JP2011052184A - Thermosetting insulating resin composition and insulating film with substrate using the same, prepreg, laminated board, and multilayer printed circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting insulating resin composition of a low thermal expansion property, with a high glass transition temperature and excellent heat resistance, an insulating film with a substrate using the same, a prepreg, a laminated board, and a multilayer printed circuit board. <P>SOLUTION: The thermosetting insulating resin composition includes (A) a curing agent having a sulfur atom in the principal molecular chain, and an acidic substituent and an N-substituted maleimide group obtained by reacting (a) a diamine compound having a sulfur atom in the principal molecular chain, (b) a maleimide compound having at least two N-substituted maleimide groups in the molecular structure and (c) a monoamine compound, (B) an epoxy resin having at least two epoxy groups in the molecule, and (C) a compound enabling chemical roughing. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a thermosetting insulating resin composition having a high glass transition temperature, excellent heat resistance, and low thermal expansion, and an insulating film with a support, a prepreg, a laminate and a multilayer printed wiring board using the same. .

In recent years, electronic devices have become smaller, lighter, and more functional, and along with this, higher integration of LSIs and chip components has progressed, and the form has rapidly changed to multi-pin and miniaturization. . For this reason, in order to improve the mounting density of electronic components, the development of micro wiring has been advanced for multilayer printed wiring boards.
There is a built-up method as a method for manufacturing a multilayer printed wiring board meeting these requirements, and it is becoming mainstream as a method suitable for weight reduction, miniaturization, and miniaturization.

In addition, there is an active movement to regulate materials including electronic parts that may generate harmful substances during combustion due to increased environmental awareness. In conventional multilayer printed wiring boards, bromo compounds have been used for flame retardancy, but harmful substances may be generated during combustion, so this bromine compound will not be usable in the near future. is expected.
Lead-free solder that does not contain lead is also being put into practical use as a solder generally used for connecting electronic components to a multilayer printed wiring board. This lead-free solder has a higher use temperature than conventional eutectic solder by about 20 to 30 ° C. Therefore, the material is required to have higher heat resistance than ever before.

  Furthermore, in the multilayer printed wiring board having the build-up structure, in order to increase the density, the number of layers is increased and the via portion is filled and stacked. However, insulation resin layers that do not contain glass cloth tend to have a large coefficient of thermal expansion to reduce the thickness of multilayer printed wiring boards, so the difference in coefficient of thermal expansion from copper in filled and stacked vias It greatly affects reliability and is a concern for reliability. For this reason, a material having a low coefficient of thermal expansion has been required for the insulating resin layer.

In order to reduce the thermal expansion coefficient in the insulating resin layer, generally, a method of filling a large amount of an inorganic filler having a small thermal expansion coefficient and reducing the thermal expansion coefficient of the entire insulating layer has been used (for example, see Patent Document 1). However, such a method tends to cause many problems such as a decrease in fluidity and a decrease in insulation reliability.
In addition, attempts have been made to achieve low thermal expansion by selecting or improving the resin. For example, as an example of an epoxy resin having an aromatic ring, there is a low thermal expansion pressure molding resin composition using an epoxy resin having a bifunctional naphthalene skeleton or a biphenyl skeleton (see Patent Document 2). 80 to 92.5% by volume of the material is blended. In addition, conventionally, a method for reducing the thermal expansion coefficient of a resin composition for a wiring board is generally a method in which the crosslinking density is increased and the glass transition temperature (Tg) is increased to reduce the thermal expansion coefficient (Patent Documents 3 and 3). 4). However, increasing the crosslink density requires shortening the molecular chain between the functional groups, but shortening the molecular chain beyond a certain level is difficult in terms of reactivity and resin strength.

  Furthermore, introduction of an imide skeleton, which is considered to be useful for heat resistance and low thermal expansion, has been attempted. For example, a thermosetting composition for build-up using an aromatic diamine having an imide group and an epoxy resin has been proposed. (See Patent Document 5). However, when a low molecular weight polyimide compound is used as a curing agent for an epoxy resin, most of them are not different from the characteristics of the epoxy resin in many cases.

JP 2004-182851 A Japanese Patent No. 2740990 JP 2000-243864 A JP 2000-114727 A JP 2000-17148 A

  An object of the present invention is to provide a thermosetting insulating resin composition having a high glass transition temperature, excellent heat resistance, and low thermal expansion, as well as an insulating film with a support and a prepreg using the same. It is to provide a laminated board and a multilayer printed wiring board.

  As a result of diligent research to solve the above problems, the present invention is obtained by reacting a diamine compound having a sulfur atom in a molecular main chain with a maleimide compound and a monoamine compound as an insulating resin composition for multilayer printed wiring boards. By using the obtained curing agent having an acidic substituent and an N-substituted maleimide group, and a resin composition containing an epoxy resin and a compound that can be chemically roughened, the glass transition temperature is high and the heat resistance is excellent, and A curable insulating resin composition having low thermal expansion was obtained, and it was found that it could be suitably used for multilayer printed wiring boards and the like, and the present invention was completed.

That is, the present invention provides the following thermosetting insulating resin composition, and an insulating film with a support, a prepreg, a laminate and a printed wiring board using the same.
1. Curing agent (A) obtained by reacting the following (a), (b) and (c), having a sulfur atom in the molecular main chain, and having an acidic substituent and an N-substituted maleimide group (1 molecule) A thermosetting insulating resin composition comprising an epoxy resin (B) having at least two epoxy groups and a compound (C) capable of chemical roughening.
(A) a diamine compound having a sulfur atom in the molecular main chain,
(B) a maleimide compound having at least two N-substituted maleimide groups in the molecular structure;
(C) Monoamine compound The thermosetting insulating resin composition according to 1 above, wherein the diamine compound (a) is a compound represented by the following formula (I) or the following formula (II), or diaminodimethyldibenzothiophenesulfone.

