TWI713531B - Thermosetting resin composition, prepreg, build-up board and printed circuit board - Google Patents

Abstract

The invention provides a thermosetting resin composition, prepreg, Laminated boards and printed wiring boards; the thermosetting resin composition has high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature and low thermal expansion, and has excellent formability and plating uniformity. The aforementioned thermosetting resin composition is specifically a thermosetting resin composition containing the following components: (A) Maleimide compound having N-substituted maleimide group 15~65 mass Parts; (B) 15-50 parts by mass of epoxy resin with at least two epoxy groups in one molecule; (C) 10~45 parts by mass of copolymer resin, which has a structure derived from an aromatic vinyl compound The unit and the structural unit derived from maleic anhydride, wherein the total of the components (A) to (C) is 100 parts by mass; and (D) dicyandiamine, which is relative to the aforementioned (A) to (C) components The sum of 100 parts by mass is 0.5-6 parts by mass.

Description

Thermosetting resin composition, prepreg, build-up board and printed circuit board

The present invention relates to a thermosetting resin composition, a prepreg, a base board, and a printed wiring board suitable for materials such as electronic equipment.

In recent years, in motherboards such as multi-function mobile phone terminals, with the increase in high-speed communication, higher line density, and extremely thin circuit boards, the ratio of the line width (L) to the space (S) of the circuit board [ L/S] also tends to narrow. With such narrowing of L/S, it has gradually become difficult to produce wiring boards with good yield and stability. In addition, in the previous circuit board design, communication failures and the like were considered, and a layer called a "skip layer" without a circuit pattern was provided on some of the layers. Although electronic devices have become highly functional and gradually increase the amount of circuit design and the number of layers of circuit boards, the provision of the aforementioned empty layers has caused the problem of further increasing the thickness of the motherboard.

As a method to improve these problems, it is effective to reduce the relative permittivity of insulating materials used in circuit boards. By reducing the relative permittivity of the insulating material, the impedance control of L/S becomes easy, so it is possible to stably produce the circuit board in a way that the L/S is close to the shape of the current design, and to reduce the voids. Can reduce the number of layers. So for the line The insulating material in the circuit board becomes required to have material characteristics with a relatively small dielectric constant.

In recent years, with the increase in the density of electronic devices, even in motherboards such as mobile phones, which are moving toward thinner and lower prices, materials with a low relative permittivity are required to cope with the thinning. In addition, communication equipment represented by servers, routers, mobile base stations, etc. have also begun to be used in higher frequency fields, and high melting point lead-free solders have also begun to be used in the soldering of electronic parts. Among these substrate materials, materials with low dielectric constant, high glass transition temperature (high Tg), and excellent reflow heat resistance have begun to be required.

In addition, the motherboard used in multi-function mobile phone terminals has increased line density and narrowed pattern width. When connecting layers, it is required to use a small-diameter laser via (laser via). The connection. From the viewpoint of connection reliability, since there are many examples of using hole filling plating, and the connectivity between the inner layer copper and the electroplated copper is very important, it is required to improve the laser processability of the substrate.

After the laser processing of the base material, a step of removing the residue component of the resin (desmear processing step) is generally performed. When the bottom surface and wall surface of the laser drilling hole are de-smeared, and the resin component of the base material is dissolved in a large amount by the de-smudge treatment, the following problems may be caused: The dissolution of the resin may cause the laser There is a concern that the shape of the drilled hole is significantly deformed, and the unevenness of the plating deposit due to the variation of the unevenness of the wall surface. Therefore, it is required: Dissolved by desmear treatment The amount of the resin component of the solution of the substrate, that is, the amount of scum removal, must be an appropriate value.

So far, the following methods have been used to make thermosetting resin compositions with a low relative permittivity: a method containing an epoxy resin with a small relative permittivity, a method of introducing a cyanate group, and a method containing polyphenylene Ether (polyphenylene ether) method, etc. However, simply combining these methods is still difficult to meet various requirements, such as a reduction in relative permittivity, high heat resistance, reliability, and halogen-free. For example, the following resin compositions have been proposed: resin compositions containing epoxy resin (see Patent Document 1); resin compositions containing polyphenylene ether and bismaleimide (see Patent Document 1) 2); A resin composition containing polyphenylene ether and cyanate resin (refer to Patent Document 3); a resin composition containing a styrene-based thermoplastic elastomer and/or cyanuric acid At least one type of allyl ester (see Patent Document 4); a resin composition containing polybutadiene (see Patent Document 5); a resin composition made of polyphenylene ether resin, Polyfunctional maleimide and/or polyfunctional cyanate ester resin and liquid polybutadiene are prereaction (refer to Patent Document 6); a resin composition containing polystyrene Polyether, triallyl cyanurate and/or triallyl isocyanate, etc., and the polyphenylene ether is made by imparting or grafting compounds with unsaturated double bonds ( Refer to Patent Document 7); A resin composition containing the reaction product of polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride, polyfunctional maleimide, etc. (see Patent Document 8).

[Prior Technical Literature] (Patent Document)

Patent Document 1: Japanese Patent Laid-Open No. 58-69046

Patent Document 2: Japanese Patent Laid-Open No. 56-133355

Patent Document 3: Japanese Patent Publication No. 61-18937

Patent Document 4: Japanese Patent Application Publication No. 61-286130

Patent Document 5: Japanese Patent Laid-Open No. 62-148512

Patent Document 6: Japanese Patent Laid-Open No. 58-164638

Patent Document 7: Japanese Patent Application Laid-Open No. 2-208355

Patent Document 8: Japanese Patent Laid-Open No. 6-179734

Although the thermosetting resin compositions described in Patent Documents 1 to 8 show relatively good relative permittivity, there are still many examples that cannot meet the stringent requirements of the market in recent years. In addition, any one of high heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating uniformity (laser processability) is often insufficient, so it is further Room for improvement. In addition, it is also true that the material development made in the past for the viewpoint of plating uniformity is not sufficient.

Therefore, the problem to be solved by the present invention is to provide the following invention: a thermosetting resin composition, a prepreg, a laminate, and a printed wiring board; the thermosetting resin composition has high heat resistance and low relative dielectric system High metal foil adhesion, high glass transition temperature and low thermal expansion, and excellent formability and plating uniformity.

The inventors of the present invention have made diligent studies to solve the above-mentioned problems and found that a thermosetting resin composition can solve the above-mentioned problems, and then completed the present invention. The thermosetting resin composition contains the following components in a specific ratio: "(A ) Maleimide compound with N-substituted maleimide group", "(B) epoxy resin with at least two epoxy groups in one molecule", "(C) has specific structural unit "Copolymer resin", "(D) Dicyandiamine" and (E) Silicon dioxide treated with aminosilane coupling agent. The present invention is based on the above findings.

The present invention relates to the following [1] to [13].

[1] A thermosetting resin composition containing the following components: (A) 15 to 65 parts by mass of a maleimine compound having an N-substituted maleimide group; (B) in one molecule 15-50 parts by mass of epoxy resin with at least two epoxy groups; (C) 10~45 parts by mass of copolymer resin, which has structural units derived from aromatic vinyl compounds and a structure derived from maleic anhydride A unit, where the total of (A)~(C) components is 100 parts by mass; (D) dicyandiamine, which is 0.5-6 parts by mass relative to 100 parts by mass of the aforementioned (A)~(C) components ;and, (E) The silicon dioxide treated with an aminosilane coupling agent is 30 to 70 parts by mass relative to 100 parts by mass of the total of the aforementioned (A) to (C) components.

[2] The thermosetting resin composition according to the above [1], wherein the component (C) is a copolymer resin having a structural unit represented by the following general formula (Ci) and Structural unit represented by formula (C-ii):

In formula (Ci), R ^C1 is a hydrogen atom or an alkyl group with 1 to 5 carbons, and R ^C2 is an alkyl group with 1 to 5 carbons, an alkenyl group with 2 to 5 carbons, and an aryl group with 6 to 20 carbons. , Hydroxy or (meth)acryloyl group, x is an integer of 0-3, but when x is 2 or 3, the plural R ^C2 may be the same or different.

[3] The thermosetting resin composition according to [2] above, wherein, in the general formula (Ci), R ^C1 is a hydrogen atom, and x is 0.

[4] The thermosetting resin composition according to the above [1], wherein, in the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound to the structural unit derived from maleic anhydride, That is, the structural unit derived from the aromatic vinyl compound/the structural unit derived from maleic anhydride, and the molar ratio is 2-9.

[5] The thermosetting resin composition according to the above [1], wherein, in the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound to the structural unit derived from maleic anhydride, That is, the structural unit derived from aromatic vinyl compound/the structural unit derived from maleic anhydride, which is 3-7 in molar ratio.

[6] The thermosetting resin composition according to any one of [1] to [5] above, wherein the weight average molecular weight of the component (C) is 4500 to 18,000.

[7] The thermosetting resin composition according to any one of [1] to [6] above, wherein the weight average molecular weight of the component (C) is 9,000 to 13,000.

