TW201835174A - Prepreg, laminate and printed wiring board - Google Patents

Abstract

To provide a thermosetting resin composition and a prepreg having high heat resistance, low relative dielectric constants, high metal foil adhesiveness, a high glass transition temperature and low thermal expansibility, and also excellent moldability and plating uniformity, and also provide a laminate and a printed wiring board. A prepreg contains a thermosetting resin composition containing (A) a maleimide compound, (B) an epoxy resin, (C) a copolymer resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a maleic anhydride, and (D) silica treated with an amino silane coupling agent.

Description

Prepreg, laminate and printed circuit board

The present invention relates to a prepreg, a laminate, and a printed wiring board which are suitable as materials for electronic equipment and the like.

In recent years, in the motherboards such as the end of a multi-function mobile phone, there is a high-speed communication, a high-density circuit, an extremely thin circuit board, and a line width (L) to a spacing (S) ratio of the circuit board [L/S ] also tends to narrow. With such a narrow L/S, it is difficult to stably produce a circuit board with good yield. Further, in the design of the conventional wiring board, a layer of a wireless road pattern called a "skip layer" is provided in a part of the layers in consideration of communication obstacles and the like. The electronic machine gradually becomes a high-performance machine and the circuit design amount is gradually increased and the number of layers of the circuit board is gradually increased, but the thickness of the motherboard is further increased due to the provision of the aforementioned skip layer. Among the methods for improving such problems, a more effective method is to reduce the relative dielectric constant of the insulating material used in the wiring board. Since the L/S impedance can be easily controlled by lowering the relative dielectric constant of the insulating material, it is possible to stabilize the production in a state where the L/S is close to the current design, and it is possible to reduce the jump layer to reduce the number of layers. Therefore, for the insulating material used in the wiring board, material properties with a relatively small dielectric constant are currently being sought.

In recent years, in a motherboard such as a mobile phone that is thinner and lower in cost as the electronic device is increased in density, a material having a relatively low dielectric constant has been sought in order to reduce the thickness. In addition, in the communication system machines represented by servers, routers, mobile base stations, etc., they have been gradually used in higher frequency band regions, and high-melting-point lead-free solders have been gradually utilized for soldering electronic components. Materials for substrates used in these materials are currently seeking materials having a low dielectric constant, a high glass transition temperature (high Tg), and excellent reflow heat resistance. Further, the motherboard used in the end of the multi-function mobile phone or the like increases in line density and narrows the pattern width, and is required to be connected by a small diameter laser through hole when connecting the layers. From the standpoint of connection reliability, there are many examples of using field plating, and the interface between the inner layer copper and the copper plating is very important, and therefore, it is seeking to increase the laser of the substrate. Processability.

The step of removing the residue of the resin (desmear treatment step) is generally performed after the laser processing of the substrate. Since the desmear treatment step is performed on the bottom surface and the wall surface of the laser through hole, when the resin component of the substrate is largely dissolved by the desmear treatment, the shape of the laser through hole is significantly deformed by the dissolution of the resin. Further, various problems such as unevenness in plating due to unevenness of the wall surface may occur. Therefore, the following amount is sought to be an appropriate value: the amount of the resin component of the substrate which is dissolved by the desmear treatment, that is, the amount of the slag-dissolved.

In order to produce a thermosetting resin composition having a relatively low dielectric constant, the following methods have been used: a method containing an epoxy resin having a relatively small dielectric constant, a method of introducing a cyanate group, and a method containing a polyphenylene ether. Method, etc. However, if only these methods are combined, it is difficult to satisfy various requirements such as a decrease in relative dielectric constant, high heat resistance, reliability, and halogen-free. For example, a resin composition containing an epoxy resin (refer to Patent Document 1); a resin composition containing polyphenylene ether and bismaleimide (refer to Patent Document 2); and a polyphenylene ether and a cyanate resin are contained. Resin composition (see Patent Document 3); a resin composition containing at least one of a styrene-based thermoplastic elastomer and/or triallyl cyanurate (see Patent Document 4); A resin composition of a diene (see Patent Document 5); a polyphenylene ether resin and a polyfunctional maleimide and/or a polyfunctional cyanate resin are reacted with liquid polybutadiene in advance. Resin composition (refer to Patent Document 6); a polyphenylene ether obtained by supplying or grafting a compound having an unsaturated double bond group, and triallyl cyanurate and/or triallyl group A resin composition obtained by isocyanurate or the like (see Patent Document 7); a resin containing a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an unsaturated acid anhydride, and a polyfunctional maleimide Composition (refer to Patent Document 8) or the like. [Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin

[Problems to be Solved by the Invention] The prepreg containing the resin composition described in Patent Documents 1 to 8 exhibits a relatively good relative dielectric constant, but cannot satisfy the strict requirements of the market in recent years. increase. In addition, there are often insufficient heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing property (laser processing property), but further improvement is possible. room. In addition, the actual situation is that materials have not been fully developed from the viewpoint of being suitable for the uniform plating property. Accordingly, the problem to be solved by the present invention is to provide a prepreg, a laminate, and a printed wiring board having high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, and low It is excellent in thermal expansion properties and formability and throwing property. [Technical means to solve the problem]

In order to solve the above problems, the present inventors have made efforts to carry out research, and as a result, have found that a prepreg can solve the above problems, and the present invention is completed by containing a thermosetting resin composition which is composed of a thermosetting resin. Contains: "(A) maleic imine compound"; "(B) epoxy resin"; "(C) copolymer resin having a specific structural unit; and, "(D) amine-based decane-based coupling agent The treated cerium oxide". The present invention has been completed in accordance with such technical ideas.

The present invention relates to the following [1] to [13]. [1] A prepreg comprising a thermosetting resin composition comprising: (A) a maleimide compound; (B) an epoxy resin; (C) copolymerization. A resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride; and (D) cerium oxide treated with an amino decane-based coupling agent. [2] The prepreg according to the above [1], wherein the component (A) is a maleic imine compound having an N-substituted maleimide group, and the N-substituted Malayan The amine-based maleimide compound is a maleic imine compound having at least two N-substituted maleimine groups in one molecule of (a1), and (a2) is represented by the following formula (a2-1) And a (a3) is obtained by reacting a diamine compound represented by the following formula (a3-1); In the formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is an integer of 1 to 5 , u is an integer of 0 to 4 and satisfies 1≦t+u≦5, wherein when t is an integer of 2 to 5, the plurality of R ^A4 may be the same or different, and when u is an integer of 2 to 4, A plurality of R ^A5 may be the same or different; In the formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group or a carboxyl group. Or a sulfonic acid group, each of v and w is independently an integer of 0-4. [3] The prepreg according to the above [1], wherein the component (C) is a copolymer resin having a structural unit represented by the following formula (Ci) and Structural unit represented by the general formula (C-ii): In the formula (Ci), R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an aryl group having 6 to 20 carbon atoms. And a hydroxyl group or a (meth) acrylonitrile group, and x is an integer of 0-3, wherein when x is 2 or 3, a plurality of R ^C2 may be the same or different. [4] The prepreg according to the above [3], wherein, in the above formula (Ci), R ^C1 is a hydrogen atom and x is 0. [5] The prepreg according to the above [1], wherein the content ratio of the structural unit derived from the aromatic vinyl compound to the structural unit derived from maleic anhydride in the component (C) That is, the structural unit derived from the aromatic vinyl compound/the structural unit derived from maleic anhydride is 2 to 9 in terms of molar ratio. [6] The prepreg according to the above [1], wherein the content ratio of the structural unit derived from the aromatic vinyl compound to the structural unit derived from maleic anhydride in the component (C) That is, the structural unit derived from the aromatic vinyl compound/the structural unit derived from maleic anhydride is 3 to 7 in terms of a molar ratio. [7] The prepreg according to any one of the above [1], wherein the component (C) has a weight average molecular weight of 4,500 to 18,000. [8] The prepreg according to any one of [1] to [7] wherein the component (C) has a weight average molecular weight of 9,000 to 13,000. The prepreg according to any one of the above [1], wherein the component (B) is a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolac. A varnish type epoxy resin, a naphthalene type epoxy resin, a fluorene type epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl type epoxy resin or a dicyclopentadiene type epoxy resin. [10] The prepreg according to any one of the above [1], wherein the thermosetting resin composition further contains (E) a curing agent. [11] The prepreg according to any one of the above [1], wherein the thermosetting resin composition further contains (F) a flame retardant. [12] A laminate comprising the prepreg according to any one of the above [1] to [11] and a metal foil. [13] A printed wiring board comprising the prepreg according to any one of [1] to [11] or the laminated board according to the above [12]. [efficacy]

According to the present invention, it is possible to obtain a prepreg, a laminate, and a printed wiring board having high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, and low thermal expansion and formability. Excellent in uniform plating.