（式中、Ｒ₁及びＲ₂は各々独立に、ハロゲン原子、炭素数１〜３のアルキル基、水酸基、カルボキシ基、またはスルホン酸基を示す。Ｍは炭素数１〜５のアルコキシレン基、または炭素数６〜１４のアリーレン基を示す。Ｂはアミノ基を有する炭素数６〜１４のアリール基、またはアリールオキシ基を示し、これらは、さらにハロゲン原子や、炭素数１〜３のハロゲン化アルキル基などで置換されてもよい。ｘ、ｙは各々独立に０〜４の整数であり、ｐ、ｑは０または１である。Ａは−Ｓ−、−ＳＯ₂−、−Ｓ−Ｓ−から選ばれる硫黄原子含有基である。）

(In the formula, R ₁ and R ₂ each independently represent a halogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a carboxy group, or a sulfonic acid group. M represents an alkoxylene group having 1 to 5 carbon atoms, Or an arylene group having 6 to 14 carbon atoms, and B represents an aryl group having 6 to 14 carbon atoms or an aryloxy group having an amino group, which further includes a halogen atom or a halogenated group having 1 to 3 carbon atoms. It may be substituted with an alkyl group, etc. x and y are each independently an integer of 0 to 4, and p and q are 0 or 1. A is —S—, —SO ₂ —, —S—S. A sulfur atom-containing group selected from-.

3. The thermosetting insulating resin composition according to 1 above, wherein the chemical roughening compound (C) is a crosslinked rubber particle.
4). 3. The thermosetting insulating resin composition according to 3 above, wherein the crosslinked rubber particles are at least one selected from core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles.
5. The thermosetting insulating resin composition according to 1 above, wherein the chemical roughening compound (C) is a polyvinyl acetal resin.
6). Furthermore, the thermosetting insulating resin composition in any one of said 1-5 containing the hardening | curing agent and / or hardening accelerator (D) of an epoxy resin.
7). Furthermore, the thermosetting insulating resin composition in any one of said 1-6 containing the phosphorus compound (E) which provides a flame retardance.
8). The content of the inorganic filler (F) of 10 to 45 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B) and (D) to (E) in terms of solid matter Any thermosetting insulating resin composition.

9. An insulating film with a support, wherein a semi-cured film of the thermosetting insulating resin composition according to any one of 1 to 8 is formed on a support surface.
10. A prepreg characterized in that the thermosetting insulating resin composition according to any one of 1 to 8 above is impregnated in a sheet-like reinforcing base material comprising fibers.
11. An insulating resin layer is formed using any one of (1) the thermosetting insulating resin composition of any one of 1 to 8, (2) the insulating film with support of 9 above, and (3) the prepreg of 10 above. The laminated board characterized by the above-mentioned.
12 A multilayer printed wiring board produced by using the above-mentioned 11 laminated board.

  As described above, the thermosetting insulating resin composition of the present invention has a sulfur atom in the molecular main chain, and includes a curing agent (A) containing a compound having an acidic substituent and an unsaturated N-substituted maleimide group, By containing the epoxy resin (B) and the chemical roughening compound (C), the glass transition temperature (Tg) is particularly high, so that it has excellent heat resistance, low thermal expansion, and excellent plating strength. An insulating resin layer can be formed, and the thermosetting insulating resin composition and an insulating film with a support using the same, a laminate and a multilayer printed wiring board manufactured from a prepreg are solder heat resistant, heat resistant with copper Properties (T-288), moisture resistance, and flame retardancy are balanced and highly reliable, and products suitable for electronic parts and the like can be obtained.

Hereinafter, the present invention will be described in detail.
The thermosetting insulating resin composition according to the present invention (hereinafter also simply referred to as an insulating resin composition) includes a curing agent (A) having an acidic substituent and an N-substituted maleimide group, an epoxy resin (B), and chemical roughening. The possible compound (C), and optionally, an epoxy resin curing agent and / or curing accelerator (D), a phosphorus compound (E) and an inorganic filler (F).

First, for the curing agent (A) used in the present invention, the following compounds (a), (b), and (c) are obtained by stirring and reacting in an organic solvent while heating and holding as necessary. A compound having a sulfur atom in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group is used.
(A) A diamine compound having a sulfur atom in the molecular main chain.
(B) A maleimide compound having at least two N-substituted maleimide groups in the molecular structure.
(C) Monoamine compound.
In addition, the compound containing an acidic substituent is used for at least one of the compounds of (a), (b), and (c).

The compound (a) is an aromatic diamine compound having a sulfur atom of —S—, —SO ₂ —, or —S—S— in the molecular skeleton. Any compound can be used as long as it is such an aromatic diamine compound. Examples of the compound include the compound represented by the formula (I) or the formula (II) or diaminodimethyldibenzothiophenesulfone. It is done.
In each formula, R ₁ and R ₂ each independently represent a halogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a carboxy group, or a sulfonic acid group. M represents an alkoxylene group having 1 to 5 carbon atoms or an arylene group having 6 to 14 carbon atoms. B represents an aryl group having 6 to 14 carbon atoms having an amino group, or an aryloxy group, and these may be further substituted with a halogen atom or a halogenated alkyl group having 1 to 3 carbon atoms. x and y are each independently an integer of 0 to 4, and p and q are 0 or 1. A is a sulfur atom-containing group selected from —S—, —SO ₂ —, and —S—S—.
Here, as a C1-C5 alkoxylene group, a methoxylene group, an ethoxylene group, etc. are mentioned. Examples of the arylene group having 6 to 14 carbon atoms include a phenylene group and a naphthylene group. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group. Examples of the aryloxy group having 6 to 14 carbon atoms include a phenoxy group and a naphthoxy group.