[8] The thermosetting resin composition according to any one of [1] to [7] above, wherein the component (A) further has an acidic substituent.

[9] The thermosetting resin composition according to any one of [1] to [8] above, wherein the component (B) is bisphenol F type epoxy resin, phenol novolak type epoxy resin, Cresol novolac type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenylarane type epoxy resin or dicyclopentadiene type epoxy resin.

[10] The thermosetting resin composition according to any one of [1] to [9] above, which further contains (F) a flame retardant.

[11] A prepreg comprising the thermosetting resin composition according to any one of [1] to [10] above.

[12] A laminated board comprising the prepreg described in [11] above and metal foil.

[13] A printed wiring board comprising the prepreg described in [11] above or the laminated board described in [12] above.

Through the present invention, the following inventions can be obtained: thermosetting resin composition, prepreg, laminate and printed wiring board; this thermosetting resin has high heat resistance, low relative permittivity, and high metal foil adhesion , High glass transition temperature and low thermal expansion, and excellent formability and plating uniformity.

Hereinafter, the present invention will be explained in detail.

[Thermosetting resin composition]

The thermosetting resin composition of the present invention is a thermosetting resin composition containing the following components: (A) 15 to 65 parts by mass of a maleimine compound having an N-substituted maleimide group (B) 15-50 parts by mass of epoxy resin with at least two epoxy groups in one molecule; (C) 10~45 parts by mass of copolymer resin, which has structural units derived from aromatic vinyl compounds With a structural unit derived from maleic anhydride, where the total of (A) ~ (C) components is 100 parts by mass; (D) dicyandiamine, which is relative to the total of the aforementioned (A) ~ (C) components 100 The part by mass is 0.5-6 parts by mass; and, (E) The second part is treated with aminosilane coupling agent Silicon oxide is 30 to 70 parts by mass relative to 100 parts by mass of the total of the aforementioned (A) to (C) components.

Hereinafter, each component contained in the thermosetting resin composition of the present invention will be explained in detail.

<(A) Maleimide compound with N-substituted maleimide group>

(A) The maleimide compound having an N-substituted maleimide group is preferably a compound having an acidic substituent from the viewpoint of the rigidity and mechanical strength of the cured product of the thermosetting resin composition . In addition, (A) the weight average molecular weight (Mw) of the maleimine compound having an N-substituted maleimine group is preferably from the viewpoint of solubility to an organic solvent and the viewpoint of mechanical strength 400~3500, more preferably 400~2300, still more preferably 800~2000. 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. More specifically, it is measured by The value measured by the method described in the example.

(A) The maleimide compound having an N-substituted maleimide group, for example, can be produced by reacting the following components: (a1) having at least two N-substituted maleimide in one molecule The maleimide compound of the amide group [hereinafter, abbreviated as the maleimide compound (a1)], (a2) and the monoamine represented by the general formula (a2-1) described later Compounds [hereinafter, abbreviated as monoamine compound (a2)] and (a3) are diamine compounds represented by general formula (a3-1) described later [hereinafter, abbreviated as diamine compound (a3)].

Among the maleimide compound (a1), monoamine compound (a2) and diamine compound (a3), preferably at least one has an acidic substituent, more preferably a monoamine compound (a2) and a diamine compound Any one of (a3) has an acidic substituent, and it is more preferable that the monoamine compound (a2) has an acidic substituent.

(Maleimide compound (a1))

The maleimine compound (a1) is a maleimine compound having at least two N-substituted maleimine groups in one molecule.

Examples of the maleimide compound (a1) include a maleimine compound having an aliphatic hydrocarbon group between any two maleimine groups among a plurality of maleimine groups [ Hereinafter, referred to as aliphatic hydrocarbon group-containing maleimines]; or, between any two maleimines among a plurality of maleimines groups, maleimines having an aromatic hydrocarbon group Imine compound [hereinafter, referred to as maleimide containing aromatic hydrocarbon group]. Among them, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating uniformity, the aromatic hydrocarbon group-containing Malay Imine. The aromatic hydrocarbon group-containing maleimines may contain an aromatic hydrocarbon group between any combination of two arbitrarily selected maleimine groups.

As the maleimide compound (a1), from the viewpoint of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating uniformity, it is relatively It is preferably a maleimide compound having 2 to 5 N-substituted maleimide groups in one molecule, and more preferably has 2 N-substituted maleimine groups in one molecule The base maleimide compound. Also, as the maleimide compound (a1), from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating uniformity , More preferably maleimide containing an aromatic hydrocarbon group represented by any one of the following general formulas (a1-1) to (a1-4), and still more preferably containing the following general formula ( a1-1), (a1-2) or (a1-4), the maleimide of the aromatic hydrocarbon group, particularly preferably one containing the aromatic hydrocarbon group represented by the following general formula (a1-2) Maleimide.

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 with 1 to 5 carbons, an alkylidene with 2 to 5 carbons, -O-, -C(=O)-, -S-, -SS- or sulfur醯基. p, q, and r are each independently an integer of 0-4. s is an integer from 0 to 10.

Examples of the aliphatic hydrocarbon groups having 1 to 5 carbon atoms represented by R ^A1 to R ^A3 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, N-pentyl and so on. As the aliphatic hydrocarbon group, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating uniformity, the carbon number is preferably 1 The aliphatic hydrocarbon group of ~3 is more preferably methyl or ethyl.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^A1 include methylenyl, 1,2-dimethylenyl, 1,3-trimethylenyl, 1,4-tetramethylenyl, 1,5-pentamethylenyl, etc. As the alkylene group, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating uniformity, the carbon number is preferably 1 The alkylene group of ~3 is more preferably a methylenyl group.

Examples of the alkylene group having 2 to 5 carbon atoms represented by X ^A1 include ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, etc. . Among them, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating uniformity, isopropylidene is preferred.

As X ^A1 , among the above options, an alkylene group having 1 to 5 carbon atoms and an alkylene group having 2 to 5 carbon atoms are preferred. The better options are as described above.

p, q, and r are each independently an integer from 0 to 4, ranging from high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, From the viewpoints of low thermal expansion, formability, and plating uniformity, all are preferably an integer of 0 to 2, more preferably all are 0 or 1, and still more preferably all are 0.

s is an integer of 0-10, and from the viewpoint of ease of purchase, it is preferably 0-5, and more preferably 0-3. In particular, the maleimide containing an aromatic hydrocarbon group represented by the general formula (a1-3) is preferably a mixture in which s is 0 to 3.

As the maleimide (a1), specifically, for example, N,N'-vinylbismaleimide, N,N'-hexamethylenemaleimide, bis(4 -Maleimide cyclohexyl) methane, 1,4-bis (maleimide methyl) cyclohexane and other maleimide containing aliphatic hydrocarbon groups; N,N'-(1,3- Phenylene) bismaleimide, N,N'-[1,3-(2-methylphenylene)] bismaleimide, N,N'-[1,3-(4 -Methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleiminophenyl)methane, Bis(3-methyl-4-maleimidphenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane Imine, bis(4-maleimidphenyl) ether, bis(4-maleimidphenyl) sulfide, bis(4-maleimidphenyl) sulfide, bis(4- Maleimidphenyl) ketone, 1,4-bis(4-maleimidphenyl)cyclohexane, 1,4-bis(4-maleimidmethyl)cyclohexane, 1,3-bis(4-maleimide phenoxy)benzene, 1,3-bis(3-maleimide phenoxy)benzene, bis[4-(3-maleimide) Phenoxy)phenyl]methane, bis[4-(4-maleimidphenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidphenoxy) Phenyl]ethane, 1,1-bis[4-(4-maleiminophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleiminophenoxy) Yl)phenyl]ethane, 1,2-bis[4-(4-maleimidephenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimide) Phenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, 2,2-bis[4-(3-maleimide) Phenoxy)phenyl]butane, 2,2-bis[4-(4-maleiminophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimide Iminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimidinphenoxy)phenyl]- 1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-maleimidphenoxy)biphenyl, 4,4-bis(4-maleimidbenzene) Oxy)biphenyl, bis[4-(3-maleiminophenoxy)phenyl]ketone, bis[4-(4-maleiminophenoxy)phenyl]ketone, 2, 2'-bis(4-maleimidphenyl) disulfide, bis(4-maleimidphenyl)disulfide, bis[4-(3-maleimidphenoxy) )Phenyl]sulfide, bis[4-(4-maleiminophenoxy)phenyl]sulfide, bis[4-(3-maleiminophenoxy)phenyl]sulfite , Bis[4-(4-maleimide phenoxy) phenyl] sulfide, bis[4-(3-maleimide phenoxy) phenyl] sulfide, bis[4-(4 -Maleimide phenoxy) phenyl] sulfide, bis[4-(3-maleimide phenoxy) phenyl] ether, bis[4-(4-maleimide phenoxy) Yl)phenyl]ether, 1,4-bis[4-(4-maleiminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-( 4-maleimide phenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimide phenoxy)-α,α- Dimethylbenzyl]benzene, 1,3-bis[4-(3-maleiminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4 -(4-maleimide phenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimide) Aminophenoxy)-3,5-dimethyl-α,α -Dimethylbenzyl]benzene, 1,4-bis[4-(3-maleiminophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl] Benzene, 1,3-bis[4-(3-maleiminophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethane maleate Maleimines containing aromatic hydrocarbon groups such as imines.

