JP2016148040A - Prepreg for printed wiring board, laminate and print circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate and a print circuit board having an excellent resin impregnation property or adhesion between a resin and glass cloth, with a low thermal expansion coefficient and excellent heat resistance and insulation reliability.SOLUTION: In a prepreg for a printed wiring board, a thermosetting resin composition including a resin (A) containing an unsaturated maleimide group and a thermosetting resin (B) is impregnated or applied to at least one kind of glass cloth selected from a group composed of S glass, D glass and Q glass treated by a specific phenylamino silane treatment agent so that the content of resin in the prepreg after drying is 20-90 mass%, and then heated and dried to form into a B-stage condition.SELECTED DRAWING: None

Description

  The present invention relates to a prepreg using a glass cloth suitable for semiconductor packages and printed wiring boards, a laminated board, and a printed wiring board. Specifically, the resin impregnation property and the adhesion between the resin and the glass cloth are good, and the thermal expansion coefficient. The present invention relates to a prepreg, a laminated board, and a printed wiring board that are low in heat resistance and insulation reliability.

  In recent years, with the trend toward miniaturization and higher performance of electronic devices, the printed wiring boards have become increasingly dense and highly integrated, and as a result, reliability has been improved by improving the heat resistance of laminated boards for wiring. There is an increasing demand for improvement. In such applications, it is required to combine excellent heat resistance and a low linear expansion coefficient. Particularly in recent years, such characteristics are particularly required for semiconductor package substrates and the like.

As a laminated board for a printed wiring board, one obtained by curing and integrally molding a resin composition mainly composed of an epoxy resin and a glass woven fabric is generally used.
Epoxy resins have an excellent balance of insulation, heat resistance, cost, etc., but in order to meet the demands for improved heat resistance due to the recent high-density mounting of printed wiring boards and multi-layer configurations, the heat resistance is unavoidable. There is a limit to the improvement.
Moreover, since the coefficient of thermal expansion is large, low thermal expansion is achieved by selecting an epoxy resin having an aromatic ring or by highly filling an inorganic filler such as silica (for example, see Patent Document 1). However, increasing the filling amount is known to cause a decrease in insulation reliability due to moisture absorption, insufficient adhesion between the resin and the wiring layer, and poor press molding.

  Polybismaleimide resin widely used for high-density packaging and multi-layered laminates is very excellent in heat resistance, but has high moisture resistance and has difficulty in adhesion. Furthermore, there is a drawback in that productivity is poor because a high temperature and a long time are required for lamination when compared with an epoxy resin. In general, an epoxy resin can be cured at a temperature of 180 ° C. or lower, but when a polybismaleimide resin is laminated, a high temperature of 220 ° C. or higher and a long-time treatment are required.

  A thermosetting resin composition containing an epoxy resin having a naphthalene skeleton and a phenol resin and a modified imide resin as main components is known (see, for example, Patent Document 2). Although this modified imide resin-containing composition is improved in moisture resistance and adhesiveness, it is modified with a low molecular weight compound containing a hydroxyl group and an epoxy group to ensure solubility in a general-purpose solvent such as methyl ethyl ketone. There is a problem that the heat resistance of the resin is significantly inferior to that of the polybismaleimide resin.

  Moreover, the glass cloth used for the laminated board for printed wiring boards generally uses a silane coupling treatment agent in order to develop resin impregnation properties and adhesiveness at the interface between the resin and the glass cloth. Examples of conventionally used silane coupling agents for epoxy resins include epoxy silane coupling agents and cationic silane coupling agents. However, in the case of a resin composition based on polybismaleimide resin, even if an epoxy-based silane coupling agent is used, the impregnation of the resin and the adhesion between the resin and the glass cloth are inferior. There is a problem that decreases.