Hereinafter, the present invention will be described in detail. The present invention provides a prepreg comprising a thermosetting resin composition described below. [Thermosetting Resin Composition] The prepreg is composed of a thermosetting resin composition containing: (A) a maleimide compound; (B) an epoxy resin; (C) a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride; and (D) cerium oxide treated with an amino decane-based coupling agent.

Hereinafter, each component contained in the thermosetting resin composition will be described in detail. <(A) Maleic imine compound> The component (A) is a maleic imine compound (hereinafter, sometimes referred to as a maleimide compound (A)), preferably having an N-substituted male 醯An imine-based maleimide compound; more preferably a maleimide compound having an N-substituted maleimide group, which is such that (a1) has at least two N-substituted horses in one molecule a maleimide compound of the quinone imine group [hereinafter, simply referred to as a maleimide compound (a1)], (a2) a monoamine compound represented by the following formula (a2-1) [hereinafter, abbreviated as The monoamine compound (a2)] and (a3) are obtained by reacting a diamine compound represented by the following formula (a3-1) (hereinafter simply referred to as a diamine compound (a3)). In the formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is an integer of 1 to 5 , u is an integer of 0 to 4 and satisfies 1≦t+u≦5, wherein when t is an integer of 2 to 5, the plurality of R ^A4 may be the same or different, and when u is an integer of 2 to 4, A plurality of R ^A5 may be the same or different. In the formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group or a carboxyl group. Or a sulfonic acid group, each of v and w is independently an integer of 0-4. Hereinafter, the description of the maleidinide compound (A) can also be interpreted as the description of the above-described maleimide compound having an N-substituted maleimide group.

From the viewpoint of solubility in an organic solvent and mechanical strength, the weight average molecular weight (Mw) of the maleimide compound (A) is preferably 400 to 3,500, more preferably 400 to 2,300, and 800 to 800. 2,000 is better. Further, in the present specification, the weight average molecular weight is a value measured by a gel permeation chromatography (GPC) method (converted in standard polystyrene) using tetrahydrofuran as a solution, more specifically, borrowing The value measured by the method described in the examples.

(Malayimide Compound (a1)) The maleimide compound (a1) is a maleic imine compound having at least two N-substituted maleimine groups in one molecule. The maleic imine compound (a1) may, for example, be a maleic imine compound having an aliphatic hydrocarbon group between any two maleimine groups among a plurality of maleimine groups. Hereinafter, it is referred to as an aliphatic hydrocarbon-containing maleimide, or a maleic imine compound containing an aromatic hydrocarbon group between any two maleimine groups among a plurality of maleimine groups. [Hereinafter, it is called an aromatic hydrocarbon-containing maleimide]. Among these, from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and throwing property, the aromatic hydrocarbon-containing Malayan Amine is preferred. The aromatic hydrocarbon-containing maleimide may be an aromatic hydrocarbon group if it is contained between any combination of any of the two selected maleimine groups. From the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion property, moldability, and throwing property, it is preferably used as the maleimide compound (a1). Is a maleic imine compound having 2 to 5 N-substituted maleimine groups in one molecule, more preferably Malaya with 2 N-substituted maleimine groups in one molecule Amine compound. Further, as a maleic imine compound (a1), from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion property, moldability, and throwing property, It is preferably an aromatic hydrocarbon-containing maleimide represented by any one of the following general formulae (a1-1) to (a1-4), more preferably by the following general formula (a1-1), The aromatic hydrocarbon-containing maleimide represented by a1-2) or (a1-4) is particularly preferably an aromatic hydrocarbon-containing maleimide represented by the following formula (a1-2).

In the above formulae (a1-1) to (a1-2), R ^A1 to R ^A3 each independently represent an alkyl group having 1 to 5 carbon atoms, and X ^A1 represents an alkylene group having 1 to 5 carbon atoms and a carbon number of 2 to 5; 5 alkylene, -O-, -C(=O)-, -S-, -S-S-, or sulfonyl, each of p, q and r is independently an integer from 0 to 4, s is An integer from 0 to 10. Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^A1 to R ^A3 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tertiary butyl group, and a positive group. Amyl and so on. From the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion property, moldability, and throwing property, the aliphatic hydrocarbon group has a carbon number of 1-3. The aliphatic hydrocarbon group is preferred, and a methyl group or an ethyl group is preferred.

The alkylene group having 1 to 5 carbon atoms represented by X ^A1 may, for example, be a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group or a 1,4-tetramethylene group. , 5-pentamethylene and the like. From the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion property, moldability, and throwing property, the alkylene group has a carbon number of 1-3. The alkyl group is preferred, and the methylene group is preferred. The alkylene group having 2 to 5 carbon atoms represented by X ^A1 may, for example, be an ethylene group, a propylene group, an isopropylidene group, a butylene group, an isobutylene group, a pentylene group or an isopentylene group. Among these, from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion property, moldability, and throwing property, as the alkylene group, Propyl is preferred. Among the above options, X ^{A1 is} preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 2 to 5 carbon atoms. Preferably, it is as described above. Each of p, q, and r is independently an integer of 0 to 4, and is derived from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion property, moldability, and throwing property. Any one of them is preferably 0 to 2, more preferably 0 or 1, and more preferably 0. s is an integer of 0 to 10, and from the viewpoint of availability, it is preferably 0 to 5, and preferably 0 to 3. In particular, the aromatic hydrocarbon-containing maleimide compound represented by the formula (a1-3) is preferably a mixture of s of 0 to 3.

Specific examples of the maleated imine compound (a1) include N,N'-extended ethyl bismaleimide, N,N'-hexamethylene bismaleimide, An aliphatic hydrocarbon-containing maleimide such as bis(4-maleimidocyclohexyl)methane or 1,4-bis(maleimidomethyl)cyclohexane; N,N'-( 1,3-phenylene) bismaleimide, N,N'-[1,3-(2-methylphenylene)] bismaleimide, N,N'-[1, 3-(4-methylphenylene)] bismaleimide, N,N'-(1,4-phenylene) bismaleimide, bis(4-maleimide) Phenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenyl Methane bismaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)anthracene, bis(4-maleimidobenzene) Thioether, bis(4-maleimidophenyl)one, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-double (malay) Iminomethyl)cyclohexane, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, Bis[4-(3-maleimidophenoxy)phenyl Methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]B Alkane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy) Phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimide) Phenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-Malayiya Aminophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3- Maleic iminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimidophenoxy) Phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-maleimidophenoxy)biphenyl, 4,4-bis(4- Maleic iminophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]one, bis[4-(4-maleimidophenoxy) Phenyl]ketone, 2,2'-bis(4-maleimidophenyl)disulfide, bis(4-maleimidophenyl)disulfide, bis[4- (3-maleimidophenoxy)benzene Thiol, bis[4-(4-maleimidophenoxy)phenyl] sulfide, bis[4-(3-maleimidophenoxy)phenyl]arene, Bis[4-(4-maleimidophenoxy)phenyl]anthracene, bis[4-(3-maleimidophenoxy)phenyl]indole, bis[4-( 4-maleimidophenoxy)phenyl]indole, bis[4-(3-maleimidophenoxy)phenyl]ether, bis[4-(4-malaiya) Aminophenoxy)phenyl]ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3- Bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy) -α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene , 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-double [ 4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-malay)醯iminophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy) )-3,5-dimethyl-α,α-dimethylbenzene An aromatic hydrocarbon-based maleimide such as benzene or polyphenylmethane maleimide. Among these, bis(4-maleimidophenyl)methane and bis(4-maleimidobenzene) are preferred from the viewpoint of high reaction rate and higher heat resistance. , bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl)disulfide, N,N'-(1,3-phenylene) Bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, preferably from the standpoint of being inexpensive (4-) Maleic iminophenyl)methane, N,N'-(1,3-phenylene) bismaleimide, from the viewpoint of solvent solubility, especially good double (4- Maleic iminophenyl)methane. The maleic imine compound (a1) may be used alone or in combination of two or more.

(Monamine Compound (a2)) The monoamine compound (a2) is a monoamine compound represented by the following formula (a2-1).

