One or more thermal radical polymerization initiators can be used.

[0054] 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 preferred range, it is possible to increase the temperature of the solvent removal process during manufacturing.

[0055] Examples of thermal radical polymerization initiators include: dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexine-3, benzoyl peroxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, and ketone peroxide of cyclohexanone peroxide; peroxyketals of 1,1-di(t-butylperoxy)cyclohexane and 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane; hydroperoxides of tert-butyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide; di(2-t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di( t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, and dialkyl peroxides of di-t-butyl peroxide; dibenzoyl peroxide, and diacyl peroxides of di(4-methylbenzoyl) peroxide; di-n-propyl peroxydicarbonate, and peroxydicarbonate of diisopropyl peroxydicarbonate Examples include peroxyesters of 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-hexylperoxybenzoate, t-butylperoxybenzoate, and t-butylperoxy-2-ethylhexanonate; and azo compounds such as 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile).In the compositions of the present invention, organic peroxides are preferred from the viewpoint of obtaining a good curing rate, peroxyesters, peroxyketals, dialkyl peroxides, and organic peroxides having a hydroperoxide skeleton are more preferred, and dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyn-3, and tert-butyl hydroperoxide are even more preferred from the viewpoint of manufacturability.

[0056] The content of component (D) in the resin composition of the present invention is preferably 0.05 to 10 parts by mass, and more preferably 0.05 to 8 parts by mass, based on 100 parts by mass of the total of component (C) and the thermosetting resin described later, in order to obtain a good curing rate.

[0057] The resin composition of the present invention may also contain a thermosetting compound (E) other than component (C) (hereinafter also referred to as "component (E)"), as this allows for easy adjustment of the curing rate. (E) Examples of component include epoxy resins, carbodiimide resins, benzoxazine compounds, and compounds having ethylenically unsaturated groups. These resins or compounds can be used individually or in appropriate mixtures of two or more, depending on the physical properties and applications of the cured resin composition.

[0058] The epoxy resin as component (E) is not particularly limited as long as it has one or more epoxy groups in one molecule, but epoxy 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. Specific examples include jER828 (manufactured by Mitsubishi Chemical Corporation), NC-3000, and XD-1000 (both manufactured by Nippon Kayaku Co., Ltd.). The epoxy resin is added for the purpose of reacting with the acid anhydride groups of component (A), which increases the crosslinking density of the cured product, improving its resistance to polar solvents, as well as its adhesion to the substrate and heat resistance. The curing temperature of the resin composition containing epoxy resin is preferably 150 to 250°C. The curing time depends on the curing temperature, but is generally several minutes to several hours.

[0059] In the resin composition of the present invention containing epoxy resin, the epoxy resin content 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 component (A).

[0060] The resin composition of the present invention, which contains an epoxy resin, may optionally contain a curing agent to accelerate the curing reaction of the epoxy resin. Examples of curing agents include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diazabicyclo(5,4,0)undecene-7; phosphines such as triphenylphosphine; and metal compounds such as tin octylate. The amount of curing agent added to the resin composition of the present invention containing epoxy resin is 0.1 to 10% by mass relative to the epoxy resin.

[0061] (E) The carbodiimide resin (compound) as component is not particularly limited as long as it has one or more carbodiimide structures in one molecule. Specific examples of carbodiimide resins (compounds) include, for example, aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); and poly(phenylenecarbodiimide). Examples of polycarbodiimides include aromatic polycarbodiimides such as poly(naphthylenecarbodiimide), poly(tylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide]. These may be used in combination of two or more types.

[0062] Examples of commercially available carbodiimide resins (compounds) include "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-07," and "Carbodilite V-09" from Nisshinbo Chemical Co., Ltd., and "Stabaxol P," "Stabaxol P400," and "Hycazil 510" from Rhein Chemie Corporation.

[0063] In the resin composition of the present invention containing a carbodiimide resin (compound), the content of the carbodiimide resin (compound) is preferably 1.0 to 40% by mass relative to 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 relative to the total of components (A) to (C).

[0064] (E) The benzoxazine resin (compound) as component 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 fluorene type benzoxazine resin. The benzoxazine resin may contain one or more of these selected types, preferably bisphenol F type benzoxazine resin, diamine type benzoxazine resin, phenolphthalein type benzoxazine resin, or bisphenol fluorene type benzoxazine resin. These may be used in combination of two or more types, and therefore include one or more selected types or a mixture of two or more types.

[0065] In the resin composition of the present invention containing a benzoxazine resin (compound), the content of the benzoxazine resin (compound) is preferably 1.0 to 40% by mass relative to the total of components (A) to (C). 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 benzoxazine resin (compound) is more preferably 10 to 25% by mass relative to the total of components (A) to (C).