Among these, bis(4-maleimidphenyl) methane, bis(maleimidphenyl) methane, bis(maleimidphenyl) methane, Bis(4-maleimidphenyl) sulfide, bis(4-maleimidphenyl) disulfide, N,N'-(1,3-phenylene) bismaleimid Amine, 2,2-bis[4-(4-maleimidphenoxy)phenyl]propane, from the viewpoint of cheapness, bis(4-maleimidphenyl)methane is preferred , N,N'-(1,3-phenylene) bismaleimide, from the viewpoint of solubility in solvents, bis(4-maleiminophenyl)methane is particularly preferred.

The maleimide compound (a1) may be used individually by 1 type, and may use 2 or more types together.

(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 above general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group, and a sulfonic acid group. R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. t is an integer from 1 to 5, u is an integer from 0 to 4, and satisfies 1≦t+u≦5. However, when t is an integer from 2 to 5, a plurality of ^RA4 may be the same or different. In addition, when u is an integer of 2 to 4, a plurality of R ^A5 may be the same or different.

As the acidic substituent represented by R ^A4 , from the viewpoint of solubility and reactivity, a hydroxyl group and a carboxyl group are preferred, and if heat resistance is also considered, a hydroxyl group is more preferred.

t is an integer from 1 to 5. From the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating uniformity, 1 is preferred It is an integer of ~3, 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 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, etc. . As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferred.

Examples of the halogen atom represented by R ^A5 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

u is an integer from 0 to 4. From the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating uniformity, 0 is preferred An integer of ~3 is more preferably an integer of 0-2, and even more preferably 0 or 1, and particularly preferably 0.

As the monoamine compound (a2), from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability and plating uniformity, it is more preferably composed of The monoamine compound represented by the following general formula (a2-2) or (a2-3) is more preferably a monoamine compound represented by the following general formula (a2-2). However, R ^A4 , R ^A5 and u in the following general formula (a2-2) or (a2-3) are the same as the compound in the general formula (a2-1), and preferred examples are also the same.

Monoamine compounds (a2) include monoamine compounds having acidic substituents, such as o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminophenol Benzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc. .

Further, examples of the monoamine compound (a2) include monoamine compounds that do not have an acidic substituent. These monoamine compounds are: aniline, o-methylaniline, m-methylaniline, p-methylaniline, o -Ethylaniline, m-ethylaniline, p-ethylaniline, o-vinylaniline, m-vinylaniline, p-vinylaniline, o-allylaniline, m-allylaniline, p -Allyl aniline, etc.

Among these, monoamine compounds having acidic substituents are preferred; from the viewpoints of solubility and reactivity, m-aminophenol, p-aminophenol, p-aminobenzoic acid, 3,5-Dihydroxyaniline; from the viewpoint of heat resistance, o-aminophenol, m-aminophenol, p- Aminophenol; if the dielectric properties, low thermal expansion and manufacturing cost are also considered, p-aminophenol is more preferred.

The monoamine compound (a2) may be used individually by 1 type, and may use 2 or more types together.

(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 linearly between two amine groups, and still more preferably A diamine compound represented by the following general formula (a3-1).

In formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or -O-. R ^A6 and R ^A7 each independently represent an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, or a sulfonic acid group. v and w are each independently an integer from 0 to 4.

Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms represented by X ^A2 include a methylene group, a vinyl group, a propenyl group, and a propylene group.

X ^{A2 is} preferably a methylenyl group.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A6 and R ^A7 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n-butyl. Pentyl etc. 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, R ^A6 and R ^A7 are a hydroxyl group, a carboxyl group or a sulfonic acid group.

v and w are preferably integers from 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 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, and 4,4'-diamine Diphenylpropane, 2,2'-bis[4,4'-diaminodiphenyl]propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3 ,3'-Diethyl-4,4'-Diaminodiphenylmethane, 3,3'-Dimethyl-4,4'-Diaminodiphenylethane, 3,3'-Di Ethyl-4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3'-di Hydroxy-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro- 4,4'-Diaminodiphenylmethane, 3,3'-Dibromo-4,4'-Diaminodiphenylmethane, 2,2',6,6'-Tetramethylchloro-4 , 4'-diaminodiphenylmethane, 2,2',6,6'-tetrabromo-4,4'-diaminodiphenylmethane, etc. Among them, from the viewpoint of cheapness, 4,4'-diaminodiphenylmethane and 3,3'-diethyl-4,4'-diaminodiphenylmethane are preferred; From the viewpoint of solubility in solvents, 4,4'-diaminodiphenylmethane is more preferable.

The reaction of maleimine (a1), monoamine compound (a2) and diamine compound (a3) is preferably in the presence of an organic solvent, and is more It is preferably carried out by performing the reaction at a reaction temperature of 70 to 200°C for 0.1 to 10 hours.

The reaction temperature is more preferably 70 to 160°C, still more preferably 70 to 130°C, and particularly preferably 80 to 120°C.

The reaction time is more preferably 1 to 6 hours, still more preferably 1 to 4 hours.

(The amount of maleimide (a1), monoamine compound (a2) and diamine compound (a3) used)

In the reaction of maleimine (a1), monoamine compound (a2) and diamine compound (a3), the amount of the three used is preferably: primary amine group equivalent [indicated as -NH ₂ group equivalent] The relationship between the sum of and the maleimide equivalent of maleimide (a1) satisfies the following formula: 0.1≦[maleimide equivalent]/[-NH ₂ equivalent sum]≦10; This primary amine group is a primary amine group possessed by the monoamine compound (a2) and the diamine compound (a3).

By setting [maleimide group equivalent]/[sum of -NH ₂ group equivalent] to 0.1 or more, gelation and heat resistance will not be reduced, and by setting it to 10 or less, it will not It is preferable to reduce the solubility to organic solvents, metal foil adhesion and heat resistance.

From the same point of view, it is more preferable to satisfy: 1≦[maleimide group equivalent]/[-NH ₂ group equivalent sum]≦9, and it is further preferable to satisfy: 2≦[maleimide group Base equivalent]/[Sum of -NH ₂ base equivalent]≦8.

(Organic solvent)

As mentioned above, the reaction of the maleimide (a1), the monoamine compound (a2), and the diamine compound (a3) is preferably carried out in an organic solvent.

As an organic solvent, there is no particular limitation as long as it does not adversely affect the reaction. Examples include alcoholic solvents such as ethanol, propanol, butanol, methyl phenosulfate, butyl phenosulfate, butanediol monomethyl ether; acetone, methyl ethyl ketone, and methyl isobutyl ketone , Ketone solvents such as cyclohexanone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, trimethylbenzene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Nitrogen-containing solvents including amide-based solvents; sulfur-containing solvents such as dimethyl sulfite, including sulfite-based solvents; ester-based solvents such as ethyl acetate and γ-butyrolactone, etc. Among these, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, and ester-based solvents are preferred; from the viewpoint of low toxicity, cyclohexanone, propylene glycol monomethyl ketone, Methyl serosol, γ-butyrolactone; if high volatility is also considered, and it is not easy to remain as a residual solvent when manufacturing prepregs, cyclohexanone, propylene glycol monomethyl ether, dimethyl Dimethylacetamide, particularly preferably dimethylacetamide.

The organic solvent may be used alone or in combination of two or more.

The amount of the organic solvent used is not particularly limited. From the viewpoint of solubility and reaction efficiency, it is relative to 100 parts by mass of the total of maleimine (a1), monoamine compound (a2) and diamine compound (a3) , It is better to set It may be 25 to 1000 parts by mass, more preferably 40 to 700 parts by mass, and still more preferably 60 to 250 parts by mass. With respect to 100 parts by mass of the total of maleimine (a1), monoamine compound (a2), and diamine compound (a3), by setting it to 25 parts by mass or more, it becomes easier to ensure solubility. If it is 1000 parts by mass or less, it is easy to suppress a significant decrease in reaction efficiency.

(Reaction catalyst)

The reaction of the maleimide (a1), the monoamine compound (a2), and the diamine compound (a3) can be carried out in the presence of a reaction catalyst as necessary. Examples of the reaction catalyst include amine-based catalysts such as triethylamine, pyridine, and tributylamine; imidazole-based catalysts such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine.

One kind of reaction catalyst may be used alone, or two or more kinds may be used in combination.

The amount of the reaction catalyst used is not particularly limited, but it is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total of the maleimide (a1), monoamine compound (a2), and diamine compound (a3).

<(B) Epoxy resin with at least two epoxy groups in one molecule>

(B) Epoxy resins having at least two epoxy groups in one molecule (hereinafter sometimes referred to as epoxy resins (B)) include: glycidyl ether type epoxy resins, ring Oxypropyl amine type epoxy resin, glycidyl ester type epoxy resin, etc. Among them, glycidyl ether type epoxy resins are preferred.

