JP5589292B2 - Thermosetting insulating resin composition, and insulating film with support, prepreg, laminate and multilayer printed wiring board using the same - Google Patents

Description

  The present invention is a thermosetting insulating resin composition for multilayer printed wiring boards having high heat resistance, low thermal expansibility, and excellent plating adhesion strength, as well as an insulating film with a support, a prepreg using the same, The present invention relates to a laminated board and a multilayer printed wiring board.

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.
A lead-free solder containing no lead is also being put into practical use as a solder generally used for connecting an electronic component 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 for the purpose of reducing the thickness of multilayer printed wiring boards, so the difference in coefficient of thermal expansion with 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.

  For such a situation, various methods have been proposed for the purpose of ensuring reliability. For the purpose of reducing the coefficient of thermal expansion, a method of filling a large amount of an inorganic filler having a small coefficient of thermal expansion to lower the thermal expansion coefficient of the entire insulating layer (for example, see Patent Document 1), and reducing the generally used inorganic filler A method of blending a filler coated with an elastic modulus resin into an insulating resin, improving crack resistance and improving connection reliability (for example, see Patent Document 2), a linear shape between a copper foil and a prepreg There are a method of providing an insulating layer added with rubber and achieving improved connection reliability (for example, see Patent Document 3), a method of introducing an imide skeleton that is considered to be useful for heat resistance and low thermal expansion, As a method for introducing an imide skeleton, for example, a thermosetting composition for build-up using an aromatic diamine having an imide group and an epoxy resin (for example, see Patent Document 4) has been proposed.

  However, the method of filling a large amount of inorganic filler (Patent Document 1) causes problems such as a decrease in fluidity and a decrease in insulation reliability. In addition, a filler coated with a resin and an insulating resin using a low-modulus silicone resin (Patent Document 2) are composed of the composition of the entire matrix, and are therefore very expensive or include a large amount of filler. Since it uses, there exists a subject that the adhesive force with copper foil falls. In the method using a substrate provided with an insulating layer to which linear rubber is added (Patent Document 3), there is a concern that the heat resistance of the insulating layer is lowered by adding a rubber component. Furthermore, when a low molecular weight polyimide compound is used as a curing agent for an epoxy resin (Patent Document 4), most of them are not different from the characteristics of the epoxy resin in many cases.

JP 2004-182851 A Japanese Patent No. 2508389 Japanese Patent Publication No. 6-9908 JP 2000-17148 A

  An object of the present invention is to provide a thermosetting insulating resin composition for a multilayer printed wiring board having high heat resistance, low thermal expansion, and excellent plating adhesion strength, as well as the above-described situation. The present invention provides an insulating film with a support, a prepreg, a laminate, and a multilayer printed wiring board.

As a result of earnest research to solve the above-mentioned problems, the present invention is a curing agent having an N-substituted maleimide group and an acidic substituent obtained by reacting in an organic solvent as an insulating resin composition for multilayer printed wiring boards. And it discovered that the said objective could be achieved by using the resin composition containing an epoxy resin and the compound which can be chemically roughened, and completed this invention.
That is, the present invention provides the following thermosetting insulating resin composition, insulating film with support, prepreg, laminate and multilayer printed wiring board.

1.1 Manufactured by reacting a maleimide compound (a) having at least two N-substituted maleimide groups in the molecule with an amine compound (b) having an acidic substituent represented by the general formula (I) in an organic solvent. A curing agent (A) having an N-substituted maleimide group and an acidic substituent, an epoxy resin (B) having at least two epoxy groups in one molecule, and a compound (C) capable of chemical roughening The thermosetting insulating resin composition characterized by the above-mentioned.

（Ｒ₁は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を示し、Ｒ₂は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基、ハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である）

(R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and R ₂ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, (x is an integer from 1 to 5, y is an integer from 0 to 4, and the sum of x and y is 5)

2. The thermosetting insulating resin composition according to 1 above, wherein the chemical roughening compound (C) is a crosslinked rubber particle.
3. 2. The thermosetting insulating resin composition according to 2 above, wherein the crosslinked rubber particles are at least one selected from the group consisting of core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles and acrylic rubber particles.
4). The thermosetting insulating resin composition according to 1 above, wherein the chemical roughening compound (C) is a polyvinyl acetal resin.