Specific examples of the compound represented by the formula (I) include bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 2,2′-diaminodiphenyl sulfide, and bis (4-aminophenyl). ) Sulfide, bis (3-aminophenyl) sulfide, bis (2,3,5,6) -tetrafluoro-4-aminophenyl) sulfide, 2,2′-dithiodianiline, 3,3′-dithiodianiline 4,4′-dithiodianiline and the like.
On the other hand, specific compounds represented by the formula (II) include, for example, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4′-bis (3-amino). -5-trifluoromethylphenoxy) diphenylsulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2'-bis [4- {2 -(4-Aminophenoxy) ethoxy} phenyl] sulfone, 3,3′-disulfonic acid-bis {4- (3-aminophenoxy) -phenyl} sulfone, 3,3 ′, 5,5′-tetramethyl-bis {4- (4-aminophenoxy) phenyl} sulfone, 4,4′-bis (6-aminonaphthoxy) diphenylsulfone, 4,4′-bis (3-aminophenoxypheny ) Such as diphenyl sulfone can be mentioned.
Among these, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfide having good reactivity and heat resistance, Preferred are 4,4′-dithiodianiline, 3,3′-dithiodianiline, bis [4- (4-aminophenoxy) phenyl] sulfone, and bis [4- (3-aminophenoxy) phenyl] sulfone, and further lower heat More preferred are bis (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfide, 4,4′-dithiodianiline, and bis [4- (4-aminophenoxy) phenyl] sulfone having expandability, and to the solvent. From the solubility point of bis (4-aminophenyl) sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4′-di Ojianirin, bis (4-aminophenyl) sulfide are especially preferred.
Examples of diaminodimethyldibenzothiophene sulfone include 3,7-diamino-2,8-dimethyldibenzothiophene sulfone.

  The maleimide compound having at least two unsaturated N-substituted maleimide groups in the molecular structure, which is the compound (b) used in the present invention, is, for example, N, N′-ethylenebismaleimide, N, N ′. -Hexamethylene bismaleimide, 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-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3, 3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidopheny ) Sulfide, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,4-bis (Maleimidomethyl) benzene, 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-maleimidophenoxy) pheny Ru] 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, '-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] 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-di Tylbenzyl] 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-dimethylbenzyl] benzene, polyphenylmethanemaleimide, and the like. These maleimide compounds may be used alone or in combination of two or more. It can have.

  Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) with high reaction rate and higher heat resistance Disulfide, N, N ′-(1,3-phenylene) bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane are preferred, and bis (4-maleimidophenyl) methane is preferred because it is inexpensive. N, N ′-(1,3-phenylene) bismaleimide is more preferable, and bis (4-maleimidophenyl) methane is particularly preferable from the viewpoint of solubility in a solvent.

The monoamine compound, which is the compound (c) used in the present invention, is a monoamine compound having an acidic substituent when the component (a) or (b) does not have an acidic substituent in the molecular structure; To do. Examples of such monoamine compounds include (o-, m-, p-) (this notation represents o-, m-, or p-) aminophenol, (o-, m-, p-) amino. Benzoic acid, (o-, m-, p-) aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like can be mentioned. From the viewpoint of low thermal expansion and solubility, (o -, M-, p-) aminophenol is particularly preferred.
On the other hand, when the compound (a) or (b) has an acidic substituent in the molecular structure, the monoamine compound may or may not have an acidic substituent. Aniline, (o-, m-, p-) methylaniline, (o-, m-, p-) ethylaniline, (o-, m-, p-) vinylaniline, (o-, m-, p -) Monoamine compounds such as allylaniline can also be used.

When the above compounds (a), (b), and (c) are reacted in an organic solvent, the reaction temperature is preferably 70 to 200 ° C, and more preferably 70 to 160 ° C.
The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.
Here, when the aromatic amine diamine compound (a) and the acidic substituent (c) are used, the amount of the monoamine compound used is the sum of the —NH ₂ group equivalents and the C═C group of the maleimide compound (b). The relationship with the equivalent is
0.1 ≦ [C = C group equivalent] / [-NH ₂ group equivalent] ≦ 10.0
It is preferable to be in the range shown in. More preferably, this relationship is
1.0 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 9.0, particularly preferably
2.0 ≦ [C = C group equivalent] / [total of —NH ₂ group equivalent] ≦ 8.0
The range.
When the amount ratio is 0.1 or more, gelation and heat resistance do not decrease, and when it is 10.0 or less, solubility in organic solvents, adhesiveness, and heat resistance decrease. There is nothing.

  The organic solvent used in this reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, Examples include sulfur atom-containing solvents such as dimethyl sulfoxide, and one or two or more kinds can be used in combination. Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility, cyclohexanone, which has low toxicity and high volatility and does not easily remain as a residual solvent during prepreg production. Propylene glycol monomethyl ether and dimethylacetamide are particularly preferred.

The amount of the organic solvent used is preferably 25 to 1000 parts by mass, more preferably 40 to 700 parts by mass, per 100 parts by mass of the sum of the components (a), (b) and (c).
By setting the blending amount of the organic solvent to 25 to 1000 parts by mass, the solubility is insufficient and a long time is not required for synthesis.

Moreover, a reaction catalyst can be arbitrarily used for this reaction. Examples of such reaction catalysts include, but are not limited to, amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. A seed or a mixture of two or more can be used.
The addition amount of the catalyst is preferably 0.001 to 5% by mass with respect to the total mass of the bismaleimide compound (b) and the monoamine compound (c).

