Polyimide resin-containing composition and cured product thereof

Abstract

The present invention addresses the problem of providing a resin composition which has excellent base material adhesion and heat resistance of a cured product and is suitable for use in a printed wiring board, and it is found that a resin composition containing a thermoplastic resin (A), a polyimide resin (B), a maleic imide resin (C), and a curing accelerator (D) can solve the problem.

Description

Technical Field

[0001] This invention relates to resin compositions containing polyimide resins and their cured forms. Background Technology

[0002] Printed circuit boards (PCBs) are indispensable components in mobile communication devices such as smartphones and tablets, communication base station equipment, and electronic devices such as computers and car navigation systems. PCBs utilize various resin materials with excellent properties such as adhesion to metal foil, heat resistance, and flexibility.

[0003] In addition, in recent years, the development of a new generation of high-speed and high-capacity high-frequency wireless printed circuit boards has been underway. In addition to the above-mentioned characteristics, the resin material is required to have low transmission loss, that is, low dielectric constant and low dielectric loss tangent.

[0004] In addition, adhesive films used as adhesives or cover films in multilayer printed circuit boards are required to exhibit excellent dielectric properties, as well as excellent adhesion strength to copper foil or substrates (polyimide film or PPE prepolymer), or the ability to withstand the heat of soldering installation.

[0005] Patent Document 1 describes a cured product containing a polyimide resin with a dimerized diamine backbone and a crosslinking agent, which has a low dielectric loss tangent and excellent dielectric properties. However, the composition in this document has insufficient adhesion to the substrate.

[0006] Patent Document 2 describes a cured product of a resin composition containing polyimide resin, modified elastomer, and epoxy resin, which exhibits excellent dielectric properties, adhesion to substrates, and resistance to welding heat. However, the cured product of the composition in this document has insufficient heat resistance, and expansion occurs upon increasing the number of reflows, thus requiring higher heat resistance.

[0007] [Existing Technical Documents]

[0008] [Patent Literature]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 2018-168369.

[0010] [Patent Document 2] WO2020 / 071154. Summary of the Invention

[0011] [The problem the invention aims to solve]

[0012] One of the objectives of this invention is to provide a resin composition suitable for printed circuit boards, wherein the cured form exhibits excellent adhesion to substrates (substrate adhesion) and heat resistance.

[0013] [Methods for solving problems]

[0014] Through in-depth investigation, the inventors discovered that a resin composition containing thermoplastic resin (A), polyimide resin (B), maleic anhydride resin (C), and curing accelerator (D) can solve the above-mentioned problems, and thus the present invention was completed.

[0015] That is, the present invention includes the following.

[0016] [1] A resin composition comprising a thermoplastic resin (A), a soluble polyimide resin (B), a maleic animide resin (C), and a curing accelerator (D).

[0017] [2] The resin composition as described in [1], wherein the thermoplastic resin (A) is a styrene-based elastomer.

[0018] [3] The resin composition as described in [1], wherein the soluble polyimide resin (B) contains an aliphatic chain having 6 to 36 carbon atoms.

[0019] [4] The resin composition as described in [1], wherein the soluble polyimide resin (B) contains a dimer diamine backbone.

[0020] [5] The resin composition as described in [1], wherein the weight-average molecular weight of the soluble polyimide resin (B) is 30,000 or more.

[0021] [6] The resin composition as described in [1], wherein the maleic anhydride resin (C) is of the following formula (1) to (3).

[0022]

[0023] (In formula (1), R) 1 Represents an alkyl or phenyl group having 1 to 5 carbon atoms, with multiple R groups present. 1 These can be the same or different. k represents an integer from 0 to 3 independently. n 1 (This represents the average of the repeated numbers, and is a real number greater than 1 and less than 5.)

[0024]

[0025] (In equation (2), R) 2 Represents an alkyl or phenyl group having 1 to 5 carbon atoms, with multiple R groups present. 2 These can be the same or different. l represents an integer from 0 to 3 independently. n 2 This represents the average of the repeated numbers, and is a real number greater than 1 and less than 10.

[0026]

[0027] (In equation (3), R) 5 and R 6 Each can be used independently to represent a hydrogen atom, a methyl group, or an ethyl group.

[0028] [7] The resin composition as described in [1], wherein the thermoplastic resin (A) is a styrene-based thermoplastic elastomer, and the content of the thermoplastic resin (A) is greater than 0.1% by mass and less than 20% by mass relative to the total content of the thermoplastic resin (A), the soluble polyimide resin (B) and the maleic diimide resin (C).

[0029] [8] The resin composition as described in [7], wherein the styrene-based thermoplastic elastomer is a hydrogenated styrene-isoprene block copolymer.

[0030] [9] The resin composition as described in [1], wherein the curing accelerator (D) is a thermal free radical initiator.

[0031]

[10] A cured material, which is a cured material of the resin composition described in any one of [1] to [9].

[0032]

[11] An article having the hardened material described in

[10] .

[0033] [1-2] An adhesive film for printed circuit boards, comprising a thermoplastic resin (A) and a soluble polyimide resin (B).

[0034] [Invention Effects]

[0035] By using the resin composition described in this specification, printed circuit boards and the like with excellent properties such as heat resistance and adhesion can be provided.

[0036] Furthermore, the adhesive film for printed circuit boards described in this specification, since it contains at least thermoplastic resin (A), provides excellent dielectric loss tangent. Detailed Implementation

[0037] The above-mentioned resin composition is a resin composition containing thermoplastic resin (A) (hereinafter referred to as component (A)), polyimide resin (B) (hereinafter referred to as component (B)), maleic anhydride resin (C) (hereinafter referred to as component (C)) and curing accelerator (D) (hereinafter referred to as component (D)).

[0038] (A) is preferably a styrene-based thermoplastic elastomer. Hydrogenated styrene-isoprene block copolymer is preferred. From the viewpoint that the (A) component has a low dielectric constant, it is preferred to be free of hydroxyl groups. (A) component is preferably having any of the structures represented by the following formulas (4) to (6).

[0039]

[0040] In equations (4) to (6) above, a, b, c, d, and e are the average number of repetitions, representing real numbers from 1 to 100,000. The order of the repeating units is not limited, and the bonding form can be any of crosslinking, block, or random. A, b, c, d, and e are preferably from 1 to 90,000, and more preferably from 1 to 80,000.

[0041] (A) The component is preferably a resin having the structure represented by the above formula (5).