The epoxy resin (B) can also be classified into various epoxy resins according to the difference of the main skeleton. Among the above-mentioned types of epoxy resins, it can be further classified into: bisphenol A type epoxy resin, bisphenol Bisphenol type epoxy resins such as F type epoxy resin and bisphenol S type epoxy resin; biphenyl aralkyl phenol type epoxy resin; phenol novolak type epoxy resin, alkyl phenol novolak type epoxy resin, Cresol novolac epoxy resin, naphthol alkyl phenol copolymer novolac epoxy resin, naphthol aralkyl cresol copolymer novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F Novolac type epoxy resin such as novolac type epoxy resin; stilbene type epoxy resin; epoxy resin containing triazabenzene skeleton; epoxy resin containing stilbene skeleton; naphthalene type epoxy resin; anthracene type ring Oxygen resin; triphenylmethane type epoxy resin; biphenyl type epoxy resin; biphenyl arane type epoxy resin; xylene type epoxy resin; alicyclic epoxy resin such as dicyclopentadiene type epoxy resin, etc. .

Among them, from the viewpoints of high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and plating uniformity, bisphenol F type is preferred Epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl arylene type epoxy resin, bicyclic Pentadiene type epoxy resin; from the viewpoint of low thermal expansion and high glass transition temperature, cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin are more preferable Oxygen resin, biphenylarane type epoxy resin, phenol novolak type epoxy resin, more preferably cresol novolak type epoxy resin.

The epoxy resin (B) may be used individually by 1 type, and may use 2 or more types together.

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, particularly preferably 170 to 240 g/eq.

Here, the epoxy equivalent is the mass (g/eq) of the resin per epoxy group, which can be measured in accordance with the method defined by the Japanese Industrial Standards JIS K 7236 (2001). Specifically, it is determined by the following method: using an automatic titration device "GT-200 (model)" manufactured by Mitsubishi Chemical ANALYTECH Co., Ltd., weighing 2 g of epoxy resin in a 200 ml beaker, and dropping 90 ml of nail After the ethyl ketone is dissolved in an ultrasonic cleaner, 10ml of glacial acetic acid and 1.5g of cetyltrimethylammonium bromide are added, and then titrated with a 0.1mol/L perchloric acid/acetic acid solution.

As a commercially available product of epoxy resin (B), cresol novolac type epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Co., Ltd., epoxy equivalent: 205 to 215 g/eq) , Naphthalene epoxy resin "HP-4032 (trade name)" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 152g/eq), biphenyl epoxy resin "YX-4000 (trade name)" (Mitsubishi Chemical Manufactured by Co., Ltd., epoxy equivalent: 186g/eq), dicyclopentadiene-type epoxy resin "HP-7200H (trade name)" (manufactured by DIC Co., Ltd., epoxy equivalent: 280g/eq), etc. In addition, the epoxy equivalent is the value stated in the catalog of the manufacturer of the product.

〈(C) Specific copolymer resin〉

The component (C) is a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride (hereinafter, it may be referred to as a copolymer resin (C)). As an aromatic vinyl compound, styrene, 1-methylstyrene, vinyl toluene, dimethylstyrene, etc. are mentioned, for example. Among them, styrene is preferred.

As the (C) component, a copolymer resin is preferable, and the copolymer resin has a structural unit represented by the following general formula (C-i) and a structural unit represented by the following formula (C-ii).

In formula (Ci), R ^C1 is a hydrogen atom or an alkyl group with 1 to 5 carbons, and R ^C2 is an alkyl group with 1 to 5 carbons, an alkenyl group with 2 to 5 carbons, and an aryl group with 6 to 20 carbons. , Hydroxy or (meth)acryloyl group, x is an integer of 0-3, but when x is 2 or 3, the plural R ^C2 may be the same or different.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^C1 and R ^C2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n-butyl. Pentyl etc. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.

As the alkenyl group having 2 to 5 carbon atoms represented by R ^C2 , for example, allyl group and crotyl group (crotyl) can be mentioned. The alkenyl group is preferably an alkenyl group having 3 to 5 carbon atoms, and 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 biphenyl group. The aryl group is preferably an aryl group having 6 to 12 carbons, and more preferably an aryl group having 6 to 10 carbons.

x is preferably 0 or 1, more preferably 0.

Among the structural units represented by the general formula (Ci), the structural unit represented by the following general formula (Ci-1) is preferred, in which R ^C1 is a hydrogen atom and x is 0, which is derived from styrene The structural unit.

In the copolymer resin (C), the content ratio of the structural unit derived from the aromatic vinyl compound to the structural unit derived from maleic anhydride, that is, the structural unit derived from the aromatic vinyl compound/the structure derived from maleic anhydride The unit, in terms of molar ratio, is preferably 1-9, more preferably 2-9, further preferably 3-8, and particularly preferably 3-7. In addition, the content ratio of the structural unit represented by the aforementioned general formula (Ci) to the structural unit represented by the aforementioned general formula (C-ii), that is, [(Ci)/(C-ii)], in terms of mo The ear ratio meter is similarly preferably 1-9, more preferably 2-9, further preferably 3-8, and particularly preferably 3-7. As long as the molar ratio of the equivalent is 1 or more, and Preferably it is 2 or more, the improvement effect of the dielectric characteristic 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 (Ci) and the structural unit represented by the formula (C-ii) The total content of the structural units represented by) is each preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably substantially 100% by mass.

The weight average molecular weight (Mw) of the copolymer resin (C) is 4500~18000, preferably 5000~18000, more preferably 6000~17000, further preferably 8000~16000, particularly preferably 8000~15000, most preferably 9000 ~13000.

Furthermore, the method of using a copolymer resin of styrene and maleic anhydride to lower the dielectric constant of epoxy resin, if used in printed circuit board materials, will cause impregnation of the substrate and copper foil In the case of insufficient peel strength, there is a general tendency to avoid use. Therefore, although there is generally a tendency to avoid the use of the aforementioned copolymer resin (C), the present invention confirmed the following fact and completed the invention, which is that even if the aforementioned copolymer resin (C) is used, the The component (A) and component (B) are also contained in component (D) described later, and the content of each component is a specific ratio, it can be a thermosetting resin composition that has high heat resistance and low relative Dielectric coefficient, high metal foil adhesion, high glass transition temperature and low thermal expansion, and excellent formability and plating uniformity.

(Method for manufacturing copolymer resin (C))

The copolymer resin (C) can be produced by copolymerizing an aromatic vinyl compound and maleic anhydride.

As the aromatic vinyl compound, as mentioned above, styrene, 1-methylstyrene, vinyl toluene, dimethylstyrene, etc. can be mentioned. These may be used alone or in combination of two or more.

Furthermore, in addition to the aforementioned aromatic vinyl compound and maleic anhydride, it may be copolymerized with various polymerizable components. Examples of various polymerizable components include vinyl compounds such as ethylene, propylene, butadiene, isobutylene, and acrylonitrile; compounds having (meth)acrylic acid groups such as methyl acrylate and methyl methacrylate.

In addition, in the aromatic vinyl compound, substitutions such as allyl, methacrylic, acrylic, and hydroxyl groups can be introduced through Friedel-Crafts reaction or using metal catalysts such as lithium. base.

As the copolymer resin (C), commercially available products can be used. Examples of commercially available products include "SMA (registered trademark) 1000" (styrene/maleic anhydride=1, Mw=5000), "SMA (registered trademark) EF30" (styrene/maleic anhydride=3, Mw=9500), "SMA (registered trademark) EF40" (styrene/maleic anhydride=4, Mw=11000), "SMA (registered trademark) EF60" (styrene/maleic anhydride=6, Mw=11500) , "SMA (registered trademark) EF80" (styrene/maleic anhydride=8, Mw=14400) [the above are made by CRAY VALLEY] etc.

〈(D)Dicyandiamine〉

(D) The component is dicyandiamine (hereinafter, it may be referred to as dicyandiamine (D)).

Dicyandiamide (D) is expressed as H ₂ NC(=NH)-NH-CN, and the melting point is usually 205~215°C, and higher purity dicyandiamine is 207~212°C.

Dicyandiamine (D) is a crystalline substance, and can be orthorhombic or plate-like crystals. Dicyandiamine (D) is preferably one having a purity of 98% or more, more preferably having a purity of 99% or more, and still more preferably having a purity of 99.4% or more.

As dicyandiamine (D), commercially available products can be used, and commercially available products manufactured by the following companies can be used, for example: Japan CARBIDE Industry Co., Ltd., Tokyo Chemical Industry Co., Ltd., KISHIDA Chemical Co., Ltd., NACALAI TESQUE Co., Ltd. etc.