  The weight average molecular weight of the curing agent (A) having a sulfur atom in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group is 400 to 3500 from the viewpoint of solubility and mechanical strength. preferable. The weight average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion) using tetrahydrofuran as an eluent.

  Next, the epoxy resin (B) having at least two epoxy groups in one molecule is not particularly limited as long as it is an epoxy resin having at least two epoxy groups in one molecule. Bisphenol F, biphenyl, novolak, polyfunctional phenol, naphthalene, alicyclic and alcoholic glycidyl ethers, glycidyl amines and glycidyl ester types, etc. Can be used. Specifically, in terms of dielectric properties, heat resistance, moisture resistance and copper foil adhesion, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, Biphenyl aralkyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc. are preferable, and naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type from the viewpoint of having good low thermal expansion and high glass transition temperature An epoxy resin, a biphenyl aralkyl type epoxy resin, and a phenol novolac type epoxy resin are more preferable.

  The compound (C) capable of chemical roughening is not particularly limited as long as it is a compound that forms a fine roughened shape on the surface of the insulating layer described later by desmear treatment, but crosslinked rubber particles and polyvinyl acetal resin are preferred, Preferably, it is a crosslinked rubber particle.

Examples of the crosslinked rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is formed of a glassy polymer and an inner core layer is formed of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glass layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber).
Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N [above, trade name, manufactured by Gantz Kasei Co., Ltd.], Metabrene KW-4426 [trade name, manufactured by Mitsubishi Rayon Co., Ltd.], EXL-2655 [Product Name: manufactured by Rohm and Haas Co., Ltd.). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 [average particle diameter of 0.5 μm, manufactured by JSR Corporation]. Specific examples of the cross-linked styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include methabrene W300A (average particle size 0.1 μm), W450A (average particle size 0.2 μm) [manufactured by Mitsubishi Rayon Co., Ltd.]. The crosslinked rubber particles may be used alone or in combination of two or more.

The average particle diameter of the rubber particles to be blended is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles used in the present invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves, etc., and a particle size distribution of the rubber particles is created on a mass basis using a concentrated particle size analyzer [FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.] And it can measure by making the median diameter into an average particle diameter.

  As a polyvinyl acetal resin, the kind, the amount of hydroxyl groups, and the amount of acetyl groups are not particularly limited, but those having a polymerization degree of 1000 to 2500 are preferable. Within this range, solder heat resistance can be secured, and the viscosity and handling properties of the varnish are good. Here, the number average degree of polymerization of the polyvinyl acetal resin can be determined, for example, from the number average molecular weight of polyvinyl acetate as a raw material (measured using a standard polystyrene calibration curve by gel permeation chromatography). Moreover, a carboxylic acid modified product etc. can also be used.

  Polyvinyl acetal resin is, for example, trade name, S-REC BX-1, BX-2, BX-5, BX-55, BX-7, BH-3, BH-S, KS-3Z manufactured by Sekisui Chemical Co., Ltd. KS-5, KS-5Z, KS-8, KS-23Z, trade names manufactured by Denki Kagaku Kogyo Co., Ltd., and electrified butyral 4000-2, 5000A, 6000C, 6000EP, and the like can be used. These resins can be used alone or in admixture of two or more.

In addition to the curing agent (A), an epoxy resin curing agent and / or a curing accelerator (D) can be optionally used in the curable insulating resin composition of the present invention.
The epoxy resin curing agent is not particularly limited as long as it has a curing action of epoxy resin, but examples include acid anhydrides such as maleic anhydride and maleic anhydride copolymers, amine compounds such as dicyandiamide, Examples thereof include phenol compounds such as phenol novolac, cresol novolac, and aminotriazine novolac resin. Among these, dicyandiamide, cresol novolak, and aminotriazine novolak are preferable from the viewpoints of curability and low thermal expansion, and dicyandiamide and aminotriazine novolak resin are particularly preferable because flame retardancy and adhesion are improved. The epoxy resin curing agent as an optional component can be used alone or in combination of two or more.
Examples of the curing accelerator include imidazoles and derivatives thereof, tertiary amines and quaternary ammonium salts.

  Examples of the phosphorus compound (E) that imparts flame retardancy include phosphorus-containing epoxy resins, phosphorus-containing phenol resins, phenoxyphosphazene compounds, condensed phosphate compounds, and diphosphinates. It is particularly effective to use these in combination.

The curable insulating resin composition of the present invention is as follows with a total amount of 100 parts by mass of (A), (B), (D), and (E) components (hereinafter also referred to as resin components) in terms of solid content. Is preferred.
(A) It is preferable to set it as 20-95 mass parts, and it is more preferable to set it as 40-90 mass parts. By increasing the content of the component (A), the characteristics of the present invention are low thermal expansion, high heat resistance, balanced with flame retardancy and hygroscopicity, etc., for a multilayer printed wiring board having high reliability. A thermosetting insulating resin composition is obtained.
(B) It is preferable to set it as 5-80 mass parts, and it is more preferable to set it as 5-60 mass parts. When the component (B) is 5 parts by mass or more, heat resistance and adhesiveness are improved, and when it is 80 parts by mass or less, low thermal expansion is satisfied.
(C) It is preferable that it is 0.5-5 mass parts, More preferably, it is 0.5-2 mass parts. By setting the content of the compound capable of chemical roughening to 0.5 parts by mass or more, the adhesive strength between the insulating resin layer and the conductor layer is increased, and by setting the content to 5 parts by mass or less, the insulation reliability between wirings is increased. It will not be insufficient.
(D) It is preferable to set it as 0-50 mass parts, and it is more preferable to set it as 0-30 mass parts. By adding the component (D), the heat resistance becomes low with low thermal expansion, and when it is 50 parts by mass or less, a thermosetting insulating resin composition having high reliability can be obtained.