[0042] Specifically, examples include the SEPTON series manufactured by Kuraray Co., Ltd., and the Tuftech series manufactured by Asahi Kasei Corporation. Regarding the total of components (A) to (C) of the resin composition (referring to the total of components (A), (B), and (C),) the content of component (A) is preferably greater than 0.1% by mass and less than 20% by mass. When the content of thermoplastic resin (A) is within the above range, it can achieve the effect of improving adhesive strength, while maintaining good compatibility with components (B) or (C), and ensuring that the mixture does not separate and the hardened product is uniform. Therefore, from this viewpoint, it is preferable that the thermoplastic resin (A) contains an amount within the above range.

[0043] The (B) component used in the resin composition is not particularly limited as long as it is a soluble polyimide resin. Examples include soluble polyimide resins obtained by the imidization reaction of a diamine component and a tetracarboxylic acid dianhydride component. Furthermore, it is not limited to either aliphatic or aromatic soluble polyimide resins. Modified soluble polyimide resins with end or side chain modifications of these soluble polyimide resins are also included in the soluble polyimide resins described in this specification. Commercially available soluble polyimide resins or synthetic ones can be used; moreover, only one type can be used, or multiple types can be used in combination.

[0044] Furthermore, the term "soluble polyimide resin" in this specification refers to polyimide resin that is soluble in organic solvents. Solubility in this specification means dissolving at 1.0% by mass or more at 23°C. Organic solvents here refer to ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ether solvents such as 1,4-dioxane, tetrahydrofuran, and diethylene glycol dimethyl ether; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether; and other solvents such as benzyl alcohol, N-methylpyrrolidone, γ-butyrolactone, ethyl acetate, N,N-dimethylformamide, and anisole.

[0045] (B) Specific examples of diamine components that can be used in the synthesis of the component include 9,9-bis(4-aminophenyl)fluorene, m-phenylenediamine, p-phenylenediamine, m-toluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3, 3'-Diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane, 3,4'-Diaminodiphenylmethane, 3,3'-Dimethoxy-4,4'-Diaminodiphenyl sulfide, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(4-aminophenyl)propane, 4,4'-Diaminodiphenyl sulfoxide, 3,3'-Diaminodiphenyl sulfone, 4,4'-Diaminodiphenyl sulfone, benzidine, 3,3'-Dimethylbenzidine, 3,3'-Dimethoxybenzidine, 3,3'-Diaminobiphenyl, p-Xylenediamine, m-Xylenediamine, o-Xylenediamine Amines, 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-dimethylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3-propylphenyl)methane and bis(4-amino-3,5-dipropylphenyl)methane, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, Examples of suitable materials include 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybenzophenone, 2,2-bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, and 9,9'-bis(3-amino-4-hydroxyphenyl)fluorene, as well as diaminopolysiloxanes with 6 to 36 carbon atoms. From the viewpoint of heat resistance, diamines containing a fluorene skeleton, such as 9,9-bis(4-aminophenyl)fluorene, or 2,2'-bis(4-aminophenoxyphenyl)propane are preferred.

[0046] These diamine components can be used in combination, either one or two or more.

[0047] (B) Specific examples of tetracarboxylic dianhydrides that can be used in the synthesis of components include pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl sulfone 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'-bis(3, Examples of anhydrides include 4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene phthalic 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. Among these, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4-benzophenone tetracarboxylic dianhydride, 3,3',4,4-biphenyl tetracarboxylic dianhydride, or 3,3',4,4-diphenyl ether tetracarboxylic dianhydride are preferred in terms of solvent solubility, adhesion to the substrate, and photosensitivity. One of these dianhydrides may be used, or two or more may be mixed.

[0048] (B) The preferred component is a soluble polyimide resin containing aliphatic chains with 6 to 36 carbon atoms introduced into the backbone. During the synthesis of (B), for example, 1,3-diaminomethylcyclohexane, norbornene diamine, isophorone diamine, dimer diamine, 2-methyl-1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebiscyclohexane, diamine H2O (manufactured by Okamura Oils), dimer diamine, or trimer triamine can be used as diamine components, thereby introducing aliphatic chains with a predetermined number of carbon atoms from these diamine components into the backbone of the soluble polyimide. From the viewpoint of improving dielectric properties and substrate adhesion, soluble polyimide resin containing aliphatic chains from dimer diamine introduced into the backbone in component (B) is preferred.

[0049] Dimeric diamines refer to dimers in which two carboxyl groups of a dimer containing unsaturated fatty acids such as oleic acid are replaced with primary amino groups (see Japanese Patent Application Publication No. 9-127121, etc.). Specific examples of commercially available dimer diamines include PRIAMINE 1074 and PRIAMINE 1075 (both manufactured by Croda Co., Ltd., Japan) and Versamin 551 (manufactured by Cognis Co., Ltd., Japan). One or more of these components may be used. The following describes non-limiting general formulas for dimer diamines (where m+n = 6 to 17 is preferred, and p+q = 8 to 19 is preferred; the dashed lines represent carbon-carbon single or double bonds).

[0050]

[0051] 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 the aforementioned range, the dielectric properties (low dielectricity) and substrate adhesion of the cured resin composition can be improved.

[0052] The content of component (B) is more preferably 20 to 89.9% by mass relative to the total mass of components (A) to (C).

[0053] (B) The weight-average molecular weight of component B is preferably 30,000 or higher. Because a weight-average molecular weight of 30,000 or higher improves resistance to weld heat, this is preferable. From this perspective, a weight-average molecular weight of 30,000 to 200,000 is more preferred. Furthermore, the weight-average molecular weight in this specification is a value for polystyrene calculated based on gel permeation chromatography (GPC) measurements.

[0054] Component (B) can be synthesized using well-known methods. For example, after dissolving the diamine and tetracarboxylic anhydride used in the synthesis in a solvent, the mixture is heated and stirred at 10 to 140°C under an inert atmosphere such as nitrogen to carry out a copolymerization reaction of the diamine and tetracarboxylic anhydride, yielding a polyamic acid resin solution. Alternatively, a dehydrating agent or catalyst can be added to the resulting polyamic acid resin solution, and the mixture is heated and stirred at 100 to 300°C to carry out an imidization reaction (dehydration and ring-closing reaction) to obtain component (B). Dehydrating agents can include toluene, xylene, triethylamine, etc., and catalysts can include tertiary amines and dehydration catalysts. Tertiary amines are preferably aliphatic or heterocyclic tertiary amines, such as triethylamine, pyridine, methylpyridine, quinoline, and isoquinoline. Dehydration catalysts can include, for example, acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, etc.

