Polyimide resin-containing composition and cured product thereof

Abstract

The present invention addresses the problem of providing a resin composition that produces a cured product having excellent heat resistance and adhesiveness to a base material and that can be suitably used in a printed wiring board. It has been found that the above problem is solved by a resin composition containing a thermoplastic resin (A), a polyimide resin (B), a maleimide resin (C), and a curing accelerator (D).

Description

Polyimide resin-containing composition and cured product thereof

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

[0002] Printed wiring boards are essential components for mobile communication devices such as smartphones and tablets, communication base station equipment, computers, car navigation systems, and other electronic devices. Various resin materials with excellent properties, such as adhesion to metal foil, heat resistance, and flexibility, are used for printed wiring boards. In recent years, development has been underway for printed wiring boards for next-generation high-speed, high-capacity radio frequency applications. In addition to the above-mentioned properties, resin materials are required to have low transmission loss, i.e., low dielectric constant and low dielectric loss tangent.

[0003] Furthermore, adhesive films used in multilayer printed wiring 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 film and PPE prepreg) and heat resistance sufficient to withstand solder mounting.

[0004] Patent Document 1 describes that a cured product of a composition containing a polyimide resin having a dimer diamine skeleton and a crosslinking agent has a low dielectric loss tangent and excellent dielectric properties. However, the composition in this document has insufficient adhesion to substrates. 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 substrates, and solder heat resistance. However, the cured product of the resin composition in this document has insufficient heat resistance and blistering occurs with increasing reflow cycles, so there is a demand for a product with higher heat resistance.

[0005] JP 2018-168369 A

[0006] One object of the present invention is to provide a resin composition that can be suitably used for printed wiring boards, and which, when cured, has excellent adhesion to substrates (substrate adhesion) and heat resistance.

[0007] As a result of extensive investigations, the present inventors have found that a resin composition containing a thermoplastic resin (A), a polyimide resin (B), a maleimide resin (C), and a curing accelerator (D) can solve the above-mentioned problems, and have thus completed the present invention.

[0008] [1] A resin composition comprising a thermoplastic resin (A), a soluble polyimide resin (B), a maleimide resin (C), and a curing accelerator (D). [2] The resin composition according to [1], wherein the thermoplastic resin (A) is a styrene-based elastomer. [3] The resin composition according to [1], wherein the soluble polyimide resin (B) contains an aliphatic chain having 6 to 36 carbon atoms. [4] The resin composition according to [1], wherein the soluble polyimide resin (B) contains a dimer diamine skeleton. [5] The resin composition according to [1], wherein the soluble polyimide resin (B) has a weight-average molecular weight of 30,000 or more. [6] The resin composition according to [1], wherein the maleimide resin (C) is represented by the following formulas (1) to (3):

[0009] (In formula (1), R １ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, R １ When a plurality of n are present, they may be the same or different. Each k independently represents an integer of 0 to 3. １ is the average number of repetitions and represents a real number greater than 1 and less than 5.)

[0010] (In formula (2), R ２ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, R ２ When a plurality of 1's are present, they may be the same or different. Each 1' independently represents an integer of 0 to 3. ２ is the average number of repetitions and represents a real number between 1 and 10.)

[0011] (In formula (3), R ５ and R ６each independently represents a hydrogen atom, a methyl group, or an ethyl group.) [7] The resin composition according to [1], wherein the thermoplastic resin (A) is a styrene-based thermoplastic elastomer, and the content of the thermoplastic resin (A) is 0.1% by mass or more and 20% by mass or less with respect to the total content of the thermoplastic resin (A), the soluble polyimide resin (B), and the maleimide resin (C). [8] The resin composition according to claim 7, wherein the styrene-based thermoplastic elastomer is a hydrogenated styrene-isoprene block copolymer. [9] The resin composition according to [1], wherein the curing accelerator (D) is a thermal radical initiator.

[10] A cured product of the resin composition according to any one of [1] to [9].

[11] An article comprising the cured product according to

[10] . [1-2] An adhesive film for printed wiring boards, comprising a thermoplastic resin (A) and a soluble polyimide resin (B).

[0012] By using the resin composition described herein, it is possible to provide a printed wiring board or the like that has excellent properties such as heat resistance and adhesiveness. Furthermore, the adhesive film for printed wiring boards described herein contains at least the thermoplastic resin (A), and therefore can provide an excellent dielectric loss tangent.

[0013] The resin composition contains a thermoplastic resin (A) (hereinafter also referred to as component (A)), a polyimide resin (B) (hereinafter also referred to as component (B)), a maleimide resin (C) (hereinafter also referred to as component (C)), and a curing accelerator (D) (hereinafter also referred to as component (D)).

[0014] Component (A) is preferably a styrene-based thermoplastic elastomer. It is preferably a hydrogenated styrene-isoprene block copolymer. From the viewpoint of low dielectric constant, component (A) preferably does not contain a hydroxyl group. Component (A) preferably has any of the structures represented by the following formulas (4) to (6).

