JP6676884B2 - Thermosetting resin composition, prepreg, laminated board and printed wiring board - Google Patents

Description

  The present invention relates to a thermosetting resin composition, a prepreg, a laminate, and a printed wiring board suitable as materials for electronic devices and the like.

2. Description of the Related Art In recent years, with respect to motherboards of multifunctional mobile phone terminals and the like, high-speed communication, high-density wiring, ultra-thin wiring boards, and the ratio of wiring width (L) to spacing (S) [L / S] have been proposed. ] Also tend to be narrower. With such a reduction in L / S, it has become difficult to stably produce wiring boards with good yield. Further, in the design of a conventional wiring board, a layer having no wiring pattern called a “skip layer” is provided in some layers in consideration of communication failure and the like. Although electronic devices have become highly functional and the amount of wiring design has increased and the number of layers of the wiring board has increased, there has been a problem that the provision of the skip layer further increases the thickness of the motherboard.
As a method for solving these problems, it is effective to lower the relative permittivity of the insulating material used for the wiring board. Since the L / S impedance can be easily controlled by lowering the relative dielectric constant of the insulating material, L / S can be stably produced in a shape close to the current design, and the number of layers can be reduced by reducing the number of skip layers. Become. For this reason, an insulating material used for a wiring board is required to have a material characteristic having a small relative dielectric constant.

In recent years, materials having a low relative dielectric constant have been required for motherboards of mobile phones and the like, which are becoming thinner and lower in price with the increase in density of electronic devices, in order to cope with the reduction in thickness. Communication equipment such as servers, routers, and mobile base stations are also being used in higher frequency bands, and high melting point lead-free solder is used for soldering electronic components. Because of the use of a material, a material having a low dielectric constant, a high glass transition temperature (high Tg), and excellent reflow heat resistance is required as a material for the substrate used in these materials. It has become.
In addition, with the increase in wiring density and narrowing of pattern width, motherboards used for multifunctional mobile phone terminals and the like are required to connect via a small-diameter laser via when connecting between layers. From the viewpoint of connection reliability, field plating is often used, and the connectivity at the interface between the inner layer copper and the plated copper is very important.

  After the laser processing of the base material, a step of removing residual components of the resin (desmear processing step) is generally performed. Since the desmear process is performed on the bottom surface and the wall surface of the laser via, when the resin component of the base material is dissolved in a large amount by the desmear process, the shape of the laser via may be significantly deformed due to the dissolution of the resin. Various problems such as non-uniformity around plating may occur. From this, it is required that the amount by which the resin component of the base material dissolves by the desmear treatment, that is, the so-called desmear dissolution amount, becomes an appropriate value.

  Heretofore, in order to obtain a thermosetting resin composition having a small relative dielectric constant, a method of containing an epoxy resin having a small relative dielectric constant, a method of introducing a cyanate group, a method of containing a polyphenylene ether, and the like have been used. Was. However, simply combining these methods has made it difficult to satisfy various requirements such as a reduction in relative dielectric constant, high heat resistance, reliability, and halogen-free. For example, a resin composition containing an epoxy resin (see Patent Document 1), a resin composition containing polyphenylene ether and bismaleimide (see Patent Document 2), and a resin composition containing polyphenylene ether and a cyanate resin (patent) Reference 3), a resin composition containing at least one of a styrene-based thermoplastic elastomer or the like and / or triallyl cyanurate (see Patent Document 4), a resin composition containing polybutadiene (see Patent Document 5), polyphenylene A resin composition obtained by pre-reacting an ether-based resin, a polyfunctional maleimide and / or a polyfunctional cyanate resin, and a liquid polybutadiene (see Patent Document 6), and a compound having an unsaturated double bond group is provided or Grafted polyphenylene ether and triallyl cyanurate and / or Resin composition containing allyl isocyanurate and the like (see Patent Document 7), resin composition containing a reaction product of polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride, and a polyfunctional maleimide and the like (See Patent Document 8) and the like.

JP-A-58-69046 JP-A-56-133355 JP-B-61-18937 JP-A-61-286130 JP-A-62-148512 JP-A-58-164638 JP-A-2-208355 JP-A-6-179834

Although the thermosetting resin compositions described in Patent Literatures 1 to 8 show relatively good relative dielectric constants, there have been many cases where strict requirements of the market in recent years cannot be satisfied. In addition, high heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating ability (laser workability) are often insufficient, leaving room for further improvement. is there. Conventionally, materials have not been sufficiently developed from the viewpoint of being suitable for the turning property with plating.
Therefore, an object of the present invention is to provide a thermosetting resin composition having excellent heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, excellent moldability and excellent spinning ability with plating, prepreg, It is to provide a laminate and a printed wiring board.

  The present inventors have conducted intensive studies to solve the above-described problems, and as a result, have found that “(A) a maleimide compound having an N-substituted maleimide group” and “(B) a compound having at least two epoxy groups in one molecule. The thermosetting resin composition containing the “epoxy resin”, the “(C) copolymer resin having a specific structural unit”, and the “(D) aminotriazinephenol novolak resin” in a specific ratio is as described above. They have found that the problem can be solved, and have completed the present invention. The present invention has been completed based on such findings.

The present invention relates to the following [1] to [12].
[1] (A) 15 to 65 parts by mass of a maleimide compound having an N-substituted maleimide group,
(B) 15 to 50 parts by mass of an epoxy resin having at least two epoxy groups in one molecule;
(C) 10 to 45 parts by mass of a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride, and (D) 2 to 7 parts by mass of an aminotriazinephenol novolak resin (provided that (The total of the components (A) to (D) is 100 parts by mass.)
A thermosetting resin composition comprising:
[2] The above-mentioned [1], wherein the component (C) is a copolymer resin having a structural unit represented by the following general formula (C-i) and a structural unit represented by the following formula (C-ii). ] The thermosetting resin composition as described in [1].

(Wherein, 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 a ^C 6-20 alkyl group. An aryl group, a hydroxyl group or a (meth) acryloyl group, wherein x is an integer of 0 to 3. However, when x is 2 or 3, a plurality of R ^C2 may be the same or different. May be.)
[3] The thermosetting resin composition according to the above [2], wherein in the general formula (C-i), R ^C1 is a hydrogen atom and x is 0.
[4] In the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride [the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride] / The structural unit derived from maleic anhydride] (molar ratio) is 2 to 9. The thermosetting resin composition according to the above [1].
[5] The thermosetting resin composition according to any one of [1] to [4], wherein the component (A) further has an acidic substituent.
[6] The component (B) is bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin or diphenyl The thermosetting resin composition according to any one of the above [1] to [5], which is a cyclopentadiene type epoxy resin.
[7] The thermosetting resin composition according to any one of [1] to [6], further comprising (E) an inorganic filler.
[8] The thermosetting resin composition according to the above [7], wherein the (E) inorganic filler is silica treated with an aminosilane-based coupling agent.
[9] The thermosetting resin composition according to any one of [1] to [8], further comprising (F) a flame retardant.
[10] A prepreg formed using the thermosetting resin composition according to any one of [1] to [9].
[11] A laminate formed using the prepreg according to [10] and a metal foil.
[12] A printed wiring board formed using the prepreg according to [10] or the laminate according to [11].

  According to the present invention, a thermosetting resin composition, a prepreg, a laminate, and a print having excellent heat resistance, low dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, excellent moldability, and excellent plating performance. A wiring board is obtained. Moreover, the laminated board using the thermosetting resin composition of the present invention is also excellent in electric corrosion resistance.

Hereinafter, the present invention will be described in detail.
[Thermosetting resin composition]
The thermosetting resin composition of the present invention comprises (A) 15 to 65 parts by mass of a maleimide compound having an N-substituted maleimide group, and (B) 15 to 50 parts by mass of an epoxy resin having at least two epoxy groups in one molecule. Parts, (C) 10 to 45 parts by mass of a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride, and (D) 2 to 7 parts by mass of an aminotriazinephenol novolak resin ( However, the total amount of the components (A) to (D) is 100 parts by mass.).