[0055] The above example is a method for synthesizing polyimide resin via polyamic acid. After dissolving the diamine and tetracarboxylic anhydride used in the synthesis in a solvent, a dehydrating agent or catalyst is optionally added, and the mixture is heated and stirred at 100 to 300°C. Copolymerization and imidization reactions can also be carried out simultaneously to obtain component (B).

[0056] 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, methyl cyclohexyl ketone, acetylacetone, γ-butyrolactone, diacetone alcohol, cyclohexen-1-one, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, tetrahydropyran, ethyl isopentyl ether, ethyl tert-butyl ether, ethyl anisole, cresol methyl ether, anisole, phenethyl ether, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methyl cyclohexyl 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., but not limited to these solvents. One or more of these solvents may be used. The preferred amount of solvent used, while adjustable depending on the viscosity of the obtained resin or its intended use, is preferably 10 to 60% by mass of solids content, and more preferably 20 to 50% by mass.

[0057] When synthesizing component (B), it is preferable to use a catalyst to promote the dehydration reaction. The amount of catalyst used is preferably 1% to 30% of twice the molar number of component (B) (the number of moles of water produced by the dehydration condensation), and more preferably 5% to 15%. Specific examples of catalysts used include known general basic catalysts such as triethylamine and pyridine. Among these, triethylamine is preferred in terms of its low boiling point and minimal residue.

[0058] The maleic anhydride resin (C) used in the resin composition is not particularly limited as long as it has one or more maleic anhydride groups per molecule. Specific examples include: N-phenylmaleic anhydride, N-hydroxyphenylmaleic anhydride, bis(4-maleic anhydride phenyl)methane, 4,4-diphenylmethane bismaleic anhydride, bis(3,5-dimethyl-4-maleic anhydride phenyl)methane, bis(3-ethyl-5-methyl-4-maleic anhydride phenyl)methane, bis(3,5-diethyl-4-maleic anhydride phenyl)methane, phenyl Methane bis-cis-butene diimide, o-phenylene bis-cis-butene diimide, m-phenylene bis-cis-butene diimide, p-phenylene bis-cis-butene diimide, p-phenylene bis-cis-butene diimide, 2,2-bis(4-(4-cis-butene diimide phenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bis-cis-butene diimide, 4-methyl-1,3-phenylene bis-cis-butene diimide, 1 6-Dibutenyl imide-(2,2,4-trimethyl)hexane, 4,4-diphenyl ether dibutenyl imide, 4,4-diphenyl sulfone dibutenyl imide, 1,3-bis(3-cis-butenyl imide phenoxy)benzene, 1,3-bis(4-cis-butenyl imide phenoxy)benzene, polyphenylmethane cis-butenyl imide, phenolic cis-butenyl imide compounds, biphenyl aralkyl cis-butenyl imide compounds, 2,2-di... (4-(4-cis-butenylimide phenoxy)phenyl)propane, 1,2-bis(cis-butenylimide)ethane, 1,4-bis(cis-butenylimide)butane, 1,6-bis(cis-butenylimide)hexane, N,N'-1,3-phenylene dicis-butenylimide, N,N'-1,4-phenylene dicis-butenylimide, N-phenylcis-butenylimide, and maleic anhydride compounds represented by formulas (1) to (5), etc. The maleic anhydride compound (C) may also be a prepolymer obtained by polymerizing maleic anhydride, or a prepolymer obtained by polymerizing maleic anhydride compounds with amine compounds or other compounds, and is included in the resin composition of this embodiment.In addition, commercially available products can also be used. Specific examples include: MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.), MIR-5000 (manufactured by Nippon Kayaku Co., Ltd.), BMI-70 (manufactured by Kei-I Chemical Co., Ltd.), BMI-80 (manufactured by Kei-I Chemical Co., Ltd.), BMI-2300 (manufactured by Daiwa Chemical Co., Ltd.), BMI-3000 (manufactured by Designer Molecules Co., Ltd.), BMI-5000 (manufactured by Designer Molecules Co., Ltd.), BMI-6000 (manufactured by Designer Molecules Co., Ltd.), BMI-689 (manufactured by Designer Molecules Co., Ltd.), BMI-1700 (manufactured by Designer Molecules Co., Ltd.), and BMI-1500 (manufactured by Designer Molecules Co., Ltd.). The following resins are preferred: Molecules Co., Ltd., BMI-TMH (Yamato Chemical Co., Ltd.), MAHD (Evonik Co., Ltd.), BMI-1000P (Kei-I Chemical Co., Ltd.), BMI-650P (Kei-I Chemical Co., Ltd.), BMI-250P (Kei-I Chemical Co., Ltd.), and CUA-4 (Kei-I Chemical Co., Ltd.). To improve the mechanical strength or flame retardancy of the cured resin composition, maleic anhydride resins having aromatic rings such as benzene rings, biphenyl rings, and naphthalene rings are preferred. Furthermore, component (C) can be one type, or two or more types can be mixed.

[0059] Of these components, from the viewpoint of solubility in organic solvents, maleic anhydride compounds represented by the following formulas (1) to (3) are more preferred. Formulas (1) to (3) will be explained below.

[0060]

[0061] In equation (1), R 1 Represents an alkyl or phenyl group having 1 to 5 carbon atoms, with multiple R groups present. 1 In this case, these groups can be the same or different from each other. Examples of alkyl groups having 1 to 5 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and neopentyl. R in formula (1) 1 The alkyl group represented has 1 to 5 carbon atoms, preferably methyl or ethyl.

[0062] In equation (1), k represents an integer from 0 to 3, preferably an integer from 0 to 2, and more preferably 0.

[0063] n １It is the average of the repeated numbers, representing a real number greater than 1 and less than 5.

[0064] When k is greater than 3, or R 1 When the alkyl group has 6 or more carbon atoms, its electrical properties may be reduced due to exposure to molecular vibrations at high frequencies.

[0065]

[0066] In equation (2), R 2 Represents an alkyl or phenyl group having 1 to 5 carbon atoms, with multiple R groups present. 2 These groups can be the same or different from each other. Examples of alkyl groups having 1 to 5 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and neopentyl.

[0067] In equation (2), l independently represents integers from 0 to 3.

[0068] In equation (2), n 2 The average of the repeated numbers is a real number greater than 1 and less than 10.

[0069]

[0070] (In equation (3), R) 5 and R 6 Each can be used independently to represent a hydrogen atom, a methyl group, or an ethyl group.