On the other hand, the glass cloth used in the laminated board for printed wiring board is generally E glass (thermal expansion coefficient: 5.6 ppm / ° C., composition SiO ₂ : 53 to 56%, Al ₂ O ₃ : 14 to 18%, CaO _{: 20~24%, B 2 O 3} : 5~10%, MgO, R 2 O: <1%) is used. However, in recent years, glass cloths (S glass, D glass, etc.) having a low coefficient of thermal expansion have been used as the thermal expansion coefficient of printed wiring board laminates has been reduced.
When glass cloth (S glass, D glass, etc.) with a low thermal expansion coefficient is used, drilling workability is poor because the glass cloth is hard, and insulation reliability is affected by the effect of cracks generated at the interface between the resin and the glass cloth during processing. There is a problem that is significantly reduced. Therefore, even when a glass cloth having a low thermal expansion coefficient is used, a glass cloth treating agent capable of ensuring insulation reliability is essential.

Japanese Patent Laid-Open No. 5-148343 JP-A-6-263843

    In view of the present situation, the object of the present invention is to select a thermosetting resin composition excellent in heat resistance and adhesiveness and a glass cloth treating agent suitable for the composition, and to impregnate the resin and adhere the resin to the glass cloth. An object of the present invention is to provide a laminate and a printed wiring board that are good, have a low coefficient of thermal expansion, and are excellent in heat resistance and insulation reliability.

  As a result of intensive studies to achieve the above object, the present inventors have made a thermosetting resin composition comprising a resin and a thermosetting resin produced by reacting a maleimide compound and an amine compound in an organic solvent. Was found to be achieved by using a prepreg for a printed wiring board obtained by impregnating a specific glass cloth treated with a phenylaminosilane treating agent, heating and drying to form a B-stage. The invention has been completed. The present invention has been completed based on such knowledge.

That is, this invention provides the following prepregs for printed wiring boards, laminates, and printed wiring boards.
1. A maleimide compound (a) having at least two N-substituted maleimide groups in a molecule and an amine compound (b) having at least two primary amino groups in one molecule are reacted in an organic solvent. A thermosetting resin composition containing an unsaturated maleimide group-containing resin (A) and a thermosetting resin (B) produced by treatment with a phenylaminosilane treating agent represented by the following general formula (I) A printed wiring board prepreg obtained by impregnating a glass cloth having a thermal expansion coefficient of 5 ppm / ° C. or less, heat drying and forming a B-stage.

(In the formula, R is an alkylene group having 1 to 5 carbon atoms, and X is independently OCH ₃ , OC ₂ H ₅ or OC ₃ H _7. )

2. The prepreg for printed wiring boards according to claim 1, further comprising an amine compound (C) having an acidic substituent represented by the general formula (II) in the thermosetting resin composition.

(In the formula, when there are a plurality of R _{1 s} , each independently represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group; and when there are a plurality of R _{2 s} , each independently represents a hydrogen atom or a carbon number. 1 to 5 aliphatic hydrocarbon groups or halogen atoms, 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.

3. The prepreg for printed wiring board according to 1 or 2 above, further comprising an inorganic filler (D) in the thermosetting resin composition.
4). The printed wiring board prepreg according to any one of the above 1 to 3, further comprising a flame retardant (E) in the thermosetting resin composition.
5. The prepreg for printed wiring boards according to any one of 1 to 4 above, wherein the thermosetting resin (B) is an epoxy resin and / or a cyanate resin.
6). A laminated board, wherein the insulating resin layer is formed by using the printed wiring board prepreg according to any one of 1 to 5 above.
7). 7. A printed wiring board obtained by subjecting a metal foil arranged on one or both sides of an insulating resin layer in the laminated board of 6 to circuit processing.

  The laminate obtained by using the prepreg for printed wiring board of the present invention has good moldability, low thermal expansion coefficient, excellent heat resistance, adhesiveness and insulation reliability, high density mounting, high multilayer Can be obtained, and can be suitably used as a material for electrical / electronic equipment with enhanced performance.