[0015]

[0016] In the above formulas (4) to (6), a, b, c, d, and e are the average values ​​of the repeating numbers and represent real numbers of 1 to 100,000. The order of each repeating unit is not limited, and the bonding pattern may be any of alternating, block, and random. a, b, c, d, and e are preferably 1 to 90,000, and more preferably 1 to 80,000.

[0017] The component (A) is preferably a resin having a structure represented by the above formula (5).

[0018] Specific examples include the SEPTON series manufactured by Kuraray Co., Ltd. and the Tuftec series manufactured by Asahi Kasei Corporation. The content of component (A) relative to the total of components (A) to (C) of the resin composition (meaning the total of components (A), (B), and (C)) is preferably 0.1% by mass or more and 20% by mass or less. When the content of thermoplastic resin (A) is within the above range, an improvement in adhesive strength is achieved, compatibility with components (B) and (C) is good, the compounded liquid does not separate, and the cured product becomes uniform. Therefore, from this perspective, it is preferable that the thermoplastic resin (A) is contained in a content within the above-mentioned range.

[0019] The component (B) used in the resin composition is not particularly limited as long as it is a soluble polyimide resin, but examples include soluble polyimide resins obtained by the imidization reaction of a diamine component and a tetracarboxylic dianhydride component. It is not limited to either aliphatic soluble polyimide resins or aromatic soluble polyimide resins. Modified soluble polyimide resins obtained by modifying the terminals or side chains of these soluble polyimide resins are also included in the soluble polyimide resins of this specification. The soluble polyimide resin may be a commercially available product or a synthesized product, and may be used alone or in combination with multiple types. In this specification, a soluble polyimide refers to a polyimide resin that is soluble in an organic solvent, and soluble means that it dissolves in an amount of 1.0% by mass or more at 23°C. The organic solvents mentioned here include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ether-based solvents such as 1,4-dioxane, tetrahydrofuran, and diglyme; glycol ether-based 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.

[0020] 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'-diaminodiphenyl thioether, 3,3'-dimethyl-4,4'-diaminodiphenyl thioether, 3,3'-diethoxy-4,4'-diaminodiphenyl thioether, and 3,3'-diaminodiphenyl ether. Phenyl 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-aminophenyl)propane, 2,2'-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenylsulfonesulfone, 4,4'-diaminodiphenyl sulfonesulfone, 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-diphenyl)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 of such diamines 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, 9,9'-bis(3-amino-4-hydroxyphenyl)fluorene, and diaminopolysiloxanes having 6 to 36 carbon atoms. From the viewpoint of heat resistance, it is particularly preferable to use diamines containing a fluorene skeleton, such as 9,9-bis(4-aminophenyl)fluorene, or 2,2'-bis(4-aminophenoxyphenyl)propane. These diamine components may be used alone or in combination of two or more.

[0021] Specific examples of tetracarboxylic dianhydride components 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'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4' -bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic dianhydride. Among these, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-diphenylethertetracarboxylic dianhydride are preferred in terms of solvent solubility, adhesion to substrates, and photosensitivity. These may be used alone or in combination of two or more.

[0022] Component (B) preferably contains a soluble polyimide resin having an aliphatic chain having 6 to 36 carbon atoms introduced into its backbone. When component (B) is synthesized, for example, 1,3-bisaminomethylcyclohexane, norbornanediamine, isophoronediamine, dimerdiamine, 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 Corporation), dimerdiamine, or trimertriamine is used as the diamine component, whereby an aliphatic chain having a predetermined number of carbon atoms derived from the diamine component can be introduced 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 having an aliphatic chain derived from dimer diamine introduced into the skeleton.

[0023] Dimer diamines are compounds in which two carboxyl groups of a dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid, have been substituted with primary amino groups (see, for example, JP 9-12712 A). Specific examples of commercially available dimer diamines 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. Non-limiting general formulas of dimer diamines are shown below (in each formula, m+n preferably equals 6 to 17, and p+q preferably equals 8 to 19, and the dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds).

[0024]

[0025] The content of component (B) in the resin composition is preferably 5 to 90% by mass relative to the total mass of components (A) to (C). By setting the content of component (B) within this range, the dielectric properties (low dielectric properties) and substrate adhesion of the cured product of the resin composition are improved. The content of component (B) is more preferably 20 to 89.9% by mass relative to the total mass of components (A) to (C).

[0026] The weight-average molecular weight of component (B) is preferably 30,000 or more. By setting the weight-average molecular weight to 30,000 or more, solder heat resistance is improved. From this viewpoint, the weight-average molecular weight is more preferably 30,000 to 200,000. In this specification, the weight-average molecular weight is a value calculated in terms of polystyrene based on the results of gel permeation chromatography (GPC).