5. Furthermore, the thermosetting insulating resin composition in any one of said 1-4 containing the amine compound (D) which has an at least 2 primary amino group in 1 molecule.
6). Furthermore, the thermosetting insulation resin composition in any one of said 1-5 containing a thermoplastic resin (E).
7). Furthermore, the thermosetting insulating resin composition in any one of said 1-6 containing the phosphorus compound (F) which provides a flame retardance.
8). Furthermore, the thermosetting insulating resin composition in any one of said 1-7 containing the hardening | curing agent and / or hardening accelerator (G) of the said epoxy resin.
9. Any of the above 1 to 8 containing 10 to 45 parts by mass of the inorganic filler (H) with respect to 100 parts by mass of the total amount of the components (A), (B) and (D) to (G) in terms of solid matter A thermosetting insulating resin composition.

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

  A thermosetting insulating resin composition for a multilayer printed wiring board according to the present invention includes a curing agent (A), an epoxy resin (B), and an N-substituted maleimide group obtained by reacting in an organic solvent and an acidic substituent. By containing the chemical roughening compound (C), it is possible to form an insulating resin layer that has particularly high glass transition temperature (Tg), high heat resistance, low thermal expansion, and excellent plating adhesion strength. A thermosetting resin composition is obtained, and the thermosetting insulating resin composition and the insulating film with a support using the same, the laminate and the multilayer printed wiring board produced from the prepreg are solder heat resistant, with copper A balance between heat resistance (T-288), moisture resistance and flame retardancy is achieved, and a highly reliable product 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 maleimide compound (a) having at least two N-substituted maleimide groups in one molecule, and a general formula (I And a curing agent (A) having an N-substituted maleimide group and an acidic substituent, which is produced by reacting an amine compound (b) having an acidic substituent shown in FIG. A thermosetting insulating resin composition comprising an epoxy resin (B) having an epoxy group and a compound (C) capable of chemical roughening.

（Ｒ₁は各々独立に、酸性置換基である水酸基、カルボキシル基又はスルホン酸基を示し、Ｒ₂は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基、ハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である。）

(R ₁ independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group which is an acidic substituent, and R ₂ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)

Examples of the maleimide compound (a) having at least two N-substituted maleimide groups in one molecule include N, N′-ethylene bismaleimide, 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-maleimidophenyl) sulfide, bis (4-maleimidophenyl) Nyl) 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-maleimide) Phenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-male Dophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4 -(4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [ 4- (4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4,4-bis (4-maleimidophenoxy) ) Biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2′-bis (4-maleimidophenyl) di Rufide, 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-dimethylbenzyl] benzene, 1,4-bis [ -(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.
Among these, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, N, N ′-(1,3-phenylene) bismaleimide, which has a high reaction rate and can have higher heat resistance, 2 , 2-bis (4- (4-maleimidophenoxy) phenyl) propane is preferred, and bis (4-maleimidophenyl) methane and N, N ′-(1,3-phenylene) bismaleimide are more preferred because of their low cost. From the viewpoint of solubility in a solvent, bis (4-maleimidophenyl) methane is particularly preferred.

  Examples of the amine compound (b) having an acidic substituent represented by the general formula (I) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o -Aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, etc., among these, From the viewpoint of solubility and synthesis yield, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable, and heat resistant M-Aminophenol and p-aminophenol are more preferable from the viewpoint, and m-aminophenol is particularly preferable from the viewpoint of low toxicity. Preferred.

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, mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, Examples include sulfur atom-containing solvents such as dimethyl sulfoxide, and one or two or more of them can be used in combination.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, γ-butyrolactone, and dimethylacetamide are preferable from the viewpoint of solubility. Cyclohexanone and propylene are low toxicity and high volatility and hardly remain as a residual solvent. Glycol monomethyl ether and dimethylacetamide are particularly preferred.

Here, the use amount of the maleimide compound (a) and the amine compound (b) having an acidic substituent is the equivalent of the maleimide group (T) of the component (a) to the equivalent (T _b ) of the —NH ₂ group of the component (b). preferably the equivalent ratio of _{a) (T a / T b} ) is in the range of 1.0 to 10.0, the corresponding amount ratio (T _a / T _b) is in the range of 2.0 to 10.0 More preferably. Appropriate amount ratio (T _a / T _b) without gelation and heat resistance is decreased by a 1.0 or more, solubility in an organic solvent by a 10.0, plating adhesion strength, And heat resistance does not fall.
The amount of the organic solvent used is preferably 10 to 1000 parts by mass, more preferably 100 to 500 parts by mass, per 100 parts by mass of the total amount of the component (a) and the component (b). It is especially preferable to set it as -500 mass parts. When the blending amount of the organic solvent is 10 parts by mass or more, sufficient solubility of the curing agent in the organic solvent can be obtained, and when it is 1000 parts by mass or less, a long reaction time is not caused.