Hereinafter, the present invention will be described in detail.
First, the present invention provides an organic solvent comprising a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule and an amine compound (b) having at least two primary amino groups in one molecule. Treatment of phenylaminosilane represented by the following general formula (I) with a thermosetting resin composition containing a resin (A) having an unsaturated maleimide group and a thermosetting resin (B) produced by reacting in the reaction: Provided is a prepreg for a printed wiring board obtained by impregnating a glass cloth treated with an agent into a glass cloth having a thermal expansion coefficient of 5 ppm / ° C. or less and drying by heating to form a B stage.

(In the formula, R is an alkylene group having 1 to 5 carbon atoms, and X is independently OCH ₃ , OC ₂ H ₅ or OC ₃ H _7. )

  Here, the resin (A) having an unsaturated maleimide group has a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule and at least two primary amino groups in one molecule. The amine compound (b) is produced by reacting in an organic solvent.

  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) sulfur 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-male Imidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4 -(3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1, 1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4,4-bis (4-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone Bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2′-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide Bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3- Maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1 , 4-Bis [4- (4-maleimide) Enoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -Α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3 , 5-Dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [ 4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, [alpha] -dimethylbenzyl] benzene, polyphenylmethanemaleimide [for example, trade name: BMI-2300 manufactured by Daiwa Kasei Co., Ltd.] and the like.

  These maleimide compounds (a) 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 and polyphenylmethanemaleimide are preferred, and bis (4-maleimidophenyl) methane is particularly preferred from the viewpoint of solubility in a solvent.

  The amine compound (b) having at least two primary amino groups in one molecule is not particularly limited, and examples thereof include 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-tert-butyl) toluene, 2,4-diaminoxylene, 2,4-diamino Pyridine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminodurene, 4,5-diamino-6-hydroxy- -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-aminobenzyl) ) 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, 3,3'-diethyl-4, 4'-diaminodiphenylmethane, 3,3'-dimethyl, 5,5'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-methyle -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-aminophenoxy) 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, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, bis [4 -(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4 , 4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl-6,6′-disulfonic acid, 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′-dichloro-4, '-Diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenyl sulfide, 4,4'-diamino-3,3'-biphenyldiol, 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) fluorene, diaminoanthraquinone, 3,7-diamino-2,8-dimethyldibenzothiophene sulfone, and other aromatic amines, ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylene Diamine, heptamethylenediamine, octamethylenediamine, Nonamethylenediamine, decamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5 -Methyl nonamethylenediamine, 1,4-diaminocyclohexane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, diaminopolysiloxane, 2,5-diamino-1,3,4-oxadiazol, bis Aliphatic amines such as (4-aminocyclohexyl) methane, melamine, benzoguanamine, acetoguanamine, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-allyl-s-triazine, 2 , 4-Diamino-6-acryloyloxy Chill -s- triazine, guanamine compound such as 2,4-diamino-6-methacryloyloxyethyl -s- triazine.

  These amine compounds (b) can be used alone or in admixture of two or more. Among these, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, and 4,4′-diaminodiphenylmethane, which are aromatic amines having good reactivity and heat resistance. 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, benzidine, 4,4′-bis (4- Aminophenoxy) biphenyl, 4,4′-diaminodiphenyl sulfide, 4,4′-diamino-3,3′-bi Benzoguanamine which is a phenyldiol and a guanamine compound is preferable, and p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 3,3 ′ from the viewpoint of low cost. -Dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and benzoguanamine are more preferred, and 4,4'-diaminodiphenylmethane is particularly preferred from the viewpoint of solubility in a solvent.

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, And sulfur atom-containing solvents such as dimethyl sulfoxide.
These organic solvents can be used alone or in combination of two or more. 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.

