JPH0713165B2 - Thermosetting resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermosetting resin composition, and more specifically, it is suitable for a multilayer printed circuit board excellent in flame retardancy and heat resistance and electrical characteristics. Regarding laminated materials.

[Conventional technology]

Conventionally, a laminated board of a phenol resin, an epoxy resin, a polyimide resin or the like has been mainly used as a laminated material for a multilayer printed circuit board. However, in recent years, a printed circuit board having excellent electric characteristics has been demanded in order to improve a signal transmission speed as a large-scale computer is operated at high speed. Particularly, in order to shorten the signal transmission delay time and reduce the circuit thickness, a low dielectric constant printed circuit board is required. As such a flame-retardant low dielectric constant laminated material, a tetrafluoroethylene resin (PTFE) laminated plate and the like have been developed.

[Problems to be solved by the invention]

However, the PTFE laminated plate has the problems that the resin is thermoplastic and the glass transition temperature is low, so the coefficient of thermal expansion is large at high temperatures and the dimensional stability is not sufficient. When applied to a multilayer printed circuit board, it has a wiring density similar to that of an epoxy resin and is not very merit as a low dielectric constant material. Further, since there is no suitable solvent for PTFE, the bonding method by heating, melting and pressing is generally used, but it has a drawback that the melting temperature is very high. As described above, compared with the conventional method, PTFE has many difficulties in workability and moldability, and thus it is necessary to significantly change the manufacturing method.

An object of the present invention is to provide a flame-retardant laminated material capable of high-density wiring comparable to that of a polyimide-based laminated material, as a material replacing the polyimide-based multilayer printed wiring board that has been conventionally used in a large-scale computer. A resin composition for that purpose is provided.

[Means for solving problems]

The present invention will be outlined. First, the first relates to a thermosetting resin composition, and its characteristics are (a) the following general formula: (Wherein A is hydrogen, other organic groups, and halogen groups, R is an alkenyl or unsaturated carboxyl group, m is 1 to 4, and n is a number of 1 to 100). Of a poly (p-hydroxystyrene) derivative, and (b) a block polymer represented by the following general formula [II] (where B is a glycidyl ether epoxy copolymer B-C-B [II]). Yes, C has a double bond in the side chain and is 0 in the main carbon chain.
Polybutadiene low polymer with ~ 10 hydroxyl groups (molecular weight
300-5000)} and an epoxy-modified polybutadiene that is an essential component.

The prepolymer which is an essential component of the thermosetting resin composition of the present invention is represented by the general formula I as described above. Specific examples thereof include the compounds corresponding to the general formula I: vinyl ether of poly (p-hydroxystyrene), isobutenyl ether, allyl ether, acrylic acid ester, methacrylic acid ester, epoxy methacrylate and the like. There is bromide. These may be used alone or in combination of two or more as desired.

In the epoxy-modified polybutadiene which is one of the essential components of the thermosetting resin of the present invention represented by the general formula [II], specific examples of the glycidyl ether-based epoxy resin used for modification include cyglycidyl. Ether bisphenol A, diglycidyl ether 2,2'-dibromobisphenol A, diglycidyl ether 2,2 ', 4,4'-
Tetrabromobisphenol A, diglycidyl ether
There are 2,2'-dimethylbisphenol A, diglycidyl ether 2,2 ', 4-trimethylbisphenol A, phenol novolak type epoxy resin, and orthocresol novolak type epoxy resin. These may be used alone or in combination of two or more, if desired. By adding (b) epoxy-modified polybutadiene to (a) poly (p-hydroxystyrene), moldability, flexibility, adhesion with copper foil, mechanical strength, etc. are improved. Further, by further adding an epoxy curing agent to the above resin compositions (a), (b) and (c), the above various characteristics were further improved and the dielectric constant was reduced.

The compounding ratio (weight) of the above-mentioned alkenyl ether of poly (p-hydroxystyrene), acrylate, methacrylate and epoxymethacrylate, and its dielectric and epoxy-modified polybutadien is selected in the range of 90:10 to 10:90. If the content of is higher than this, the relative permittivity of the thermosetting resin will be high, and if it is too low, flame retardancy,
The effects of alkenyl ethers of poly (p-hydroxystyrene), acrylates, methacrylates and their derivatives on laminate properties such as heat resistance and adhesion to copper foil become insignificant. A particularly preferable mixture ratio of both components is 70:30.
~ 30: 70.

Next, a general method for manufacturing a laminated plate in the present invention will be described.

First, a varnish is prepared by dissolving a poly (p-hydroxystyrene) derivative and epoxy-modified polybutadiene in an organic solvent. At this time, for the purpose of promoting dissolution, heating may be performed at a temperature of 80 ° C. or lower for about 30 minutes.