Hereinafter, each component contained in the thermosetting resin composition of the present invention will be described in detail.
<(A) Maleimide compound having N-substituted maleimide group>
(A) The maleimide compound having an N-substituted maleimide group preferably has an acidic substituent from the viewpoint of rigidity and mechanical strength of a cured product of the thermosetting resin composition. The weight average molecular weight (Mw) of the maleimide compound (A) having an N-substituted maleimide group is preferably from 400 to 3500, more preferably from 400 to 2300, from the viewpoints of solubility in an organic solvent and mechanical strength. And more preferably 800 to 2000. In addition, the weight average molecular weight in this specification is a value measured by a gel permeation chromatography (GPC) method (standard polystyrene conversion) using tetrahydrofuran as an eluent.
(A) A maleimide compound having an N-substituted maleimide group includes, for example, (a1) a maleimide compound having at least two N-substituted maleimide groups in one molecule [hereinafter, abbreviated as maleimide compound (a1)]; (A2) a monoamine compound represented by the following general formula (a2-1) [hereinafter abbreviated as monoamine compound (a2)] and (a3) a diamine compound represented by a general formula (a3-1) described below [hereinafter , Abbreviated as diamine compound (a3)].
It is preferable that at least one of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) has an acidic substituent, and among the monoamine compound (a2) and the diamine compound (a3) It is more preferable that any one has an acidic substituent, and it is further preferable that the diamine compound (a3) has an acidic substituent.

(Maleimide compound (a1))
The maleimide compound (a1) is a maleimide compound having at least two N-substituted maleimide groups in one molecule.
Is the maleimide compound (a1) a maleimide compound having an aliphatic hydrocarbon group between any two maleimide groups of a plurality of maleimide groups [hereinafter referred to as an aliphatic hydrocarbon group-containing maleimide] Or a maleimide compound containing an aromatic hydrocarbon group between any two maleimide groups of a plurality of maleimide groups [hereinafter referred to as an aromatic hydrocarbon group-containing maleimide]. Among these, an aromatic hydrocarbon group-containing maleimide is preferred from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating coverage. The aromatic hydrocarbon group-containing maleimide only needs to contain an aromatic hydrocarbon group between any two combinations of arbitrarily selected maleimide groups.
As the maleimide compound (a1), from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating coverage, two or more per molecule are used. A maleimide compound having five N-substituted maleimide groups is preferable, and a maleimide compound having two N-substituted maleimide groups in one molecule is more preferable. Further, as the maleimide compound (a1), from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability and plating turnability, the following general formula (a1) -1) to an aromatic hydrocarbon group-containing maleimide represented by any one of (a1-4), more preferably the following general formula (a1-1), (a1-2) or (a1-4) Is more preferable, and an aromatic hydrocarbon group-containing maleimide represented by the following general formula (a1-2) is particularly preferable.

In the above formula, R ^{A1 to} R ^A3 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms. X ^A1 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, -C (= O)-, -S-, -SS- or a sulfonyl group. p, q and r are each independently an integer of 0-4. s is an integer of 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, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. As the aliphatic hydrocarbon group, from the viewpoint of high heat resistance, low dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability and plating coverage, preferably the number of carbon atoms is 1 to 1. And 3 is an aliphatic hydrocarbon group, more preferably a methyl group or an ethyl group.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^A1 include a methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like. Is mentioned. As the alkylene group, from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability and plating ability, preferably alkylene having 1 to 3 carbon atoms And more preferably a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^A1 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, and the like. Among these, an isopropylidene group is preferable from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating coverage.
X ^A1 is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options. More preferred are as described above.
p, q, and r are each independently an integer of 0 to 4, and have high heat resistance, low dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating turnability. In view of the above, each is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
s is an integer of 0 to 10, and preferably 0 to 5, more preferably 0 to 3, from the viewpoint of availability. In particular, the aromatic hydrocarbon group-containing maleimide compound represented by the general formula (a1-3) is preferably a mixture of s = 0 to 3.

Specific examples of the maleimide compound (a1) include, for example, N, N′-ethylenebismaleimide, N, N′-hexamethylenebismaleimide, bis (4-maleimidocyclohexyl) methane, 1,4-bis (maleimide N, N ′-(1,3-phenylene) bismaleimide, N, N ′-[1,3- (2-methylphenylene)] bismaleimide, N, N ′-(1,3-phenylene) bismaleimide N '-[1,3- (4-methylphenylene)] bismaleimide, N, N'-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-) (Maleimidophenyl) methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, bis (4-maleimidophenyl) A , Bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) ) 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] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4 -(3-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimide) Enoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) 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-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [ 4- (4-maleimidophenoxy) phenyl] ketone, 2,2′-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide ) Phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) 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-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4 -(3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethyl Rubenjiru] benzene, aromatic hydrocarbon group-containing maleimides such as polyphenyl methane maleimide.
Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4) are preferred from the viewpoint that the reaction rate is high and the heat resistance can be further increased. -Maleimidophenyl) disulfide, N, N '-(1,3-phenylene) bismaleimide and 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are preferred, and from the viewpoint of low cost, bis (4-maleimidophenyl) methane and N, N '-(1,3-phenylene) bismaleimide are preferred, and bis (4-maleimidophenyl) methane is particularly preferred from the viewpoint of solubility in a solvent.
As the maleimide compound (a1), one type may be used alone, or two or more types may be used in combination.

(Monoamine compound (a2))
The monoamine compound (a2) is preferably a monoamine compound having an acidic substituent represented by the following general formula (a2-1).

In the general formula ^{(a2-1), R A4} represents a hydroxyl group, an acidic substituent selected from a carboxy group and sulfonic acid groups. ^RA5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. t is an integer of 1 to 5, u is an integer of 0 to 4, and satisfies 1 ≦ t + u ≦ 5. However, when t is an integer of 2 to 5, a plurality of ^RA4s may be the same or different. When u is an integer of 2 to 4, a plurality of ^RA5s may be the same or different.
The acidic substituent represented by ^RA4 is preferably a hydroxyl group or a carboxy group from the viewpoint of solubility and reactivity, and more preferably a hydroxyl group in consideration of heat resistance.
t is an integer of 1 to 5, preferably 1 to 3 from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability and plating coverage. Is an integer, more preferably 1 or 2, and still more preferably 1.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A5, for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group, n- pentyl group, and the No. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
As the halogen atom represented by R ^A5, fluorine atom, chlorine atom, bromine atom, and an iodine atom.
u is an integer of 0 to 4, preferably 0 to 3 from the viewpoints of high heat resistance, low dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating coverage. , More preferably 0 to 2, further preferably 0 or 1, particularly preferably 0.
As the monoamine compound (a2), from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability and plating coverage, more preferably the following general formula ( It is a monoamine compound represented by a2-2) or (a2-3), and more preferably a monoamine compound represented by the following general formula (a2-2). However, R ^A4 , R ^A5 and u in the general formulas (a2-2) and (a2-3) are the same as those in the general formula (a2-1), and preferable ones 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, o-aminobenzenesulfonic acid, Monoamine compounds having an acidic substituent such as m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline are exemplified.
Further, as the monoamine compound (a2), aniline, o-methylaniline, m-methylaniline, p-methylaniline, o-ethylaniline, m-ethylaniline, p-ethylaniline, o-vinylaniline, m-vinyl Monoamine compounds having no acidic substituent, such as aniline, p-vinylaniline, o-allylaniline, m-allylaniline, and p-allylaniline, may also be used.
Among these, a monoamine compound having an acidic substituent is preferable, and from the viewpoint of solubility and reactivity, m-aminophenol, p-aminophenol, p-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable. From the viewpoint of properties, o-aminophenol, m-aminophenol, and p-aminophenol are preferable, and p-aminophenol is more preferable in consideration of dielectric properties, low thermal expansion, and manufacturing cost.
As the monoamine compound (a2), one type may be used alone, or two or more types may be used in combination.

(Diamine compound (a3))
The diamine compound (a3) is preferably a diamine compound having at least two benzene rings, more preferably a diamine compound having at least two benzene rings in a straight chain between two amino groups, and has the following general formula (a3) The diamine compound represented by -1) is more preferable.

(Wherein X ^A2 is an aliphatic hydrocarbon group having 1 to 3 carbon atoms or an ether bond. RA ⁶ and ^{RA 7} are each independently an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, Represents a carboxy group or a sulfonic group, and v and w are each independently an integer of 0 to 4.)

Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms which X ^A2 represents, for example, methylene group, ethylene group, propylene group, propylidene group, and the like.
X ^A2 is preferably a methylene group.
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, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl. And the like. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
When the diamine compound (a3) is a compound having an acidic substituent, ^RA6 and ^RA7 are a hydroxyl group, a carboxy group or a sulfonic acid group.
v and w are preferably an integer of 0 to 2, more preferably 0 or 1. When the diamine compound (a3) is a compound having no acidic substituent, v and w are preferably 0.

  Specific examples of the diamine compound (a3) include, for example, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylpropane, 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'-diethyl-4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylthioether, 3,3'-dihydroxy-4,4'-diamino Diphenylmethane, 2,2 ′, 6,6′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3′-dic B-4,4'-Diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane, 2,2 ', 6,6'-tetramethylchloro-4,4'-diaminodiphenylmethane, 2,2 ', 6,6'-Tetrabromo-4,4'-diaminodiphenylmethane and the like. Among these, 4,4′-diaminodiphenylmethane and 3,3′-diethyl-4,4′-diaminodiphenylmethane are preferred from the viewpoint of inexpensiveness, and 4,4′-diaminodiphenylmethane is preferred from the viewpoint of solubility in a solvent. Diaminodiphenylmethane is more preferred.

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

(Use amount of maleimide compound (a1), monoamine compound (a2) and diamine compound (a3))
In the reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3), the amount of the three used is the primary amino group equivalent [-NH] of the monoamine compound (a2) and the diamine compound (a3). It is preferable that the relationship between the total sum of the _two equivalents] and the maleimide group equivalent of the maleimide compound (a1) satisfy the following formula.
0.1 ≦ [maleimide group equivalent] / [total of —NH ₂ group equivalents] ≦ 10
By setting [maleimide group equivalent] / [total of -NH ₂ group equivalents] to 0.1 or more, gelation and heat resistance do not decrease. It is preferable because the solubility, the metal foil adhesion and the heat resistance do not decrease.
From a similar viewpoint, more preferably,
1 ≦ [maleimide group equivalent] / [total of —NH ₂ group equivalents] ≦ 9,
More preferably,
2 ≦ [maleimide group equivalent] / [sum of —NH ₂ group equivalents] ≦ 8.

(Organic solvent)
As described above, the reaction of the maleimide compound (a1), the monoamine compound (a2), and the diamine compound (a3) is preferably performed in an organic solvent.
The organic solvent is not particularly limited as long as it does not adversely affect the reaction. For example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as tetrahydrofuran; toluene, xylene and mesitylene Aromatic solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; nitrogen atom-containing solvents including amide solvents such as dimethylsulfoxide; sulfur atom-containing solvents including sulfoxide solvents such as dimethylsulfoxide; ethyl acetate; And ester solvents such as butyrolactone. Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents, and ester solvents are preferable.From the viewpoint of low toxicity, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are more preferable, and Considering that it has high properties and hardly remains as a residual solvent during the production of prepreg, cyclohexanone, propylene glycol monomethyl ether and dimethylacetamide are more preferred, and dimethylacetamide is particularly preferred.
One organic solvent may be used alone, or two or more organic solvents may be used in combination.
There is no particular limitation on the amount of the organic solvent used, but from the viewpoint of solubility and reaction efficiency, preferably 25 parts per 100 parts by mass of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) in total. The amount may be from 1000 to 1000 parts by mass, more preferably from 40 to 700 parts by mass, still more preferably from 60 to 250 parts by mass. When the total amount of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) is 25 parts by mass or more with respect to 100 parts by mass in total, the solubility is easily ensured. It is easy to suppress a significant decrease in reaction efficiency.

(Reaction catalyst)
The reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3) may be carried out in the presence of a reaction catalyst, if necessary. Examples of the reaction catalyst include amine catalysts such as triethylamine, pyridine and tributylamine; imidazole catalysts such as methylimidazole and phenylimidazole; phosphorus catalysts such as triphenylphosphine.
One type of reaction catalyst may be used alone, or two or more types may be used in combination.
The amount of the reaction catalyst is not particularly limited, but is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total mass of the maleimide compound (a1) and the monoamine compound (a2).

<(B) Epoxy resin having at least two epoxy groups in one molecule>
(B) As an epoxy resin having at least two epoxy groups in one molecule (hereinafter sometimes simply referred to as epoxy resin (B)), glycidyl ether type epoxy resin, glycidylamine type epoxy resin, glycidyl Ester type epoxy resins and the like can be mentioned. Among these, a glycidyl ether type epoxy resin is preferable.
The epoxy resin (B) is classified into various epoxy resins depending on the difference in the main skeleton. Among the above types of epoxy resins, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, etc. Bisphenol type epoxy resin; biphenyl aralkyl phenol type epoxy resin; phenol novolak type epoxy resin, alkylphenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthol alkylphenol copolymerized novolak type epoxy resin, naphthol aralkyl cresol copolymerized novolak type epoxy resin, Novolak type epoxy resins such as bisphenol A novolak type epoxy resin and bisphenol F novolak type epoxy resin; stilbene type epoxy resin Epoxy resin containing triazine skeleton; epoxy resin containing fluorene skeleton; naphthalene epoxy resin; anthracene epoxy resin; triphenylmethane epoxy resin; biphenyl epoxy resin; biphenylaralkyl epoxy resin; xylylene epoxy resin; It is classified into an alicyclic epoxy resin such as a pentadiene type epoxy resin.
Among them, bisphenol F type epoxy resin, phenol novolak type epoxy resin, from the viewpoint of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability and plating coverage. , Cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, dicyclopentadiene type epoxy resin are preferable, and from the viewpoint of low thermal expansion property and high glass transition temperature, cresol Novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, phenol novolak type epoxy resin are more preferable, and cresol novolak type epoxy resin A further preferred.
As the epoxy resin (B), one type may be used alone, or two or more types may be used in combination.

The epoxy equivalent of the epoxy resin (B) is preferably 100 to 500 g / eq, more preferably 120 to 400 g / eq, further preferably 140 to 300 g / eq, and particularly preferably 170 to 240 g / eq.
Here, the epoxy equivalent is the mass (g / eq) of the resin per epoxy group, and can be measured according to the method specified in JIS K7236. Specifically, using an automatic titrator “GT-200 type” manufactured by Mitsubishi Chemical Analytech Co., Ltd., 2 g of an epoxy resin was weighed into a 200 ml beaker, 90 ml of methyl ethyl ketone was dropped, and an ultrasonic washer was melted. It is determined by adding 10 ml of acetic acid and 1.5 g of cetyltrimethylammonium bromide and titrating with a 0.1 mol / L perchloric acid / acetic acid solution.
Commercial products of the epoxy resin (B) include a cresol novolak type epoxy resin “EPICLON (registered trademark) N-673” (manufactured by DIC Corporation, epoxy equivalent: 205 to 215 g / eq), and a naphthalene type epoxy resin “HP-4032” (Mitsubishi Chemical Corporation, epoxy equivalent: 152 g / eq), biphenyl type epoxy resin "YX-4000" (Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / eq), dicyclopentadiene type epoxy resin "HP-7200H" (Made by DIC Corporation, epoxy equivalent: 280 g / eq). The epoxy equivalent is a value described in a catalog of a 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, may be referred to as a copolymer resin (C)). Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene and the like. Of these, styrene is preferred.
As the component (C), 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) is preferable.

(Wherein, 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 a ^C 6-20 alkyl group. An aryl group, a hydroxyl group or a (meth) acryloyl group, wherein x is an integer of 0 to 3. However, when x is 2 or 3, a plurality of R ^C2 may be the same or different. May be.)

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, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl. And the like. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ^C2 include an allyl group and a crotyl 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.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ^C2 include a phenyl group, a naphthyl group, an anthryl group, and a biphenylyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.
x is preferably 0 or 1, and more preferably 0.
In the structural unit represented by the general formula (Ci), a structural unit represented by the following general formula (Ci-1) in which R ^C1 is a hydrogen atom and x is 0 is preferable.