The ratio of the amount of the maleimide compound in the reaction (a) with an amine compound (b), equivalent of the equivalent of the maleimide group _{(T a)} of (a) to equivalents of -NH ₂ group of (b) _{(T b)} The ratio (T _a / T _b ) is preferably in the range of 1.0 to 10.0, and the relevant amount ratio (T _a / T _b ) is more preferably in the range of 2.0 to 10.0. . When the ratio (T _a / T _b ) is 1.0 or more, gelation and heat resistance do not decrease, and when it is 10.0 or less, solubility in organic solvents and copper foil adhesion And heat resistance does not decrease.
Moreover, it is preferable to set it as 10-1000 mass parts with respect to 100 mass parts of total amounts of a maleimide compound (a) and an amine compound (b), and, as for the usage-amount of an organic solvent, it is more preferable to set it as 100-500 mass parts. 200 to 500 parts by mass is particularly preferable. The amount of the organic solvent used is 10 parts by mass or more from the viewpoint of solubility, and 1000 parts by mass or less from the viewpoint of reaction time.

The reaction temperature of the maleimide compound (a) and the amine compound (b) 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.
A reaction catalyst can be arbitrarily used for this reaction, and is not particularly limited. Examples of the reaction catalyst include amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and triphenyl. Examples thereof include phosphorus-based catalysts such as phosphine, and one kind or a mixture of two or more kinds can be used.

  Examples of the thermosetting resin (B) include epoxy resins, phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene. Resins, silicone resins, triazine resins, melamine resins and the like can be mentioned, and one or more of these can be mixed and used. Among these, epoxy resins and cyanate resins are preferable from the viewpoint of moldability and electrical insulation.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin. , Stilbene type epoxy resin, Triazine skeleton containing epoxy resin, Fluorene skeleton containing epoxy resin, Triphenolphenol methane type epoxy resin, Biphenyl type epoxy resin, Xylylene type epoxy resin, Biphenyl aralkyl type epoxy resin, Naphthalene type epoxy resin, Dicyclopentadiene -Type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and diglycidyl ether compounds of polycyclic aromatics such as anthracene And these phosphorus-containing epoxy resin obtained by introducing a phosphorus compound listed, among these, heat resistance, biphenyl aralkyl type epoxy resin from the viewpoint of flame retardancy, naphthalene type epoxy resins are preferred. These can be used alone or in combination of two or more.

  Examples of the cyanate resin include novolak-type cyanate resin, bisphenol A-type cyanate resin, bisphenol E-type cyanate resin, and bisphenol-type cyanate resin such as tetramethylbisphenol F-type cyanate resin, and prepolymers in which these are partially triazine. Can be mentioned. Among these, a novolak type cyanate resin is preferable from the viewpoint of heat resistance and flame retardancy. These can be used alone or in combination of two or more.

For the thermosetting resin (B), a curing agent and a curing accelerator can be used as necessary.
Examples of the curing agent include polyfunctional phenol compounds such as phenol novolak, cresol novolak, aminotriazine novolak resin, amine compounds such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, phthalic anhydride, pyromellitic anhydride, maleic anhydride, Examples thereof include acid anhydrides such as maleic anhydride copolymer, and these can be used alone or in combination.

  Examples of the curing accelerator include zinc metal naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III) and the like, imidazole And derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, and the like, and these can be used alone or in combination.

In the thermosetting resin composition used for the prepreg of the present invention, an amine compound (C) having an acidic substituent represented by the following general formula (II) is optionally added together with a resin (A) having an unsaturated maleimide group. Can be contained.
When the amine compound (C) having an acidic substituent is contained, the resin (A) having an unsaturated maleimide group and the amine compound (C) having an acidic substituent should be reacted in an organic solvent before blending. Is preferred.

(In the formula, when there are a plurality of R _{1 s} , each independently represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group; and when there are a plurality of R _{2 s} , each independently represents a hydrogen atom or a carbon number. 1 to 5 aliphatic hydrocarbon groups or halogen atoms, 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 amine compound (C) having an acidic substituent represented by the general formula (II) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, and m-aminobenzoic acid. O-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, and the like. In view of solubility and synthesis yield, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxyaniline are preferable, M-Aminophenol and p-aminophenol are more preferable from the viewpoint of sex, and m-aminophenol from the viewpoint of low toxicity. It is particularly preferred.