In the above formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, and R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is 1 to 5; An integer, u is an integer of 0 to 4 and satisfies 1≦t+u≦5, wherein when t is an integer of 2 to 5, the plurality of R ^A4 may be the same or different, and when u is an integer of 2 to 4 , a plurality of R ^A5 may be the same or different. From the viewpoint of solubility and reactivity, as the acidic substituent represented by R ^A4 , a hydroxyl group or a carboxyl group is preferred, and in view of heat resistance, a hydroxyl group is preferred. t is an integer of 1 to 5, and is 1 to 3 from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion property, moldability, and throwing property. The integer is preferably one, preferably 1 or 2, and more preferably 1. The alkyl group having 1 to 5 carbon atoms represented by R ^A5 may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tertiary butyl group or a n-pentyl group. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferred. The halogen atom represented by R ^A5 may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. u is an integer of 0 to 4, and is 0 to 3 from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion property, moldability, and throwing property. The integer is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. From the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion property, moldability, and throwing property, as the monoamine compound (a2), it is preferred to The monoamine compound represented by the above formula (a2-2) or (a2-3) is more preferably a monoamine compound represented by the following formula (a2-2). Wherein the general formula (A2-2) and ^{(a2-3), R A4, R} A5 , and u is the general formula R ^A4 (a2-1) is the same as R ^A5 and u, preferred embodiments are also the same.

Examples of the monoamine compound (a2) include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, and o-aminobenzenesulfonate. A monoamine compound having an acidic substituent such as an acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline or 3,5-dicarboxyaniline. Among these, from the viewpoint of solubility and reactivity, m-aminophenol, p-aminophenol, p-aminobenzoic acid, and 3,5-dihydroxyaniline are preferred from the viewpoint of heat resistance. Preferred are o-aminophenol, m-aminophenol, and p-aminophenol, and in view of dielectric properties, low thermal expansion, and production cost, aminophenol is preferred. The monoamine compound (a2) may be used alone or in combination of two or more.

(Diamine Compound (a3)) The diamine compound (a3) is a diamine compound represented by the following formula (a3-1). In the formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group or a carboxyl group. Or a sulfonic acid group, each of v and w is independently an integer of 0-4.

The aliphatic hydrocarbon group having 1 to 3 carbon atoms represented by X ^A2 may, for example, be a methylene group, an exoethyl group, a propyl group or a propylene group. As X ^A2 , a methylene group is preferred. Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A6 and R ^A7 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tertiary butyl group, and a n-pentyl group. Base. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferred. V and w are preferably an integer of 0 to 2, preferably 0 or 1, more preferably 0.

Specific examples of the diamine compound (a3) include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, and 4,4'-diamine. Diphenylpropane, 2,2'-bis[4,4'-diaminodiphenyl]propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3 , 3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylethane, 3,3'-di Ethyl-4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3'-di Hydroxy-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro- 4,4'-Diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetramethyl chloride-4 4'-Diaminodiphenylmethane, 2,2',6,6'-tetrabromo-4,4'-diaminodiphenylmethane, and the like. Among these, from the viewpoint of low cost, 4,4'-diaminodiphenylmethane and 3,3'-diethyl-4,4'-diaminodiphenylmethane are preferred. From the viewpoint of solubility in a solvent, 4,4'-diaminodiphenylmethane is more preferable.

The reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) is preferably carried out by reacting in the presence of an organic solvent at a reaction temperature of 70 to 200 ° C. It is allowed to react for 0.1 to 10 hours. The reaction temperature is preferably 70 to 160 ° C, more preferably 70 to 130 ° C, and particularly preferably 80 to 120 ° C. The reaction time is preferably from 1 to 6 hours, more preferably from 1 to 4 hours.

(Amount of maleated imine compound (a1), monoamine compound (a2), and diamine compound (a3)) Maleimide compound (a1), monoamine compound (a2), and diamine compound (a3) In the reaction, the amount of the three is preferably the sum of the primary amine equivalent of the monoamine compound (a2) and the diamine compound (a3) [described as -NH ₂ group equivalent] and the maleimide. The relationship between the maleimide group equivalents of the compound (a1) satisfies the following formula. 0.1 ≦ [malay ylidene equivalent] / [sum of -NH ₂ group equivalents] ≦ 10 by setting the sum of [maleimide equivalent] / [-NH ₂ group equivalent] to 0.1 or more, In other words, it is possible to prevent the solubility in an organic solvent without reducing the gelation and heat resistance, and by setting the sum of [maleimide equivalent]/[-NH ₂ group equivalent] to 10 or less. , metal foil adhesion and heat resistance, it is better. From the same viewpoint, it is preferred to satisfy the following formula. 1 ≦ [Malay ylidene equivalent] / [sum of -NH ₂ group equivalents] ≦ 9 More preferably, the following formula is satisfied. 2≦[Malayimine equivalent]/[-NH ₂ base equivalent]≦8

(Organic solvent) As described above, the reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) is preferably carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not adversely affect the reaction. For example, an alcohol solvent such as ethanol, propanol, butanol, methyl cyproterone, butyl cyanidin, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexyl a ketone solvent such as a ketone; an ether solvent such as tetrahydrofuran; an aromatic solvent such as toluene, xylene or trimethylbenzene; or a guanamine such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone. A solvent containing a nitrogen atom such as a solvent; a solvent containing a sulfur atom such as an anthraquinone solvent such as dimethyl hydrazine; an ester solvent such as ethyl acetate or γ-butyrolactone; Among these, from the viewpoint of solubility, an alcohol solvent, a ketone solvent, or an ester solvent is preferred, and from the viewpoint of low toxicity, cyclohexanone, propylene glycol monomethyl ether, and more preferably Kesai sulphate and γ-butyrolactone are also considered to have high volatility and are not easily left as a residual solvent when manufacturing a prepreg, and further preferably cyclohexanone, propylene glycol monomethyl ether, dimethyl ketone The guanamine is particularly preferred as dimethyl acetamide. The organic solvent may be used alone or in combination of two or more. The amount of the organic solvent to be used is not particularly limited, and is 100 parts by mass based on the total solubility of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3) from the viewpoint of solubility and reaction efficiency. The amount of the organic solvent used is preferably from 25 to 1,000 parts by mass, more preferably from 40 to 700 parts by mass, even more preferably from 60 to 250 parts by mass. By using the total amount of the organic solvent in an amount of 25 parts by mass based on 100 parts by mass of the total of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3), it is easy to ensure solubility. By using the total amount of the organic solvent in an amount of 1,000 parts by mass or less based on 100 parts by mass of the total of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3), it is easy to suppress The reaction efficiency is greatly reduced.

(Reaction Catalyst) The reaction of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3) can be carried out in the presence of a reaction catalyst as needed. The reaction catalyst may, for example, be an amine-based catalyst such as triethylamine, pyridine or tributylamine; an imidazole-based catalyst such as methylimidazole or phenylimidazole; or a phosphorus-based catalyst such as triphenylphosphine. The reaction catalyst may be used singly or in combination of two or more. The amount of the reaction catalyst used is not particularly limited, and is preferably 0.001 to 5 parts by mass based on the total of the maleimide compound (a1) and the monoamine compound (a2).

<(B) Epoxy Resin> The component (B) is an epoxy resin (hereinafter sometimes referred to as an epoxy resin (B)), and preferably an epoxy resin having at least two epoxy groups in one molecule. Examples of the epoxy resin having at least two epoxy groups in one molecule include a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, and a glycidyl ester type epoxy resin. Among these, a glycidyl ether type epoxy resin is preferred. The epoxy resin (B) can also be classified into various epoxy resins depending on the main skeleton, and each of the above-mentioned epoxy resins can be further classified into bisphenol A type epoxy resin and bisphenol F type epoxy resin. Bisphenol type epoxy resin such as resin, bisphenol S type epoxy resin; biphenyl aralkyl phenol type epoxy resin; phenol novolak type epoxy resin, alkyl phenol novolak type epoxy resin, cresol novolac Type epoxy resin, naphthol alkyl phenol copolymer novolac type epoxy resin, naphthol aralkyl phenol phenol copolymer novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type ring A novolac type epoxy resin such as an oxygen resin; a stilbene type epoxy resin; a triazine skeleton epoxy resin; an anthracene skeleton-containing epoxy resin; a naphthalene type epoxy resin; a fluorene type epoxy resin; Epoxy resin; biphenyl type epoxy resin; biphenyl aralkyl type epoxy resin; xylene type epoxy resin; alicyclic epoxy resin such as dicyclopentadiene type epoxy resin. Among these, bisphenol F type epoxy is preferred from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion property, moldability, and throwing property. Resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, bismuth type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, dicyclopentane The diene type epoxy resin is preferably a cresol novolak type epoxy resin, a naphthalene type epoxy resin, a fluorene type epoxy resin, a biphenyl type epoxy resin from the viewpoint of low thermal expansion property and high glass transition temperature. The resin, the biphenyl aralkyl type epoxy resin, the phenol novolac type epoxy resin, and more preferably a cresol novolak type epoxy resin. The epoxy resin (B) may be used alone or in combination of two or more.