The reaction temperature of the component (a) and the component (b) is preferably 50 to 200 ° C, more preferably 70 to 160 ° C. The reaction time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours.
Moreover, a reaction catalyst can be arbitrarily used for this reaction, and it is not specifically limited. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, phosphorus-based catalysts such as triphenylphosphine, and the like. Can be used.

  Next, the component (B) is not particularly limited as long as it is an epoxy resin having at least two epoxy groups in one molecule. For example, bisphenol A, bisphenol F, biphenyl, novolac, polyfunctional phenol Examples thereof include glycidyl ethers, glycidyl ethers, glycidyl amines, glycidyl esters, and the like such as naphthyl, naphthalene, alicyclic, and alcohols, which can be used alone or in combination. 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 novolak type epoxy resin, etc. are preferable, and naphthalene ring-containing epoxy resin, anthracene type epoxy resin, biphenyl type from the viewpoint of 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 mass ratio of the (A) component and the (B) component in terms of solid content in the insulating resin composition of the present invention is preferably such that the total amount is 100 parts by mass and the (A) component is 20 to 90 parts by mass. 40 to 90 parts by mass is more preferable. By setting the component (A) to 20 parts by mass or more, flame retardancy, heat resistance, adhesiveness and dielectric properties are improved. Further, when the content is 90 parts by mass or less, there is no decrease in insulation reliability due to moisture absorption, and molding at a high temperature of 220 ° C. or higher and for a long time is not necessary.

  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 resin layer to be 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 glassy polymer 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 Methbrene 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 size of the crosslinked rubber particles 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 crosslinked rubber particles can be measured using a dynamic light scattering method. For example, the crosslinked rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, and the particle size distribution of the rubber particles is measured on a mass basis using a concentrated particle size analyzer [FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.]. It is measured by making the median diameter as 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 number average polymerization degree of 1000 to 2500 are preferred. 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.

As a polyvinyl acetal resin, for example, Sekisui Chemical Co., Ltd. trade name, ESREC BX-1, BX-2, BX-5, BX-55, BX-7, BH-3, BH-S, KS-3Z , 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.
Polyvinyl acetal resins can be used alone or in admixture of two or more.

  The insulating resin composition of the present invention can further contain an amine compound (D) having at least two primary amino groups in one molecule. The amine compound (D) reacts with the curing agent (A) to give a compound that acts as a curing agent. In this case, the amine compound (D) may be reacted with the curing agent (A) in an organic solvent before blending.

  The component (D) is not particularly limited as long as it is an amine compound having at least two primary amino groups in one molecule. For example, m-phenylenediamine, p-phenylenediamine, 4,6 -Dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4-diaminomesitylene, m-xylene-2,5- Diamine, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-bis (amino-t-butyl) toluene, 2,4-diaminoxylene, 2 , 4-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminodurene, 4,5-diamino-6-hydride Xyl-2-mercaptopyrimidine, 3-bis (3-aminobenzyl) benzene, 4-bis (4-aminobenzyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (3- Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3-bis (3- (3-aminophenoxy) phenoxy) benzene, 4-bis (4- (4-aminophenoxy) phenoxy) benzene, 3-bis (3- (3- (3-aminophenoxy) phenoxy) phenoxy) benzene, 4-bis (4- (4- (4-aminophenoxy) phenoxy) ) Phenoxy) benzene, 3-bis (α, α-dimethyl-3-aminobenzyl) benzene, 1,4-bis (α, α-dimethyl-3-amino) Nobenzyl) benzene, 3-bis (α, α-dimethyl-4-aminobenzyl) benzene, bis (4-methylaminopentyl) benzene, p-bis (2-methyl-4-aminopentyl) benzene, 1,4- Bis (3-aminopropyldimethylsilyl) benzene, bis [(4-aminophenyl) -2-propyl] 1,4-benzene, 2,5-diaminobenzenesulfonic acid, 3,3′-diaminodiphenylmethane, 4,4 '-Diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-methylene-bis ( 2-chloroaniline), 3,3′-diaminodiphenylethane, 4,4′-diaminodiphenylethane, 2,2′-diaminodiphenylpropane 3,3′-diaminodiphenylpropane, 4,4′-diaminodiphenylpropane, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-amino) Phenoxy) phenyl] hexafluoropropane, 3- (2 ′, 4′-diaminophenoxy) propanesulfonic acid, bis (4-aminophenyl) diethylsilane, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenyl ether, bis (4-amino-tert-butylphenyl) ether, 4,4 ′ -Diaminodiphenyl ether-2,2'-disulfonic acid, 1,5-diaminonaphthalene, 1,4-diaminonaphthalene 2,6-diaminonaphthalene, 9,9′-bis (4-aminophenyl) fluorene, 9,9′-bis (4-aminophenyl) fluorene-2,7-disulfonic acid, 9,9′-bis (4 -Aminophenoxyphenyl) aromatic amines such as fluorene and diaminoanthraquinone, ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,5- Dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminosilane Aliphatic acids such as rhohexane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, diaminopolysiloxane, 2,5-diamino-1,3,4-oxadiazol, bis (4-aminocyclohexyl) methane Amines, melamine, benzoguanamine, acetoguanamine, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-allyl-s-triazine, 2,4-diamino-6-acryloyloxyethyl- Examples thereof include guanamine compounds such as s-triazine and 2,4-diamino-6-methacryloyloxyethyl-s-triazine.