  The maleimide compound (a) and the amine compound (b) are reacted with an organic solvent used when the resin (A) having an unsaturated maleimide group and the amine compound (C) having an acidic substituent are reacted. Solvents similar to the organic solvents used are used.

Wherein the amount of the resin having an unsaturated maleimide group-containing amine compound (A) is an acidic substituent (C) is, (C) to equivalents of -NH ₂ group of the component (T _C) of the component (A) maleimide preferably the equivalent ratio of equivalents of groups _{(T a) (T a /} T C) is in the range of 1.0 to 10.0, the corresponding amount ratio _(T a / T _C) is 2.0 to 10. A range of 0 is more preferable. It is preferred to in terms of gelation and heat resistance appropriate amount ratio _(T A _/ T _C) and 1.0 or more, solubility in an organic solvent, 10.0 or less from the viewpoint of plating adhesion strength and heat resistance and It is preferable to do.

  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 (C). It is especially preferable to set it as -500 mass parts. The blending amount of the organic solvent is preferably 10 parts by mass or more from the viewpoint of the solubility of the component (C), and is preferably 1000 parts by mass or less from the viewpoint of reaction time.

The reaction temperature of the component (A) and the component (C) 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.
A reaction catalyst can be optionally used for this reaction, and is not particularly 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 thermosetting resin composition used for the prepreg of the present invention may further optionally contain an inorganic filler (D).
As inorganic filler (D), silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, sulfuric acid Examples thereof include glass powder such as barium, aluminum borate, potassium titanate, E glass, T glass, and D glass, hollow glass beads, and the like, and these can be used alone or in combination.
Among these, silica is particularly preferable from the viewpoints of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include a precipitated silica produced by a wet method and having a high water content, and a dry method silica produced by a dry method and containing almost no bound water. The dry method silica further includes differences in production methods. Examples include crushed silica, fumed silica, and fused spherical silica. Among these, fused spherical silica is preferable because of its low thermal expansion and high fluidity when filled in a resin.
Among the inorganic fillers (D), aluminum hydroxide, boehmite, magnesium hydroxide, etc. act as a flame retardant. These flame retardant inorganic fillers are preferably used in combination.

  When fused spherical silica is used as the inorganic filler (D), the average particle size is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm. By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and by setting it to 10 μm or less, the mixing probability of coarse particles is reduced. Generation of defects due to coarse particles can be suppressed. Here, the average particle size is a particle size at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%, and the laser diffraction scattering method is used. It can be measured with the used particle size distribution measuring device or the like.

  The content of the inorganic filler (D) is preferably 10 to 60% by volume in the thermosetting resin composition, and more preferably 20 to 55% by volume. By setting the content of the inorganic filler to 10 to 60% by volume, the moldability and low thermal expansion of the prepreg can be kept good.

The thermosetting resin composition used in the prepreg of the present invention can further optionally contain a flame retardant (E).
As the flame retardant, other than aluminum hydroxide, boehmite and magnesium hydroxide listed in the inorganic filler (D), halogen-containing flame retardant containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl Phosphate, phosphoric acid ester compounds, phosphorus flame retardants such as red phosphorus, guanidine sulfamate, melamine sulfate, melamine polyphosphate, melamine cyanurate and other nitrogen flame retardants, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, Examples include inorganic flame retardants such as antimony trioxide.

  In addition to the above components, the thermosetting resin composition used in the prepreg of the present invention has a thermoplastic resin, an elastomer, an organic filler, an ultraviolet absorber, as long as the thermosetting properties of the resin composition are not impaired. Antioxidants, photopolymerization initiators, fluorescent brighteners, adhesion improvers and the like can be used.

  The thermoplastic resins include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, polyetherether. Examples include ketone resins, polyetherimide resins, silicone resins, and tetrafluoroethylene resins.

  Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.