The epoxy equivalent of the epoxy resin (B) is preferably 100 to 500 g/eq, preferably 120 to 400 g/eq, more preferably 140 to 300 g/eq, and particularly preferably 170 to 240 g/eq. . Here, the epoxy equivalent is the equivalent (g/eq) of the resin per unit epoxy group, and can be measured in accordance with the method defined in JIS K 7236 (2001). Specifically, it can be obtained by using an automatic titrator "GT-200 type" manufactured by Mitsubishi Chemical Corporation, and weighing 2 g of epoxy resin into a 200 mL beaker, followed by dropping. After 90 mL of methyl ethyl ketone and dissolved in an ultrasonic cleaner, 10 mL of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide were added, and a 0.1 mol/L perchloric acid/acetic acid solution was added. To titrate. As a commercially available product of the epoxy resin (B), for example, a cresol novolac type epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Corporation, epoxy equivalent: 205 to 215 g/ Eq), naphthalene type epoxy resin "HP-4032" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 152 g/eq), and biphenyl type epoxy resin "YX-4000" (manufactured by Mitsubishi Chemical Corporation, Epoxy equivalent: 186 g/eq), dicyclopentadiene type epoxy resin "HP-7200H" (manufactured by DIC Corporation, epoxy equivalent: 280 g/eq). Further, the epoxy equivalent is a value described in the catalogue of the manufacturer of the product.

<(C) Specific copolymer resin> The component (C) is a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride (hereinafter, sometimes referred to as a copolymer resin (C)) . Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, and dimethylstyrene. Among these, styrene is preferred. The component (C) is preferably a copolymer resin having a structural unit represented by the following formula (C-i) and a structural unit represented by the following formula (C-ii).

In the formula (Ci), R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an aryl group having 6 to 20 carbon atoms. And a hydroxyl group or a (meth) acrylonitrile group, and x is an integer of 0-3, wherein when x is 2 or 3, a plurality of R ^C2 may be the same or different.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^C1 and R ^C2 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tertiary butyl group, and a n-pentyl group. Base. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferred. The alkenyl group having 2 to 5 carbon atoms represented by R ^C2 may, for example, be an allyl group or a crotonyl group. The alkenyl group is preferably an alkenyl group having 3 to 5 carbon atoms, more preferably an alkenyl group having 3 or 4 carbon atoms. The aryl group having 6 to 20 carbon atoms represented by R ^C2 may, for example, be a phenyl group, a naphthyl group, an anthracenyl group or a biphenyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and preferably an aryl group having 6 to 10 carbon atoms. x is preferably 0 or 1, and 0 is preferred. In the structural unit represented by the formula (Ci), a structural unit represented by the following formula (Ci-1) wherein R ^C1 is a hydrogen atom and x is 0, that is, a structural unit derived from styrene is preferred.

In the copolymer resin (C), the content ratio of the structural unit derived from the aromatic vinyl compound to the structural unit derived from maleic anhydride, that is, the structural unit derived from the aromatic vinyl compound / the structure derived from maleic anhydride The unit, in terms of molar ratio, is preferably from 1 to 9, preferably from 2 to 9, more preferably from 3 to 8, and particularly preferably from 3 to 7. Further, the content ratio of the structural unit represented by the above formula (Ci) to the structural unit represented by the above formula (C-ii), that is, the molar ratio of (Ci) / (C-ii), is also the same The ground is preferably from 1 to 9, preferably from 2 to 9, more preferably from 3 to 8, and particularly preferably from 3 to 7. When the molar ratio of these is 1 or more, preferably 2 or more, the effect of improving the dielectric properties tends to be more sufficient, and if the molar ratio is 9 or less, the compatibility is good. . In the copolymer resin (C), the total content of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride, and the structural unit represented by the general formula (Ci) and the general formula (C-ii) The total content of the structural units to be represented is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass. The weight average molecular weight (Mw) of the copolymer resin (C) is preferably 4,500 to 18,000, more preferably 5,000 to 18,000, still more preferably 6,000 to 17,000, still more preferably 8,000 to 16,000, and particularly preferably 8,000 to 15,000. 9,000 to 13,000 is the best.

Further, by using a copolymer resin of styrene and maleic anhydride to lower the dielectric constant of the epoxy resin, if it is applied to a material for a printed wiring board, the impregnation property to the substrate and the peeling strength of the copper foil may be Insufficient, there is a general tendency to avoid the above method. Therefore, there is a general tendency to avoid the use of the above-mentioned copolymer resin (C), but the present invention has been found to be accomplished by using the above-mentioned (A) component and (B) by using the aforementioned copolymer resin (C). The component is a thermosetting resin composition which has high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, and low thermal expansion property, and is excellent in formability and throwing property.

(Method for Producing Copolymer Resin (C)) The copolymer resin (C) can be produced by copolymerizing an aromatic vinyl compound with maleic anhydride. As described above, examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, and dimethylstyrene. These may be used alone or in combination of two or more. Further, in addition to the aromatic vinyl compound and maleic anhydride, various components capable of being polymerized may be copolymerized. Examples of the component which can be polymerized include vinyl compounds such as ethylene, propylene, butadiene, isobutylene, and acrylonitrile; and compounds having a (meth)acryl fluorenyl group such as methyl acrylate or methyl methacrylate. . Further, a substituent such as an allyl group, a methacryl fluorenyl group, an acryl fluorenyl group or a hydroxyl group may be introduced into the aromatic vinyl compound by a reaction such as: Friedel-Crafts reaction; The reaction of a metal catalyst.

A commercially available product can also be used as the copolymer resin (C). As a commercially available product, for example, "SMA (registered trademark) 1000" (styrene/maleic anhydride = 1, Mw = 5,000) and "SMA (registered trademark) EF30" (styrene/maleic anhydride = 3, Mw=9,500), "SMA (registered trademark) EF40" (styrene/maleic anhydride = 4, Mw = 11,000), "SMA (registered trademark) EF60" (styrene/maleic anhydride = 6, Mw = 11,500) "SMA (registered trademark) EF80" (styrene/maleic anhydride = 8, Mw = 14,400) [The above is manufactured by CRAY VALLEY Co., Ltd.].

<(D) Cerium oxide treated with an amine decane-based coupling agent> The thermosetting resin composition contains an inorganic filler in order to lower the thermal expansion coefficient of the insulating resin layer, but in the present invention, oxidation is used. Cerium oxide treated with an amino decane-based coupling agent (hereinafter, sometimes referred to as cerium oxide (D) treated with an amine decane-based coupling agent) is used as the component (D). By containing the cerium oxide (D) treated with the amino decane-based coupling agent in the thermosetting resin composition, in addition to the effect of improving the low thermal expansion property, the above (A) can be improved. Since the adhesion between the components (C) suppresses the cerium oxide from falling off, it is also possible to obtain an effect of suppressing the deformation of the shape of the laser through-hole due to the excessive amount of the desmear.

Specifically, the amine decane-based coupling agent is preferably a decane coupling agent having a mercapto group-containing group and an amine group represented by the following formula (D-1). In the formula (D-1), R ^D1 is an alkyl group having 1 to 3 carbon atoms or an anthracene group having 2 to 4 carbon atoms, and y is an integer of 0 to 3.

The alkyl group having 1 to 3 carbon atoms represented by R ^D1 may, for example, be a methyl group, an ethyl group, a n-propyl group or an isopropyl group. Among these, methyl is preferred. The fluorenyl group having 2 to 4 carbon atoms represented by R ^D1 may, for example, be an ethyl fluorenyl group, a propyl fluorenyl group or an acrylonitrile group. Among these, it is preferable to use an ethyl group.

The amino decane-based coupling agent may have one amine group, and may have two or more, and may have three or more, and usually have one or two amine groups. Examples of the amine decane-based coupling agent having one amine group include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and N-phenyl-3-amino group. Propyltrimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethylbutylidene)propylamine, [3-(trimethoxydecyl)propyl]aminocarboxylic acid 2- Propargyl esters and the like, but are not particularly limited by these. The amine decane-based coupling agent having two amine groups may, for example, be N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane or N-2-(amino group). Ethyl)-3-aminopropyltrimethoxydecane, 1-[3-(trimethoxydecyl)propyl]urea, 1-[3-(triethoxydecyl)propyl]urea, etc. , but not particularly limited by these.