In the present invention, even if chain aliphatic amines, cycloaliphatic amines, and aromatic amines other than dicyandiamine are used instead of dicyandiamine (D), the adhesion and low thermal expansion of the metal foil are not sufficient; The chain aliphatic amines other than dicyandiamine are: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethyldiamine, diethylaminopropylamine, tetraformin, triethanolamine, etc. ; The cyclic aliphatic amines are: isophorone diamine, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, bis(4-amino-3-methyldicyclohexyl)methane , N-aminoethylpiper, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxspiro[5.5]undecane, etc.; these aromatic amines Yes: Xylene diamine, phenylene diamine, diamino diphenyl methane, diamino diphenyl sulfide, etc.

As long as dicyandiamine (D) is used, at least one selected from the group consisting of chain aliphatic amines, cyclic aliphatic amines, and aromatic amines can be used in combination within a range that does not impair the effects of the present invention (however, the combined use These amines are not considered as the (D) component.). When these components are used in combination, relative to 100 parts by mass of dicyandiamine (D), it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 15 parts by mass or less, particularly preferably It is 10 parts by mass or less, and most preferably 5 parts by mass or less.

〈(E)Silica dioxide treated with aminosilane coupling agent〉

In the thermosetting resin composition, in order to reduce the thermal expansion coefficient of the insulating resin layer, it can be implemented by containing an inorganic filler, but in the present invention, it is used in the silicon dioxide as the (E) component Silica treated with aminosilane coupling agent (hereinafter, sometimes referred to as silica (E) treated with aminosilane coupling agent). By making the thermosetting resin composition contain silicon dioxide (E) treated with an aminosilane coupling agent, in addition to the effect of improving low thermal expansion, the following effects can also be obtained: by improving and the aforementioned (A) The adhesion of the component (C) can prevent the silicon dioxide from falling off, so it can prevent the deformation of the laser drill hole shape due to excessive desmear.

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

In the formula (E-1), R ^E1 is an alkyl group having 1 to 3 carbons or an acyl group having 2 to 4 carbons. y is an integer from 0 to 3.

Examples of the alkyl group having 1 to 3 carbon atoms represented by R ^E1 include methyl, ethyl, n-propyl, and isopropyl. Among these, methyl is preferred.

Examples of the acyl group having 2 to 4 carbon atoms represented by R ^E1 include acetyl group, acryl group, and acrylic group. Among them, acetyl is preferred.

The amino silane coupling agent may have one amine group, or two, and may have three or more, and usually one or two amine groups.

As an aminosilane coupling agent with one amino group, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane Silane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, 2-propynyl [3-(trimethoxysilyl) propyl] carbamate Etc., but are not particularly limited to these aminosilane coupling agents.

As an aminosilane coupling agent having two amino groups, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl) -3-Aminopropyltrimethoxysilane, 1-[3-(trimethoxysilyl)propyl]urea, 1-[3-(triethoxysilyl)propyl]urea, etc., but not Especially limited to these aminosilane coupling agents.

If silicon dioxide treated with other coupling agents is used instead of silicon dioxide (E) treated with aminosilane coupling agents, the adhesion to the aforementioned (A) ~ (C) components will be reduced, and two Silicon oxide tends to fall off easily, and the effect of suppressing the deformation of the laser drill hole shape caused by excessive desmearing will be weakened. Such other coupling agents are, for example, epoxy silane coupling agents. , Phenyl silane coupling agent, alkyl silane coupling agent, alkenyl silane coupling agent, alkynyl silane coupling agent, haloalkyl silane coupling agent, silicone coupling agent, hydrogen silane coupling agent, Silazane coupling agent, alkoxysilane coupling agent, chlorosilane coupling agent, (meth)acrylic silane coupling agent, aminosilane coupling agent, triisocyanate silane coupling agent, urea silane Coupling agent, mercaptosilane coupling agent, thioether silane coupling agent, isocyanate silane coupling agent, etc.

As long as the silica (E) treated with an aminosilane coupling agent is used, the silica (E) treated with the above-mentioned other coupling agents can also be used in combination without losing the effect of the present invention. When the silica treated with the above other coupling agent is used in combination, the silica (E) treated with the aminosilane coupling agent is preferably 50 parts by mass relative to 100 parts by mass of the silica (E) treated with the other coupling agent Hereinafter, it is more preferably 30 parts by mass or less, still more preferably 15 parts by mass or less, particularly preferably 10 parts by mass or less, and most preferably 5 parts by mass or less.

As silicon dioxide that can be used for silicon dioxide (E) treated with aminosilane coupling agents, for example, precipitated silicon dioxide with high moisture content produced by a wet method, and precipitated silicon dioxide produced by a dry method almost not Dry process silica containing bound water. As dry-process silica, further, depending on the manufacturing method, broken silica, fumed silica, and fused silica (fused spherical silica) can be cited. Silica is preferably molten silica from the viewpoint of low thermal expansion and high fluidity when filled in a resin.

The average particle size of the silicon dioxide is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 6 μm, still more preferably 0.1 to 3 μm, particularly preferably 1 to 3 μm. By setting the average particle size of silicon dioxide to 0.1μm or more, the fluidity during high filling can be ensured well. Moreover, by setting it to 10μm or less, it is possible to reduce the probability of mixing large particles and suppress the occurrence of large particles. The occurrence of defects. Here, the so-called average particle size refers to the particle size at the point corresponding to 50% of the volume when the total volume of the particles is set to 100% and the cumulative frequency distribution curve is obtained from the particle size. The measurement is performed by a particle size distribution measuring device of the laser diffraction scattering method.

And a specific surface area of silicon dioxide, preferably from 4cm ² / g, more preferably is 4 ~ 9cm ² / g, further preferably is 5 ~ 7cm 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 the component (F). Here, although the aforementioned dicyandiamine (D) also has an effect as a flame retardant, in the present invention, the component (F) does not include the aforementioned dicyandiamine (D).

Examples of flame retardants include halogen-containing flame retardants containing bromine or chlorine; phosphorus flame retardants; guanidine sulfonate, melamine sulfate, poly Nitrogen-based flame retardants such as melamine phosphate and melamine cyanurate; phosphazene-based flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame-retardants such as antimony trioxide, etc. Among these, phosphorus-based flame retardants are preferred.

As phosphorus-based flame retardants, there are inorganic phosphorus-based flame retardants and organic phosphorus-based flame retardants.

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 phosphides such as amide phosphate; phosphoric acid; phosphine Oxide etc.

Examples of organic phosphorus-based flame retardants include aromatic phosphoric acid esters, 1-substituted phosphonic acid diesters, 2-substituted hypophosphites, metal salts of 2-substituted hypophosphorous acids, organic nitrogen-containing phosphides, and cyclic organic Phosphate, phosphorus-containing phenol resin, etc. Among these, aromatic phosphate esters and metal salts of 2-substituted hypophosphorous acid are preferred. Here, as the metal salt, any of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, and zinc salt is preferred, and aluminum salt is preferred. In addition, among organic phosphorus-based flame retardants, aromatic phosphates are more preferable.

Examples of aromatic phosphate esters include triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl bis-2,6-xylenyl phosphate, and isophthalic acid. Phenol bis (diphenyl phosphate), 1,3-phenylene bis (di-2,6-diphenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylene bis (Diphenyl phosphate) and so on.

Examples of monosubstituted phosphonic acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butene) phenylphosphonate, and the like.

Examples of 2-substituted hypophosphites include phenyl diphenyl hypophosphite, methyl diphenyl hypophosphite, and the like.

Examples of metal salts of 2-substituted hypophosphorous acid include metal salts of dialkyl hypophosphite, metal salts of diallyl hypophosphite, metal salts of divinyl hypophosphite, and metal salts of diaryl hypophosphite. . These metal salts, as mentioned above, are preferably any one of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, and zinc salt.

Examples of organic nitrogen-containing phosphorus compounds include phosphazene compounds such as bis(2-allylphenoxy)phosphazene and xylenol phosphazene; melamine phosphate, melamine pyrophosphate, and polyphosphoric acid Melamine ester, melam polyphosphate, etc.

Examples of the cyclic organophosphate include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) , 10-(2,5-Dihydroxyphenyl)-9,10-dihydro-9-oxo-10-phosphophenanthrene-10-oxide, etc.

Among these, at least one selected from the group consisting of aromatic phosphates, metal salts of di-substituted hypophosphorous acid, and cyclic organophosphorus compounds is preferred, and aromatic phosphates are more preferred.

In addition, the aforementioned aromatic phosphate is preferably an aromatic phosphate represented by the following general formula (F-1) or (F-2), and the aforementioned metal salt of 2-substituted hypophosphorous acid is preferably composed of The metal salt of 2-substituted hypophosphorous acid represented by general formula (F-3).

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 independently an integer of 0 to 4.

R ^F6 and R ^F7 are each independently an alkyl group having 1 to 5 carbons or an aryl group having 6 to 14 carbons. M is lithium atom, sodium atom, potassium atom, calcium atom, magnesium atom, aluminum atom, titanium atom, zinc atom. j is an integer from 1 to 4.