  Organic fillers include resin fillers of uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc., acrylate ester resins, methacrylate ester resins, conjugated diene resins, etc. And a core-shell resin filler having a glassy shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like.

  In addition, benzotriazole UV absorbers as UV absorbers, hindered phenol and hindered amine antioxidants as antioxidants, benzophenones, benzyl ketals, and thioxanthone photopolymerization initiators as photopolymerization initiators. Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative, and examples of the adhesion improver include urea compounds such as urea silane, and coupling agents such as silane, titanate, and aluminate.

The prepreg of the present invention is preferably produced as a varnish in which the above components are dissolved or dispersed in an organic solvent.
Examples of the organic solvent used here include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and butyl acetate. , Ester solvents such as propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide Examples thereof include sulfur atom-containing solvents such as 1 type or a mixture of two or more types.
Among these, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity.
Further, at the time of blending, it is also preferable that the inorganic filler is pretreated with a silane-based or titanate-based coupling agent or a surface-treating agent such as a silicone oligomer, or an integral blend treatment.
It is preferable that the resin composition in the varnish finally obtained is 40 to 90 mass% of the whole varnish, and it is more preferable that it is 50 to 80 mass%. By setting the content of the resin composition in the varnish to 40 to 90% by mass, it is possible to maintain good coatability and obtain a prepreg having an appropriate resin composition adhesion amount.

In the prepreg of the present invention, a glass cloth having a low thermal expansion coefficient of 5 ppm / ° C. or less is used for the purpose of reducing the thermal expansion coefficient of the laminate.
The type of the glass cloth is not particularly limited as long as the thermal expansion coefficient is 5 ppm / ° C. or less. For example, S glass (thermal expansion coefficient: 2.4 ppm / ° C., composition SiO ₂ : 62 to 65%, Al ₂ O ₃ : 20 to 25%, MgO: 10 to 15%, R ₂ O, B ₂ O ₃ : 0 to 1%, D glass (thermal expansion coefficient: 3.1 ppm / ° C., composition SiO ₂ : 75 to 76%, Al ₂ O ₃ : 20 to 25%, B ₂ O ₃ : 19 to 20%, R ₂ O: <3%, Al ₂ O ₃ , CaO, MgO: <1%), Q glass (thermal expansion coefficient: 0. 5 ppm / ° C., composition SiO ₂ : 99.9%).

  In the present invention, the above glass cloth treated with a phenylaminosilane treating agent represented by the following general formula (I) is used. The treatment amount of the phenylaminosilane treating agent is preferably 0.05 to 1.0 part by mass with respect to 100 parts by mass of the glass cloth.

(In the formula, R is an alkylene group having 1 to 5 carbon atoms, and X is independently OCH ₃ , OC ₂ H ₅ or OC ₃ H _7. )

  The prepreg of the present invention was obtained by impregnating the above thermosetting resin composition into a glass cloth treated with a phenylaminosilane treating agent and having a thermal expansion coefficient of 5 ppm / ° C. or less, and drying by heating to obtain a B stage. Is. Hereinafter, the prepreg of the present invention will be described in detail.

  The prepreg of the present invention is obtained by applying the above-mentioned thermosetting resin composition to the glass cloth by a method such as impregnation, spraying or extrusion, and semi-curing (B-stage) by heating or the like. Prepreg can be manufactured. The thickness in particular of glass cloth is not restrict | limited, For example, about 0.02-0.5 mm can be used. After impregnating or coating the glass cloth so that the amount of the resin composition attached to the glass cloth is 20 to 90% by mass with the resin content of the prepreg after drying, it is usually at a temperature of 100 to 200 ° C. The prepreg of the present invention can be obtained by heating and drying for 1 to 30 minutes and semi-curing (B-stage).