[0071] The content of component (C) in the resin composition is preferably 1 to 40% by mass relative to the total of components (A) to (C). By setting the content of component (C) within the aforementioned range, the heat resistance, substrate adhesion, low water absorption, and dielectric properties of the cured resin composition can be improved.

[0072] The content of component (C) is more preferably 5 to 25% by mass relative to the total of components (A) to (C).

[0073] Because the resin composition contains component (C), the curing speed of the resin composition can be adjusted, and in addition, the resin composition can be given appropriate formability.

[0074] (D) is any compound that can promote the curing of thermosetting resin (E) other than (C) and any of the components described below, without any particular limitation. (D) may be one or a mixture of two or more.

[0075] (D) There are no particular limitations on the components, and examples include: thermal free radical polymerization initiators, imidazole compounds, and tertiary amines such as triethylamine and tributylamine. Among these, thermal free radical polymerization initiators are preferred in terms of obtaining a good curing speed.

[0076] The thermal free radical polymerization initiator is not particularly limited to any compound that releases free radicals upon heating, as long as it is an active substance (free radical) capable of polymerizing the maleic anhydride group contained in component (C) and the free radical polymerizable functional groups contained in the thermosetting resin described later. One thermal free radical polymerization initiator may be used, or a mixture of two or more may be used.

[0077] The 10-hour half-life temperature of the thermal free radical polymerization initiator is preferably 100°C or higher, and from a manufacturing point of view, 110°C or higher is more preferred. By setting the 10-hour half-life temperature of the thermal free radical polymerization initiator to the aforementioned preferred range, the temperature of the solvent removal step in the process can be increased.

[0078] Examples of thermal free radical polymerization initiators include: ketone peroxides, such as dicumyl peroxide, 2-(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, benzoyl peroxide, di-tert-butyl peroxide, methyl ethyl ketone peroxide, and cyclohexanone peroxide; peroxy ketals, such as 1,1-di(tert-butylperoxy)cyclohexane and 2,2-di(4,4-di(tert-butylperoxy)cyclohexyl)propane; hydrogen peroxides, such as tert-butyl hydroperoxide, p-methane hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide; and dialkyl peroxides, such as di(2-tert-butylperoxyisopropyl)benzene and 2,5-dimethyl-2,5-di(tert-butylperoxy) Hexane, tert-butyl cumene peroxide, di-tert-hexyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne and di-tert-butyl peroxide; diacyl peroxides, such as dibenzoyl peroxide and di(4-methylbenzoyl) peroxide; peroxydicarbonates, such as di-n-propyl peroxydicarbonate and diisopropyl peroxydicarbonate; peroxy esters, such as 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-hexyl peroxybenzoate, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate, etc.; azo compounds such as 2,2'-azobis(2,4-dimethylpentanonitrile) and 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile). In terms of achieving a good curing speed, organic peroxides are preferred in the resin composition, with peroxide esters, peroxide acetals, dialkyl peroxides and organic peroxides having a hydrogen peroxide skeleton being more preferred. From a manufacturing point of view, dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3 and tert-butyl hydroperoxide are more preferred.

[0079] The content of component (D) is preferably 0.05 to 10 parts by mass relative to the total of component (C) and the thermosetting resin described later, in order to obtain a good curing speed. More preferably, it is 0.05 to 8 parts by mass.

[0080] In order to facilitate the adjustment of the curing speed, thermosetting compound (E) other than component (C) may also be used in the resin composition (hereinafter also referred to as "component (E)").

[0081] (E) Components may include, for example, epoxy resins, carbodiimide resins, benzoxazine compounds, and compounds having vinyl unsaturated groups. These resins or compounds may be used alone or in combination of two or more suitable compounds, depending on the properties of the cured resin composition and its intended use.

[0082] As for the epoxy resin as component (E), there are no particular restrictions as long as it has one or more epoxy groups in one molecule. From the viewpoint of improving the mechanical strength or flame retardancy of the cured resin composition, epoxy resins having aromatic rings such as benzene rings, biphenyl rings and naphthalene rings are preferred. Specific examples include jER828 (manufactured by Mitsubishi Chemical Co., Ltd.), NC-3000, and XD-1000 (both manufactured by Nippon Kayaku Co., Ltd.).

[0083] The purpose of adding epoxy resin is to react with the anhydride groups of component (B), thereby increasing the crosslinking density of the cured material, improving its resistance to polar solvents, and improving its adhesion to the substrate or its heat resistance.

[0084] The curing temperature of the resin composition containing epoxy resin is preferably between 150 and 250°C. The curing time depends on the curing temperature, but is approximately from several minutes to several hours.

[0085] The epoxy resin content in the resin composition containing epoxy resin is preferably 0.1 to 500 equivalents relative to the anhydride groups of 1 equivalent of component (B).

[0086] In resin compositions containing epoxy resin, a curing agent may optionally be added 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-diazabicyclo(5,4,0)undecyl-7-ene; phosphines such as triphenylphosphine; and metal compounds such as tin octoate.

[0087] The amount of curing agent added to the resin composition containing epoxy resin is 0.1 to 10 by mass relative to the epoxy resin.

[0088] There are no particular restrictions on the carbodiimide resin (compound) that is a component (E), as long as it has more than one carbodiimide structure in one molecule.

[0089] Specific examples of carbodiimide resins (compounds) include: aliphatic carbodiimides such as tetramethylene-bis(tert-butylcarbodiimide) and cyclohexane-bis(methylene-tert-butylcarbodiimide); aromatic carbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylene dicyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); and poly(phenylenecarbodiimide). Polycarbodiimides, including aromatic polycarbodiimides such as poly(naphthalene carbodiimide), poly(xylene carbodiimide), poly(methyl diisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylene carbodiimide), poly(diisopropylphenylene carbodiimide), poly(xylene-xylene carbodiimide), poly(tetramethylxylene-xylene carbodiimide), poly(methylene diphenylene carbodiimide), and poly[methylene bis(methylphenylene)carbodiimide].

[0090] These carbodiimide resins can be used in combination of two or more types.

[0091] 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 Co., Ltd.; and "Stavaxol P", "Stavaxol P400" and "Haikasil 510" manufactured by Rhein Chemie Co., Ltd.

[0092] When the resin composition contains 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) to 1.0 to 40% by mass, the heat resistance, substrate adhesion, low water absorption, and dielectric properties of the cured resin composition can be improved.

[0093] The content of the carbodiimide resin (compound) is more preferably 10 to 250% by mass relative to the total of components (A) to (C).