Among these amine compounds, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 4,4′-, which are aromatic amines having good reactivity and heat resistance. Diaminodiphenylmethane, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, and benzoguanamines, which are guanamine compounds, are preferred and inexpensive. From the viewpoint, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, and benzoguanamine are more preferable, and 4,4′-diaminodiphenylmethane is particularly preferable from the viewpoint of solubility in a solvent.
Amine compounds can be used alone or in admixture of two or more.

The organic solvent used when the amine compound (D) is reacted with the curing agent (A) is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, etc. , Ketone solvents such as 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, dimethylformamide, dimethyl Examples thereof include nitrogen atom-containing solvents such as acetamide and N-methylpyrrolidone, sulfur atom-containing solvents such as dimethyl sulfoxide, and the like.
Among these, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are preferable from the viewpoint of solubility. Cyclohexanone, propylene glycol monomethyl ether are preferable because of low toxicity and high volatility and hardly remain as a residual solvent. Dimethylacetamide is particularly preferred.

Here, the amount of the amine compound (D) used relative to the curing agent (A) is the equivalent ratio of the equivalent (T _A ) of the maleimide group of the (A) component to the equivalent (T _D ) of the —NH ₂ group of the (D) component. preferably (T _a / T _D) is in the range of 1.0 to 10.0, more preferably appropriate amount ratio (T _a / T _D) is in the range of 2.0 to 10.0. Appropriate amount ratio (T _A / T _D) without gelation and heat resistance is decreased by a 1.0 or more, solubility in an organic solvent by a 10.0, plating adhesion strength, And heat resistance does not fall.
Moreover, it is preferable to set it as 10-1000 mass parts per 100 mass parts of sum total of a hardening | curing agent (A) and an amine compound (D), and, as for the usage-amount of an organic solvent, it is more preferable to set it as 100-500 mass parts. It is especially preferable to set it as 200-500 mass parts. When the blending amount of the organic solvent is 10 parts by mass or more, the solubility of the curing agent in the organic solvent is not insufficient, and when it is 1000 parts by weight or less, the reaction does not take a long time.

The reaction temperature of the amine compound (D) and the curing agent (A) is preferably 50 to 200 ° C, and particularly preferably 70 to 160 ° C. The reaction time is preferably from 0.1 to 10 hours, particularly preferably from 1 to 6 hours.
Moreover, a reaction catalyst can be arbitrarily used for this reaction, and it is not specifically limited. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. Can be used.

  The insulating resin composition of the present invention can further contain a thermoplastic resin (E). Examples of the thermoplastic resin include phenoxy resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, and polyester resin. , Polyarylate resins, polybutadiene resins, and the like. Phenoxy resins are particularly preferable from the viewpoints of compatibility in the insulating resin composition of the present invention and storage stability of the resin composition.

  The phenoxy resin is not particularly limited, and examples thereof include phenoxy resins such as bisphenol type phenoxy resin, novolac type phenoxy resin, naphthalene type phenoxy resin, and biphenyl type phenoxy resin. These may be used alone or in combination of two or more. The phenoxy resin is particularly preferably a biphenyl type phenoxy resin from the viewpoint of heat resistance and moisture resistance. Although the weight average molecular weight of a thermoplastic resin is not specifically limited, Preferably it is 5000-100000.