[0027] Component (B) can be synthesized by known methods. For example, the diamine and tetracarboxylic anhydride used in the synthesis are dissolved in a solvent, and then the mixture is heated and stirred at 10 to 140°C under an inert atmosphere such as nitrogen, thereby causing a copolymerization reaction between the diamine and the tetracarboxylic anhydride, thereby obtaining a polyamic acid resin solution. Alternatively, a dehydrating agent or catalyst can be added to the polyamic acid resin solution obtained above, if necessary, and the mixture is heated and stirred at 100 to 300°C, thereby causing an imidization reaction (a ring-closing reaction accompanied by dehydration), thereby obtaining component (B). Examples of dehydrating agents that can be used include toluene, xylene, and triethylamine, and examples of catalysts that can be used include tertiary amines and dehydration catalysts. Examples of tertiary amines that can be used include aliphatic and heterocyclic tertiary amines, such as triethylamine, pyridine, picoline, quinoline, and isoquinoline. Examples of dehydration catalysts include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride. The above example is a method for synthesizing a polyimide resin via a polyamic acid. Alternatively, component (B) may be obtained by dissolving the diamine and tetracarboxylic acid anhydride used in the synthesis in a solvent, adding a dehydrating agent and / or catalyst as needed, and heating and stirring at 100 to 300°C to carry out the copolymerization reaction and imidization reaction simultaneously.

[0028] Examples of solvents that can be used in 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, ethyl isoamyl ether, ethyl t-butyl ether, ethyl benzyl ether, cresyl methyl ether, anisole, phenetole, 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, and methyl acetoacetate. Examples of suitable solvents include, but are not limited to, 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, and dimethyl sulfoxide. These may be used alone or in combination of two or more. The amount of the solvent used should be adjusted appropriately depending on the viscosity and intended use of the resulting resin, but a solids content of 10 to 60% by mass, and more preferably 20 to 50% by mass, is preferred.

[0029] During the synthesis of 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%, more preferably 5 to 15%, of twice the number of moles of component (B) (the number of moles of water generated by dehydration condensation). Specific examples of catalysts that can be used include known general basic catalysts such as triethylamine and pyridine. Among these, triethylamine is preferred because of its low boiling point and low residue.

[0030] The maleimide resin (C) used in the resin composition is not particularly limited as long as it has one or more maleimide groups in one molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 4,4-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, p-phenylene biscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, and 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide. Examples of the maleimide include maleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4-diphenylether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, polyphenylmethane maleimide, novolac-type maleimide compounds, biphenylaralkyl-type maleimide compounds, 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) can also be contained 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 another compound such as an amine compound.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.), BMI-689 (manufactured by Designer Molecules Inc.), BMI-1700 (manufactured by Designer Molecules Inc.), and BMI-1500 (manufactured by Designer Molecules Inc.). Examples of suitable maleimide resins include BMI-TMH (manufactured by Daiwa Chemical Industry Co., Ltd.), MAHD (manufactured by Evonik), BMI-1000P (manufactured by K.I. Chemical Industry Co., Ltd.), BMI-650P (manufactured by K.I. Chemical Industry Co., Ltd.), BMI-250P (manufactured by K.I. Chemical Industry Co., Ltd.), and CUA-4 (manufactured by K.I. Chemical Industry Co., Ltd.). Maleimide resins having an aromatic ring such as a benzene ring, biphenyl ring, or naphthalene ring are preferred because the cured product of the resin composition has excellent properties such as mechanical strength and flame retardancy. Furthermore, the component (C) may be used alone or in combination of two or more types.

[0031] Among these, from the viewpoint of solubility in organic solvents, maleimide compounds represented by the following formulas (1) to (3) are more preferred. Formulas (1) to (3) will be explained below.

[0032]

[0033] In formula (1), R １ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, R １ When a plurality of R groups are present, they may be the same or different. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and a neopentyl group. １The alkyl group having 1 to 5 carbon atoms represented by is preferably a methyl group or an ethyl group. In formula (1), k's each independently represent an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0. １ is the average number of repetitions and represents a real number greater than 1 and less than 5. When k is greater than 3, or R １ If is an alkyl group having 6 or more carbon atoms, the electrical properties may be degraded due to molecular vibration when the alkyl group is exposed to high frequency.

[0034]

[0035] In formula (2), R ２ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, R ２ When a plurality of groups are present, they may be the same or different. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and a neopentyl group. In formula (2), each l independently represents an integer of 0 to 3. In formula (2), n ２ is the average number of repetitions and represents a real number between 1 and 10.

[0036]

[0037] (In formula (3), R ５ and R ６ each independently represents a hydrogen atom, a methyl group, or an ethyl group.

[0038] The content of component (C) in the resin composition is preferably 1 to 40 mass% based on the total of components (A) to (C). By setting the content of component (C) within this 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 component (C) is more preferably 5 to 25 mass% based on the total of components (A) to (C).

[0039] By including the component (D), the curing rate of the resin composition can be adjusted and the resin composition is endowed with appropriate moldability. The component (D) is not particularly limited as long as it is a compound that can promote the curing of the component (C) and the thermosetting resin (E) other than the component (C), which is an optional component described below. The component (D) can be used alone or in combination of two or more.