[0094] There are no particular restrictions on the benzoxazine resin (compound) that is a component (E), as long as it has more than one benzoxazine structure in one molecule.

[0095] Specific examples of benzoxazine resins (compounds) include: containing one or more of the following: 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, with bisphenol F type benzoxazine resin, diamine type benzoxazine resin, phenolphthalein type benzoxazine resin and / or bisphenol fluorene type benzoxazine resin being preferred.

[0096] These resins are mixtures of any one or more resins selected from which two or more resins can be mixed.

[0097] The content of benzoxazine resin (compound) in the resin composition containing 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 benzoxazine resin (compound) in the range of 1.0 to 40% by mass, the heat resistance, substrate adhesion, low water absorption and dielectric properties of the cured resin composition can be improved.

[0098] The content of benzoxazine resin (compound) is more preferably 10 to 25% by mass relative to the total of components (A) to (C).

[0099] There are no particular restrictions on compounds containing vinyl unsaturated groups as component (E), as long as one molecule contains vinyl unsaturated groups.

[0100] Specific examples of compounds containing vinyl unsaturated groups include: methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, ethyl phenyl methacrylate, isobornyl methacrylate, isocyclohexyl methacrylate, benzyl methacrylate, tetrahydrofuran methacrylate, butyl methacrylate, hexyl methacrylate, neopentyl methacrylate, nonadiyl methacrylate, diol di(meth)acrylate, diethylenedi(meth)acrylate, polyethylene glycol di(meth)acrylate, tri(meth)propionyloxyisocyanurate, and polypropylene glycol dimethacrylate. (Meth)acrylates, adipate epoxy di(meth)acrylates, bisphenol ethylene oxide di(meth)acrylates, hydrogenated bisphenol ethylene oxide (meth)acrylates, bisphenol di(meth)acrylates, ε-caprolactone-modified hydroxyneopentanoic acid neopentyl glycol di(meth)acrylates, ε-caprolactone-modified diisopentylenetetrol hexa(meth)acrylates, ε-caprolactone-modified diisopentylenetetrol poly(meth)acrylates, diisopentylenetetrol poly(meth)acrylates, trimethylolpropane tri(meth)acrylates, trimethylolpropane tri(meth)acrylates and their ethylene oxide adducts; isopentylenetetrol tri(meth)acrylates and their ethylene oxide adducts; isopentylenetetrol tetra(meth)acrylates, diisopentylenetetrol hexa(meth)acrylates and their ethylene oxide adducts, etc.

[0101] In addition, other examples include: urethane (meth)acrylates containing both (meth)acrylyl and urethane bonds within a single molecule; polyester (meth)acrylates containing both (meth)acrylyl and ester bonds within a single molecule; epoxy (meth)acrylates containing (meth)acrylyl groups derived from epoxy resins; and reactive oligomers using these bonds in combination, which are also specific examples of compounds having vinyl unsaturated groups.

[0102] Examples of urethane (meth)acrylates include hydroxyl-containing (meth)acrylates and polyisocyanates, reacting with other alcohols that may be used optionally. Examples include: hydroxy(meth)acrylates such as ethyl hydroxy(meth)acrylate, propyl hydroxy(meth)acrylate, and butyl hydroxy(meth)acrylate; glycerol(meth)acrylates such as glycerol mono(meth)acrylate and glycerol di(meth)acrylate; glycosyl(meth)acrylates such as isopentetrol di(meth)acrylate, isopentetrol tri(meth)acrylate, diisopentetrol penta(meth)acrylate, and diisopentetrol hexa(meth)acrylate; as well as urethane(meth)acrylates such as toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and polyisocyanates that react these cyanates, burette reactants, etc.

[0103] Examples of polyester (meth)acrylates include: monofunctional (poly)acrylate (meth)acrylates such as caprolactone-modified ethyl 2-hydroxy (meth)acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth)acrylate, ethylene oxide-modified succinic acid (meth)acrylate, and caprolactone-modified tetrahydrofuranyl (meth)acrylate; di(poly)acrylate (meth)acrylates such as hydroxypentanoate neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypentanoate 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 more than 1 mole of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerol to 1 mole of trimethylolpropane or glycerol.

[0104] In addition, examples include mono-, di-, tri-, or tetra(meth)acrylates of triols obtained by adding 1 or more moles of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, or δ-valerol to 1 mole of isopentethyl alcohol, di- or tri-methylolpropane, tri- or tetra-methylolpropane; mono(meth)acrylates of triols obtained by combining 1 or more moles of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, or δ-valerol to 1 mole of diisopentethyl alcohol; or mono(meth)acrylates or poly(meth)acrylates of polyols such as triols, tetraols, pentaols, or hexaols.

[0105] In addition, examples include (meth)acrylates of polyester polyols containing diols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butanediol, 3-methyl-1,5-pentanediol, and hexanediol; (meth)acrylates of polyester polyols containing reactants of maleic acid (or maleic acid), fumaric acid (or fumaric acid), succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, sodium 5-sulfoisophthalate, etc.; and (meth)acrylates of polyester diols modified with cyclic lactones formed by diols and polyacids and their anhydrides such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone.

[0106] Epoxy (meth)acrylates refer to compounds containing epoxy groups and carboxylic acid esters of (meth)acrylic acid. Examples include: phenolic aldehyde type epoxy (meth)acrylates, cresol phenolic aldehyde type epoxy (meth)acrylates, trihydroxyphenylmethane type epoxy (meth)acrylates, dicyclopentadienol type epoxy (meth)acrylates, bisphenol A type epoxy (meth)acrylates, bisphenol F type epoxy (meth)acrylates, bisphenol type epoxy (meth)acrylates, bisphenol A phenolic aldehyde type epoxy (meth)acrylates, epoxy (meth)acrylates containing a naphthalene skeleton, glyoxal type epoxy (meth)acrylates, heterocyclic epoxy (meth)acrylates, and their anhydride-modified epoxy (meth)acrylates, etc.

[0107] Examples of examples include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrene-based compounds such as styrene, methylstyrene, ethylstyrene, and divinylbenzene; and compounds containing vinyl groups such as triallyl isocyanurate, trimethylallyl isocyanurate, and bisallyl diimide.