In the laminated board of the present invention, the insulating resin layer is formed using the above prepreg, and can be formed by laminating using the prepreg. For example, it can be manufactured by laminating 1 to 20 prepregs of the present invention and laminating and forming a metal foil such as copper and aluminum on one or both sides thereof.
The metal foil is not particularly limited as long as it is used for the laminate for electrical insulating material. The molding conditions may be, for example, a laminated plate for an electrical insulating material and a multilayer plate. For example, a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine or the like is used, and the temperature is 100 to 250 ° C. and the pressure is 0. It can be molded in a range of 2 to 10 MPa and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.

  The printed wiring board of the present invention is obtained by processing a metal foil disposed on one or both sides of the insulating resin layer in the laminated board, and is manufactured by forming a circuit on the surface of the laminated board. The That is, the conductor layer of the laminated board according to the present invention is subjected to wiring processing by a normal etching method, and a plurality of laminated boards subjected to wiring processing through the above-described prepreg are laminated and subjected to hot press processing to be multilayered at once. Then, a multilayer printed wiring board can be manufactured through formation of a through hole or blind via hole by drilling or laser processing and formation of an interlayer wiring by plating or conductive paste.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
In addition, the performance of the copper clad laminates obtained in each example and comparative example was measured and evaluated by the following method.

(1) Coefficient of thermal expansion A 5 mm square evaluation board from which a copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and the evaluation board X was measured using a TMA test apparatus (manufactured by DuPont, TMA2940). The coefficient of thermal expansion below the Tg in the direction was measured.

(2) 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 the pressure cooker test apparatus manufactured by Hirayama Mfg. Co., Ltd. was used. After performing pressure-cooker treatment for up to 4 hours under the condition of 0.2 MPa, 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.

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

(4) Heat resistance with copper (T-300)
A 5 mm square evaluation board was produced from the copper clad laminate, and evaluation was performed by measuring the time until the evaluation board swells at 300 ° C. using a TMA test apparatus (manufactured by DuPont, TMA2940).

(5) Insulation reliability A copper-clad laminate was processed with a drill having a diameter of 0.15 mm to a hole interval of 0.25 mm, a voltage of 5.5 V was applied between the holes, and conditions of 130 ° C. and 85% RH Evaluation was made by measuring the insulation resistance after standing for 200 hours.

Production Example 1: Production of Resin (A-1) Having Unsaturated Maleimide Group 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, was charged with bis (4 -Maleimidophenyl) methane: 569.30 g, 4,4′-diaminodiphenylmethane: 59.04 g, and propylene glycol monomethyl ether: 350.00 g, a resin having an unsaturated maleimide group by reacting for 5 hours while refluxing A solution of (A-1) was obtained.

Production Example 2: Production of Resin (A-2) Having Unsaturated Maleimide Group A reaction vessel having a thermometer, a stirrer, and a moisture quantifier with a reflux condenser is provided with a bis (4 -Maleimidophenyl) methane: 555.04 g, 3,3′-diethyl-4,4′-diaminodiphenylmethane: 73.84 g, and propylene glycol monomethyl ether: 350.00 g, and reacted for 5 hours while refluxing. A solution of resin (A-2) having an unsaturated maleimide group was obtained.

Production Example 3: Production of Resin (A-3) Having Unsaturated Maleimide Group Into 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 -Maleimidophenyl) Methane: 556.53 g, 3,3′-diaminodiphenylsulfone: 72.29 g, and dimethylacetamide: 350.00 g were added and reacted at 100 ° C. for 5 hours to give a resin having an unsaturated maleimide group ( A solution of A-3) was obtained.

Production Example 4: Production of Curing Agent (A-4) Having Acidic Substituent and Unsaturated Maleimide Group 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. Bis (4-maleimidophenyl) methane: 556.53 g, 3,3′-diethyl-4,4′-diaminodiphenylmethane: 74.03 g, m-aminophenol: 21.19 g, and dimethylacetamide: 350.00 g And reacted at 100 ° C. for 5 hours to obtain a resin (A-4) solution having an acidic substituent and an unsaturated maleimide group. In Production Example 4, the amine compound having an acidic substituent of the component (C) is reacted with the component (A) in advance.