[0040] The component (D) 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 because they provide a good curing rate. The thermal radical polymerization initiator is not particularly limited as long as it is a compound that, upon heating, releases an active substance (radical) that can polymerize the maleimide group contained in the component (C) and the radically polymerizable functional group contained in the thermosetting resin described below, and known thermal radical polymerization initiators can be used. The thermal radical polymerization initiators can be used alone or in combination of two or more.

[0041] The 10-hour half-life temperature of the thermal radical polymerization initiator is preferably 100° C. or higher, and from the viewpoint of manufacturability, more preferably 110° C. or higher. By setting the 10-hour half-life temperature of the thermal radical polymerization initiator within the above-mentioned preferred range, the solvent removal step during production can be carried out at a higher temperature.

[0042] Examples of the thermal radical polymerization initiator include ketone peroxides such as dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, benzoyl peroxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, and cyclohexanone peroxide; peroxyketals of 1,1-di(t-butylperoxy)cyclohexane and 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane; 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( Dialkyl peroxides such as t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, and di-t-butyl peroxide; diacyl peroxides such as dibenzoyl peroxide and di(4-methylbenzoyl) peroxide; peroxydica such as di-n-propyl peroxydicarbonate and diisopropyl peroxydicarbonate. peroxyesters of 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-hexylperoxybenzoate, t-butylperoxybenzoate, and t-butylperoxy-2-ethylhexanoate; 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 resin composition, organic peroxides are preferred from the viewpoint of obtaining a good curing rate, and 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)hexyne-3, and tert-butyl hydroperoxide are even more preferred from the viewpoint of manufacturability.

[0043] The content of the component (D) is preferably 0.05 to 10 parts by mass, and more preferably 0.05 to 8 parts by mass, per 100 parts by mass of the total of the component (C) and the thermosetting resin described below, in order to obtain a good curing rate.

[0044] The resin composition may contain a thermosetting compound (E) (hereinafter also referred to as "component (E)") other than component (C) in order to easily adjust the curing rate. Examples of component (E) include epoxy resins, carbodiimide resins, benzoxazine compounds, and compounds having an ethylenically unsaturated group. These resins or compounds may be used alone or in combination of two or more, depending on the physical properties and application of the cured product of the resin composition.

[0045] The epoxy resin used as component (E) is not particularly limited as long as it has one or more epoxy groups per molecule. However, because 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 rings, biphenyl rings, and naphthalene rings are preferred. Specific examples include jER828 (manufactured by Mitsubishi Chemical Corporation), NC-3000, and XD-1000 (all manufactured by Nippon Kayaku Co., Ltd.). The epoxy resin is added for the purpose of reacting with the acid anhydride groups of component (B), which increases the crosslink density of the cured product, improves resistance to polar solvents, and improves 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 generally from several minutes to several hours.

[0046] The content of the epoxy resin in the resin composition containing the epoxy resin is preferably an amount 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 (B).

[0047] A curing agent may be added to a resin composition containing an epoxy resin, if necessary, to promote 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-diaza-bicyclo(5,4,0)undecene-7; phosphines such as triphenylphosphine; and metal compounds such as tin octoate. The amount of curing agent added to a resin composition containing an epoxy resin is 0.1 to 10% by mass relative to the epoxy resin.

[0048] 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 the carbodiimide resin (compound) include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane-bis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); poly(phenylenecarbodiimide); Examples of polycarbodiimides include aromatic polycarbodiimides such as poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide]. Two or more of these may be used in combination.

[0049] Commercially available carbodiimide resins (compounds) include, for example, "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-07," and "Carbodilite V-09," manufactured by Nisshinbo Chemical Inc.; and "Stavaxol P," "Stavaxol P400," and "Hykasil 510," manufactured by Rhein Chemie.

[0050] When the resin composition contains a carbodiimide resin (compound), the content of the carbodiimide resin (compound) is preferably 1.0 to 40 mass% based on the total of components (A) to (C). By setting the content of the carbodiimide resin (compound) to 1.0 to 40 mass%, the heat resistance, substrate adhesion, low water absorption, and dielectric properties of the cured product of the resin composition can be improved. The content of the carbodiimide resin (compound) is more preferably 10 to 25 mass% based on the total of components (A) to (C).

[0051] The benzoxazine resin (compound) as component (E) is not particularly limited as long as it has one or more benzoxazine structures per molecule. Specific examples of the benzoxazine resin (compound) include bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, diamine benzoxazine resin, phenolphthalein benzoxazine resin, dicyclopentadiene benzoxazine resin, and bisphenolfluorene benzoxazine resin. The benzoxazine resin may contain one or a mixture of two or more selected from the above. Bisphenol F benzoxazine resin, diamine benzoxazine resin, phenolphthalein benzoxazine resin, and / or bisphenolfluorene benzoxazine resin are preferred. These may be used in combination of two or more, and the benzoxazine resin may contain one or a mixture of two or more selected from the above.