Content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride [the structural unit derived from the aromatic vinyl compound / the structural unit derived from maleic anhydride] in the copolymer resin (C) (Molar ratio) is preferably 2 to 9, more preferably 3 to 8, and still more preferably 3 to 7. Further, the content ratio of the structural unit represented by the general formula (Ci) to the structural unit represented by the formula (C-ii) [(Ci) / (C-ii)] (molar ratio) Similarly, it is preferably 2 to 9, more preferably 3 to 8, and still more preferably 3 to 7. If the molar ratio is 2 or more, the effect of improving the dielectric properties tends to be sufficient, and if it is 9 or less, the compatibility tends to be 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 (C-i) and the formula The total content with the structural unit represented by (C-ii) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably substantially 100% by mass or more. % By mass.
The weight average molecular weight (Mw) of the copolymer resin (C) is preferably 5,000 to 18,000, more preferably 6,000 to 17,000, still more preferably 8,000 to 16,000, and particularly preferably. It is between 8,000 and 15,000, most preferably between 9,000 and 13,000.

  In addition, the method of lowering the dielectric constant of an epoxy resin by using a copolymer resin of styrene and maleic anhydride, when applied to a material for a printed wiring board, impregnation into a substrate and peel strength of a copper foil become insufficient. Therefore, it tends to be generally avoided. Therefore, it is easy to avoid using the copolymer resin (C). However, the present invention will be described later together with the components (A) and (B) while using the copolymer resin (C). By including the component (D) and setting the content of each component to a specific ratio, high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability and It has been found that a thermosetting resin composition having excellent plating turnability has been achieved.

(Production method of copolymer resin (C))
The copolymer resin (C) can be produced by copolymerizing an aromatic vinyl compound and 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 polymerizable components may be copolymerized. Examples of various polymerizable components include vinyl compounds such as ethylene, propylene, butadiene, isobutylene, and acrylonitrile; and compounds having a (meth) acryloyl group such as methyl acrylate and methyl methacrylate.
Further, a substituent such as an allyl group, a methacryloyl group, an acryloyl group, or a hydroxy group may be introduced into the aromatic vinyl compound through a Friedel-Crafts reaction or a reaction using a metal catalyst such as lithium.

  As the copolymer resin (C), a commercially available product may be used. Examples of the commercially available product include “SMA (registered trademark) EF30” (styrene / maleic anhydride = 3, Mw = 9,500), and “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) Trademark EF80 "(styrene / maleic anhydride = 8, Mw = 14,400) [all manufactured by Sartomer Co., Ltd.].

<(D) aminotriazine phenol novolak resin>
The component (D) is an aminotriazinephenol novolak resin (hereinafter sometimes referred to as aminotriazinephenol novolak resin (D)).
The aminotriazine phenol novolak resin (D) is not particularly limited as long as it is a phenol novolak resin having an amino group and a triazine skeleton. The resin preferably has a structural unit represented by 2) and a structural unit represented by the following general formula (D-2). Naturally, it also has a structural unit derived from a phenol compound. The phenol compound will be described later.

(In the formula, R ^D1 is —NH ₂ , an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a carboxy group.)

(In the formula, R ^D2 is a hydrogen atom or a methyl group, and R ^D3 is a hydrogen atom, a methyl group, or a phenyl group.)

Examples of the alkyl group having 1 to 3 carbon atoms represented by R ^D1 in the formula (D-1-1) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Among these, a methyl group is preferred.
Examples of the aryl group having 6 to 20 carbon atoms which R ^D1 represents, for example, a phenyl group, a naphthyl group, an anthryl group, etc. biphenylyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, and further preferably a phenyl group.
Among the ^above, the ^{R D1,} is preferably -NH ₂ or an alkyl group having 1 to 3 carbon atoms, a phenyl group, more preferably -NH _2.
R ^D2 in the general formula (D-2) is preferably a hydrogen atom. Further, ^RD3 is preferably a hydrogen atom.

  In the aminotriazine phenol novolak resin (D), the structural unit represented by the general formula (D-1-1) or the formula (D-1-2) has a structure represented by the formula (D-2). A compound having a molecular structure bonded to a phenol compound via a unit, or a structural unit represented by the general formula (D-1-1) or the formula (D-1-2), It is preferable that the compound has a molecular structure in which it is bonded to a condensation reaction product of a phenol compound and an aldehyde via a structural unit represented by the formula (D-2).

More preferably, the aminotriazine phenol novolak resin (D) is obtained by reacting a phenol compound, a triazine compound substituted with an amino group, and an aldehyde compound.
Examples of the phenol compound include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-isopropylphenol, m-propylphenol, and p-propyl. Phenol compounds such as phenol, p-sec-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol; α-naphthol, β-naphthol Naphthol compound such as 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, etc .; resorcinol, catechol, hydroquinone, 2,2-bis (4'-hydroxyphenyl) pro 1,1,1′-bis (dihydroxyphenyl) methane, 1,1′-bis (dihydroxynaphthyl) methane, tetramethylbiphenol, biphenol, hexamethylbiphenol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2, Diol compounds such as 7,7-dihydroxynaphthalene; and triol compounds such as trishydroxyphenylmethane.
Among them, phenol, o-cresol, m-cresol, naphthol compound, 2,2-bis (4′-hydroxyphenyl) propane, 2,6-xylenol, resorcinol, hydroquinone from the viewpoint of industrial ease of production , 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene are preferred, and phenol and o-cresol are more preferred in view of their excellent curability.

Examples of the triazine compound substituted with the amino group include melamine, acetoguanamine, benzoguanamine, carboxyphenyl-1,3,5-triazine-2,4-diamine, carboxynaphthyl-1,3,5-triazine-2. , 4-diamine, carboxybiphenyl-1,3,5-triazine-2,4-diamine and the like.
Among them, melamine, acetoguanamine and benzoguanamine are preferable from the viewpoint of flame retardancy, and carboxyphenyl-1,3,5-triazine-2,4-diamine is preferable from the viewpoint of heat resistance.

Examples of the aldehyde compound include aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, and crotonaldehyde; aromatic aldehydes such as benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, biphenylaldehyde, and naphthylaldehyde; salicylaldehyde 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2-hydroxy-3,4-dimethylbenzaldehyde, 4-hydroxybiphenylaldehyde, 2-hydroxy-1-naphthaldehyde, 5-hydroxy- Hydroxyl-substituted groups such as 1-naphthaldehyde, 6-hydroxy-1-naphthaldehyde and 7-hydroxy-2-naphthaldehyde; Such as family aldehyde, and the like.
Among these, formaldehyde, paraformaldehyde, benzaldehyde, and salicylaldehyde are preferable, and formaldehyde and paraformaldehyde are more preferable from the viewpoints of industrial supply stability and heat resistance, flame retardancy, and dielectric characteristics.

  The aminotriazine phenol novolak resin (D) is produced by reacting a phenol compound, the triazine compound, and an aldehyde compound, and the reaction can be carried out without a catalyst or in the presence of a catalyst. The order of the reaction of each raw material is not particularly limited, and the phenol compound and the aldehyde compound may be reacted first and then the triazine compound may be added, or the aldehyde compound and the triazine compound may be reacted and then the phenol compound may be reacted. May be. Alternatively, all the raw materials may be mixed and reacted at once.

In the reaction, the ratio (molar ratio) of the amount of the aldehyde compound used to the amount of the phenol compound used is not particularly limited, but aldehyde compound / phenol compound is preferably 0.1 to 1.1, more preferably 0.1 to 1.1. Is 0.2 to 0.8.
In the reaction, the ratio (molar ratio) of the amount of the triazine compound used to the amount of the phenol compound used is such that the triazine compound / phenol compound is preferably 0.03 to 1.50, more preferably 0.03 to 1.50. ０．５0.50.

When a catalyst is used in the reaction, a basic catalyst or an acid catalyst can be used as the catalyst.
Examples of the basic catalyst include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide and barium hydroxide; alkali metals or alkaline earth metals such as sodium oxide, potassium oxide and barium oxide Oxides; ammonia, primary to tertiary amine compounds, nitrogen-containing compounds such as hexamethylenetetramine, and the like; sodium carbonate and the like.
Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, sulfonic acid, and phosphoric acid; organic acids such as oxalic acid and acetic acid; Lewis acids; and divalent metal salts such as zinc acetate.
As the basic catalyst, a nitrogen-containing compound is preferable, and primary to tertiary amine compounds are more preferable. Organic acids are preferred as the acid catalyst.