  The component (E) in the thermosetting insulating resin composition of the present invention preferably has a phosphorus atom content of 0.1 to 3 parts by mass in the insulating resin composition, and 0.2 to 3.0 parts by mass. Part is more preferable, and 0.5 to 3.0 parts by mass is particularly preferable. When the phosphorus atom content is low, the flame retardancy is insufficient, so it is necessary to increase the nitrogen atom content by increasing the content of the component (A) and to impart flame retardancy.

  In the insulating resin composition of the present invention, it is preferable to contain an inorganic filler (F) in order to reduce the thermal expansion coefficient of the insulating resin layer. Examples of the inorganic filler (F) include silica, mica, talc, short glass fiber or fine powder and hollow glass, antimony trioxide, calcium carbonate, quartz powder, aluminum hydroxide, magnesium hydroxide, and the like. Among these, silica, aluminum hydroxide, and magnesium hydroxide are preferable from the viewpoint of dielectric properties, heat resistance, and flame retardancy, and silica and aluminum hydroxide are more preferable because of low thermal expansion. Moreover, in order to embed a lower wiring layer, the adhesive film for multilayer printed wiring boards is required to have high fluidity. Therefore, it is desirable from the viewpoint of fluidity that the inorganic filler is spherical.

It is preferable that content of an inorganic filler (F) is 10-50 mass parts with respect to 100 mass parts of resin component total amount, More preferably, it is 25-45 mass parts. By making the inorganic filler 10 parts by mass or more, the low thermal expansion coefficient of the insulating resin layer after curing is lowered. Further, when the inorganic filler is 50 parts by mass or less, the insulating resin layer does not become brittle and cracks do not occur in a temperature cycle test or the like.
These inorganic fillers can be treated with a coupling agent for the purpose of enhancing dispersibility, and the inorganic filler can be dispersed by a known kneading method such as a kneader, ball mill, bead mill, or three rolls.
The average particle diameter of the inorganic filler is preferably 1 μm or less, more preferably 0.5 μm or less, considering that the miniaturization of wiring is advanced. An inorganic filler having a size of 1 μm or more may cause an etching residue to increase surface unevenness after a desmear process, which will be described later.

  Furthermore, in the insulating resin composition of the present invention, other components can be blended as necessary within a range not inhibiting the effects of the present invention. Examples of other components include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, flame retardants such as metal hydroxides, and organic fillings such as silicon powder, nylon powder, and fluorine powder. Agents, thickeners such as olben, benton, etc., silicone-based, fluorine-based, polymer-based antifoaming agents or leveling agents, imidazole-based, thiazole-based, triazole-based, silane-based coupling agents, etc. UV absorbers such as triazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, thioxanthones, fluorescent whitening agents such as stilbene derivatives, phthalocyanine blue , Phthalocyanine green, Iodine green, Disazo yellow, Carbon Coloring agents such as racks and the like.

  In the insulating resin composition used for the insulating film with support and the prepreg of the present invention, an organic solvent can be arbitrarily used as a diluting solvent. The organic solvent is not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohol solvents such as methyl cellosolve, ether solvents such as tetrahydrofuran, and aromatic solvents such as toluene, xylene, and mesitylene. Examples of the solvent include one type or a mixture of two or more types.

  The insulating resin composition of the present invention can be suitably used for forming an insulating resin layer in the production of a multilayer printed wiring board. Although the insulating resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating resin layer, it is generally industrially in the form of a sheet-like laminated material such as an insulating film with a support, a prepreg, etc. Is preferably used.

  The insulating film with a support of the present invention comprises an insulating resin composition in which components (A), (B) and (C) are blended, or an insulating resin composition in which components (D), (E) and (F) are further added. The insulating resin composition layer is formed by coating on a support film, volatilizing the solvent in the varnish by drying and semi-curing (B-stage). However, this semi-cured state is within the range where the adhesive strength between the insulating resin layer and the circuit pattern substrate forming the insulating resin layer is secured when the insulating resin composition is cured, and the embedding property (fluidity) of the circuit pattern substrate. ) Is desirable. As a coating method (coating machine), a die coater, a comma coater, a bar coater, a kiss coater, a roll coater or the like can be used, and it is appropriately used depending on the thickness of the insulating resin layer. As a drying method, heating, hot air blowing, or the like can be used.

  Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the insulating resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the amount of the organic solvent in the varnish and the boiling point of the organic solvent, for example, by drying a varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes, A semi-cured film is formed. It is preferable to set suitable drying conditions as appropriate by simple experiments in advance.

  The thickness of the insulating resin composition layer formed in the insulating film with support is usually not less than the thickness of the conductor layer. The thickness of the conductor layer included in the circuit board is preferably 5 to 70 μm, more preferably 5 to 50 μm, and most preferably 5 to 30 μm in order to reduce the thickness of the printed wiring board.

  Support in the insulating film with support is a film made of polyolefin such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes referred to as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, etc. Furthermore, release paper, copper foil, metal foil such as aluminum foil, and the like can be mentioned. Note that the support and the protective film described later may be subjected to a release treatment in addition to the mat treatment and the corona treatment.

Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable, More preferably, it is 25-50 micrometers. A protective film according to the support can be further laminated on the surface of the insulating resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, foreign matter can be prevented from being mixed.
The insulating film with a support can be wound and stored in a roll shape.

  As a form of the method of forming a laminated board using the insulating film with a support of the present invention and producing a multilayer printed wiring board, for example, the insulating film with a support is used on one side or both sides of a circuit board using a vacuum laminator. Laminate. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Further, in a laminated board obtained by alternately laminating conductor layers and insulating layers, and a multilayer printed wiring board manufactured from the laminated board, a conductor layer in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned ( Circuits) are also included in the circuit board here. The surface of the conductor layer may be subjected to a roughening process in advance by a blackening process or the like.