When cerium oxide (D) treated with an amine decane-based coupling agent is replaced by cerium oxide treated with a specific coupling agent, adhesion to the above components (A) to (C) may occur. The tendency of the cerium oxide to be easily detached is lowered, and the effect of suppressing the deformation of the shape of the laser through hole due to an excessive amount of the desmear is known, and the specific coupling agent is, for example, an epoxy decane-based coupling agent or a phenyl decane. Coupling agent, alkyl decane coupling agent, alkenyl decane coupling agent, alkynyl decane coupling agent, haloalkyl decane coupling agent, siloxane coupling agent, hydrodecane coupling agent, decazane system Coupling agent, alkoxydecane-based coupling agent, chlorodecane-based coupling agent, (meth)acrylonitrile-based decane-based coupling agent, amine-based decane-based coupling agent, isocyanuric acid-based decane-based coupling agent, urea-based decane system A coupling agent, a mercapto decane-based coupling agent, a thioether decane-based coupling agent, or an isocyanatodecane-based coupling agent. As long as the cerium oxide (D) treated with the amine decane-based coupling agent is used, cerium oxide which can be treated by the above-described other couplant can be used within a range not impairing the effects of the present invention. When cerium oxide is treated with the above other couplant, the cerium oxide treated with the above other couplant is 100 parts by mass of cerium oxide (D) treated with an amine decane-based coupling agent, It is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, and most preferably 5 parts by mass or less.

The cerium oxide used in the cerium oxide (D) treated with the amine decane-based coupling agent may, for example, be a deposited cerium oxide obtained by a wet method and having a high water content; and, by a dry method A dry method of cerium oxide which is produced and contains almost no bonding water or the like. As the dry method cerium oxide, for example, pulverized cerium oxide, fumed cerium oxide, or fused cerium oxide (melting spherical cerium oxide) may be used depending on the production method. From the viewpoint of low thermal expansion property and high fluidity when filled in a resin, cerium oxide is preferably fused cerium oxide. The average particle diameter of the cerium oxide is not particularly limited, and is preferably 0.1 to 10 μm, more preferably 0.1 to 6 μm, still more preferably 0.1 to 3 μm, and particularly preferably 1 to 3 μm. When the average particle diameter of cerium oxide is 0.1 μm or more, the fluidity at the time of high filling can be kept good, and the average particle diameter of cerium oxide can be 10 μm or less, that is, the mixing probability of coarse particles can be reduced and the mixing can be suppressed. A bad condition caused by coarse particles occurs. Here, the average particle diameter refers to a particle diameter at a point corresponding to a volume of 50% when the total volume of the particles is 100% and the cumulative particle size distribution curve is obtained by the particle diameter, and laser diffraction can be used. The measurement is performed by a particle size distribution measuring apparatus of a scattering method or the like. Further, the specific surface area of the cerium oxide is preferably 4 cm ² /g or more, more preferably 4 to 9 cm ² /g, still more preferably 5 to 7 cm ² /g.

<(E) Hardener> The thermosetting resin composition may further contain a curing agent as the component (E) (hereinafter sometimes referred to as a curing agent (E)). Examples of the curing agent (E) include dicyandiamide, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, and diethylaminopropyl. a chain aliphatic amine other than dicyandiamide such as amine, tetramethylguanidine or triethanolamine; isophorone diamine, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, bis (4) -amino-3-methyldicyclohexyl)methane, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[ 5.5] a cyclic aliphatic amine such as undecane; an aromatic amine such as xylylenediamine, phenylenediamine, diaminodiphenylmethane or diaminodiphenylphosphonium. Among these, dicyandiamide is preferred from the viewpoint of metal foil adhesion and low thermal expansion. The dicyandiamide is represented by H ₂ N-C(=NH)-NH-CN, and has a melting point of usually 205 to 215 ° C. The higher purity dicyandiamide has a melting point of 207 to 212 ° C. The dicyandiamide is a crystalline substance and may be orthorhombic, and may also be a plate crystal. The dicyandiamide is preferably 98% or more in purity, preferably 99% or more in purity, and more preferably 99.4% or more in purity. For the dicyandiamide, a commercially available product such as a product manufactured by Tokyo Chemical Industry Co., Ltd., manufactured by Tokyo Chemical Industry Co., Ltd., manufactured by Kishida Chemical Co., Ltd., or manufactured by Nacalai Tesque Co., Ltd. can be used.

<(F) Flame Retardant> The thermosetting resin composition of the present invention may further contain a flame retardant as the component (F) (hereinafter sometimes referred to as a flame retardant (F)). Here, although dicyandiamide or the like in the curing agent has an effect of a flame retardant, in the present invention, a substance capable of generating a curing agent is classified into a curing agent, and it is not included ( F) Ingredients. Examples of the flame retardant include a halogen-containing flame retardant containing bromine and chlorine, a phosphorus-based flame retardant, a sulfonium amine sulfate, melamine sulfate, melamine polyphosphate, and melamine cyanurate. a phosphazene-based flame retardant such as cyclophosphazene or polyphosphazene; an inorganic flame retardant such as antimony trioxide. Among these, a phosphorus-based flame retardant is preferred. Examples of the phosphorus-based flame retardant include an inorganic phosphorus-based flame retardant and an organic phosphorus-based flame retardant. Examples of the inorganic phosphorus-based flame retardant include ammonium phosphate such as red phosphorus, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphoniumamine; and phosphoric acid; Phosphine oxide and the like. Examples of the organic phosphorus-based flame retardant include aromatic phosphates, monosubstituted phosphonic diesters, disubstituted phosphinates, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, and rings. An organophosphorus compound, a phosphorus-containing phenol resin, or the like. Among these, a metal salt of an aromatic phosphate or a disubstituted phosphinic acid is preferred. Here, as the metal salt, any of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt, and a zinc salt is preferred, and an aluminum salt is preferred. Among the organic phosphorus-based flame retardants, aromatic phosphates are preferred.

Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, tris(xylylene phosphate), toluene diphenyl phosphate, and toluene phosphate di(2,6-xylylene). Hydroquinone bis(diphenyl phosphate), 1,3-phenylene bis(bis(2,6-xylylene) phosphate), bisphenol A bis(diphenyl phosphate), 1,3-benzene Base double (diphenyl phosphate) and the like. Examples of the monosubstituted phosphonic acid diester include diphenyl phenylphosphonate, diallyl phenylphosphonate, and bis(1-butenyl) phenylphosphonate. The disubstituted phosphinate may, for example, be phenyl diphenylphosphinate or methyl diphenylphosphinate. The metal salt of the disubstituted phosphinic acid may, for example, be a metal salt of a dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid or a diarylphosphinic acid. Acid metal salts, etc. These metal salts are preferably any of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt, and a zinc salt as described above. Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis(2-allylphenoxy)phosphazene and xylylphosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, and honey polyphosphate. White amine and the like. The cyclic organophosphorus compound may, for example, be 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or 10-(2,5-dihydroxyphenyl)-9,10. - Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Among these, at least one selected from the group consisting of an aromatic phosphate, a metal salt of a disubstituted phosphinic acid, and a cyclic organophosphorus compound is more preferred, and an aromatic phosphate is more preferred.

Further, the aromatic phosphate is preferably an aromatic phosphate represented by the following formula (F-1) or (F-2), and the metal salt of the disubstituted phosphinic acid is preferably the following A metal salt of a disubstituted phosphinic acid represented by the formula (F-3).

In the formulae (F-1) to (F-3), R ^F1 to R ^F5 are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom; and e and F are each independently an integer of 0 to 5, g, h and i are each independently an integer of 0-4. R ^F6 and R ^F7 are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 14 carbon atoms; and M is a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom, Zinc atom; j is an integer of 1-4.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^F1 to R ^F5 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tertiary butyl group, and a n-pentyl group. Base. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferred. The halogen atom represented by R ^F1 to R ^F5 may, for example, be a fluorine atom or the like. E and f are preferably an integer of 0 to 2, and preferably 2 is preferred. g, h and i are preferably an integer of 0 to 2, preferably 0 or 1, more preferably 0. The alkyl group having 1 to 5 carbon atoms represented by R ^F6 and R ^F7 may, for example, be the same group as in the case of R ^F1 to R ^F5 . Examples of the aryl group having 6 to 14 carbon atoms represented by R ^F6 and R ^F7 include a phenyl group, a naphthyl group, a biphenyl group, and an anthracenyl group. The aromatic hydrocarbon group is preferably an aryl group having 6 to 10 carbon atoms. j is equal to the valence of the metal ion, that is, it varies within the range of 1 to 4 depending on the type of M. M is preferably an aluminum atom. Further, when M is an aluminum atom, j is 3.