The aminotriazine phenol novolak resin (D) has a softening point of preferably from 75 to 150C, more preferably from 90 to 135C, and still more preferably from 110 to 135C. When the softening point is within this range, the cured product of the finally obtained phosphorus atom-containing phenol resin tends to have an excellent balance between flame retardancy and heat resistance. Here, the softening point is a value measured by a ring and ball method (based on “JIS K7234-86”) at a rate of temperature increase of 5 ° C./min.
The hydroxyl equivalent of the aminotriazine phenol novolak resin (D) is preferably 70 to 300 g / eq, more preferably 100 to 250 g / eq, further preferably 100 to 200 g / eq, particularly preferably 100 to 160 g / eq, Most preferably, it is 110-140 g / eq.

<(E) Inorganic filler>
The thermosetting resin composition may contain an inorganic filler (hereinafter sometimes referred to as an inorganic filler (E)) as the component (E). The inorganic filler (E) has an effect of lowering the coefficient of thermal expansion.
Examples of the inorganic filler include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, Examples include calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay such as calcined clay, talc, aluminum borate, silicon carbide, short glass fiber, glass fine powder, and hollow glass. Preferred examples of the glass include E glass, T glass, and D glass. One type of inorganic filler may be used alone, or two or more types may be used in combination.
In the present invention, it is preferable to use silica as the inorganic filler (E), and among silica, it is more preferable to use silica treated with an aminosilane-based coupling agent.
(Silica treated with aminosilane coupling agent)
By including the silica treated with the aminosilane-based coupling agent in the thermosetting resin composition, in addition to the effect of improving the low thermal expansion property, the adhesiveness with the components (A) to (D) is improved. As a result, the silica is prevented from falling off, and an effect of suppressing deformation of the laser via shape due to excessive desmear can be obtained.

As the aminosilane-based coupling agent, specifically, a silane coupling agent having a silicon-containing group represented by the following general formula (E-1) and an amino group is preferable.

(In the formula, RE ¹ is an alkyl group having 1 to 3 carbon atoms or an acyl group having 2 to 4 carbon atoms. Y is an integer of 0 to 3.)

The alkyl group having 1 to 3 carbon atoms R ^E1 represents a methyl group, an ethyl group, n- propyl group, an isopropyl group. Among these, a methyl group is preferred.
The acyl group having 2 to 4 carbon atoms R ^E1 represents an acetyl group, a propionyl group, and acrylic group. Among these, an acetyl group is preferable.

The aminosilane-based coupling agent may have one amino group, may have two amino groups, may have three or more amino groups, and usually has one or more amino groups. I have two.
Examples of the aminosilane-based coupling agent having one amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-triethoxysilyl- Examples thereof include N- (1,3-dimethyl-butylidene) propylamine and 2-propynyl [3- (trimethoxysilyl) propyl] carbamate, but are not particularly limited thereto.
Examples of the aminosilane-based coupling agent having two amino groups include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, Examples thereof include 1- [3- (trimethoxysilyl) propyl] urea and 1- [3- (triethoxysilyl) propyl] urea, but are not particularly limited thereto.

  Silica treated with another coupling agent may be used together with or instead of silica treated with an aminosilane-based coupling agent. Examples of the silica treated with another coupling agent include, for example, an epoxysilane coupling agent, a phenylsilane coupling agent, an alkylsilane coupling agent, an alkenylsilane coupling agent, an alkynylsilane coupling agent, Haloalkylsilane-based coupling agent, siloxane-based coupling agent, hydrosilane-based coupling agent, silazane-based coupling agent, alkoxysilane-based coupling agent, chlorosilane-based coupling agent, (meth) acrylsilane-based coupling agent, aminosilane-based Treated with a coupling agent, an isocyanurate silane coupling agent, a ureido silane coupling agent, a mercapto silane coupling agent, a sulfide silane coupling agent, or an isocyanate silane coupling agent. And silica.

Examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry silica produced by a dry method and containing substantially no bound water. The dry method silica further includes crushed silica, fumed silica, and fused silica (fused spherical silica) depending on the difference in the production method. Silica is preferably fused silica from the viewpoint of low thermal expansion and high fluidity when filled into a resin.
The average particle size of the silica is not particularly limited, but is preferably from 0.1 to 10 μm, more preferably from 0.1 to 6 μm, even more preferably from 0.1 to 3 μm. By setting the average particle diameter of silica to 0.1 μm or more, it is possible to maintain good fluidity at the time of high filling, and by setting the average particle diameter to 10 μm or less, the mixing probability of coarse particles is reduced, and It is possible to suppress the occurrence of the resulting defect. Here, the average particle diameter is a particle diameter at a point corresponding to exactly 50% by volume when a cumulative frequency distribution curve based on the particle diameter is determined with the total volume of the particles being 100%. It can be measured by the used particle size distribution measuring device or the like.
The specific surface area of the silica is preferably 4 cm ² / g or more, more preferably 4 to 9 cm ² / g, and still more preferably 5 to 7 cm ² / g.

<(F) Flame retardant>
The thermosetting resin composition of the present invention may contain a flame retardant (hereinafter sometimes referred to as a flame retardant (F)) as a component (F). Here, the aminotriazinephenol novolak resin (D) also has an effect as a flame retardant, but in the present invention, the component (F) does not include the component (D).
Examples of the flame retardant include halogen-containing flame retardants containing bromine and chlorine; phosphorus-based flame retardants; nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate; cyclophosphazene and polyphosphazene And the like; and inorganic flame retardants such as antimony trioxide. Among these, phosphorus-based flame retardants are preferred.
Examples of the phosphorus-based flame retardant include an inorganic phosphorus-based flame retardant and an organic phosphorus-based flame retardant.
Examples of inorganic phosphorus-based flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphate amide Phosphoric acid; phosphine oxide and the like.
Examples of organic phosphorus-based flame retardants include aromatic phosphate esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds, Phosphorus-containing phenol resins and the like can be mentioned. Among these, aromatic phosphoric acid esters and metal salts of disubstituted phosphinic acids are preferred. Here, the metal salt is preferably any one 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, and more preferably an aluminum salt. Further, among organic phosphorus-based flame retardants, aromatic phosphate esters are more preferable.

Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), and 1,3. -Phenylenebis (di-2,6-xylenylphosphate), bisphenol A-bis (diphenylphosphate), 1,3-phenylenebis (diphenylphosphate) and the like.
Examples of the monosubstituted phosphonic acid diester include divinyl phenylphosphonate, diallyl phenylphosphonate, bis (1-butenyl) phenylphosphonate, and the like.
Examples of the disubstituted phosphinic acid ester include phenyl diphenylphosphinate and methyl diphenylphosphinate.
Examples of the metal salt of a disubstituted phosphinic acid include a metal salt of a dialkyl phosphinic acid, a metal salt of a diallyl phosphinic acid, a metal salt of a divinyl phosphinic acid, and a metal salt of a diaryl phosphinic acid. As described above, these metal salts are preferably any of lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts.
Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresylphosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, and the like.
Examples of the cyclic organic phosphorus compound include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-. And phosphaphenanthrene-10-oxide.
Among these, at least one selected from aromatic phosphate esters, metal salts of disubstituted phosphinic acids and cyclic organic phosphorus compounds is preferred, and aromatic phosphate esters are 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 as follows. The metal salt of a disubstituted phosphinic acid represented by the general formula (F-3) is preferable.

(In the formula, R ^{F1 to} R ^F5 are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom. E and f are each independently an integer of 0 to 5, and g, h and i are each It is an integer of 0 to 4 independently.
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. M is a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom, and a zinc atom. j is an integer of 1 to 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, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl. And the like. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the halogen atom represented by R ^{F1 to} R ^F5 include a fluorine atom.
e and f are preferably integers of 0 to 2, and more preferably 2. g, h and i are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^F6 and R ^F7 include the same ones 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 biphenylyl group, and an anthryl group. As the aromatic hydrocarbon group, an aryl group having 6 to 10 carbon atoms is preferable.
j represents the valence of the metal ion, that is, changes in the range of 1 to 4 depending on the type of M.
As M, an aluminum atom is preferable. When M is an aluminum atom, j is 3.