[0052] The content of the benzoxazine resin (compound) in the resin composition containing the benzoxazine resin (compound) is preferably 1.0 to 40 mass% based on the total of components (A) to (C). By setting the content of the benzoxazine resin (compound) in the range of 1.0 to 40 mass%, the heat resistance, substrate adhesion, low water absorption, and dielectric properties of the cured product of the resin composition can be improved. The content of the benzoxazine resin (compound) is more preferably 10 to 25 mass% based on the total of components (A) to (C).

[0053] 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 the compound having an ethylenically unsaturated group 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, 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 neopen 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, triethylolpropane tri(meth)acrylate, and ethylene oxide adducts thereof; pentaerythritol tri(meth)acrylate, and ethylene oxide adducts thereof; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide adducts thereof.

[0054] Other specific examples of the compound having an ethylenically unsaturated group include urethane (meth)acrylates having both a (meth)acryloyl group and a urethane bond in the same molecule; polyester (meth)acrylates having both a (meth)acryloyl group and an ester bond in the same molecule; epoxy (meth)acrylates derived from epoxy resins and having both a (meth)acryloyl group; and reactive oligomers in which these bonds are used in combination.

[0055] Examples of urethane (meth)acrylates include reaction products of a hydroxyl group-containing (meth)acrylate with a polyisocyanate and other alcohols used as needed. Examples include 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, dipentaerythritol hexa(meth)acrylate; Examples of the urethane (meth)acrylates include those obtained by reacting sugar alcohol (meth)acrylates such as urethane (meth)acrylate with polyisocyanates such as toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and their isocyanurates and biuret reaction products.

[0056] Examples of polyester (meth)acrylates include 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 hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalic acid 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.

[0057] Further 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; mono- or poly(meth)acrylates of polyhydric alcohols such as triols, tetraols, pentaols, or hexaols, of 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, or tetraols, pentaols, or hexaols.

[0058] Further examples include polyfunctional (poly)ester (meth)acrylates such as (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, sebacic acid, azelaic acid, and 5-sodium sulfoisophthalic acid, and anhydrides thereof; and (meth)acrylates of cyclic lactone-modified polyester diols formed from diol components, polybasic acids, anhydrides thereof, and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc.

[0059] The epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. Examples thereof include phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, trishydroxyphenylmethane epoxy (meth)acrylate, dicyclopentadienephenol epoxy (meth)acrylate, bisphenol A epoxy (meth)acrylate, bisphenol F epoxy (meth)acrylate, biphenol epoxy (meth)acrylate, bisphenol A novolac epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal epoxy (meth)acrylate, heterocyclic epoxy (meth)acrylate, and the acid anhydride-modified epoxy acrylates thereof.

[0060] Specific examples of the compound having an ethylenically unsaturated group include 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, trimethallyl isocyanurate, and bisallylnadimide.

[0061] The compound having an ethylenically unsaturated group can be a commercially available product, and examples thereof include KAYARAD (registered trademark) ZCA-601H (trade name, manufactured by Nippon Kayaku Co., Ltd.), propylene glycol monomethyl ether acetate of TrisP-PA epoxy acrylate compound (manufactured by Nippon Kayaku Co., Ltd. under the trade name 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 appropriate mixtures of two or more types.

[0062] The content of the compound having an ethylenically unsaturated group in the resin composition containing the compound having an ethylenically unsaturated group is preferably an amount that is 0.1 to 500 equivalents relative to the ethylenically unsaturated double bond group equivalent of component (C).

[0063] The resin composition can be dissolved in an organic solvent to form a varnish-like composition (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 so that the solids concentration in the varnish, excluding the organic solvent, is preferably 10 to 80% by mass, more preferably 20 to 70% by mass.

[0064] If necessary, known additives may be used in combination with the resin composition.Specific examples of the additives that can be used in combination include polybutadiene or its modified product, 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 antifoaming agents, hydroquinone, hydroquinone monomethyl ether, phenol-based polymerization inhibitors, stabilizers, antioxidants, photopolymerization initiators, photobase generators, and photoacid generators. The amount of these additives to be added 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. As the additive, a silane coupling agent having an acrylic group or a methacrylic group is particularly preferred from the viewpoint of heat resistance.

[0065] The curing temperature and curing time of the resin composition may be selected taking into consideration the combination of functional groups (reactive groups) possessed by the components (A) to (C), etc. For example, the curing temperature of a resin composition that does not contain the optional component (E) or a resin composition that uses an optional epoxy resin in combination is preferably 120 to 250°C, and the curing time is generally from several tens of minutes to several hours.

[0066] A prepreg can be obtained by heating and melting the resin composition to reduce its viscosity and impregnating reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber. Alternatively, a prepreg can be obtained by impregnating reinforcing fibers with the varnish and then heating and drying. The prepreg can be cut into a desired shape and, if necessary, laminated with copper foil or the like. The resin composition can then be heated and cured while applying pressure to the laminate using a press molding method, autoclave molding method, sheet winding molding method, or the like, to obtain an article containing a cured product of the resin composition and a substrate such as an electrical / electronic laminate (printed wiring board) or a carbon fiber reinforced material.