Examples 1-5, Comparative Examples 1-5
The following components were mixed at the blending ratios (parts by mass) shown in Tables 1 and 2, and methyl ethyl ketone was used as a solvent to obtain a uniform varnish having a resin content of 65% by mass. The flame retardant inorganic filler AlOOH of component (D) also serves as the flame retardant of component (E), and (D) inorganic filler in the thermosetting resin composition in all examples and comparative examples. Is 50% by mass (32% by volume).
Next, the obtained varnish was impregnated and applied to an S-glass cloth or E-glass cloth having a thickness of 0.1 mm and treated with the treating agents shown in Tables 1 and 2, and at 160 ° C. for 10 minutes. Heat drying was performed 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 KPa and a temperature of 185 ° C. for 90 minutes to obtain a copper clad laminate.
The measurement and evaluation results of the obtained copper-clad laminate are shown in Tables 1 and 2.

(A) Resin having an unsaturated maleimide group: Solutions (A-1) to (A-4) obtained in Production Examples 1 to 4.
(B) Thermosetting resin: biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000-H).
(D) Inorganic filler: fused silica (manufactured by Admatechs, trade name: SO-25R).
Curing accelerator: an addition reaction product of a bisphenol A type epoxy resin having a structure represented by the following formula (III) and 2-phenylimidazole.
Flame retardant: Boehmite type aluminum hydroxide (manufactured by Kawai Lime Industry Co., Ltd., trade name: BMT-3L).
Glass cloth (# 2116: thickness 0.095mm)
S glass (manufactured by Nittobo Co., Ltd., trade name: GAT-7010, coefficient of thermal expansion: 2.4 ppm / ° C.).
E glass (manufactured by Nitto Boseki Co., Ltd., trade name: GA-7010, thermal expansion coefficient: 5.6 ppm / ° C.).
Glass cloth treatment agent:
KBM573: N-phenyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.).
KBM403: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.).

As is apparent from Table 1, all of the examples of the present invention have a low coefficient of thermal expansion and are excellent in all of solder heat resistance, moisture absorption resistance, heat resistance with copper, and insulation reliability.
On the other hand, in Comparative Examples 1 to 4 in Table 2, since the glass cloth is not treated with the phenylaminosilane treating agent, the solder heat resistance, the heat resistance with copper, and the insulation reliability are remarkably inferior. Comparative Example 5 uses a phenylaminosilane treating agent as a glass cloth treating agent, and is excellent in solder heat resistance, moisture absorption resistance, heat resistance with copper, and insulation reliability. The expansion coefficient is greatly inferior compared with the examples of the present invention.
Therefore, it can be seen that the present invention provides a prepreg, a laminate and a printed wiring board having a low thermal expansion coefficient and excellent heat resistance and insulation reliability.

  According to the present invention, a prepreg, a laminated board and a printed wiring board having a low thermal expansion coefficient and excellent heat resistance and insulation reliability can be obtained, and can be suitably used as a material for high-performance electric / electronic equipment. .

Claims (2)

S glass treated with a phenylaminosilane treating agent represented by the following general formula (I), a thermosetting resin composition containing a resin (A) having an unsaturated maleimide group and a thermosetting resin (B), At least one glass cloth selected from the group consisting of D glass and Q glass is impregnated or coated so that the resin content of the prepreg after drying is 20 to 90% by mass, dried by heating, and B stage. A method for producing a prepreg for a printed wiring board.

(In the formula, R is an alkylene group having 1 to 5 carbon atoms, and X is independently OCH ₃ , OC ₂ H ₅ or OC ₃ H _7. )   A plurality of printed wiring board prepregs obtained by the manufacturing method according to claim 1 are laminated, and a laminated board in which a metal foil is disposed on one or both sides thereof is formed on the laminated board by drilling or laser processing. A method for manufacturing a multilayer printed wiring board, wherein a blind via hole is formed.