(Content of each component)
In the thermosetting resin composition, the content of the components (A) to (D) is such that the component (A) is 15 to 65 parts by mass with respect to 100 parts by mass in total of the components (A) to (D). Component (B) is 15 to 50 parts by mass, component (C) is 10 to 45 parts by mass, and component (D) is 2 to 7 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 (D), high heat resistance, a low dielectric constant, a high glass transition temperature, and a low thermal expansion property can be obtained. . On the other hand, when it is at most 65 parts by mass, the fluidity and moldability of the thermosetting resin composition will be good.
When the component (B) is 15 parts by mass or more based on 100 parts by mass of the total of the components (A) to (D), high heat resistance, a high glass transition temperature, and low thermal expansion are obtained. On the other hand, when the amount is 50 parts by mass or less, high heat resistance, low relative dielectric constant, high glass transition temperature, and low thermal expansion are obtained.
When the component (C) is at least 10 parts by mass with respect to the total of 100 parts by mass of the components (A) to (D), high heat resistance and a low dielectric constant can be obtained. On the other hand, when the amount is 45 parts by mass or less, high heat resistance, high metal foil adhesion, and low thermal expansion can be obtained.
When the component (D) is at least 2 parts by mass with respect to the total of 100 parts by mass of the components (A) to (D), excellent low thermal expansion properties can be obtained. A low relative dielectric constant and high metal foil adhesion are obtained, and the fluidity and moldability of the thermosetting resin composition are improved.
By setting the content of the components (A) to (D) in the thermosetting resin composition within the above range, high heat resistance, low dielectric constant, high metal foil adhesion, high glass transition temperature, and low thermal expansion property are obtained. Thus, a highly reliable thermosetting resin composition for a multilayer printed wiring board, which is excellent in moldability and turning property with plating, and is also excellent in electric corrosion resistance, can be obtained.

When the component (E) is contained in the thermosetting resin composition of the present invention, the content is preferably 20 to 80 parts by mass, based on 100 parts by mass of the total of the components (A) to (D). Preferably it is 25-75 mass parts, More preferably, it is 30-70 mass parts. When the component (E) is at least 20 parts by mass with respect to the total of 100 parts by mass of the components (A) to (D), excellent low thermal expansion tends to be obtained, while it is at most 80 parts by mass. Thereby, a low relative dielectric constant and a high metal foil adhesiveness are obtained, and the flowability and moldability of the thermosetting resin composition tend to be improved.
Further, when the component (F) is contained in the thermosetting resin composition of the present invention, the content is preferably from 100 parts by mass of the total of the components (A) to (D) from the viewpoint of flame retardancy. Preferably it is 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, the phosphorus atom content is 0.1 to 3 parts by mass relative to 100 parts by mass of the total of the components (A) to (D). Is preferably an amount of 0.2 to 3 parts by mass, more preferably 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, if necessary, as long as the effects of the present invention are not impaired. One of these may be contained alone, or two or more thereof may be contained.

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

(Organic solvent)
The thermosetting resin composition of the present invention may contain an organic solvent from the viewpoint of facilitating handling by dilution and facilitating the production of a prepreg described later. 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, for example, methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, Alcohol solvents such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as tetrahydrofuran Aromatic solvents such as toluene, xylene and mesitylene; form Nitrogen atom-containing solvents including amide solvents such as amide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; sulfur atom containing sulphoxide solvents such as dimethylsulfoxide Solvents: Ester solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, propylene glycol monomethyl ether acetate, and ethyl acetate.
Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents, and nitrogen atom-containing solvents are preferable, and methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are more preferable, and methyl ethyl ketone and methyl isobutyl ketone are preferable. Even more preferred is methyl ethyl ketone.
One organic solvent may be used alone, or two or more organic solvents may be used in combination.
The content of the organic solvent in the thermosetting resin composition of the present invention may be appropriately adjusted to an extent that the thermosetting resin composition is easily handled, and a range in which the coating property of the resin varnish is good. There is no particular limitation as long as the solid content concentration (the concentration of components other than the organic solvent) derived from the thermosetting resin composition is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and still more preferably. It is adjusted to be 50 to 80% by mass.

[Prepreg]
The present invention also provides a prepreg formed using the thermosetting resin composition.
The prepreg of the present invention can be manufactured by impregnating or coating the thermosetting resin composition on a sheet-like reinforcing base material and semi-curing (B-stage) by heating or the like.
As the sheet-like reinforcing base material of the prepreg, well-known ones used for various kinds of laminates for electric insulating materials can be used. Examples of the material of the sheet-shaped reinforcing substrate include paper, natural fibers such as cotton linter; inorganic fibers such as glass fiber and asbestos; organic fibers such as aramid, polyimide, polyvinyl alcohol, polyester, tetrafluoroethylene and acrylic; And mixtures thereof. Among these, glass fibers are preferred from the viewpoint of flame retardancy. As the glass fiber base material, a woven fabric using E glass, C glass, D glass, S glass or the like or a glass woven fabric in which short fibers are bonded with an organic binder; a mixture of glass fibers and cellulose fibers; No. More preferably, it is a glass woven fabric using E glass.
These sheet-like reinforcing substrates have a shape such as a woven fabric, a nonwoven fabric, a roving, a chopped strand mat, or a surfacing mat. The material and shape are selected depending on the intended use and performance of the molded product, and one type may be used alone or two or more types and materials 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 preferable.
The hot melt method is a method in which an organic solvent is not contained in a thermosetting resin composition, and (1) a method of once coating a coated paper having good releasability from the composition and laminating it on a sheet-like reinforcing substrate Or (2) a method of directly applying to a sheet-like reinforcing substrate by a die coater.
On the other hand, in the solvent method, a varnish is prepared by adding an organic solvent to the thermosetting resin composition, a sheet-like reinforcing substrate is immersed in the varnish, and the varnish is impregnated into the sheet-like reinforcing substrate, and then, It is a method of drying.

The thickness of the sheet-shaped reinforcing base material is not particularly limited, and for example, about 0.03 to 0.5 mm can be used. The coating is preferable from the viewpoints of heat resistance, moisture resistance and workability. After the substrate is impregnated or coated with the thermosetting resin composition, it is usually heated and dried at a temperature of preferably 100 to 200 ° C. for 1 to 30 minutes to be semi-cured (B-staged). Prepreg can be obtained.
The obtained prepregs are used singly or, if necessary, preferably 2 to 20 laps are used.

[Laminated plate]
The laminate of the present invention is formed using the prepreg. For example, it can be manufactured by using one prepreg or by laminating 2 to 20 prepregs as necessary, and laminating and forming a metal foil on one or both surfaces thereof. In addition, the laminated board on which the metal foil is arranged may be referred to as a metal-clad laminated board.
The metal of the metal foil is not particularly limited as long as it is used for an electrical insulating material, but from the viewpoint of conductivity, preferably, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, Iron, titanium, chromium, or an alloy containing at least one of these metal elements is preferable, copper and amylnium are more preferable, and copper is still more preferable.
As the molding conditions for the laminate, known molding techniques for laminates and multilayer boards for electric insulating materials can be applied, for example, using a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, and the like. Molding can be performed at 100 to 250 ° C, pressure of 0.2 to 10 MPa, and heating time of 0.1 to 5 hours.
Further, the prepreg of the present invention and the printed wiring board for the inner layer may be combined 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 and the like. The thickness of the metal foil is preferably 0.5 to 150 μm, more preferably 1 to 100 μm, further preferably 5 to 50 μm, and particularly preferably 5 to 30 μm.

In addition, it is also preferable 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 copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements. Preferably, it is selected.
The plating method is not particularly limited, and a known method such as an electrolytic plating method or an electroless plating method can be used.