  In the above laminate, when the insulating film with a support has a protective film, after removing the protective film, the insulating film with a support and the circuit board are preheated as necessary, and the adhesive film is pressurized and Crimp to circuit board while heating. In the insulating film with a support of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 0.1 to 1.1 MPa, and the air pressure is 20 mmHg (26.7 hPa). Lamination is preferably performed under the following reduced pressure. The laminating method may be a batch method or a continuous method using a roll.

  After laminating the insulating film with the support on the circuit board, after cooling to near room temperature, the support can be peeled off and then thermally cured to form an insulating resin layer on the circuit board. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the insulating resin composition, but are preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to It is selected in the range of 30 to 120 minutes at 200 ° C.

  If the support is not peeled off after the insulating resin layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.

  Next, a conductor layer is formed on the insulating resin layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the cured insulating resin composition layer is permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid. Roughening treatment is performed with an oxidizing agent such as to form an uneven anchor. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a known subtractive method or semi-additive method can be used.

  The prepreg of the present invention is a fiber sheet reinforcing substrate impregnated with the insulating resin composition of the present invention, and the fiber sheet reinforcing substrate is coated with the insulating resin composition of the present invention by a hot melt method or a solvent method. After impregnating with, it is manufactured by heating to B-stage.

  As the fiber sheet reinforcing substrate, for example, known materials used for various types of laminated sheets for electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and polytetrafluoroethylene, and mixtures thereof. These base materials have, for example, shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, A single material or two or more materials and shapes can be combined. The thickness of the base material is not particularly limited, and for example, about 0.03 to 0.5 mm can be used, and the surface is treated with a silane coupling agent or the like or mechanically subjected to a fiber opening treatment. However, it is suitable from the aspects of heat resistance, moisture resistance, and workability.

  The above hot-melt method is a method in which the resin is once coated on a coated paper having good releasability from the resin without dissolving the resin in the organic solvent, and then laminated on the sheet-like reinforcing substrate, or the resin is added to the organic solvent. In this method, the prepreg is produced by, for example, coating directly on a sheet-like reinforcing substrate with a die coater without being dissolved in the substrate. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying.

  Next, as a method for producing a multilayer printed wiring board using the prepreg produced as described above, for example, one or more of the prepregs of the present invention are stacked on a circuit board, and a metal is disposed through a release film. It is sandwiched between plates and press laminated under pressure and heating conditions. The pressurizing / heating conditions are preferably a pressure of 0.5 to 4 MPa and a temperature of 120 to 200 ° C. for 20 to 100 minutes. Similarly to the insulating film with support, the prepreg can be laminated on a circuit board by a vacuum laminating method and then cured by heating. Thereafter, in the same manner as described above, the surface of the cured prepreg is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.

Next, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these descriptions.
In addition, the performance of the insulating resin layer and the copper-clad laminate of the insulating film with support obtained in each Example and Comparative Example was measured and evaluated by the following method.

(1) Glass transition temperature (Tg) and coefficient of thermal expansion The insulating resin layer of the insulating film with support is laminated facing the copper foil [F3-WS-18, trade name, manufactured by Furukawa Circuit Foil Co., Ltd.]. The PET film was peeled off and cured at 180 ° C. for 90 minutes. Thereafter, the entire surface of the copper foil was etched to prepare a sample for evaluating the thermal expansion coefficient of the cured insulating resin layer.
The obtained sheet-like cured product was cut into a length of 20 mm and a width of 3 mm, and using a TMA test apparatus (manufactured by DuPont, TMA2940), the heating rate was 10 ° C./min, the measurement length was 15 mm, the load was 5 g, and the tension was The measurement was performed twice in succession by the weight method. The glass transition temperature (Tg) in the second measurement and the average linear thermal expansion coefficient from 30 to 120 ° C. were calculated.

(2) Plating adhesion strength Both sides of glass cloth base epoxy resin double-sided copper-clad laminate [manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-679F, copper foil thickness: 12 μm] made by MEC The roughening process was performed using "CZ8100" (brand name).
The insulating film with a support was laminated on both surfaces of the circuit board that had been roughened as described above. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at a pressure of 0.5 MPa for 30 seconds.
The PET film was peeled from the laminated insulating film with a support, and the insulating resin composition layer was cured under curing conditions at 180 ° C. for 60 minutes to form an insulating resin layer.
Next, fine irregularities were formed on the surface of the insulating resin layer by immersing the laminate in a desmear treatment liquid. A semi-additive method is used for plating, and a laminated copper plate is dipped in a copper etching solution to form a 3 mm-wide plated copper foil to produce an evaluation substrate, which is plated and adhered using an autograph (AG-100C manufactured by Shimadzu Corporation). The strength was measured.

(3) Solder heat resistance A 5 cm square evaluation board from which the copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared and 121 ° C. using a pressure cooker test apparatus manufactured by Hirayama Mfg. Co., Ltd. After performing the pressure-cooker treatment for up to 4 hours under the condition of 2 atm, the evaluation substrate was immersed in a solder bath at a temperature of 288 ° C. for 20 seconds, and then the solder heat resistance was evaluated by observing the appearance.

(4) Heat resistance with copper (T-288)
An evaluation board of 5 mm square was produced from a copper clad laminate, and evaluation was performed by measuring the time until the evaluation board swells at 288 ° C. by a compression method using a TMA test apparatus (manufactured by DuPont, TMA2940). .

(5) Hygroscopicity (water absorption rate)
A copper-clad laminate was immersed in a copper etching solution to produce an evaluation substrate from which the copper foil was removed, and pressure was applied for up to 4 hours under the conditions of 121 ° C. and 2 atm using a pressure cooker test apparatus manufactured by Hirayama Seisakusho. -After the cooker treatment, the water absorption rate of the evaluation substrate was measured.