[0066] (E) The compound having an ethylenically unsaturated group as component is not particularly limited as long as it has an ethylenically unsaturated group in one molecule. Specific examples of compounds containing ethylenically unsaturated groups include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)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, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, glycol di(meth)acrylate, diethylenedi(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, and polypropylene glycol di(meth)acrylate. Examples include epoxy di(meth)acrylate adipic acid, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone-modified hydroxypivalic acid neopeneglycol 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, triethylolpropane tri(meth)acrylate, and their ethylene oxide adducts; pentaerythritol tri(meth)acrylate and its ethylene oxide adduct; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and their ethylene oxide adducts.

[0067] In addition, other specific examples of compounds having ethylenically unsaturated groups include urethane (meth)acrylates that have both a (meth)acryloyl group and a urethane bond within the same molecule; polyester (meth)acrylates that have both a (meth)acryloyl group and an ester bond within the same molecule; epoxy (meth)acrylates derived from epoxy resins that also have a (meth)acryloyl group; and reactive oligomers in which these bonds are used in combination.

[0068] Urethane (meth)acrylates include reaction products of hydroxyl group-containing (meth)acrylates with polyisocyanates and other alcohols used as needed. For example, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; glycerin (meth)acrylates such as glycerin mono(meth)acrylate and glycerin di(meth)acrylate; pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa( Examples of urethane (meth)acrylates include those obtained by reacting sugar alcohols (meth)acrylates such as meth)acrylate with toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and polyisocyanates such as their isocyanurates and biuret reaction products.

[0069] Polyester (meth)acrylates include, for example, monofunctional (poly)ester (meth)acrylates such as caprolactone-modified 2-hydroxyethyl (meth)acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth)acrylate, ethylene oxide-modified succinic acid (meth)acrylate, and caprolactone-modified tetrahydrofurfuryl (meth)acrylate; di(poly)ester (meth)acrylates such as hydroxypivalate ester neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol di(meth)acrylate, and epichlorohydrin-modified phthalic acid di(meth)acrylate; and mono, di, or tri(meth)acrylates of triols obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of trimethylolpropane or glycerin.

[0070] Furthermore, examples include mono, di, tri, or tetra(meth)acrylates of triols obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane; and mono or poly(meth)acrylates of triols obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of dipentaerythritol; and mono(meth)acrylates or poly(meth)acrylates of polyhydric alcohols such as triols, tetraols, pentaols, or hexaols.

[0071] Furthermore, examples include (meth)acrylates of polyester polyols, which are reaction products of diol components such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butylene glycol, 3-methyl-1,5-pentanediol, and hexanediol with polybasic acids such as maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebatic acid, azelaic acid, and 5-sodium sulfoisophthalic acid, and their anhydrides; and polyfunctional (poly)ester (meth)acrylates such as (meth)acrylates of cyclic lactone-modified polyester diols consisting of diol components, polybasic acids, and their anhydrides, such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone.

[0072] Epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. Examples include phenol novolac 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 (meth)acrylate, and acid anhydride-modified epoxy (meth)acrylates thereof.

[0073] 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; and compounds having a vinyl group such as triallyl isocyanurate, trimaallyl isocyanurate, and bisarylnadiimide are also specific examples of compounds having an ethylenically unsaturated group.

[0074] As compounds having an ethylenically unsaturated group, commercially available products can be used, for example, KAYARADZCA(registered trademark)-601H (trade name, manufactured by Nippon Kayaku Co., Ltd.), and propylene glycol monomethyl ether acetate of TrisP-PA epoxy acrylate compounds (manufactured by Nippon Kayaku Co., Ltd., such as 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 individually or in appropriate mixtures of two or more.

[0075] In the resin composition of the present invention containing a compound having an ethylenically unsaturated group, the content of the compound having an ethylenically unsaturated group is preferably 0.1 to 500 equivalents relative to the equivalent amount of ethylenically unsaturated double bond groups of component (C).

[0076] The resin composition of the present invention can be a varnish-like composition dissolved in an organic solvent (hereinafter simply referred to as varnish). 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; sulfones such as tetramethylene sulfone; ether solvents such as 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 and tetrahydrofuran; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic solvents such as toluene and xylene. The organic solvent is used in a range such that the solid content concentration in the varnish, excluding the organic solvent, is preferably 10 to 80% by mass, more preferably 20 to 70% by mass.