[0067] Alternatively, a substrate having a cured product can be obtained by coating the varnish on copper foil, drying the solvent, laminating a polyimide film or LCP (liquid crystal polymer), hot pressing, and then heat curing. In some cases, a substrate having a cured product of the present invention can be obtained by coating the polyimide film or LCP side and laminating it with copper foil. Alternatively, a substrate having a cured product can be obtained by coating the varnish on copper foil, drying the solvent, laminating a prepreg in which the resin is impregnated into reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, or alumina fiber, hot pressing, and then heat curing. Substrates having a thin film of the cured product of the resin composition can be used for copper-clad laminates (CCLs), or printed wiring boards and multilayer wiring boards having a circuit pattern on the copper foil of the CCL.

[0068] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the examples, "parts" means parts by mass, and "%" means % by mass. 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

[0069] Synthesis Example 1 (Synthesis of Soluble Polyimide Resin (B-1)) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen introducing apparatus, and a stirrer, 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 were placed and heated to 70°C. Next, 13.029 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Corporation, molecular weight 310.22 g / mol), 0.850 parts of triethylamine, and 15,000 parts of toluene were added, and the mixture was reacted at 130°C for 8 hours while removing water generated by ring closure of the amic acid by azeotropy with toluene. Thereafter, the remaining triethylamine and toluene were subsequently removed at 130°C, thereby obtaining a solution of soluble polyimide resin (B-1) (molecular weight 81,300).

[0070] Synthesis Example 2 (Synthesis of Soluble Polyimide Resin (B-2)) A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen introducing apparatus, and a stirrer was charged with 0.782 parts of DAPBAF2,2-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, and heated to 70°C. Next, 12.409 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Corporation, molecular weight 310.22 g / mol), 0.810 parts of triethylamine, and 14.987 parts of toluene were added, and the mixture was reacted for 8 hours at 130 ° C. while removing the water generated by ring closure of the amic acid by azeotropy with toluene to obtain an intermediate polyimide resin (phenolic OH equivalent, 6780 g / eq., molecular weight 78,600). Subsequently, 0.663 parts of Karenz MOI (manufactured by Resonac Corporation, 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 for 4 hours at 130 ° C. After that, the remaining triethylamine and toluene were subsequently removed at 130 ° C. to obtain a soluble polyimide resin (B-2) (molecular weight 72,400) solution.

[0071] Synthesis Example 3 (Synthesis of Soluble Polyimide Resin (B-3)) A 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a raw material inlet, a nitrogen introducing apparatus, and a stirrer was charged with 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 PRIAMINE 1075 (C36 dimer diamine, 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, and heated to 120 ° C. to dissolve the raw materials. The reaction was carried out for 4 hours at 135° C. while removing water generated 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 the mixture was heated at 130° C. for 3 hours to obtain a solution of soluble polyimide resin (B-3) (molecular weight 65,900).

[0072] Synthesis Example 4 (Synthesis of Soluble Polyimide Resin (B-4)) A 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen introducing apparatus, and a stirrer was charged with 1.58 parts of DAPBAF2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol), 12.88 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), 27.92 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Corporation, molecular weight 310.22 g / mol), and 154.05 parts of anisole, and heated to 120°C. Next, 26.90 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 542.13 g / mol) was added dropwise, and the mixture was cooled to 70 ° C., and 1.82 parts of triethylamine and 10.94 parts of toluene, and 33.67 parts of anisole were added. After reacting at 135 ° C. for 16 hours, the mixture was cooled to room temperature, and Karenz MOI (manufactured by Resonac Co., Ltd., molecular weight 155.15 g / mol) 1.34 parts, 0.21 parts of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor, and 10.10 parts of anisole were added, and the mixture was reacted at 85 ° C. for 1.5 hours to obtain a soluble polyimide resin (B-4) (molecular weight 87,500) solution.

[0073] Synthesis Example 5 (Synthesis of Soluble Polyimide Resin (B-5)) A 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen introducing apparatus, and a stirrer was charged with 2.22 parts of DAPBAF 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol), 19.65 parts of BAPP (2,2-bis[4-(4-aminophenoxy)phenyl]propane, molecular weight 410.517 g / mol), 37.23 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Corporation, molecular weight 310.22 g / mol), and 212.91 parts of anisole, and heated to 120°C. Next, 36.47 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 542.13 g / mol) was added dropwise, and the mixture was cooled to 52 ° C., 2.43 parts of triethylamine, and 25.21 parts of toluene, and 21.73 parts of anisole were added. After reacting at 135 ° C. for 19 hours, the mixture was cooled to room temperature, and Karenz MOI (manufactured by Resonac Corporation, molecular weight 155.15 g / mol) 1.88 parts, 0.27 parts of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor, and 39.11 parts of anisole were added, and the mixture was reacted at 85 ° C. for 2 hours to obtain a soluble polyimide resin (B-5) (molecular weight 78,200) solution.