Examples of the alkyl groups having 1 to 5 carbon atoms represented by R ^F1 to R ^F5 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n-butyl. Pentyl etc. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the halogen atoms represented by R ^F1 to R ^F5 include fluorine atoms and the like.

e and f are preferably an integer of 0-2, more preferably 2. g, h and i are preferably an integer of 0-2, 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 alkyl groups 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 phenyl, naphthyl, biphenyl, and anthryl. The aromatic hydrocarbon group is preferably an aryl group having 6 to 10 carbon atoms.

j is equal to the valence of the metal ion, that is, the type of corresponding M varies from 1 to 4.

As M, an aluminum atom is preferable. Furthermore, when M is an aluminum atom, j is 3.

(Content of each ingredient)

In the thermosetting resin composition, the content of (A) to (D) components is 15 to 65 parts by mass relative to the total of (A) to (C) 100 parts by mass, (A) component is 15 to 65 parts by mass, (B) The component is 15-50 parts by mass, the (C) component is 10 to 45 parts by mass, the (D) component is 0.5-6 parts by mass, and the (E) component is 30-70 parts by mass.

When the (A) component is 15 parts by mass or more relative to 100 parts by mass of the total of the (A) to (C) components, high heat resistance, low relative permittivity, high glass transition temperature, and low thermal expansion can be obtained. On the other hand, by being 65 parts by mass or less, the fluidity and moldability of the thermosetting resin composition are good.

When the (B) component is 15 parts by mass or more relative to the total 100 parts by mass of the (A) to (C) components, high heat resistance, high glass transition temperature, and low thermal expansion can be obtained. On the other hand, by being 50 parts by mass or less, It has high heat resistance, low relative permittivity, high glass transition temperature and low thermal expansion.

When the (C) component is 10 parts by mass or more relative to the total 100 parts by mass of the (A) to (C) components, high heat resistance and low relative permittivity can be obtained. On the other hand, by being 45 parts by mass or less, high heat resistance, high metal foil adhesion, and low thermal expansion can be obtained.

When the (D) component is 0.5 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), high metal foil adhesion and excellent low thermal expansion can be obtained. On the other hand, by 6 mass parts Parts below, high heat resistance can be obtained.

When the (E) component is 30 parts by mass or more relative to the total 100 parts of the (A) to (C) components, excellent low thermal expansion can be obtained. On the other hand, when it is 70 parts by mass or less, heat resistance can be obtained The fluidity and moldability of the thermosetting resin composition are good.

With the content of (A) to (E) in the thermosetting resin composition within the above range, a thermosetting resin composition for multilayer printed wiring boards can be obtained, which has high reliability and is High heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, low thermal expansion, and excellent formability and plating uniformity.

In addition, when the thermosetting resin composition of the present invention contains the component (F), the content is higher than 100 parts by mass of the total of the components (A) to (C) from the standpoint of flame retardancy. It is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass. In particular, when a phosphorus-based flame retardant is used as the (F) component, from the point of view of flame retardancy, it is relative to (A) to (C) The sum of the components is 100 parts by mass, and the content of phosphorus atoms is preferably 0.1 to 3 parts by mass, more preferably 0.2 to 3 parts by mass, and still more preferably 0.5 to 3 parts by mass.

(Other ingredients)

The thermosetting resin composition of the present invention may contain other components such as additives and organic solvents as needed within a range that does not impair the effects of the present invention. These components may be contained alone or in two or more kinds.

(additive)

Examples of additives include hardeners, hardening accelerators, colorants, antioxidants, reducing agents, ultraviolet absorbers, fluorescent brighteners, adhesion promoters, organic fillers, and the like. These components may be used individually by 1 type, and may use 2 or more types together.

(Organic solvents)

The thermosetting resin composition of the present invention may contain an organic solvent from the viewpoint of easy handling by dilution and the viewpoint of easy production of a prepreg described later. In this specification, the thermosetting resin composition containing an organic solvent may be referred to as a resin varnish.

The organic solvent is not particularly limited, and examples thereof include methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, and triethylene glycol monomethyl Alcohol solvents such as ether, triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, and dipropylene glycol monopropyl ether; including amide series A solvent containing nitrogen atoms, the amide solvent is acetone, methyl ethyl Ketone solvents such as ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and trimethylbenzene; formamide, N-methylformamide, N, N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.; a sulfur atom-containing solvent containing a sulfite-based solvent, the sulfite-based solvent is dimethylsulfide Ester solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, etc.

Among them, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, and nitrogen-containing solvents are preferred, and methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl ethyl ketone are more preferred. Gycerol and propylene glycol monomethyl ether are more preferably methyl ethyl ketone and methyl isobutyl ketone, and particularly preferably methyl ethyl ketone.

An organic solvent may be used individually by 1 type, and may use 2 or more types together.

The content of the organic solvent in the thermosetting resin composition of the present invention may be as long as the thermosetting resin composition can be appropriately adjusted to a degree that is easy to handle, and as long as the coatability of the resin varnish is within a good range, There is no particular limitation. The solid content concentration (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 50~80% by mass.

[Prepreg]

The present invention also provides a prepreg containing the aforementioned thermosetting resin composition.

The prepreg of the present invention can be produced by impregnating or coating the aforementioned thermosetting resin composition on a sheet-like reinforcing base material, and then semi-curing (B-staged) by heating or the like.

As the sheet-like reinforcing base material of the prepreg, known base materials can be used, and these base materials are used in various laminated sheets for electrical insulating materials. As the material of the sheet-like reinforcing substrate, examples include: natural fibers such as paper and cotton linter; inorganic fibers such as glass fibers and asbestos; polyaramide, polyimide, polyvinyl alcohol, polyester, tetrafluoroethylene, and Organic fibers such as acrylic; and, mixtures of these, etc. Among them, from the viewpoint of flame retardancy, glass fiber is preferred. Examples of glass fibers include: glass fiber woven fabrics formed by bonding woven fabrics or short fibers with organic adhesives. The woven fabrics or short fibers are made of E glass, C glass, D glass, S glass, etc.; Glass fiber and cellulose fiber are blended into glass fiber, etc. It is better to use glass cloth made of E glass.

Such sheet-like reinforcing substrates, for example, have the following shapes: woven fabric, non-woven fabric, roving, chopped strand mat, or surfacing mat. Furthermore, the material and shape can be selected according to the purpose or performance of the target molded article, and one kind can be used alone, or two or more materials and shapes can be combined as required.

As a method of impregnating or applying the thermosetting resin composition to the sheet-shaped reinforcing substrate, the subsequent hot melt method or solvent method is preferred.

The hot-melt method is the following method in which no organic solvent is contained in the thermosetting resin composition: (1) The composition is temporarily applied to peel off the composition A method of coating paper with good properties and then laminating it on a sheet-like reinforcing substrate; or (2) a method of directly coating the sheet-shaped reinforcing substrate with a die coater.

On the other hand, the solvent method is a method of preparing a varnish by containing an organic solvent in a thermosetting resin composition, and then immersing a flaky reinforcing base material in the varnish to impregnate the varnish in the flaky reinforcing base Afterwards, dry.

The thickness of the flaky reinforcing substrate is not particularly limited. For example, about 0.03 to 0.5 mm can be used. From the viewpoints of heat resistance, moisture resistance, and processability, it is preferable to use a silane coupling agent or the like for surface treatment. It is made by mechanically performing open fiber processing. After impregnating or coating the thermosetting resin composition on the substrate, it is usually preferable to heat and dry at a temperature of 100 to 200° C. for 1 to 30 minutes to perform semi-curing (B) to obtain The prepreg of the present invention.

The obtained prepreg can be used as one sheet, or as needed, it is preferable to overlap 2-20 sheets for use.

[Laminates]

The laminated board of the present invention contains the aforementioned prepreg. For example, it can be manufactured by the following method: using one piece of the aforementioned prepreg or stacking 2-20 pieces as needed, and arranging metal foils on one or both sides of the prepreg to perform lamination molding . In addition, the laminated board formed by disposing metal foil is sometimes called a metal-clad laminated board.

The metal of the metal foil is not particularly limited as long as it can be used for electrical insulating materials. From the viewpoint of conductivity, copper, Gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements, more preferably copper, aluminum, and still more preferably copper.

As the forming conditions of the laminated board, a known forming technique of a laminated board for electrical insulating materials and a multilayer board can be used. For example, it can be molded in the following manner: using multi-stage pressing, multi-stage vacuum pressing, continuous forming, hot pressing (Autoclave) molding machine, etc., molding at a temperature of 100 to 250°C, a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours.

In addition, the prepreg of the present invention and the printed wiring board for the inner layer can be combined and laminated to form 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, particularly preferably 5 to 30 μm.

Furthermore, it is preferable to form the electroplated layer by electroplating the metal foil.

The metal of the plating layer is not particularly limited as long as it is a metal that can be used for plating. The metal of the plating layer is preferably selected from copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements .

The electroplating method is not particularly limited, and well-known methods such as electrolytic plating and electroless plating can be used.

[Printed Circuit Board]

The present invention also provides a printed wiring board which contains the aforementioned prepreg or the aforementioned laminate.