(6) Flame Retardancy Evaluation A test piece cut out to 127 mm in length and 12.7 mm in width was prepared from an evaluation board from which a copper foil was removed by immersing a copper-clad laminate in a copper etching solution, and tested for UL94. Evaluation was made according to the method (Method V).

Production Example 1: Production of Curing Agent (A-1) Bis (4-aminophenyl) sulfone was added to a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 26.40 g, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane: 484.50 g, p-aminobenzoic acid: 29.10 g, and dimethylacetamide: 360.00 g The reaction was carried out at 140 ° C. for 5 hours to obtain a solution of a curing agent (A-1) having a sulfone group in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group.

Production Example 2: Production of curing agent (A-2)
In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, bis (4-aminophenyl) sulfone: 40.20 g and bis (4-maleimidophenyl) Methane: 464.40 g, p-aminophenol: 35.40 g, and dimethylacetamide: 360.00 g were added and reacted at 100 ° C. for 4 hours to have a sulfone group in the molecular main chain. A solution of a curing agent (A-2) having a saturated N-substituted maleimide group was obtained.

Production Example 3: Production of Curing Agent (A-3) Bis (4-aminophenyl) sulfide was added to a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. : 43.40 g, 4-methyl-1,3-phenylenebismaleimide: 452.90 g, p-aminophenol: 43.70 g, and dimethylacetamide: 360.00 g, and reacted at 100 ° C. for 2 hours. A solution of a curing agent (A-3) having a sulfide group in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

Production Example 4: Production of curing agent (A-4) Bis [4- (4-amino) was added to a reaction vessel with a volume of 2 liters that can be heated and cooled equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Phenoxy) phenyl] sulfone: 44.80 g, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane: 472.60 g, p-aminophenol: 22.60 g, and propylene glycol monomethyl ether: 360 0.000 g was added and reacted at reflux temperature for 2 hours to obtain a solution of a curing agent (A-4) having a sulfone group in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group.

Production Example 5 Production of Curing Agent (A-5) In a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, bis [4- (4-amino] Phenoxy) phenyl] sulfone: 66.30 g, polyphenylmethanemaleimide: 440.30 g, p-aminophenol: 33.40 g, and propylene glycol monomethyl ether: 360.00 g were allowed to react at reflux temperature for 2 hours. A solution of a curing agent (A-5) having a sulfone group in the molecular main chain and having an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

Production Example 6: Production of curing agent (A-6) A reaction vessel with a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, was charged with bis [4- (4-amino]. Phenoxy) phenyl] sulfone: 79.40 g, bis (4-maleimidophenyl) sulfone: 420.50 g, p-aminophenol: 40.10 g, and propylene glycol monomethyl ether: 360.00 g were added at reflux temperature. It was made to react for a time and the solution of the hardening | curing agent (A-6) which has a sulfone group in a molecular principal chain, and has an acidic substituent and unsaturated N-substituted maleimide group was obtained.

Production Example 7: Production of curing agent (A-7) In a reaction vessel with a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, o-tolidine sulfone: 44.10 g Bis (4-maleimidophenyl) methane: 460.80 g, p-aminophenol: 35.10 g, and dimethylacetamide: 360.00 g, and reacted at 100 ° C. for 2 hours to give a sulfone group in the molecular main chain. And a solution of a curing agent (A-7) having a biphenyl skeleton and having an acidic substituent and an unsaturated N-substituted maleimide group.

Comparative Production Example 1: Production of Curing Agent (A-8) With reference to the example of JP-B 63-34899, a 1 liter kneader equipped with a steam heating device was charged with bis (4-maleimidophenyl) methane: 358. 0.000 g and m-aminophenol: 54.50 g, heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled, pulverized, and a curing agent having an acidic substituent and an unsaturated N-substituted maleimide group (A-8 ) Was obtained.

Comparative production example 2: Production of curing agent (A-9) bis (4-maleimidophenyl) methane: 358 in a 1 liter kneader equipped with a steam heating device with reference to the example of JP-B-6-8342 0.000 g and m-aminobenzoic acid: 68.50 g, heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled and pulverized to have a curing agent having an acidic substituent and an unsaturated N-substituted maleimide group (A- The powder of 9) was obtained.

Comparative Production Example 3: Production of Curing Agent (A-10) In a reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume of 2 liters, diaminodiphenylmethane: 32.60 g and bis (4 -Maleimidophenyl) Methane: 471.50 g, p-aminophenol: 35.90 g, and dimethylacetamide: 360.00 g were added and reacted at 100 ° C. for 2 hours to convert acidic substituents and unsaturated N-substituted maleimide groups. A solution of the curing agent (A-10) was obtained.

Comparative Production Example 4: Production of Curing Agent (A-11) 2,2′-bis [4- (4) was added to a 2 liter reaction vessel with a thermometer, a stirrer, a reflux condenser and a heatable and coolable volume. -Aminophenoxy) phenyl] propane: 63.40 g, bis (4-maleimidophenyl) methane: 471.20 g, p-aminophenol: 33.70 g, and dimethylacetamide: 360.00 g. It was made to react for the time and the solution of the hardening | curing agent (A-11) which has an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