(Content of each component) The content of the components (A) to (D) in the thermosetting resin composition is not particularly limited, but is preferably 100 parts by mass based on the total of the components (A) to (C). The component A) is 15 to 65 parts by mass, the component (B) is 15 to 50 parts by mass, the component (C) is 10 to 45 parts by mass, and the component (D) is 30 to 70 parts by mass. When the component (A) is 15 parts by mass or more based on 100 parts by mass of the total of the components (A) to (C), high heat resistance, low relative dielectric constant, high glass transition temperature, and low thermal expansion property can be obtained. Propensity. On the other hand, when the component (A) is 65 parts by mass or less based on 100 parts by mass of the total of the components (A) to (C), the fluidity and formability of the thermosetting resin composition tend to be good. When the component (B) is 15 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), high heat resistance, high glass transition temperature, and low thermal expansion property tend to be obtained. On the other hand, when the component (B) is 50 parts by mass or less based on 100 parts by mass of the total of the components (A) to (C), the heat resistance is high, the relative dielectric constant is low, and the glass transition temperature is high. And a tendency to low thermal expansion. When the component (C) is 10 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), the high heat resistance and the low relative dielectric constant tend to be obtained. On the other hand, when the component (C) is 45 parts by mass or less based on 100 parts by mass of the total of the components (A) to (C), high heat resistance, high metal foil adhesion, and low relative dielectric properties can be obtained. The tendency of constants. When the component (D) is 30 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), excellent low thermal expansion property tends to be obtained. On the other hand, when the component (D) is 70 parts by mass or less based on 100 parts by mass of the total of the components (A) to (C), the heat resistance and the fluidity and formation of the thermosetting resin composition can be obtained. Good tendencies.

In addition, when the thermosetting resin composition of the present invention contains the component (E), the content thereof is preferably 0.5 to 6 parts by mass based on 100 parts by mass of the total of the components (A) to (C). When the component (E) is 0.5 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), it is possible to obtain high metal foil adhesion and excellent low thermal expansion property. On the other hand, when the component (E) is 6 parts by mass or less based on 100 parts by mass of the total of the components (A) to (C), high heat resistance tends to be obtained.

In addition, when the thermosetting resin composition of the present invention contains the component (F), from the viewpoint of flame retardancy, it is preferably 100 parts by mass based on the total of the components (A) to (C). The content is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass. In particular, when a phosphorus-based flame retardant is used as the component (F), from the viewpoint of flame retardancy, it is preferred to use phosphorus in an amount of 100 parts by mass based on the total of the components (A) to (C). The atomic content is preferably from 0.1 to 3 parts by mass, and the phosphorus atom content is preferably from 0.2 to 3 parts by mass, and the phosphorus atom content is preferably from 0.5 to 3 parts by mass.

(Other components) The thermosetting resin composition of the present invention may contain other components such as an additive and an organic solvent, as needed, insofar as the effects of the present invention are not impaired.

(Additive) Examples of the additive include a curing accelerator, a colorant, an antioxidant, a reducing agent, an ultraviolet absorber, a fluorescent whitening agent, an adhesion improving agent, and an organic filler. These may be used alone or in combination of two or more.

(Organic solvent) The thermosetting resin composition may contain an organic solvent from the viewpoint that the treatment can be easily performed by dilution, and the prepreg described later can be easily produced. In the present specification, a thermosetting resin composition containing an organic solvent may be referred to as a resin varnish. The organic solvent is not particularly limited, and examples thereof include methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, and triethylene glycol monomethyl ether. , an alcohol solvent such as triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether or dipropylene glycol monopropyl ether; acetone, methyl ethyl a ketone solvent such as a ketone, methyl isobutyl ketone or cyclohexanone; an ether solvent such as tetrahydrofuran; an aromatic solvent such as toluene, xylene or trimethylbenzene; and a formamide, N-methylformamide, a nitrogen atom-containing solvent including a guanamine solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone; A solvent containing a sulfur atom such as an oxime solvent; an ester solvent such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, propylene glycol monomethyl ether acetate or ethyl acetate. Among these, from the viewpoint of solubility, an ethanol solvent, a ketone solvent, and a nitrogen atom-containing solvent are preferred, and more preferably methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or methyl group. Celluloid, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone is more preferred, methyl ethyl ketone is particularly preferred. The organic solvent may be used alone or in combination of two or more. In the thermosetting resin composition, the content of the organic solvent may be appropriately adjusted to the extent that the thermosetting resin composition is easily treated, and if the coating property of the resin varnish is good, no In particular, it is preferable that the solid content concentration (concentration of the component other than the organic solvent) derived from the thermosetting resin composition is 30 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 80% by mass.

[Prepreg] The prepreg of the present invention contains the above-mentioned thermosetting resin composition, and the production method thereof is not particularly limited, and can be produced, for example, by impregnation or application to a sheet-like reinforcing substrate. It is semi-hardened by heating or the like (B-staged). As the sheet-like reinforcing substrate of the prepreg, various conventional materials used for laminated sheets for electrical insulating materials can be used. Examples of the material of the sheet-like reinforcing substrate include natural fibers such as paper and cotton linters; inorganic fibers such as glass fibers and asbestos; linaloside, polyimine, polyvinyl alcohol, polyester, and tetrafluoroethylene. And organic fibers such as acrylic; such mixtures and the like. Among these, from the viewpoint of flame retardancy, glass fiber is preferred. The glass fiber substrate may, for example, be a woven fabric obtained by using E glass, C glass, D glass, or S glass, or a glass fiber cloth obtained by adhering short fibers with an organic binder; A substrate obtained by mixing cellulose fibers. A glass woven fabric obtained by using E glass is preferred. These sheet-like reinforcing substrates have a shape such as a woven fabric, a non-woven fabric, a yarn bundle, a stranded felt or a surface felt. In addition, the material and shape are selected depending on the use and performance of the target molded product, and one type may be used alone, and two or more types of materials and shapes may be combined as needed.

As a method of impregnating or applying the thermosetting resin composition to the sheet-like reinforcing substrate, the following hot melt method or solvent method is preferred. In the case where the thermosetting resin composition does not contain an organic solvent, (1) is temporarily applied to a coated paper having good peeling property with the composition, and then laminated in a sheet form. The substrate is reinforced or (2) directly applied to the sheet-like reinforcing substrate using a die coater. On the other hand, the solvent method is a method in which a thermosetting resin composition contains an organic solvent to prepare a varnish, and a sheet-like reinforcing substrate is immersed in the varnish to impregnate the varnish in a sheet-like reinforcing substrate, and then Let it dry.

The thickness of the sheet-like reinforcing substrate is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and from the viewpoint of heat resistance, moisture resistance, and processability, a substrate surface-treated with a decane coupling agent or the like is preferable. Or a substrate that has been mechanically opened. The prepreg of the present invention can be obtained by impregnating or applying a thermosetting resin composition to a substrate, and usually drying at a temperature of 100 to 200 ° C for 1 to 30 minutes. Semi-hardening (B-staged). The obtained prepreg is used by using one sheet or preferably 2 to 20 sheets as needed.

[Laminated Board] The laminated board of the present invention comprises the above prepreg. It can be manufactured by laminating, for example, by using one sheet of the above-mentioned prepreg or by arranging 2 to 20 sheets of the above-mentioned prepreg and arranging a metal foil on one or both sides thereof. Forming is carried out. Further, a laminated board in which a metal foil is disposed may be referred to as a metal-clad laminate. The metal of the metal foil is not particularly limited as long as it is used for the use of the electrical insulating material, and is preferably copper, gold, silver, nickel, platinum, molybdenum or rhenium from the viewpoint of conductivity. Aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements is preferred, copper and aluminum are preferred, and copper is more preferred. As a molding condition of the laminated board, a conventional forming method of a laminated board and a multilayer board for an electrically insulating material can be applied, and for example, a multi-stage pressurization, a multi-stage vacuum press, a continuous molding, an autoclave molding machine, or the like can be used, and the temperature is 100 to ～. It is formed at 250 ° C, a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention can be combined with the inner layer printed wiring board, and laminated and molded to produce a multilayer board. The thickness of the metal foil is not particularly limited, and can be appropriately selected depending on the use of the printed wiring board or the like. The thickness of the metal foil is preferably 0.5 to 150 μm, more preferably 1 to 100 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 30 μm.