[0108] Compounds containing vinyl unsaturated groups can be commercially available, such as: KAYARAD (registered trademark) ZCA-601H (trade name, manufactured by Nippon Kayaku Co., Ltd.), TrisP-PA epoxy acrylate compounds in the form of propylene glycol monomethyl ether acetate (manufactured by Nippon Kayaku Co., Ltd.), KAYARAD (registered trademark) ZCR-6007H (trade name), KAYARAD (registered trademark) ZCR-6001H (trade name), KAYARAD (registered trademark) ZCR-6002H (trade name), and KAYARAD (registered trademark) ZCR-6006H (trade name). These compounds containing vinyl unsaturated groups can be used alone or in suitable mixtures of two or more.

[0109] The content of the compound having vinyl unsaturated groups in the resin composition containing the compound having vinyl unsaturated groups is preferably in an amount of 0.1 to 500 equivalents relative to the equivalent of vinyl unsaturated double bond groups in component (C).

[0110] The resin composition can be made into a varnish-like composition (hereinafter referred to as varnish) that is soluble in an organic solvent.

[0111] Examples of solvents that can be used include: amide solvents such as γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylimidazolinone; sulfone solvents 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, 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.

[0112] The organic solvent is preferably used in a range of 10 to 80% by mass, and more preferably in a range of 20 to 70% by mass, so that the solids content of the organic solvent removed from the varnish is in the range of 10 to 80% by mass.

[0113] Known additives may be optionally incorporated into the resin composition. Specific examples of additives that may be incorporated include polybutadiene or its modified forms, modified acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluoropolymers, cyanate esters, and other ester compounds; silicone gels, silicone oils, 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; filler surface treatment agents such as silane coupling agents; release agents; colorants such as carbon black, phthalocyanine blue, and phthalocyanine green; thixotropic agents such as gaseous silica; silicone-based and fluorine-based leveling agents or defoamers; hydroquinone, hydroquinone monomethyl ether, and phenolic polymerization inhibitors; stabilizers; antioxidants; photopolymerization initiators; photoalkali-generating materials; and photooxidation generators. The amount of these additives formulated relative to 100 parts by weight of the resin composition is preferably 1,000 parts by weight or less, and more preferably 700 parts by weight or less. From the viewpoint of heat resistance, silane coupling agents having acrylic or methacrylic groups are particularly preferred as additives.

[0114] The curing temperature and curing time of the resin composition can be selected by taking into account 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 with any component is preferably 120 to 250°C, and the curing time is approximately several tens of minutes to several hours.

[0115] A prepolymer can be obtained by heating and melting a resin composition to reduce its viscosity, and then impregnating it with reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber. Alternatively, a prepolymer can also be obtained by impregnating the aforementioned varnish with reinforcing fibers and then heating and drying it.

[0116] The above-mentioned material is cut into the desired shape, and copper foil is optionally stacked. Pressure is applied to the stacked material using pressing, autoclave forming, sheet winding, or other methods, while the resin composition is heated and hardened. This yields an article containing a hardened resin composition and an electrical and electronic laminate (printed circuit board) or a carbon fiber reinforced substrate.

[0117] Alternatively, a substrate with the cured material can be obtained by coating a copper foil with a varnish, allowing the solvent to dry, then laminating a polyimide film or LCP (liquid crystal polymer), hot-pressing it, and then heating and curing it. Alternatively, depending on the situation, the varnish can be coated onto the surface of a polyimide film or LCP and laminated with a copper foil to obtain a substrate with the cured material of this invention.

[0118] In addition, by coating copper foil with varnish and allowing the solvent to dry, resin is impregnated in reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber to form a prepolymer, which is then hot-pressed and heated to harden, a substrate with a hardened material can also be obtained.

[0119] A substrate having a film of a cured material composed of a resin composition can be used on copper foil laminates (CCLs), or on printed circuit boards or multilayer circuit boards with circuit patterns on the copper foil of a CCL.

[0120] [Example]

[0121] The present invention will now be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the scope of these examples. Additionally, in the examples, "parts" refers to parts by mass and "%" refers to percentage by mass. Furthermore, the measurement conditions for GPC in the examples are as follows.

[0122] Model: TOSOH ECOSEC Elite HLC-8420GPC

[0123] Separation column: TSKgel Super AWM-H

[0124] Eluent: NMP (N-methylpyrrolidone); 0.5 ml / min, 40°C

[0125] Detector: UV (Differential Refractometer)

[0126] Molecular weight standard: Polystyrene

[0127] Synthesis Example 1 (Synthesis of soluble polyimide resin (B-1))

[0128] In a 300 mL reactor equipped with a thermometer, reflux cooler, Dean Stark Apparatus device, powder inlet, nitrogen inlet, and stirrer, 10.640 parts of PRIAMINE 1075 (manufactured by Croda Corporation, Japan, molecular weight 534.38 g / mol) and BASF 9,9-bis(4-aminophenyl)fluorene (manufactured by JFE Chemical Co., Ltd., molecular weight 348.16) were added. 7.066 parts of oxydiphthalic anhydride (molecular weight 310.22 g / mol) and 67.254 parts of anisole were added and heated to 70°C. Next, 13.029 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Inc., molecular weight 310.22 g / mol), 0.850 parts of triethylamine, and 15.000 parts of toluene were added. The mixture was azeotropically reacted with toluene to remove the water generated by the cyclization of the ammonium acid, and then reacted at 130°C for 8 hours. The remaining triethylamine and toluene were then removed at 130°C to obtain a soluble polyimide resin (B-1) (molecular weight 81,300) solution.

[0129] Synthesis Example 2 (Synthesis of soluble polyimide resin (B-2))

[0130] In a 300 mL reactor equipped with a thermometer, reflux cooler, Dean Stark apparatus, powder inlet, nitrogen inlet, and stirrer, 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 PRIAMINE1075 (manufactured by Croda Co., Ltd., Japan, molecular weight 534.38 g / mol), 5.723 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Co., Ltd., molecular weight 348.16 g / mol), and 68.238 parts of anisole were added, and the mixture was heated to 70°C. Next, 12.409 parts of ODPA (oxydiphthalic anhydride, manufactured by Maneco Inc., molecular weight 310.22 g / mol), 0.810 parts of triethylamine, and 14.987 parts of toluene were added. While removing water generated from the ammonium acid ring closure in an azeotropic reaction with toluene, the mixture was reacted at 130°C for 8 hours to obtain an intermediate polyimide resin solution (phenolic OH equivalent 6,780 g / eq., molecular weight 78,600). Then, 0.663 parts of Karens MOI (manufactured by Resonac Inc., 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. The mixture was reacted at 130°C for 4 hours, and then the remaining triethylamine and toluene were removed by continuing to react at 130°C to obtain a soluble polyimide resin (B-2) solution (molecular weight 72,400).