[0074] Examples 1 to 13 and Comparative Examples 1 to 6 (Preparation of Resin Compositions) The components were blended in the amounts shown in Table 1 (unit: "parts," and the number of parts of component (B) and component (C) is the number of parts converted to solid content excluding solvent), and then anisole was added as a solvent in an amount such that the solid content concentration became 20% by mass, and the mixture was mixed uniformly to prepare the resin compositions of the Examples and Comparative Examples.

[0075] The components in Table 1 are as follows: <Component (A)> SEPTON 2104: styrene-based thermoplastic elastomer (corresponding to the above formula (5)), manufactured by Kuraray Co., Ltd. <Component (B)> (B-1) to (B-5): soluble polyimide resins (B-1) to (B-5) obtained in Synthesis Examples 1 to 5 <Component (C)> (C-1): MIR-3000-70MT: maleimide resin, manufactured by Nippon Kayaku Co., Ltd. (corresponding to the above formula (2)) (C-2): MIR-5000-60T: maleimide resin, manufactured by Nippon Kayaku Co., Ltd. (corresponding to the above formula (1)) (C-3): BMI-70: maleimide resin, manufactured by K.I. Kasei Co., Ltd. (corresponding to the above formula (3)) <Component (D)> DCP: dicumyl peroxide, manufactured by Kayaku Nouryon Co., Ltd.

[0076] Using each of the resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2, the adhesive strength to copper foil and thermal properties of the cured resin compositions were evaluated by the following methods.

[0077] (Evaluation of Adhesion Strength) The resin composition was applied to the 12 μm rough surface of ultra-low roughness, unroughened electrolytic copper foil CF-T9DA-SV manufactured by Fukuda Metal Foil & Powder Co., Ltd. using an automatic applicator, and then heated and dried at 120°C for 10 minutes. The thickness of the coating film after drying was 5 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 220°C for 60 minutes under conditions of 3 MPa. The obtained test specimens were cut into 10 mm widths, and the 90° peel strength (peel rate: 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.

[0078] (Evaluation of thermal properties) Test pieces prepared in the same manner as in the "Evaluation of adhesive strength" above were floated in a solder bath heated to 288°C using a POT-200C (manufactured by Taiyo Electric Industrial Co., Ltd.), and the thermal properties were evaluated based on the time until blisters appeared. ◯ (Excellent): No blisters for 600 seconds or more △ (Fair): No blisters for 60 seconds or more but less than 600 seconds × (Fail): Blisters appeared in less than 60 seconds The results are shown in Table 1.

[0079]

[0080] The results in Table 1 show that the resin compositions of the present invention are excellent in adhesive strength and heat resistance, whereas the resin compositions of the comparative examples are inferior in adhesive strength and heat resistance.

[0081] Using the resin compositions obtained in Examples 7 and 8 and Comparative Examples 3 and 4, the adhesive strength to copper foil and thermal properties of the cured resin compositions were evaluated by the following methods.

[0082] (Evaluation of Adhesion Strength) The resin composition was applied to the 18 μm rough surface of an ultra-low roughness, unroughened electrolytic copper foil (CF-T9DA-SV) manufactured by Fukuda Metal Foil & Powder Co., Ltd. using an automatic applicator, and then heated and dried at 120°C for 10 minutes. The thickness of the coating film after drying was 5 μm. A PPE prepreg (Megtron 6, manufactured by Panasonic Industries 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 specimens were cut into 10 mm widths, and the 90° peel strength (peel rate: 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 2.

[0083] (Evaluation of thermal properties) Test pieces prepared in the same manner as in the "Evaluation of adhesive strength" above were floated in a solder bath heated to 288°C using a POT-200C (manufactured by Taiyo Electric Industrial Co., Ltd.), and the thermal properties were evaluated based on the time until blisters appeared. ◯ (Excellent): No blisters for 600 seconds or more △ (Fair): No blisters for 60 seconds or more less than 600 seconds × (Fail): Blisters appeared in less than 60 seconds The results are shown in Table 2.

[0084]

[0085] The results in Table 2 show that the resin compositions of the present invention are excellent in adhesive strength and heat resistance, whereas the resin compositions of the comparative examples are inferior in adhesiveness.

[0086] Using the resin compositions shown in Table 3, the adhesive strength to copper foil and thermal properties of the cured resin compositions were evaluated by the following methods.

[0087] (Evaluation of Adhesion Strength) The resin composition was applied to the 12 μm rough surface of ultra-low roughness, unroughened electrolytic copper foil CF-T9DA-SV manufactured by Fukuda Metal Foil & Powder Co., Ltd. using an automatic applicator, and then heated and dried at 120°C for 10 minutes. The thickness of the coating film after drying was 5 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 220°C for 60 minutes under conditions of 3 MPa. The obtained test specimens were cut into 10 mm widths, and the 90° peel strength (peel rate: 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 3.