[0077] The resin composition of the present invention may be used in combination with known additives as needed. Specific examples of additives that can be used in combination include polybutadiene or a modified version thereof, a modified acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, cyanate ester compounds, silicone gel, silicone oil, and inorganic fillers such as silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, and glass powder; surface treatment agents for fillers such as silane coupling agents; release agents; colorants such as carbon black, phthalocyanine blue, and phthalocyanine green; thixotropy imparting agents such as Aerosil; silicone-based and fluorine-based leveling agents and defoaming agents; hydroquinone, hydroquinone monomethyl ether, phenol-based polymerization inhibitors, stabilizers, antioxidants, photopolymerization initiators, photobase generators, and photoacid generators. The amount of these additives is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, per 100 parts by mass of the resin composition. Among the additives, silane coupling agents having an acrylic group or a methacrylic group are particularly preferred from the viewpoint of heat resistance.

[0078] The curing temperature and curing time of the resin composition of the present invention may be selected by considering the combination of functional groups (reactive groups) of components (A) to (C), for example, the curing temperature of a resin composition that does not contain any component (E), or a resin composition that uses epoxy resin as an optional component, is preferably 120 to 250°C, and the curing time is generally several tens of minutes to several hours.

[0079] A prepreg can be obtained by heating and melting the resin composition of the present invention to reduce its viscosity and impregnating it with reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers. Alternatively, a prepreg can also be obtained by impregnating the reinforcing fibers with the varnish and then heating and drying it. By cutting the above-mentioned prepreg into a desired shape, laminating it with copper foil or the like as necessary, and then applying pressure to the laminate using methods such as press molding, autoclave molding, or sheet winding molding while heating and curing the resin composition, a substrate (article) equipped with the cured material of the present invention, such as an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material, can be obtained.

[0080] Alternatively, a substrate containing the cured product of the present invention can be obtained by coating copper foil with varnish, drying the solvent medium, laminating a polyimide film or LCP (liquid crystal polymer), and then heat-curing it after hot pressing. In some cases, the varnish can be applied to the polyimide film or LCP side and then laminated with copper foil to obtain a substrate containing the cured product of the present invention. Alternatively, a substrate comprising the cured product of the present invention can be obtained by coating copper foil with varnish, drying the solvent medium, laminating a prepreg in which reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers are impregnated with resin, and then heat-curing it after hot pressing. A substrate having a thin film made of the above resin composition can be used in copper-clad laminates (CCLs), or in printed circuit boards and multilayer wiring boards having circuit patterns on the copper foil of the CCL. [Examples]

[0081] The present invention will be described in further detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the examples, "parts" refers to parts by mass, and "%" refers to mass percent. The GPC measurement conditions in the examples are as follows. Model:TOSOH ECOSEC Elite HLC-8420GPC Column: TSKgel Super AWM-H Eluent: NMP (N-methylpyrrolidone); 0.5 ml / min, 40°C Detector: UV (differential refractometer) Molecular weight standard: Polystyrene

[0082] Synthesis Example 1 (Synthesis of soluble polyimide resin (B-1)) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer was filled with 10,640 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 7,066 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), and 67,254 parts of anisole, 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. The mixture was reacted at 130°C for 8 hours while removing the water generated by the cyclization of amicalcium with toluene by azeotropy. The remaining triethylamine and toluene were then removed at 130°C to obtain a soluble polyimide resin (B-1) (molecular weight 81,300) solution.

[0083] Synthesis Example 2 (Synthesis of soluble polyimide resin (B-2)) A 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer was heated to 70°C with 0.782 parts of DAPBAF 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol), 11.784 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 5.723 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), and 68.238 parts of anisole. 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 mixture was reacted at 130°C for 8 hours while removing the water generated by the cyclization of amic acid by azeotropy with toluene to obtain an intermediate polyimide resin solution (phenolic OH equivalent, 6780 g / eq., molecular weight 78,600). Subsequently, 0.663 parts of karens 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, and the mixture was reacted at 130°C for 4 hours. After that, the remaining triethylamine and toluene were removed at 130°C to obtain a soluble polyimide resin (B-2) solution.

[0084] Synthesis Example 3 (Synthesis of soluble polyimide resin (B-3)) In a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, raw material inlet, nitrogen inlet, and stirrer, 5.37 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.45 g / mol), 13.14 parts of PRIAMINE1075 (C36 dimer amine, manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 14.89 parts of 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 the mixture was heated to 120°C to dissolve the raw materials. The reaction was carried out at 135°C for 4 hours, while removing the water generated during the ring closure of amico acid by azeotrope 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.

[0085] Examples 1 to 11, Comparative Examples 1 and 2 (Preparation of resin compositions for the present invention and comparison) The resin compositions of the present invention and comparative compositions were prepared by blending each component in the amounts shown in Table 1 (units are "parts," and the parts for components (B) and (C) are calculated on a solid content basis without solvent), and then adding anisole as a solvent in an amount that results in a solid content concentration of 20% by mass, and mixing uniformly.