[Printed wiring board]
The present invention also provides a printed wiring board formed using the prepreg or the laminate.
The printed wiring board of the present invention can be manufactured by subjecting the metal foil of the metal-clad laminate to circuit processing. For circuit processing, for example, after forming a resist pattern on the metal foil surface, removing unnecessary portions of the metal foil by etching, peeling off the resist pattern, forming necessary through holes with a drill, forming a resist pattern again, The plating can be performed by applying plating for conducting through holes and finally removing the resist pattern. The above-mentioned metal-clad laminate is further laminated on the surface of the printed wiring board thus obtained under the same conditions as described above, and further, circuit processing is performed in the same manner as described above to obtain a multilayer printed wiring board. Can be. In this case, it is not always necessary to form a through hole, and a via hole may be formed, or both can be formed. Such multilayering is performed for a required number of sheets.

  Next, the present invention will be described in more detail with reference to the following Examples, which do not limit the present invention in any way. Using the thermosetting resin composition according to the present invention, a prepreg and a copper-clad laminate were produced, and the produced copper-clad laminate was evaluated. The evaluation method is described below.

[Evaluation method]
<1. Heat resistance (reflow soldering heat resistance)>
Using the four-layer copper-clad laminate prepared in each example, the maximum temperature was set to 266 ° C., and flowing the four-layer copper-clad laminate for 30 seconds in a constant temperature bath environment of 260 ° C. or more was defined as one cycle, and was visually observed. The number of cycles until the substrate was confirmed to be swollen was determined. The greater the number of cycles, the better the heat resistance.

<2. Relative permittivity (Dk)>
The relative permittivity of the double-sided copper-clad laminate was measured at 1 GHz using a network analyzer “8722C” (manufactured by Hewlett-Packard) by a triplate structure straight line resonator method. The test piece size is 200 mm x 50 mm x 0.8 mm in thickness. A 1.0 mm wide straight line (line length 200 mm) is formed by etching at the center of one side of one double-sided copper-clad laminate. Copper was left on the entire surface to form a ground layer. With respect to the other double-sided copper-clad laminate, one surface was entirely etched, and the back surface was a ground layer. These two double-sided copper-clad laminates were overlapped with the ground layer on the outside to form a strip line. The measurement was performed at 25 ° C.
The smaller the relative permittivity, the more preferable.

<3. Metal foil adhesion (copper foil peel strength)>
The metal foil adhesion was evaluated by the copper foil peel strength. The evaluation board was prepared by immersing the double-sided copper-clad laminate prepared in each example in a copper etching solution “ammonium persulfate (APS)” (manufactured by ADEKA Corporation) to form a copper foil having a width of 3 mm to prepare an evaluation board. The peel strength of the copper foil was measured using "AG-100C" (manufactured by Shimadzu Corporation). The larger the value, the better the metal foil adhesion.

<4. Glass transition temperature (Tg)>
The double-sided copper-clad laminate prepared in each example was immersed in a copper etching solution “ammonium persulfate (APS)” (manufactured by ADEKA Corporation) to prepare a 5 mm square evaluation substrate from which the copper foil had been removed, and a TMA test device “ Using “Q400EM” (manufactured by TA Instruments), the thermal expansion characteristics of the evaluation substrate in the surface direction (Z direction) at 30 to 260 ° C. were observed, and the inflection point of the expansion amount was defined as the glass transition temperature.

<5. Low thermal expansion>
The double-sided copper-clad laminate prepared in each example was immersed in a copper etching solution “ammonium persulfate (APS)” (manufactured by ADEKA Corporation) to prepare a 5 mm square evaluation substrate from which the copper foil had been removed, and a TMA test device “ Q400EM "(manufactured by TA Instruments) was used to measure the thermal expansion coefficient (linear expansion coefficient) in the surface direction of the evaluation substrate. In addition, in order to remove the influence of the thermal strain of the sample, the heating / cooling cycle was repeated twice, and the coefficient of thermal expansion [ppm / ° C.] of 30 ° C. to 260 ° C. in the second temperature displacement chart was measured. It was an index of low thermal expansion. The smaller the value, the better the low thermal expansion. In the table, the coefficient of thermal expansion below Tg and the coefficient of thermal expansion above Tg are separately described.
Measurement conditions 1 ^st Run: room temperature → 210 ° C. (heating rate 10 ° C. / min)
^{2 nd Run: 0 ℃ → 270} ℃ ( heating rate 10 ° C. / min)
A further reduction in the thickness of the copper-clad laminate is desired, and a reduction in the thickness of a prepreg constituting the copper-clad laminate is also being studied. Since the thinned prepreg is likely to be warped, it is desired that the prepreg has a small warp during the heat treatment. In order to reduce the warpage, it is effective that the coefficient of thermal expansion in the surface direction of the substrate is small.

<6. Rotation with plating (laser workability)>
Using the laser machine “LC-2F21B / 2C” (manufactured by Hitachi Via Mechanics Co., Ltd.), the four-layer copper-clad laminate prepared in each example was subjected to the copper direct method using a target hole diameter of 80 μm, Gaussian, and cycle mode. The pulse width was 15 μs × 1 time and 7 μs × 4 times, and laser drilling was performed.
With respect to the obtained laser drilled substrate, a swelling solution “Swelling Dip Securiganto P” (manufactured by Atotech Japan Co., Ltd.) was used at 70 ° C. for 5 minutes. Desmear treatment was performed at 70 ° C. for 9 minutes at 40 ° C. for 5 minutes using a neutralizing solution “Reduction Conditioner Securiganto P500” (manufactured by Atotech Japan KK). After that, the electroless plating solution “Prigant MSK-DK” (manufactured by Atotech Japan KK) was applied at 30 ° C. for 20 minutes, and the electroplating solution “Kapalaside HL” (manufactured by Atotech Japan KK) was applied at 24 ° C., 2 A / dm ² , The laser processing substrate was plated for 2 hours.
A cross section of the obtained laser drilled substrate was observed, and the throwing power of the plating was confirmed. As a method for evaluating the throwing power of plating, it is preferable that the difference between the plating thickness at the top of the laser hole and the plating thickness at the bottom of the laser hole is within 10% of the plating thickness at the top of the laser hole. The existing ratio (%) of holes included in this range in the holes was determined.

<7. Moldability>
For the four-layer copper-clad laminate prepared in each example, after removing the outer layer copper, as a resin embedding property, the presence or absence of voids and blurring in a plane of 340 × 500 mm was visually checked, and an index of formability was obtained. And The absence of voids and blurring indicates good moldability.

<8. Electrolytic corrosion resistance>
A circuit pattern was prepared on the double-sided copper-clad laminate prepared in each example, in which the front and back circuits were electrically connected at a wall-to-wall distance (the shortest distance between the side walls of the hole) of 350 μm and a hole diameter of 0.4 mm, and the temperature was 85 ° C. A voltage of 100 V DC was applied between the circuits in a thermo-hygrostat at a relative humidity of 85%, and the time until the breakdown occurred was measured. In addition, when conduction breakdown did not occur even after 1000 hours, it was described as “≧ 1000”.

  Hereinafter, each component used in Examples and Comparative Examples will be described.

(A) Component: The solution produced in Production Example 1 below was used.
[Production Example 1]
19.2 g of 4,4′-diaminodiphenylmethane, 174.0 g of bis (4-maleimidophenyl) methane, and p-aminophenol were placed in a 1-L reaction vessel equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 6.6 g and 330.0 g of dimethylacetamide were added and reacted at 100 ° C. for 2 hours to obtain a dimethylacetamide solution of a maleimide compound (A) having an acidic substituent and an N-substituted maleimide group (Mw = 1379). (A) Used as a component.
The weight average molecular weight (Mw) was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is a standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation] Was approximated by a cubic equation. The conditions of GPC are shown below.
Equipment: (pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]),
(Detector: RI-3300 type RI [manufactured by Hitachi High-Technologies Corporation]),
(Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation])
Column: TSKgel SuperHZ2000 + TSKgel SuperHZ2300 (all manufactured by Tosoh Corporation)
Column size: 6.0 × 40 mm (guard column), 7.8 × 300 mm (column)
Eluent: tetrahydrofuran Sample concentration: 20 mg / 5 mL
Injection volume: 10 μL
Flow rate: 0.5 mL / min Measurement temperature: 40 ° C

Component (B): Cresol novolac epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Corporation)
Component (C): “SMA (registered trademark) EF40” (styrene / maleic anhydride = 4, Mw = 11,000, manufactured by Sartomer)
Component (D): aminotriazine phenol novolak resin “PHENOLITE (registered trademark) LA-7054” (manufactured by DIC Corporation, softening point 121 ° C., hydroxyl equivalent 125 g / eq)

Component (E):
“Megasil 525 ARI” (fused silica treated with an aminosilane-based coupling agent, average particle size: 1.9 μm, specific surface area: 5.8 m ² / g, manufactured by Cibelco Japan Ltd.)