The printed wiring board of the present invention can be manufactured by performing circuit processing on the metal foil of a metal-clad laminate. Circuit processing can be performed, for example, by forming a resist pattern on the surface of the metal foil, removing unnecessary parts of the metal foil by etching, and peeling off the resist pattern, and then forming it by a drill. The necessary through holes (through holes), and then after the resist pattern is formed again, electroplating for conducting the through holes is performed, and finally the resist pattern is stripped off. On the surface of the printed wiring board obtained after performing this operation, further, the above-mentioned metal-clad laminate is laminated under the same conditions as the above, and further, the circuit processing is performed in the same manner as the above, and a multilayer can be formed Printed circuit board. At this time, it is not necessary to form a through hole, and a through hole (via hole) may be formed, and a through hole and a through hole may also be formed. Such multi-layering can implement the necessary number of pieces.

[Example]

Then, the following embodiments are used to illustrate the present invention in detail, but these embodiments are not intended to limit the present invention in any case. Using the thermosetting resin composition in the present invention, a prepreg was produced and a copper-clad laminate was further produced, and then the produced copper-clad laminate was evaluated. The evaluation method is shown below.

[Evaluation method]

<1. Heat resistance (heat resistance of reflow solder)>

Using the 4-layer copper-clad laminate produced in each example, set the maximum reach temperature to 266°C, spread the 4-layer copper-clad laminate in a constant temperature bath environment of 260°C or higher for 30 seconds and set it to After one cycle, the number of cycles until the expansion of the substrate can be confirmed visually is determined. The greater the number of cycles, the better the heat resistance.

〈2. Relative permittivity (Dk)〉

A network analyzer (NETWORK ANALYZER) "8722C (model)" (manufactured by Hewlett-Packard Company) was used to measure the relative permittivity of copper-clad laminates on both sides at 1 GHz by the three-layer structure linear line resonance method. The size of the test piece is 200mm×50mm×0.8mm thick, and by etching the center of one side of a two-sided copper-clad laminate to form a straight line with a width of 1.0mm (linear length 200mm), and the entire back surface The ground leaves copper to form a ground layer. One side of the other two-sided copper-clad laminate is etched entirely, and the back side is used as a grounding layer. The two copper-clad laminates on both sides are overlapped so that the ground layer is set to the outside to form a strip line. The measurement is carried out at 25°C.

The smaller the relative permittivity, the better.

〈3. Metal foil adhesion (peel strength of copper foil)〉

Metal foil adhesion can be evaluated by copper foil peel strength. The double-sided copper-clad laminate produced in each example was immersed in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.) to form a copper foil with a width of 3 mm to produce an evaluation substrate. Use autograph "AG-100C (model)" (Shimadzu Corporation Co., Ltd.) to measure the peel strength of copper foil. The larger the value, the better the adhesion of the metal foil.

〈4. Glass transition temperature (Tg)〉

The double-sided copper-clad laminate produced in each example was immersed in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.) to produce a 5mm square evaluation of the copper foil removed Then use the TMA (Thermal Mechanical Analysis) test device "Q400EM (model)" (manufactured by TA Instruments) to observe and evaluate the thermal expansion characteristics of the substrate in the surface direction (Z direction) at 30 to 260°C, and determine the amount of expansion The inflection point of is set as the glass transition temperature.

〈5. Low thermal expansion〉

The double-sided copper-clad laminates produced in each example were immersed in a copper etching solution "ammonium persulfate (APS)" (manufactured by ADEKA Co., Ltd.) to produce a mm square with the copper foil removed After evaluating the substrate, a TMA test device "Q400EM (model)" (manufactured by TA Instruments) was used to measure the thermal expansion coefficient (linear expansion coefficient) in the surface direction of the evaluation substrate. Furthermore, in order to remove the original thermal stress (heat strain) of the sample, repeat the cycle of heating-cooling twice, and then measure the thermal expansion coefficient [ppm/℃] in the 30~260℃ in the second temperature change graph. , As an index of low thermal expansion. The smaller the value, the better the low thermal expansion. Furthermore, in the table, the coefficient of thermal expansion is divided into the coefficient of thermal expansion in less than Tg (labeled as "<Tg") and the coefficient of thermal expansion in excess of Tg (labeled as ">Tg").

(Measurement conditions)

1 ^st Run: Room temperature→210°C (heating rate 10°C/min)

2 ^nd Run: 0℃→270℃ (heating rate 10℃/min)

Copper-clad laminates have been further reduced in thickness, and the thinning of prepregs constituting the copper-clad laminates has also been studied. Since the thinned prepreg becomes easy to warp, the characteristic of less warpage of the prepreg during heat treatment is required. In order to reduce the warpage, it is effective to reduce the coefficient of thermal expansion in the plane direction of the base material.

〈6. Coating uniformity (laser processability)〉

Laser drilling was performed on the 4-layer copper-clad laminates produced in each of the examples in the following way: using the laser machine "LC-2F21B/2C (model)" (Hitachi Via Machinery Co., Ltd.), the target aperture It is 80μm, with Gaussian beams and cyclic mode, the pulse period is 15μs×1 time and 7μs×4 times in the copper direct method.

Regarding the obtained laser-drilled substrate, the desmear treatment is performed in the following manner: Swelling Dip Securiganth P (trade name) (manufactured by ATTO Technology Japan Co., Ltd.) is used at 70°C. 5 Use the roughening solution "Dozing Securiganth P500J (trade name)" (manufactured by Atotech Japan Co., Ltd.) at 70°C for 9 minutes, and use the neutralizing solution "Reduction conditoner Securiganth P500 (trade name)" at 40°C for 5 minutes . After that, electroplating is performed on the laser-processed substrate in the following manner: electroless plating solution "brigand MSK-DK (trade name)" (manufactured by Atotech Japan Atotech Japan Co., Ltd.) at 30°C for 20 minutes, and The electrolytic plating solution "Cupracid HL (trade name)" (manufactured by Atotech Japan Co., Ltd.) was carried out at 24°C and 2A/dm ² for two hours.

Cross-sectional observation of the obtained laser-drilled substrate was carried out to confirm the plating uniformity. As an evaluation method of plating uniformity, the difference between the plating thickness at the upper part of the laser hole and the plating thickness at the bottom of the laser hole is less than 10% of the plating thickness at the upper part of the laser hole as the better depositability. , In 100 holes, find the ratio (%) of holes included in the range.

<7. Formability>

The 4-layer copper-clad laminate produced in each example is used as the embedding property of the resin after removing the outer layer of copper. Visually confirm whether there are pores and blurs in the 340×500mm surface. It is an indicator of formability. The absence of voids and stains shows that the moldability is good.

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

(A) Component: A solution of the maleimide compound (A) produced in Production Example 1 below was used.

[Manufacturing Example 1]

Into a reaction vessel with a volume of 1L, 19.2g of 4,4'-diaminodiphenylmethane, 174.0g of bis(4-maleiminophenyl)methane, 6.6g of p-aminophenol and dimethyl 330.0 g of methylacetamide, reacted at 100°C for 2 hours to obtain a dimethylacetamide solution of maleimide compound (A) (Mw=1370), which is used as component (A); this container Equipped with thermometer, stirring device and moisture meter with reflux cooling tube; The maleimide compound (A) has an acidic substituent and an N-substituted maleimide group.

In addition, the above-mentioned weight average molecular weight (Mw) is converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve uses standard polystyrene: TSK standard POLYSTYRENE (Type: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [TOSOH Made by Co., Ltd.], approximated by the cubic equation. The conditions of GPC are shown below.

[Device]

Pump: Type L-6200 [manufactured by Hitachi Advanced Technology Co., Ltd.]

Detector: L-3300 RI [manufactured by Hitachi Advanced Technology Co., Ltd.]

Chromatograph: L-655A-52 [manufactured by Hitachi Advanced Technology Co., Ltd.]

Column: TSK gel SuperHZ2000+TSK gel SuperHZ2300 (all manufactured by TOSOH Co., Ltd.)

Column size: 6.0×40mm (guard column), 7.8×300mm (pipe column)

Eluent: Tetrahydrofuran

Sample concentration: 20mg/5mL

Injection volume: 10μm

Flow rate: 0.5mL/min

Measuring temperature: 40℃

(B) Ingredient: Cresol novolac type epoxy resin "EPICLON (registered trademark) N-673" (manufactured by DIC Co., Ltd.)

(C-1) Ingredients: "SMA (registered trademark) EF40" (styrene/maleic anhydride=4, Mw=11000, manufactured by CRAY VALLEY)

(C-2) Ingredients: "SMA (registered trademark) 3000" (styrene/maleic anhydride=2, Mw=7500, manufactured by CRAY VALLEY)

(C-3) Ingredients: "SMA (registered trademark) EF80" (styrene/maleic anhydride=8, Mw=14400, manufactured by CRAY VALLEY)

(C-4) Ingredients: "SMA (registered trademark) 1000" (styrene/maleic anhydride=1, Mw=5000, manufactured by CRAY VALLEY)

(D) Ingredient: Dicyandiamine (manufactured by CARBIDE Industry Co., Ltd.)