[0088] (Evaluation of thermal properties) Test pieces prepared in the same manner as in the "Evaluation of adhesive strength" above were floated in a solder bath heated to 288°C using a POT-200C (manufactured by Taiyo Electric Industrial Co., Ltd.), and the thermal properties were evaluated based on the time until blisters appeared. ◯ (Excellent): No blisters for 600 seconds or more △ (Fair): No blisters for 60 seconds or more but less than 600 seconds × (Fail): Blisters appeared in less than 60 seconds The results are shown in Table 3.

[0089]

[0090] The results in Table 3 show that the resin compositions of the present invention are excellent in adhesive strength, whereas the resin compositions of the comparative examples are inferior in adhesiveness.

[0091] The resin compositions obtained in Example 13 (the same composition as in Example 8) and Comparative Example 6 (the same composition as in Comparative Example 5) were used to evaluate the adhesive strength of the cured resin compositions to copper foil by the following method.

[0092] (Evaluation of Adhesion Strength) The resin composition was applied to the 18 μm rough surface of an ultra-low roughness, unroughened electrolytic copper foil (CF-T9DA-SV) manufactured by Fukuda Metal Foil & Powder Co., Ltd. using an automatic applicator, and then heated and dried at 120°C for 10 minutes. The thickness of the coating film after drying was 5 μm. A PPE prepreg (Megtron 8, manufactured by Panasonic Industries Co., Ltd.) was superimposed on the coating film on the copper foil obtained above, and vacuum pressed at 220°C for 60 minutes at 3 MPa. The obtained test specimens were cut into 10 mm widths, and the 90° peel strength (peel rate: 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 4.

[0093]

[0094] The results in Table 4 show that the resin compositions of the examples were excellent in adhesive strength, whereas the resin compositions of the comparative examples were inferior in adhesiveness.

[0095] (Measurement of Dielectric Loss Tangent) Using the resin compositions listed in Table 5, the dielectric loss tangent of the cured resin composition was evaluated using the following method. Each of the resin compositions of the Examples and Comparative Examples was applied to a polyimide film, Upilex 75S (manufactured by UBE Corporation), using an automatic applicator, in an amount such that the resin composition layer would have a thickness of 40 μm after application and drying, and then heated and dried at 120°C for 10 minutes. The resin composition obtained above was heat-cured in an inert oven in a nitrogen atmosphere at 205°C for 60 minutes. Test specimens peeled from the Upilex 75S at room temperature were placed in an environmental test chamber at 23°C and 50% humidity for 24 hours. The dielectric loss tangent at 10 GHz was measured using an EM Lab CR710 split cylinder resonator and a KEYSIGHT Technology N5234A network analyzer.

[0096]

[0097] The results in Table 5 show that the resin compositions of the Examples were excellent in dielectric loss tangent, while the resin compositions of the Comparative Examples were inferior in dielectric loss tangent. It was found that the addition of component (A) improved the dielectric properties. It was also found that the compatibility of the resin compositions was good when the amount of component (A) added was 0.5% to 20%.

[0098] By using a resin composition containing a thermoplastic resin (A), a soluble polyimide resin (B), a maleimide resin (C), and a curing accelerator (D), it is possible to provide a printed wiring board or the like having excellent properties such as heat resistance and adhesiveness.

Claims

1. A resin composition comprising a thermoplastic resin (A), a soluble polyimide resin (B), a maleimide resin (C) and a curing accelerator (D).

2. The resin composition according to claim 1, wherein the thermoplastic resin (A) is a styrene-based elastomer.

3. The resin composition according to claim 1, wherein the soluble polyimide resin (B) contains an aliphatic chain having 6 to 36 carbon atoms.

4. The resin composition according to claim 1, wherein the soluble polyimide resin (B) contains a dimer diamine skeleton.

5. The resin composition according to claim 1, wherein the weight average molecular weight of the soluble polyimide resin (B) is 30,000 or more.

6. The resin composition according to claim 1, wherein the maleimide resin (C) is represented by the following formulas (1) to (3): (In formula (1), R １ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group; R １ When a plurality of n are present, they may be the same or different. Each k independently represents an integer of 0 to 3. １ is the average 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; R ２ When a plurality of n are present, they may be the same or different. Each 1 independently represents an integer of 0 to 3. ２ is the average number of repetitions and represents a real number between 1 and 10.) (In formula (3), R ５ and R ６ each independently represents a hydrogen atom, a methyl group, or an ethyl group.

7. The resin composition according to claim 1, wherein the thermoplastic resin (A) is a styrene-based thermoplastic elastomer, and the content of the thermoplastic resin (A) is 0.1% by mass or more and 20% by mass or less with respect to the total content of the thermoplastic resin (A), the soluble polyimide resin (B), and the maleimide resin (C).

8. The resin composition according to claim 7, wherein the styrene-based thermoplastic elastomer is a hydrogenated styrene-isoprene block copolymer.

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

10. A cured product of the resin composition according to any one of claims 1 to 9.

11. An article comprising the cured product according to claim 10.

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