[0086] The components listed in Table 1 are 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 Engineering 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 obtained in Synthesis Examples 1 to 3 (B-1) to (B-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. Chemicals Co., Ltd. (C-3); BMI-80; Maleimide resin, manufactured by K.I. Chemicals Co., Ltd. <(E) component> (E-1); XD-1000; Epoxy resin, manufactured by Nippon Kayaku Co., Ltd. (E-2); ZXR-1889H; Epoxy acrylate resin, manufactured by Nippon Kayaku Co., Ltd. <(D) component> DCP; Dicumyl peroxide, manufactured by Nuurion Co., Ltd.

[0087] The adhesive strength, thermal properties, and other characteristics of the cured resin compositions to copper foil were evaluated using the following methods, based on the resin compositions obtained in Examples 1 to 11 and Comparative Examples 1 and 2.

[0088] (Evaluation of adhesive strength) Resin compositions were 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 & Powder Industry Co., Ltd. using an automatic applicator, and heated and dried at 120°C for 10 minutes. The thickness of the coating after drying was 30 μm. A PPE prepreg (Meteorwave 4000, manufactured by AGC nelco Co., Ltd.) was placed on top of the coating obtained on the copper foil, and vacuum pressed at 200°C for 60 minutes under conditions of 3 MPa. The obtained test pieces were cut to a width of 10 mm, and the 90° peel strength (peel speed of 50 mm / min) was measured using an Autograph AGS-X-500N (manufactured by Shimadzu Corporation) to evaluate the adhesive strength between the copper foil and the PPE prepreg. The results are shown in Table 1.

[0089] (Evaluation of thermal properties) Test specimens prepared using the same method as described in "Evaluation of Adhesion Strength" above were floated in a solder bath heated to 288°C using a POT-200C (manufactured by Taiyo Electric Industries Co., Ltd.), and their thermal properties were evaluated by the time it took for blistering to occur. ○...No swelling for over 600 seconds △··600 seconds or less, 60 seconds or more, no swelling ×...Swelling occurs in less than 60 seconds The results are shown in Table 1.

[0090] [Table 1]

[0091] As shown in Table 1, the resin composition of the present invention was superior in terms of adhesive strength and heat resistance, while the comparative resin composition was inferior in terms of adhesion and heat resistance. [Industrial applicability]

[0092] By using the polyimide resin of the specific structure of the present invention, it is possible to provide printed circuit boards and the like with excellent properties such as heat resistance, mechanical properties, low dielectric properties, adhesiveness, and flame retardancy.

Claims

1. A resin composition comprising a copolymer of styrene and an unsaturated monomer containing maleic anhydride (A), a soluble polyimide resin (B), a maleimide resin (C), and a curing accelerator (D), wherein 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, A resin composition in which the soluble polyimide resin (B) is a soluble polyimide resin (B) that dissolves in anisole at 23°C in an amount of 1.0% by mass or more.

2. The resin composition according to claim 1, wherein the soluble polyimide resin (B) contains fatty chains having 6 to 36 carbon atoms.

3. The resin composition according to claim 2, wherein the soluble polyimide resin (B) comprises a dimer amine skeleton.

4. The resin composition according to claim 1, wherein the number average molecular weight of the soluble polyimide resin (B) is 10,000 or more.

5. Maleimide resin (C) is a compound of the following formulas (1) to (5) 【Chemistry 1】 (In formula (1), R １ R represents an alkyl group or phenyl group having 1 to 5 carbon atoms. １ If multiple ks exist, they may be the same or different from each other. Each k independently represents an integer from 0 to 3. １ (This represents the average number of repetitions, a real number greater than 1 and less than 5.) 【Chemistry 2】 (In formula (2), R ２ R represents an alkyl group or phenyl group having 1 to 5 carbon atoms. ２ If multiple values ​​exist, they may be the same or different from one another. Each l independently represents an integer from 0 to 3. ２ (This represents the average number of repetitions, a real number between 1 and 10.) 【Transformation 3】 (In formula (3), R ３ represents a methyl group. Each of R ４ independently represents a hydrogen atom or a methyl group. Each of m independently represents an integer of 0 to 3. n ３ is an average value of the number of repetitions and represents a real number of 1 or more and 10 or less.) 【Chemistry 4】 (In formula (4), R ５ and R ６ (Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group.) 【Transformation 5】 (In formula (5), n ４ (This represents the average number of repetitions, a real number between 1 and 30.) The resin composition according to claim 1, comprising one or more compounds selected from the group consisting of compounds represented by .

6. The resin composition according to claim 1, wherein the copolymer (A) of styrene and maleic anhydride is an unsaturated monomer copolymer that satisfies the relationship: number of moles of styrene / number of moles of maleic anhydride = 5.0 to 40.

7. The resin composition according to claim 1, wherein the curing accelerator (D) is a thermal radical initiator.

8. A cured product of the resin composition according to any one of claims 1 to 7.

9. An article comprising the cured product described in claim 8.

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