[0131] Synthesis Example 3 (Synthesis of soluble polyimide resin (B-3))

[0132] In a 300 mL reactor equipped with a thermometer, reflux cooler, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer, 5.37 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Co., Ltd., molecular weight 348.45 g / mol), 13.14 parts of PRIAMINE1075 (C36 dimer diamine, manufactured by Croda Co., Ltd., molecular weight 534.38 g / mol), 14.89 parts of ODPA (oxyphthalic anhydride, manufactured by Maneco 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. The mixture was heated to 120°C to dissolve the raw materials. The reaction mixture was then azeotropically reacted with toluene to remove water generated from the cyclization of the ammonium acid while simultaneously reacting at 135°C for 4 hours. 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 soluble polyimide resin (B-3) (molecular weight 65,900) solution.

[0133] Synthesis Example 4 (Synthesis of soluble polyimide resin (B-4))

[0134] In a 300 mL reactor equipped with a thermometer, reflux cooler, Dean Stark apparatus, powder inlet, nitrogen inlet, and stirrer, 1.58 parts of DAPBAF 2,2-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 Co., Ltd., molecular weight 348.16 g / mol), 27.92 parts of ODPA (oxydiphthalic anhydride, manufactured by Maneco Co., Ltd., molecular weight 310.22 g / mol), and 154.05 parts of anisole were added, and the mixture was heated to 120°C. Next, 26.90 parts of PRIAMINE1075 (manufactured by Croda Corporation, Japan, molecular weight 542.13 g / mol) were added dropwise, and the mixture was cooled to 70°C. Then, 1.82 parts of triethylamine, 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 1.34 parts of Karens MOI (manufactured by Resonac Corporation, molecular weight 155.15 g / mol), 0.21 parts of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor, and 10.10 parts of anisole were added. The mixture was then reacted at 85°C for 1.5 hours to obtain a soluble polyimide resin (B-4) solution (molecular weight 87,500).

[0135] Synthesis Example 5 (Synthesis of soluble polyimide resin (B-5))

[0136] In a 500 mL reactor equipped with a thermometer, reflux cooler, Dean Stark apparatus, powder inlet, nitrogen inlet, and stirrer, 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 Maneco Co., Ltd., molecular weight 310.22 g / mol), and 212.91 parts of anisole were added, and the mixture was heated to 120°C. Next, 36.47 parts of PRIAMINE1075 (manufactured by Croda Corporation, Japan, molecular weight 542.13 g / mol) were added dropwise, and the mixture was cooled to 52°C. Then, 2.43 parts of triethylamine, 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 1.88 parts of Karens MOI (manufactured by Resonac Corporation, molecular weight 155.15 g / mol), 0.27 parts of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor, and 39.11 parts of anisole were added. The mixture was then reacted at 85°C for 2 hours to obtain a soluble polyimide resin (B-5) solution (molecular weight 78, 200).

[0137] Examples 1 to 13, Comparative Examples 1 to 6 (Preparation of Resin Compositions)

[0138] After preparing each component according to the mixing amounts shown in Table 1 (the units are "parts", and the parts of components (B) and (C) are the converted solids parts without solvent), anisole as a solvent was added to make the solids concentration 20% by mass and mixed evenly to prepare the resin compositions of the Examples and Comparative Examples respectively.

[0139] In addition, the components in Table 1 are as follows.

[0140] <(A)Component>

[0141] SEPTON 2104; a styrene-based thermoplastic elastomer (corresponding to formula (5) above), manufactured by Kuraray Inc.

[0142] <(B) Component>

[0143] (B-1) to (B-5); the soluble polyimide resins (B-1) to (B-5) obtained in Synthetic Examples 1 to 5.

[0144] <(C) Ingredients>

[0145] (C-1); MIR-3000-70MT; maleic anhydride resin, manufactured by Nippon Kayaku Co., Ltd. (corresponding to formula (2) above)

[0146] (C-2); MIR-5000-60T; maleic anhydride resin, manufactured by Nippon Kayaku Co., Ltd. (corresponding to formula (1) above)

[0147] (C-3); BMI-70; maleic anhydride resin, manufactured by Kei-I Chemical Co., Ltd. (corresponding to formula (3) above)

[0148] <(D) component>

[0149] DCP; dicumyl peroxide, manufactured by Nouryon Pharmaceutical Co., Ltd.

[0150] Using the resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2, the adhesive strength and thermal properties of the cured resin compositions to copper foil were evaluated by the following method.

[0151] (Assessment of adhesive strength)

[0152] Using an automated applicator, the resin composition was applied to the rough surface of 12 μm of ultra-low roughness, unroughened electrolytic copper foil CF-T9DA-SV manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., and dried at 120°C for 10 minutes. The thickness of the dried coating was 5 μm. A PPE prepolymer (Meteorwave 4000, manufactured by AGC Nelco Co., Ltd.) was laminated onto the coating obtained on the copper foil, and vacuum-pressed at 220°C for 60 minutes at 3 MPa. The resulting test pieces were cut to 10 mm widths, 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 prepolymer. The results are shown in Table 1.

[0153] (Evaluation of thermal properties)

[0154] Using POT-200C (manufactured by Taiyang Electric Industry Co., Ltd.), test pieces prepared in the same manner as the above-mentioned "evaluation of adhesive strength" were floated in a solder bath heated to 288°C, and the thermal properties were evaluated by the time until bubbling occurred.

[0155] 〇 (Excellent) ... No expansion for over 600 seconds

[0156] △ (Optional) ... No expansion for 60 seconds or more but less than 600 seconds.

[0157] × (Not allowed)... Expansion occurs before 60 seconds have elapsed.

[0158] The results are shown in Table 1.

[0159] [Table 1]

[0160]

[0161] As shown in Table 1, compared to the excellent adhesive strength and heat resistance of the resin composition of the present invention, the resin composition of the comparative example has poor adhesive strength and heat resistance.

[0162] Using the resin compositions obtained in Examples 7, 8, and Comparative Examples 3 and 4, the adhesive strength and thermal properties of the cured resin compositions to copper foil were evaluated using the following method.

[0163] (Assessment of adhesive strength)

[0164] Using an automated applicator, the resin composition was applied to the rough surface of an 18 μm roughened, unroughened electrolytic copper foil CF-T9DA-SV manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., and dried at 120°C for 10 minutes. The dried coating thickness was 5 μm. A PPE prepolymer (Megtron6, manufactured by Panasonic Corporation) was laminated onto the coating on the copper foil obtained above, and vacuum pressure was applied at 200°C for 60 minutes at 3 MPa. The resulting test pieces were cut to 10 mm widths, 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 prepolymer. The results are shown in Table 2.