  Commercially available phenoxy resins include, as bisphenol A type phenoxy resins, phenotote YP50 [trade name, manufactured by Tohto Kasei Co., Ltd.], E-1256 [trade name, manufactured by Japan Epoxy Resin Co., Ltd.], fluorene type phenoxy. Examples of the resin include FX280, FX293 [trade name, manufactured by Toto Kasei Co., Ltd.], and examples of the biphenyl type phenoxy resin include YX8100, YL6954, and YL6974 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.).

  The insulating resin composition of the present invention may further contain a phosphorus compound (F) that imparts flame retardancy. Examples of the phosphorus compound (F) imparting flame retardancy include a phosphorus-containing epoxy resin, a phosphorus-containing phenol resin, a phenoxyphosphazene compound, a condensed phosphate ester compound, and a diphosphinate. It is particularly effective to use these in combination.

In addition to the curing agent (A) having an N-substituted maleimide group and an acidic substituent, the insulating resin composition of the present invention may optionally include an epoxy resin curing agent and / or a curing accelerator (G). it can.
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 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.

The insulating resin composition according to the present invention has the following components (A) (B) and (D) to (G) in terms of solid content (hereinafter, these components are also referred to as resin components) per 100 parts by mass. It is preferable to set it as a mass part.
The content of the curing agent (A) is preferably 20 to 90 parts by mass, and more preferably 40 to 90 parts by mass. By setting the component (A) to 20 parts by mass or more, flame retardancy, heat resistance, adhesiveness and dielectric properties are improved.
The content of the epoxy resin (B) is preferably 10 to 80 parts by mass, and more preferably 10 to 60 parts by mass. When the component (B) is 10 parts by mass or more, the moisture absorption resistance and chemical resistance are improved, and when it is 80 parts by mass or less, the adhesiveness and flame retardancy are not reduced.

  It is preferable that content of the compound (C) which can be chemically roughened shall be 0.5-5 mass parts, More preferably, it is 1-4 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.

  The content of the amine compound (D) is preferably 0 to 30 parts by mass, and more preferably 5 to 20 parts by mass. By containing the component (D), heat resistance and dielectric properties are improved, and when it is 30 parts by mass or less, gelation and heat resistance are not lowered.

Content of a thermoplastic resin (E) becomes like this. Preferably it is 0-60 mass parts, More preferably, it is 2-20 mass parts. If the content of the thermoplastic resin is too small, the plating adhesion strength tends to decrease, and if it is too large, the roughness of the insulating layer tends to increase and the coefficient of thermal expansion tends to increase.
The content of the phosphorus compound is preferably 3% by mass or less, more preferably 0.2 to 3.0% by mass, and more preferably 0.5 to 3.0% in the resin component. Mass% is particularly preferred. When the phosphorus atom content is low, the flame retardancy is insufficient. Therefore, it is necessary to increase the nitrogen atom content by increasing the content of the curing agent (A) to impart flame retardancy.

  In the insulating resin composition of the present invention, it is preferable to add an inorganic filler (H) in order to reduce the thermal expansion coefficient of the insulating resin layer. Examples of the inorganic filler (H) 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 insulating film with a support for a multilayer printed wiring board 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 (H) is 10-45 mass parts with respect to 100 mass parts of resin component total amount, More preferably, it is 20-35 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 45 parts by mass or less, the insulating resin layer becomes brittle and cracks do not occur in a temperature cycle test or the like.
These inorganic fillers can be treated with a coupling agent in order to increase dispersibility, and the inorganic filler can be dispersed by a known kneading method such as a kneader, a ball mill, a bead mill, or a three roll.
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. By setting the thickness to 1 μm or less, the surface unevenness after the desmear process described later is reduced, so that no etching residue occurs and the insulating property is not insufficient. The average particle diameter can be measured by a laser diffraction / scattering particle size distribution measuring apparatus.