Further, it is also preferred to form a plating layer by plating a metal foil. The metal of the plating layer is not particularly limited as long as it can be used for plating. The metal of the plating layer is preferably selected from the group consisting of copper, gold, silver, nickel, platinum, molybdenum, niobium, aluminum, tungsten, iron, titanium, chromium, and at least one of the metal elements. An alloy of one type. The plating method is not particularly limited, and a conventional method such as an electrolytic plating method or an electroless plating method can be used.

[Printed Circuit Board] The present invention also provides a printed wiring board comprising the above prepreg or the above laminated board. The printed wiring board of the present invention can be manufactured by performing circuit processing on a metal foil of a metal-clad laminate. The circuit processing can be performed by, for example, after forming a resist pattern on the surface of the metal foil, removing the excess portion of the metal foil by etching, and peeling off the resist pattern, thereby forming a desired shape by using a drill bit. After the through holes are formed and the resist pattern is formed again, the through holes are plated for conduction, and finally the resist pattern is peeled off. Under the same conditions as described above, the metal-clad laminate can be further laminated on the surface of the printed wiring board obtained as described above, and further processed in the same manner as described above to form a multilayer printed wiring board. At this time, it is not always necessary to form a through hole, and a via hole may be formed, and both of these may be formed. Such multi-layering is the number of sheets required. [Examples]

The invention is described in more detail by the following examples, which are not intended to limit the invention in any way. A prepreg and a copper clad laminate were produced using the thermosetting resin composition of the present invention, and the obtained copper clad laminate was evaluated. The evaluation method is as follows.

[Evaluation method] <1. Heat resistance (reflow heat resistance)> Using the four-layer copper-clad laminate produced in each example, and setting the maximum temperature to 266 ° C, the four-layer copper-clad laminate was placed. In a thermostat bath environment of 260 ° C or higher, the flow was performed for 30 seconds, and the number of cycles until the substrate was swollen was confirmed by the naked eye. The more the number of cycles, the more excellent the heat resistance.

<2. Relative dielectric constant (Dk)> Using a network analyzer "8722C" (manufactured by HP), the relative dielectric of a 1 GHz double-sided copper-clad laminate was carried out by a three-plate linear line resonator method. Determination of the constant. The test piece has a size of 200 mm × 50 mm × thickness of 0.8 mm, and a linear line (line length of 200 mm) having a width of 1.0 mm is formed by etching at the center of one side of one double-sided copper-clad laminate, and the copper remains. It is set as a coating layer on the entire back surface. For another double-sided copper clad laminate, the entire surface of one side is etched, and the back side is made into a cladding layer. These two double-sided copper clad laminates were laminated so that the clad layer became the outer side, and a strip line was formed. The measurement was carried out at 25 °C. The smaller the relative dielectric constant, the better.

<3. Metal foil adhesion (copper foil peel strength)> Metal foil adhesion was evaluated by the peel strength of copper foil. The double-sided copper-clad laminate produced in each of the examples was immersed in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.) to form a copper foil having a width of 3 mm to prepare an evaluation substrate. The peel strength of the copper foil was measured using an autoclave "AG-100C" (manufactured by Shimadzu Corporation). The larger the value, the more excellent the adhesion of the metal foil.

<4. Glass transition temperature (Tg)> Copper was immersed in a copper etching solution "ammonium persulfate (APS)" (made by ADEKA Co., Ltd.) in the double-sided copper-clad laminate obtained in each example. The foil was removed, and a 5 mm square evaluation substrate was prepared, and a thermal mechanical analysis (TMA) test apparatus "Q400EM" (manufactured by TA Instruments Co., Ltd.) was used to observe the thermal expansion of the substrate in the plane direction (Z direction) at 30 to 260 °C. Characteristics, and the inflection point of the expansion amount is set to the glass transition temperature.

<5. Low thermal expansion property> The copper foil was removed by immersing the double-sided copper-clad laminate produced in each example in a copper etching solution "ammonium persulfate (APS)" (made by ADEKA CORPORATION). An evaluation substrate of 5 mm square was produced, and the thermal expansion coefficient (linear expansion coefficient) of the surface direction of the substrate was measured using a TMA test apparatus "Q400EM" (manufactured by TA Instruments Co., Ltd.). Further, in order to remove the influence of the thermal distortion of the sample, the temperature expansion-cooling cycle of the second temperature-displacement chart is measured, and the thermal expansion coefficient [ppm/° C.] of 30 ° C to 260 ° C of the second temperature-displacement chart is measured. Set as an indicator of low thermal expansion. The smaller the value, the more excellent the low thermal expansion property. Further, the table is described as a coefficient of thermal expansion that does not reach Tg (labeled "<Tg") and a coefficient of thermal expansion that exceeds Tg (labeled as ">Tg"). Measurement condition 1 ^st Run: room temperature → 210 ° C (temperature rising rate 10 ° C / min) 2 ^nd Run: 0 → 270 ° C (temperature rising rate 10 ° C / min) The copper clad laminate is expected to be further thinned, and this expectation is also met. The thinning of the prepreg constituting the copper clad laminate is being studied. Since the thinned prepreg is easily warped, it is desirable that the warpage of the prepreg during heat treatment is small. In order to reduce warpage, a more effective method is to make the coefficient of thermal expansion of the substrate in the plane direction small.

<6. Average plating property (laser processing property)> For the four-layer copper-clad laminate produced in each example, a laser device "LC-2F21B/2C" (manufactured by Hitachi Via Mechanics Co., Ltd.) was used. The laser direct method was performed by a target aperture of 80 μm, Gaussian, and a cyclic mode, and the pulse width was 15 μs × 1 time, 7 μs × 4 times, and laser opening was performed. Using the swelling solution "Swelling Dip Securiganth P" (manufactured by Atotech Japan Co., Ltd.) for 5 minutes at 70 ° C for 5 minutes, the roughening solution "Dosing" was used at 70 ° C for 9 minutes. Securiganth P500J (manufactured by Atotech Japan Co., Ltd.) was subjected to desmear treatment using a neutralization solution "Reduction Conditioner Securiganth P500" (manufactured by Atotech Japan Co., Ltd.) under the conditions of 40 ° C for 5 minutes. Then, the electroless plating solution "Puriganto MSK-DK" (manufactured by Atotech Japan Co., Ltd.) was used at 30 ° C for 20 minutes, and the plating solution "Cupracid HL" was used at 24 ° C and 2 A/dm ² (Atotech Japan Limited) The company made) plating for the laser processing substrate for 2 hours. The obtained laser-perforated substrate was subjected to cross-sectional observation to confirm the throwing property. As a method for evaluating the uniformity, when the difference between the thickness of the plating layer on the upper portion of the laser hole and the thickness of the plating layer at the bottom of the laser hole is within 10% of the thickness of the plating layer on the upper portion of the laser hole, the uniform plating property is better, The ratio (%) of the pores contained in this range in 100 wells was determined.

<7. Formability> After the outer layer of copper was removed from the four-layer copper-clad laminate obtained in each example, the presence or absence of voids and scratches in the plane of 340 × 500 mm was visually confirmed, and it was set as an index of formability. . Non-pores and scratches show good formability.

Hereinafter, each component used in the examples and comparative examples will be described.