[0165] (Evaluation of thermal properties)

[0166] Using POT-200C (manufactured by Taiyang Electric Industry Co., Ltd.), test pieces prepared in the same manner as the above-mentioned "evaluation of adhesive strength" were floated in a solder bath heated to 288°C, and the thermal properties were evaluated by the time until bubbling occurred.

[0167] 〇 (Excellent) ... No expansion for over 600 seconds

[0168] △ (Optional) ... No expansion for 60 seconds or more but less than 600 seconds.

[0169] × (Not allowed)... Expansion occurs before 60 seconds have elapsed.

[0170] The results are shown in Table 2.

[0171] [Table 2]

[0172]

[0173] As shown in Table 2, compared to the excellent adhesive strength and heat resistance of the resin composition of the present invention, the resin composition of the comparative example has poor adhesive properties.

[0174] Using the resin composition described in Table 3, the adhesive strength and thermal properties of the cured resin composition to copper foil were evaluated using the following method.

[0175] (Assessment of adhesive strength)

[0176] Using an automated applicator, the resin composition was applied to the rough surface of 12 μm of ultra-low roughness, unroughened electrolytic copper foil CF-T9DA-SV manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., and dried at 120°C for 10 minutes. The thickness of the dried coating was 5 μm. A PPE prepolymer (Meteorwafe 4000, manufactured by AGC Nelco Co., Ltd.) was laminated onto the coating on the copper foil obtained above, and vacuum pressure was applied at 220°C for 60 minutes at 3 MPa. The resulting test pieces were cut to 10 mm widths, 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 prepolymer. The results are shown in Table 3.

[0177] (Evaluation of thermal properties)

[0178] Using POT-200C (manufactured by Taiyang Electric Industry Co., Ltd.), test pieces prepared in the same manner as the above-mentioned "evaluation of adhesive strength" were floated in a solder bath heated to 288°C, and the thermal properties were evaluated by the time until bubbling occurred.

[0179] 〇 (Excellent) ... No expansion for over 600 seconds

[0180] △ (Optional) ... No expansion for 60 seconds or more but less than 600 seconds.

[0181] × (Not allowed)... Expansion occurs before 60 seconds have elapsed.

[0182] The results are shown in Table 3.

[0183] [Table 3]

[0184]

[0185] As shown in Table 3, the resin compositions of the comparative examples exhibit poor adhesion compared to the excellent adhesive strength of the resin compositions of the present invention.

[0186] Using the resin compositions obtained in Example 13 (same composition as Example 8) and Comparative Example 6 (same composition as Comparative Example 5), the adhesion strength of the cured resin compositions to copper foil was evaluated by the following method.

[0187] (Assessment of adhesive strength)

[0188] Using an automated applicator, the resin composition was applied to the rough surface of an 18 μm roughened, unroughened electrolytic copper foil CF-T9DA-SV manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., and dried at 120°C for 10 minutes. The thickness of the dried coating was 5 μm. A PPE prepolymer (Megtron8, manufactured by Panasonic Corporation) was laminated onto the coating on the copper foil obtained above, and vacuum pressure was applied at 220°C for 60 minutes at 3 MPa. The resulting test pieces were cut to 10 mm widths, 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 prepolymer. The results are shown in Table 4.

[0189] [Table 4]

[0190]

[0191] As shown in Table 4, the resin compositions of the comparative examples exhibit poor adhesion compared to the excellent adhesive strength of the resin compositions of the examples.

[0192] (Determination of dielectric loss tangent)

[0193] Using the resin compositions described in Table 5, the dielectric loss tangent of the cured resin compositions was evaluated as follows. The resin compositions of the examples and comparative examples were applied to Upilex 75S polyimide film manufactured by UBE Corporation using an automated applicator. The application amount was such that the dried resin composition layer had a film thickness of 40 μm, and the film was dried at 120°C for 10 minutes. The resin compositions obtained above were then cured in an oxygen-free oven with a nitrogen atmosphere at 205°C for 60 minutes. Test pieces peeled from 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 discrete cylindrical resonator and a KEYSIGHT N5234A network analyzer.

[0194] [Table 5]

[0195]

[0196] As shown in Table 5, compared to the excellent dielectric loss tangent of the resin composition of the Examples, the resin composition of the Comparative Examples has a poor dielectric loss tangent.

[0197] The dielectric properties can be improved by adding component (A). In addition, it is known that when the amount of component (A) added is 0.5% to 20%, the compatibility of the resin composition is good.

[0198] [Potential for industrial applications]

[0199] By using a resin composition containing thermoplastic resin (A), soluble polyimide resin (B), maleic anhydride resin (C), and curing accelerator (D), printed circuit boards and other products with excellent heat resistance and adhesion properties can be provided.

Claims

1. A resin composition comprising a thermoplastic resin (A), a soluble polyimide resin (B), a maleic anhydride 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 aliphatic chains with 6 to 36 carbon atoms.

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

5. The resin composition according to claim 1, wherein, The soluble polyimide resin (B) has a weight-average molecular weight of 30,000 or higher.

6. The resin composition according to claim 1, wherein, The maleic diimide resin (C) is of the following formulas (1) to (3): (In formula (1), R 1 represents an alkyl group having a carbon number of 1 to 5 or a phenyl group, and when a plurality of R 1 may be the same or different; k each independently represents an integer of 0 to 3; n 1 represents an average value of the number of repetitions, and is a real number greater than 1 and less than 5) (In equation (2), R) 2 Represents an alkyl or phenyl group having 1 to 5 carbon atoms, with multiple R groups present. 2 At this time, these can be the same or different; l represents integers from 0 to 3 independently; n 2 The average of the repeated numbers is a real number greater than 1 and less than 10. (In equation (3), R) 5 and R 6 Each can be represented independently as a hydrogen atom, methyl group, or ethyl group.

7. The resin composition according to claim 1, wherein, The thermoplastic resin (A) is a styrene-based thermoplastic elastomer. The content of the thermoplastic resin (A) is greater than 0.1% by mass and less than 20% by mass relative to the total content of the thermoplastic resin (A), the soluble polyimide resin (B), and the maleic diimide 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 hardening accelerator (D) is a thermal free radical initiator.

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

11. An article comprising the hardened material according to claim 10.

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