  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. Materials, thickeners such as olben, benton, silicone, fluorine, polymer defoamers or leveling agents, imidazole, thiazole, triazole, silane 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, 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 is such that a semi-cured film of an insulating resin composition is formed on the surface of the support. An insulating resin composition containing the components (A), (B), and (C), or an insulating resin composition further containing the components (D) to (G) or the component (H) is added to the support film. The insulating resin composition layer can be formed by applying and drying to volatilize the solvent in the varnish and semi-curing (B-stage). However, this semi-cured state is a state in which the adhesive strength between the insulating resin layer and the circuit pattern substrate forming the insulating resin layer is ensured when the insulating resin composition is cured, and the embedding property (fluidity) of the circuit pattern substrate is ensured. ) 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.

  The drying conditions after applying the insulating resin composition to the support film are not particularly limited, but the content of the organic solvent in the insulating resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Let dry. 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, the insulating resin composition layer becomes It 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 of the circuit board. The thickness of the conductor layer 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.

  The support in the insulating film with the support is made of polyolefin such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and the like. Examples of the film include metal foil such as release paper, copper foil, and aluminum foil. In addition, you may give a mold release process to a support body and the protective film mentioned later other than a mat | matte process and a 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, Crimp to circuit board while pressing and 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-like reinforcing base impregnated with an insulating resin composition, and the fiber sheet-like reinforcing base is impregnated with a hot melt method or a solvent method. After that, 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, the resin is dissolved in an organic solvent in the same manner as the insulating film with a support to prepare a resin varnish, the sheet-like reinforcing base material is immersed in the varnish, and the sheet-like reinforcing base material is impregnated with the resin varnish. And then drying.

  Next, as a method for producing a laminate using the prepreg produced as described above, for example, one or several prepregs of the present invention are laminated on a circuit board, and a metal plate is interposed through a release film. Press and laminate 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. The obtained laminate can then be used to produce a multilayer printed wiring board by roughening the cured prepreg surface in the same manner as described above, and then forming a conductor layer by plating.

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) Copper foil adhesion (plating adhesion strength)
“CZ8100” (trade name) manufactured by MEC Co., Ltd. on both sides of a 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] ) Was used for roughening treatment.
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 has been removed by immersing a copper clad laminate in a copper etching solution is prepared and 121 ° C. using a pressure cooker test apparatus manufactured by Hirayama Seisakusho. 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-maleimidophenyl) methane 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. : 358.00 g, m-aminophenol: 54.50 g, and propylene glycol monomethyl ether: 412.50 g were added and reacted for 5 hours while refluxing to obtain a solution of the curing agent (A-1).

Production Example 2: Production of curing agent (A-2) Bis (4-maleimidophenyl) methane was added to a reaction vessel having 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. : 358.00 g, p-aminophenol: 54.50 g, and propylene glycol monomethyl ether: 412.50 g were added and reacted for 5 hours while refluxing to obtain a solution of the curing agent (A-2).

Production Example 3: Production of Curing Agent (A-3) Bis (4-maleimidophenyl) methane was placed 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. : 358.00 g, p-aminobenzoic acid: 68.50 g, and dimethylacetamide: 426.50 g were added and reacted at 140 ° C. for 5 hours to obtain a solution of the curing agent (A-3).

Production Example 4: Production of Curing Agent (A-4) 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, N, N ′-(1, 3-Phenylene) bismaleimide: 268.00 g, m-aminophenol: 54.50 g, and dimethylacetamide: 322.50 g were added and reacted at 140 ° C. for 5 hours to obtain a solution of the curing agent (A-4). It was.

Production Example 5: Production of curing agent (A-5) Bis (4-maleimidophenyl) sulfone was placed in a reaction vessel having 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. : 408.00 g, p-aminophenol: 54.50 g, and dimethylacetamide: 462.50 g were added and reacted at 100 ° C. for 2 hours to obtain a solution of the curing agent (A-5).

Production Example 6: Production of curing agent (A-6) Bis (4-maleimidophenyl) ether was added to a 2 liter reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser and capable of heating and cooling. : 360.00 g, p-aminophenol: 54.50 g, and dimethylacetamide: 414.50 g were added and reacted at 100 ° C. for 2 hours to obtain a solution of the curing agent (A-6).

Comparative production example 1: Production of curing agent (A-7) Bis (4-maleimidophenyl) methane: 358.00 g and m-aminophenol: 54.50 g were placed in a 1 liter kneader equipped with a steam heating device. The mixture was heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled, and pulverized to obtain a hardener (A-7) powder having an N-substituted maleimide group and an acidic substituent.