(E) Ingredient: "Megasil 525 ARI (trade name)" (Molten silica treated with aminosilane coupling agent, average particle size: 1.9μm, specific surface area 5.8m ² /g, Sibelco Japan Co., Ltd. Company manufacturing)

Inorganic filler: "F05-30 (trade name)" (untreated crushed silica, average particle size: 4.2μm, specific surface area 5.8m ² /g, manufactured by Fukushima Ceramics Co., Ltd.)

(F) Ingredient: "PX-200 (trade name)" (aromatic phosphate ester (refer to the following structural formula), manufactured by Dahachi Chemical Industry Co., Ltd.)

[Examples 1 to 13, Comparative Examples 1 to 11]

The above-mentioned components are prepared according to the following Tables 1 to 5 (However, when it is a solution, the solid content conversion amount is shown.), and the methyl group is added so that the non-volatile content of the solution becomes 65 to 75% by mass Ethyl ketone was prepared into the thermosetting resin composition of each example and each comparative example.

Each obtained thermosetting resin composition was impregnated in a glass fiber cloth (0.1 mm) of IPC specification #3313, and dried at 160°C for 4 minutes to obtain a prepreg.

A copper foil of 18μm "3EC-VLP-18 (trade name)" (manufactured by Mitsui Metals Co., Ltd.) was laminated on both sides of a stack of 8 pieces of this prepreg, at a temperature of 190°C and a pressure of 25kgf/cm ² ( 2.45MPa), heat and press forming for 90 minutes to produce a double-sided copper-clad laminate with a thickness of 0.8mm (eight pieces of prepreg), and use the copper-clad laminate to measure and evaluate the relative Dielectric coefficient, metal foil adhesion, glass transition temperature (Tg) and low thermal expansion.

On the other hand, using a piece of the aforementioned prepreg, an 18μm copper foil "YGP-18 (trade name)" (manufactured by Nippon Electrolytic Co., Ltd.) is laminated on both sides at a temperature of 190°C and a pressure of 25kgf/cm ² (2.45MPa ), heat and press molding for 90 minutes to produce a double-sided copper-clad laminate with a thickness of 0.1mm (one piece of prepreg), and then perform inner layer adhesion treatment on both copper foil surfaces (using "BF treatment liquid" (Manufactured by Hitachi Chemical Co., Ltd.)), on both sides of a prepreg with a thickness of 0.05mm, layer 18μm copper foil "YGP-18 (trade name)" (manufactured by Nippon Electrolytic Co., Ltd.), Heat and press molding was performed at 190°C and a pressure of 25 kgf/cm ² (2.45 MPa) for 90 minutes to produce a 4-layer copper-clad laminate. Using this four-layer copper-clad laminate, evaluations of heat resistance, plating uniformity, and formability were performed in accordance with the aforementioned method.

The results are shown in Tables 1 to 5.

*¹：磷原子換算量。

* ¹ : Phosphorus atom conversion amount.

In the examples, the heat resistance of the reflow solder reached 10 cycles or more above the required heat resistance level, low relative permittivity, high metal foil adhesion, high glass transition temperature, and low thermal expansion. In addition, it was confirmed that the glass fiber cloth oozes from the wall surface or has a moderately roughened shape, and that it has good plating uniformity. In the moldability, the resin has good embedding properties, and no abnormalities such as stains and voids are found. Among them, in Examples 1 to 10, compared with Examples 11 to 13, the relative permittivity and the adhesion of the metal foil are better, and other characteristics are also stably exhibited.

On the other hand, in Comparative Example 1 in which the content of component (A) is 10 parts by mass, the results of heat resistance, relative permittivity, glass transition temperature, and thermal expansion coefficient are not sufficient, and the content of component (A) is The 70 parts by mass of Comparative Example 2 had insufficient moldability due to the increased viscosity of the thermosetting resin composition. In Comparative Example 3 in which the content of the component (B) is 10 parts by mass, the heat resistance is significantly lowered, the glass transition temperature is lowered, and the thermal expansion coefficient is improved. In Comparative Example 4 in which the content of the component (B) is 60 parts by mass, the heat resistance is significantly lowered, the glass transition temperature is lowered, and the relative permittivity and thermal expansion coefficient are further improved. (C) Comparative Example 5 in which the content of the component is 5 parts by mass has a decrease in heat resistance and an increase in the relative dielectric constant. Comparative Example 6 in which the content of the component (C) is 50 parts by mass, heat resistance and The decrease in the adhesion of the metal foil becomes significant, and the coefficient of thermal expansion also increases. In Comparative Example 7 in which the content of the component (E) is 20 parts by mass, the thermal expansion coefficient is increased, and in Comparative Example 8 in which the content of the component (E) is 80 parts by mass, the moldability becomes insufficient. (D) Comparative Example 9 in which the content of the component is 0.2 parts by mass has reduced metal foil adhesion, and Comparative Example 10 in which the content of the (D) component is 8 parts by mass has deteriorated heat resistance.

In addition, in Comparative Example 11, where silicon dioxide that has not been treated with an aminosilane coupling agent was used as an inorganic filler, the amount of scum removal increased, and the unevenness of the laser hole wall and the exudation of the glass fiber cloth would become more severe. The tendency of large hole shape, and the plating uniformity is greatly reduced.

[Industrial availability]

The prepreg containing the thermosetting resin composition of the present invention and the laminated board containing the prepreg have high heat resistance, low relative permittivity, high metal foil adhesion, and high glass transition temperature It has low thermal expansion and excellent formability and plating uniformity, so it is useful as a printed wiring board for electronic equipment.

Claims (12)

A thermosetting resin composition containing the following components: (A) 15-65 parts by mass of maleimide compound having N-substituted maleimide group; (B) having at least two parts in one molecule 15-50 parts by mass of epoxy resin of each epoxy group; (C) 10~45 parts by mass of copolymer resin, which has structural units derived from aromatic vinyl compounds and structural units derived from maleic anhydride, wherein , The total of (A) ~ (C) components is 100 parts by mass; (D) dicyandiamine, which is 0.5-6 parts by mass relative to 100 parts by mass of the aforementioned (A) ~ (C) components; and, (E) Silica treated with an aminosilane coupling agent, which is 30 to 70 parts by mass relative to 100 parts by mass of the total of components (A) to (C); in the thermosetting resin composition, the aforementioned The component (A) is obtained by reacting the following components: (a1) a maleimide compound having at least two N-substituted maleimide groups in one molecule, and (a2) is represented by the following general formula ( The monoamine compound represented by a2-1) and (a3) the diamine compound represented by the following general formula (a3-1),

In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxyl group and a sulfonic acid group, R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, t is an integer of 1 to 5, u It is an integer from 0 to 4, and satisfies 1≦t+u≦5. However, when t is an integer from 2 to 5, multiple R ^A4 may be the same or different, and when u is an integer from 2 to 4 , A plurality of R ^A5 can be the same or different;

In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group with 1 to 3 carbons or -O-, and R ^A6 and R ^A7 each independently represent an alkyl group with 1 to 5 carbons, a halogen atom, a hydroxyl group, The carboxyl group or the sulfonic acid group, v and w, are each independently an integer of 0-4. The thermosetting resin composition according to claim 1, wherein the component (C) is a copolymerized resin having a structural unit represented by the following general formula (Ci) and the following formula (C- ii) The structural unit indicated:

In the general formula (Ci), R ^C1 is a hydrogen atom or an alkyl group with 1 to 5 carbons, and R ^C2 is an alkyl group with 1 to 5 carbons, an alkenyl group with 2 to 5 carbons, and an aromatic group with 6 to 20 carbons. X is an integer of 0 to 3, but when x is 2 or 3, a plurality of R ^C2 may be the same or different. The thermosetting resin composition according to claim 2, wherein in the aforementioned general formula (Ci), R ^C1 is a hydrogen atom, and x is zero. The thermosetting resin composition according to claim 1, wherein, in the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound to the structural unit derived from maleic anhydride is derived from The structural unit of the aromatic vinyl compound/the structural unit derived from maleic anhydride is 2-9 in molar ratio. The thermosetting resin composition according to claim 1, wherein, in the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound to the structural unit derived from maleic anhydride is derived from The structural unit of the aromatic vinyl compound/the structural unit derived from maleic anhydride is 3-7 in molar ratio. The thermosetting resin composition according to any one of claims 1 to 5, wherein the weight average molecular weight of the component (C) is 4500 to 18000. The thermosetting resin composition according to any one of claims 1 to 5, wherein the weight average molecular weight of the component (C) is 9,000 to 13,000. Thermosetting resin as described in any one of claims 1 to 5 Composition, wherein the aforementioned component (B) is bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, and biphenyl Type epoxy resin, biphenylarane type epoxy resin or dicyclopentadiene type epoxy resin. The thermosetting resin composition according to any one of claims 1 to 5, which further contains (F) a flame retardant. A prepreg containing the thermosetting resin composition according to any one of claims 1 to 9. A laminated board comprising the prepreg described in claim 10 and metal foil. A printed circuit board comprising the prepreg described in claim 10 or the laminated board described in claim 11.