Component (F): “PX-200” (aromatic phosphate ester (see the following structural formula), manufactured by Daihachi Chemical Industry Co., Ltd.)

[Examples 1 to 10, Comparative Examples 1 to 8]
The respective components shown above are blended as shown in Tables 1 to 4 below (however, in the case of a solution, the solid content is shown). Methyl ethyl ketone is further added so that the nonvolatile content of the solution is 65 to 75% by mass. In addition, thermosetting resin compositions of each Example and each Comparative Example were prepared.
Each of the obtained thermosetting resin compositions was impregnated in a glass cloth (0.1 mm) of IPC standard # 3313, and dried at 160 ° C. for 4 minutes to obtain a prepreg.
Eight pieces of the prepreg are stacked with 18 μm copper foil “3EC-VLP-18” (manufactured by Mitsui Kinzoku Co., Ltd.) on both sides, and heated at 190 ° C. under a pressure of 25 kgf / cm ² (2.45 MPa) for 90 minutes. A double-sided copper-clad laminate having a thickness of 0.8 mm (for 8 prepregs) is formed by pressure molding, and using the copper-clad laminate according to the method described above, the relative dielectric constant, the metal foil adhesion, and the glass transition. The temperature (Tg), the low thermal expansion property and the electrolytic corrosion resistance were measured and evaluated.
On the other hand, using one prepreg, 18 μm copper foil “YGP-18” (manufactured by Nippon Electrolysis Co., Ltd.) is laminated on both sides, and the temperature is 190 ° C., the pressure is 25 kgf / cm ² (2.45 MPa) for 90 minutes. After forming a double-sided copper-clad laminate with a thickness of 0.1 mm (for one prepreg) by heat and pressure molding, an inner layer adhesion treatment (“BF treatment solution” (manufactured by Hitachi Chemical Co., Ltd.)) was applied to both copper foil surfaces. ), And a prepreg having a thickness of 0.05 mm is laminated one by one, and copper foil “YGP-18” (manufactured by Nippon Electrolysis Co., Ltd.) having a thickness of 18 μm is laminated on both sides, and the temperature is 190 ° C., the pressure is 25 kgf / cm ² (2 .45 MPa) for 90 minutes to produce a four-layer copper-clad laminate. Using the four-layer copper-clad laminate, evaluation of heat resistance, wraparound with plating, and moldability was performed in accordance with the above method.
The results are shown in Tables 1 to 4.

In the examples, the reflow soldering heat resistance achieved 10 cycles or more, which is higher than the required heat resistance level, a low relative dielectric constant, a high metal foil adhesion, a high glass transition temperature, and a low thermal expansion were exhibited. In addition, since the glass cloth protruded from the wall surface and had a moderately roughened shape, it was confirmed that the glass cloth had good turnability with plating. As for the moldability, the embedding property of the resin was good, and abnormalities such as blurring and voids were not confirmed. Furthermore, it had excellent electric corrosion resistance.
On the other hand, in Comparative Example 1 in which the content of the component (A) was 10 parts by mass, the results of the heat resistance, the relative dielectric constant, the glass transition temperature, and the coefficient of thermal expansion were insufficient. In Comparative Example 2 in which the amount is 70 parts by mass, the moldability is not sufficient due to the increase in viscosity of the thermosetting resin composition. In Comparative Example 3 in which the content of the component (B) was 10 parts by mass, the heat resistance was significantly reduced, the glass transition temperature was reduced, and the coefficient of thermal expansion at a temperature higher than the glass transition temperature (Tg) was increased. In Comparative Example 4 in which the content of the component (B) was 60 parts by mass, the heat resistance significantly decreased, the glass transition temperature decreased, and the relative dielectric constant and the coefficient of thermal expansion increased. In Comparative Example 5, in which the content of the component (C) is 5 parts by mass, heat resistance is reduced, the relative dielectric constant is increased, and in Comparative Example 6, in which the content of the component (C) is 50 parts by mass, The heat resistance and the metal foil adhesion were remarkably reduced, and the coefficient of thermal expansion was increased. In Comparative Example 7 in which the content of the component (D) was 1 part by mass, the metal foil adhesion was reduced, and in Comparative Example 8 in which the content of the component (D) was 10 parts by mass, the heat resistance was reduced.

  A prepreg formed using the thermosetting resin composition of the present invention and a laminate formed using the prepreg have high heat resistance, low dielectric constant, high metal foil adhesion, high glass transition temperature, low heat. Since it is excellent in expandability, moldability, turning ability with plating, and electric corrosion resistance, it is useful as a printed wiring board for electronic equipment.

Claims (12)

(A) 15 to 65 parts by mass of a maleimide compound having an N-substituted maleimide group,
(B) 15 to 50 parts by mass of an epoxy resin having at least two epoxy groups in one molecule;
(C) 10 to 45 parts by mass of a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride, and (D) 2 to 7 parts by mass of an aminotriazinephenol novolak resin (provided that (The total of the components (A) to (D) is 100 parts by mass.)
A thermosetting resin composition comprising,
The component (A) comprises (a1) a maleimide compound having at least two N-substituted maleimide groups in one molecule, (a2) a monoamine compound represented by the following general formula (a2-1), and (a3) A thermosetting resin composition obtained by reacting a diamine compound represented by the following general formula (a3-1).

(Wherein, R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxy group and a sulfonic acid group. R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. T represents 1 to 5) The integer u is an integer of 0 to 4 and satisfies 1 ≦ t + u ≦ 5, provided that when t is an integer of 2 to 5, a plurality of ^RA4s may be the same or different. When u is an integer of 2 to 4, a plurality of ^RA5s may be the same or different.

( Wherein X ^A2 is an aliphatic hydrocarbon group having 1 to 3 carbon atoms or an ether bond. RA ⁶ and ^{RA 7} are each independently an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, Represents a carboxy group or a sulfonic group, and v and w are each independently an integer of 0 to 4.) The component (C) according to claim 1, wherein the component (C) is a copolymer resin having a structural unit represented by the following general formula (C-i) and a structural unit represented by the following formula (C-ii). Thermosetting resin composition.

(Wherein, 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 a ^C 6-20 alkyl group. An aryl group, a hydroxyl group or a (meth) acryloyl group, wherein x is an integer of 0 to 3. However, when x is 2 or 3, a plurality of R ^C2 may be the same or different. May be.) The thermosetting resin composition according to claim 2, wherein in the general formula (C-i), R ^C1 is a hydrogen atom and x is 0.   In the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride [the structural unit derived from the aromatic vinyl compound / the structural unit derived from maleic anhydride] (mol The thermosetting resin composition according to claim 1, wherein (ratio) is 2 to 9. The component (B) is a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a naphthalene type epoxy resin, an anthracene type epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl type epoxy resin or a dicyclopentadiene type. The thermosetting resin composition according to any one of claims 1 to 4 , which is an epoxy resin. The thermosetting resin composition according to any one of claims 1 to 5 , further comprising (E) an inorganic filler. The thermosetting resin composition according to claim 6 , wherein the (E) inorganic filler is silica treated with an aminosilane-based coupling agent. The thermosetting resin composition according to any one of claims 1 to 7 , further comprising (F) a flame retardant. The thermosetting composition according to any one of claims 1 to 8 , wherein the content of the component (C) is 10 to 25 parts by mass based on 100 parts by mass of the total of the components (A) to (D). Resin composition. A prepreg formed using the thermosetting resin composition according to any one of claims 1 to 9 . A laminate formed using the prepreg according to claim 10 and a metal foil. A printed wiring board formed using the prepreg according to claim 10 or the laminate according to claim 11 .