Comparative Production Example 2: Production of Curing Agent (A-8) Bis (4-maleimidophenyl) methane: 358.00 g and m-aminobenzoic acid: 68.50 g were added to a 1 liter kneader equipped with a steam heating device. The mixture was heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled, and pulverized to obtain a powder of a curing agent (A-8) having an N-substituted maleimide group and an acidic substituent.

(Examples 1-12, Comparative Examples 1-6)
(A) As a curing agent, a solution of the curing agent obtained in Production Examples 1 to 6 and Comparative Production Examples 1 and 2,
(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) Cross-linked acrylonitrile butadiene rubber (NBR) particles [manufactured by JSR Corporation, trade name: XER-91], core-shell rubber particles [trade name, Rohm and Harm Co., Ltd.] Product name: XEL-2655] and polyvinyl acetal resin [product name: KS-23Z] manufactured by Sekisui Chemical Co., Ltd. were used.
(D) As an amine compound having at least two primary amino groups in one molecule, 4,4′-diaminodiphenylmethane [Mitsui Chemical Polyurethane Co., Ltd., trade name: MDA-220], 2,2′-bis [4- (4-aminophenoxy) phenyl] propane [Wakayama Seika Kogyo Co., Ltd., trade name: BAPP],
(E) As a thermoplastic resin, a vinyl-type phenoxy resin [manufactured by Japan Epoxy Resin Co., Ltd., trade name: YL6954]
(F) As a phosphorus compound imparting flame retardancy, a phosphorus-containing phenol resin [manufactured by Sanko Chemical Co., Ltd., trade name: HCA-HQ, phosphorus content 9.6% by mass],
(G) 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],
(H) 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 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 low thermal expansion coefficient of 35 to 40 ppm / ° C. and a glass transition temperature (Tg). It has a high heat resistance of 200 to 240 ° 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 thermosetting resin composition of the comparative example is inferior in any one of solder heat resistance, heat resistance with copper (T-288), moisture resistance and flame resistance, and has low reliability.

Claims (11)

It is produced by reacting a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule and an amine compound (b) having an acidic substituent represented by the general formula (I) in an organic solvent. the multilayer printed containing a curing agent having a N- substituted maleimide group and an acidic substituent (a), epoxy resin (B) and chemical roughening compounds having at least two epoxy groups in a molecule (C) A thermosetting insulating resin composition for wiring boards ,
The thermosetting insulating resin composition for multilayer printed wiring boards, wherein the chemical roughening compound (C) is a crosslinked rubber particle (excluding an acrylic rubber having a functional group) or a polyvinyl acetal resin. .

(R ₁ independently represents a hydroxyl group, carboxyl group or sulfonic acid group which is an acidic substituent, and R ₂ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom. X is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.) The thermosetting insulating resin composition for multilayer printed wiring boards according to claim 1, wherein the crosslinked rubber particles are at least one selected from the group consisting of core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles and crosslinked styrene butadiene rubber particles. . Furthermore, the thermosetting insulating resin composition for multilayer printed wiring boards of Claim 1 or 2 containing the amine compound (D) which has an at least 2 primary amino group in 1 molecule. The multilayer print according to any one of claims 1 to 3, further comprising a thermoplastic resin (E) (however, excluding crosslinked rubber particles (excluding acrylic rubber having a functional group) and polyvinyl acetal resin). A thermosetting insulating resin composition for wiring boards . Furthermore, the thermosetting insulating resin composition for multilayer printed wiring boards in any one of Claims 1-4 containing the phosphorus compound (F) which provides a flame retardance. The thermosetting insulation for multilayer printed wiring boards according to any one of claims 1 to 5, further comprising a curing agent (excluding the curing agent (A)) and / or a curing accelerator (G) of the epoxy resin. Resin composition. The amount of the inorganic filler (H) is 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 (G) in terms of solid matter. The thermosetting insulating resin composition for multilayer printed wiring boards according to any one of the above. A semi-cured film of the thermosetting insulating resin composition for a multilayer printed wiring board according to any one of claims 1 to 7 is formed on the surface of the support. A prepreg, wherein the thermosetting insulating resin composition for a multilayer printed wiring board according to any one of claims 1 to 7 is impregnated in a sheet-like reinforcing base material comprising fibers. The insulating resin layer is (1) a thermosetting insulating resin composition for multilayer printed wiring boards according to any one of claims 1 to 7, (2) an insulating film with a support according to claim 8, (3) A laminated board formed using any one of the prepregs according to claim 9.   A multilayer printed wiring board manufactured using the laminated board according to claim 10.