(A) component: The solution of the maleic imine compound (A) obtained by the manufacturing example 1 below was used. [Production Example 1] In a reaction vessel having a volume of 1 L including a thermometer, a stirring device, and a moisture meter equipped with a reflux cooling tube, 4,4'-diaminodiphenylmethane 19.2 g, bis (4- 174.0 g of maleic iminophenyl)methane, 6.6 g of p-aminophenol and 330.0 g of dimethylacetamide, and reacted at 100 ° C for 2 hours to obtain an acidic substituent and an N-substituted group. A solution of the maleic imide group of the maleimide compound (A) (Mw = 1,370) in dimethylacetamide and used as the component (A). Further, the above weight average molecular weight (Mw) is converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is using standard polystyrene: TSK standard POLYSTYRENE (Model: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [Dongcao Co., Ltd.] is approximated by a cubic equation. The conditions for GPC are as follows. Device: (pump: L-6200 type [made by Hitachi High-Technologies Co., Ltd.]), (detector: L-3300 type RI [made by Hitachi High-Technologies Co., Ltd.]), (column oven: L- 655A-52[made by Hitachi High-Technologies Co., Ltd.] Pipe column: TSKgel SuperHZ2000+TSKgel SuperHZ2300 (both manufactured by Tosoh Corporation) Column size: 6.0 × 40 mm (protective column), 7.8 × 300 mm (tube Column) Lysate: Tetrahydrofuran Sample concentration: 20 mg/5 mL Injection volume: 10 μL Flow rate: 0.5 mL/min Measurement temperature: 40 °C

(B) Ingredients: cresol novolac type epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Corporation) (C-1) Component: "SMA (registered trademark) EF40" (styrene / horse (Acid anhydride = 4, Mw = 11,000, manufactured by CRAY VALEY Co., Ltd.) (C-2) Component: "SMA (registered trademark) 3000" (styrene/maleic anhydride = 2, Mw = 7,500, manufactured by CRAY VALEY Co., Ltd.) (C -3) Ingredients: "SMA (registered trademark) EF80" (styrene/maleic anhydride = 8, Mw = 14,400, manufactured by CRAY VALEY Co., Ltd.) (C-4) Component: "SMA (registered trademark) 1000" (styrene) /maleic anhydride=1, Mw=5,000, manufactured by CRAY VALEY Co., Ltd.)

(D) component: "Megasil 525 ARI" (melted cerium oxide treated with an amine decane-based coupling agent, average particle diameter: 1.9 μm, specific surface area: 5.8 m ² /g, manufactured by Sibelco Japan Co., Ltd.) Material: "F05-30" (untreated crushed cerium oxide, average particle size: 4.2 μm, specific surface area 5.8 m ² /g, manufactured by Fukushima Kiln Co., Ltd.)

(E) component: dicyandiamide (made by Japan CARBIDE INDUSTRIAL CO., LTD.) (F) component: "PX-200" (aromatic phosphate (see the following structural formula), manufactured by Daiba Chemical Industry Co., Ltd.)

[Examples 1 to 13 and Comparative Example 1] As shown in the following Tables 1 to 4, each component shown above (in the case of a solution, a solid content conversion amount) was prepared, and the nonvolatile content of the solution was made. Further, methyl ethyl ketone was added in an amount of 65 to 75% by mass to prepare a thermosetting resin composition of each of the examples and the comparative examples. Each of the obtained thermosetting resin compositions was impregnated into a glass cloth (0.1 mm) of IPC standard #3313, and dried at 160 ° C for 4 minutes to obtain a prepreg. After the prepreg was superposed on eight sheets, 18 μm copper foil "3EC-VLP-18" (manufactured by Mitsui Metals, Inc.) was superposed on both sides thereof at a temperature of 190 ° C and a pressure of 25 kgf / cm ² ( 2.45 MPa) heating and press forming for 90 minutes, and making a double-sided copper-clad laminate having a thickness of 0.8 mm (8 sheets of prepreg), and using the copper-clad laminate, the relative dielectric was measured and evaluated according to the aforementioned method. Constant, metal foil adhesion, glass transition temperature (Tg) and low thermal expansion. On the other hand, 18 μm of copper foil "YGP-18" (manufactured by Nippon Electrolysis Co., Ltd.) was superposed on both sides of the prepreg, and the temperature was 190 ° C and the pressure was 25 kgf / cm ² ( 2.45 MPa) Heat and pressure forming for 90 minutes, and making a double-sided copper-clad laminate having a thickness of 0.1 mm (one prepreg), and then performing inner layer adhesion treatment on both copper foil surfaces (using "BF treatment liquid" (made by Hitachi Chemical Co., Ltd.), a 18 μm copper foil "YGP-18" (manufactured by Nippon Electrolysis Co., Ltd.) was superimposed on both sides of the prepreg having a thickness of 0.05 mm. Then, it was subjected to heat and pressure molding at a temperature of 190 ° C and a pressure of 25 kgf / cm ² (2.45 MPa) for 90 minutes to prepare a four-layer copper clad laminate. Using the four-layer copper clad laminate, evaluation of heat resistance, throwing property, and formability was carried out in accordance with the above method. The results are shown in Tables 1-4.

[Table 1] *1: Phosphorus atomic conversion

[Table 2] *1: Phosphorus atomic conversion

[table 3] *1: Phosphorus atomic conversion

[Table 4] *1: Phosphorus atomic conversion

In the examples, the reflow heat resistance was 10 cycles or more higher than the heat resistance requirement level, and a low relative dielectric constant, a high metal foil adhesion, and a high glass transition temperature were obtained, and the low thermal expansion property was exhibited. Further, since the glass woven fabric was protruded from the wall surface and moderately roughened, it was confirmed that it had good throwing properties. In terms of formability, the resin was also well-filled, and it was not confirmed that there were abnormalities such as scratches and holes. Among these, in Examples 1 to 10, in Examples 1 to 10, the relative dielectric constant and the metal foil adhesion were better, and other characteristics were stably exhibited. On the other hand, in Comparative Example 1, cerium oxide which was not treated with an amino decane-based coupling agent was used as the inorganic filler, and the amount of the slag dissolved was increased to become the unevenness of the wall surface of the laser hole and the glass woven fabric. The tendency of the cloth to protrude larger in the shape of the hole, so that the uniform plating property is greatly reduced. [Industrial availability]

The prepreg of the present invention and the laminate comprising the prepreg have high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature and low thermal expansion, and formability and uniformity. Excellent, it is more suitable for use as a printed circuit board for electronic equipment.

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Claims (13)

A prepreg comprising a thermosetting resin composition comprising: (A) a maleimide compound; (B) an epoxy resin; (C) a copolymer resin, wherein the thermosetting resin composition comprises: A structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride; and (D) cerium oxide treated with an amino decane-based coupling agent. The prepreg according to claim 1, wherein the component (A) is a maleic imine compound having an N-substituted maleimine group, and the horse having an N-substituted maleimine group The quinone imine compound is a maleic imine compound having at least two N-substituted maleimine groups in one molecule of (a1), and (a2) a single represented by the following formula (a2-1) The amine compound and (a3) are obtained by reacting a diamine compound represented by the following formula (a3-1); In the formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, and t is an integer of 1 to 5 , u is an integer of 0 to 4 and satisfies 1≦t+u≦5, wherein when t is an integer of 2 to 5, the plurality of R ^A4 may be the same or different, and when u is an integer of 2 to 4, A plurality of R ^A5 may be the same or different; In the formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-, and R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group or a carboxyl group. Or a sulfonic acid group, each of v and w is independently an integer of 0-4. The prepreg according to claim 1 or 2, wherein the component (C) is a copolymer resin having a structural unit represented by the following formula (Ci) and a formula (C-ii) ) the structural unit represented: In the formula (Ci), R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an aryl group having 6 to 20 carbon atoms. And a hydroxyl group or a (meth) acrylonitrile group, and x is an integer of 0-3, wherein when x is 2 or 3, a plurality of R ^C2 may be the same or different. The prepreg according to claim 3, wherein, in the above formula (Ci), R ^C1 is a hydrogen atom and x is 0. The prepreg according to claim 1 or 2, wherein among the components (C), the content ratio of the structural unit derived from the aromatic vinyl compound to the structural unit derived from maleic anhydride is derived from aromatic The structural unit of the group-based vinyl compound/structural unit derived from maleic anhydride is 2 to 9 in terms of a molar ratio. The prepreg according to claim 1 or 2, wherein among the components (C), the content ratio of the structural unit derived from the aromatic vinyl compound to the structural unit derived from maleic anhydride is derived from aromatic The structural unit of the group-based vinyl compound/the structural unit derived from maleic anhydride is 3 to 7 in terms of a molar ratio. The prepreg according to any one of claims 1 to 6, wherein the component (C) has a weight average molecular weight of 4,500 to 18,000. The prepreg according to any one of claims 1 to 7, wherein the component (C) has a weight average molecular weight of 9,000 to 13,000. The prepreg according to any one of claims 1 to 8, wherein the component (B) is a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, Naphthalene type epoxy resin, fluorene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin or dicyclopentadiene type epoxy resin. The prepreg according to any one of claims 1 to 9, wherein the thermosetting resin composition further contains (E) a curing agent. The prepreg according to any one of claims 1 to 10, wherein the thermosetting resin composition further contains (F) a flame retardant. A laminate comprising the prepreg according to any one of claims 1 to 11 and a metal foil. A printed wiring board comprising the prepreg according to any one of claims 1 to 11 or the laminate according to claim 12.