Examples 1-12, Comparative Examples 1-6
(A) As a hardening | curing agent, the solution of the hardening | curing agent obtained by manufacture examples 1-7 and comparative manufacture examples 1-4,
(B) As an epoxy resin, a bifunctional naphthalene type epoxy resin [Dainippon Ink Chemical Co., Ltd., trade name, HP-4032D], biphenylaralkyl type epoxy resin [Nippon Kayaku Co., Ltd., trade name: NC -3000-H],
(C) As a compound capable of chemical roughening, crosslinked acrylonitrile butadiene rubber (NBR) particles [manufactured by JSR Corporation, trade name: XER-91], core-shell type rubber particles [trade name, Rohm and Harm Corporation] Product name: XEL-2655] and polyvinyl acetal resin [manufactured by Sekisui Chemical Co., Ltd., product name: KS-23Z],
(D) Aminotriazine novolak resin [manufactured by Dainippon Ink & Chemicals, Inc., trade name: LA-3018] as an epoxy resin curing agent, and an imidazole derivative [Daiichi Kogyo Seiyaku Co., Ltd., trade name) as a curing accelerator. : G8009L],
(E) As a phosphorus compound imparting flame retardancy, a phosphorus-containing phenol resin [manufactured by Sanko Chemical Co., Ltd., trade name: HCA-HQ],
(F) As an inorganic filler, fused silica [manufactured by Admatech Co., Ltd., trade name: SC1050] is used,
In addition, a uniform insulating resin composition varnish having a resin content (total of resin components) of 65% by mass using methyl ethyl ketone as a diluent solvent and mixing at a blending ratio (parts by mass) shown in Tables 1 to 3 is used. Produced.

Next, the insulating resin composition varnish was uniformly coated on a polyethylene terephthalate film (thickness 38 μm, hereinafter referred to as PET film) with a die coater so that the thickness of the insulating resin composition layer after drying was 40 μm. And dried at 100 ° C. for 6 minutes. Subsequently, it wound up in roll shape, bonding the 15-micrometer-thick polypropylene film on the surface of the insulating resin composition layer. The obtained roll-shaped film was slit to a width of 507 mm to produce a sheet-like insulating film with a support having a size of 507 × 336 mm.
Moreover, the insulating resin composition varnish was impregnated and applied to an E glass cloth having a thickness of 0.1 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 50% by mass. Next, four prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.5 MPa and a temperature of 185 ° C. for 90 minutes to obtain a copper clad laminate.
With respect to the insulating resin layer and the copper-clad laminate of the insulating film with support thus produced, the performance was measured and evaluated by the method described above. The results are shown in Tables 1 to 3.

As is apparent from Tables 1 to 3, the insulating resin compositions of the examples according to the present invention have a high glass transition temperature (Tg) of 250 ° C. or higher, good heat resistance, and a coefficient of thermal expansion of 31. It has a low thermal expansion property of ˜36 ppm / ° C., and the plating adhesion strength is significantly higher than that of the comparative example.
In addition, the copper clad laminate obtained from the insulating resin composition of the examples is balanced in all of solder heat resistance, heat resistance with copper (T-288), moisture resistance and flame resistance, and has high reliability. Have
On the other hand, the copper clad laminate obtained from the thermosetting resin composition of the comparative example is inferior in any of the characteristics of solder heat resistance, heat resistance with copper (T-288), moisture resistance and flame resistance, Low reliability.

Claims (12)

Curing agent (A) obtained by reacting the following (a), (b) and (c), having a sulfur atom in the molecular main chain, and having an acidic substituent and an N-substituted maleimide group (1 molecule) A thermosetting insulating resin composition comprising an epoxy resin (B) having at least two epoxy groups and a compound (C) capable of chemical roughening.
(A) a diamine compound having a sulfur atom in the molecular main chain,
(B) a maleimide compound having at least two N-substituted maleimide groups in the molecular structure;
(C) Monoamine compound The thermosetting insulating resin composition according to claim 1, wherein the diamine compound (a) is a compound represented by the following formula (I) or the following formula (II), or diaminodimethyldibenzothiophenesulfone.

(In the formula, R ₁ and R ₂ each independently represent a halogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a carboxy group, or a sulfonic acid group. M represents an alkoxylene group having 1 to 5 carbon atoms, Or an arylene group having 6 to 14 carbon atoms, and B represents an aryl group having 6 to 14 carbon atoms or an aryloxy group having an amino group, which further includes a halogen atom or a halogenated group having 1 to 3 carbon atoms. It may be substituted with an alkyl group, etc. x and y are each independently an integer of 0 to 4, and p and q are 0 or 1. A is —S—, —SO ₂ —, —S—S. A sulfur atom-containing group selected from-.   The thermosetting insulating resin composition according to claim 1, wherein the chemical roughening compound (C) is crosslinked rubber particles.   The thermosetting insulating resin composition according to claim 3, wherein the crosslinked rubber particles are at least one selected from core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles.   The thermosetting insulating resin composition according to claim 1, wherein the chemical roughening compound (C) is a polyvinyl acetal resin.   Furthermore, the thermosetting insulating resin composition in any one of Claims 1-5 containing the hardening | curing agent and / or hardening accelerator (D) of an epoxy resin.   Furthermore, the thermosetting insulating resin composition in any one of Claims 1-6 containing the phosphorus compound (E) which provides a flame retardance.   The content of the inorganic filler (F) of 10 to 45 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B) and (D) to (E) in terms of solid matter. The thermosetting insulating resin composition according to any one of the above.   A semi-cured film of the thermosetting insulating resin composition according to any one of claims 1 to 8, wherein the insulating film with a support is formed on a support surface.   A prepreg characterized in that the thermosetting insulating resin composition according to any one of claims 1 to 8 is impregnated in a sheet-like reinforcing base material comprising fibers.   The insulating resin layer is (1) the thermosetting insulating resin composition according to any one of claims 1 to 8, (2) the insulating film with support according to claim 9, and (3) the claim 10. A laminate formed by using any of the prepregs.   A multilayer printed wiring board produced by using the laminated board according to claim 11.