Examples of the organic solvent include toluene, xylene acetone,
Methyl ethyl ketone, ethanol, methanol, 3-methoxypropanol, N, N'-dimethylformamide,
There are N-methylpyrrolidone, dimethyl sulfoxide, trichloroethylene, 1,1,2-trichloroethane, etc.,
Any solvent can be used without limitation as long as it can uniformly mix the component polymers. A radical polymerization initiator and an epoxy curing agent are added to the prepared varnish to prepare an impregnating varnish.

Typical examples of the radical polymerization agent include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxylaurate,
Di-t-butyl peroxy phthalate, dibenzyl oxide, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane, t-butyl cumyl peroxide, t-butyl hydroperoxide, di-t -Butyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne (3), diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, pinanbairooxide, 2,5- Examples include dimethylhexane-2,5-dihydroperoxide and cumene hydroperoxide. These are preferably added in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin composition.

Typical examples of epoxy curing agents are 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, m-phenylenediamine, p-phenylenediamine, 4,4'- Diaminodiphenylmethane, 2,2'-bis (4-aminophenyl) propane, benzine, 4,4'-diaminophenyl oxide,
4,4'-diaminophenyl sulfone, bis (4-aminophenyl) methylphosphine oxide, bis (4-aminophenyl) phenylphosphine oxide, bis (4-
Aminophenyl) methylamine, 1,5-diaminonaphthalene, m-xylylenediamine, 1,1′-bis (paminophenyl) furatane, p-xylylenediamine, hexamethylenediamine, 6,6′-diamino-2,2 ′ -Dipyridyl, 4,4′-diaminobenzophenone, 4,4′-diaminoazobenzene, bis (4-aminophenyl) phenylmethane, 1,1-bis (4-aminophenyl) cyclohexane, 1,1-bis (4- Amino-3-methylphenyl)
Cyclohexane, 2,5-bis (m-aminophenyl)-
1,3,4-oxadiazole, 2,5-bis (p-aminophenyl) -1,3,4-oxadiazole, 2,5-bis (m-aminophenyl) thiazolo (4,5-d) thiazole , 5,5-
Di (m-aminophenyl)-(2,2 ') bis (1,3,4-oxydiazolyl), 4,4'-diaminodiphenyl ether, 4,4'-bis (paminophenyl) -2,2 ′ -Dithiazole, m-bis (4-p-aminophenyl-2-thiazolyl) benzene, 4,4′-diaminobenzanilide,
4,4'-diaminophenylbenzoate, N, N'-bis (4-aminobenzyl) -p-phenylenediamine, 4,
4'-methylenebis (2-dichloroaniline), benzoquanamine, methylguanamine, tetramethylbutadiamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrimellitate) ), Glycerol tris (anhydrotrimellitate), maleic anhydride, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2
-Undecyl imidazole and the like, and at least one kind or more is used. The blending amount is 0.1 to 30 parts by weight, preferably 0.3 to 1 part by weight with respect to 100 parts by weight of epoxy-modified polybutadiene.
It is suitable to use in the range of 0 parts by weight.

Next, the obtained varnish for impregnation is impregnated and coated on a sheet-shaped substrate and dried at room temperature to 170 ° C. to obtain a prepreg having no tackiness. The setting of the drying temperature at this time depends on the solvent and the initiator used. Finally, a required number of the obtained prepregs are stacked and a heat curing reaction is performed at 100 to 250 ° C. under a pressure of 1 to 100 kgf / cm ² to obtain a laminated plate.

As the sheet-shaped substrate, almost all those generally used for laminated materials can be used. As the inorganic fibers, various glass fibers such as E glass, C glass, A glass, S glass, D glass YM-31-A glass and Q glass using quartz, which contain SiO ₂ , Al ₂ O ₃ etc. is there. Examples of the organic fibers include aramid fibers containing a polymer compound having an aromatic polyamideimide skeleton as a component.

〔Example〕

Example 1 Poly (p-hydroxystyrene) bromide (Maruzen Oil Co., Ltd.)
Of the methacrylate prepolymer and epoxy-modified polybutadiene modified with diglycidyl ether bisphenol A were heated and dissolved in xylene at 80 ° C for 30 minutes to obtain a varnish having a polymer compounding ratio of 5: 5 (weight ratio) and a solid content of 40%. Further, dicumyl peroxide as a radical polymerization initiator and 404'-diaminodiphenylmethane as an epoxy curing agent were added to the resin in an amount of 5% and 1%, respectively. Applied to 110
It was dried in a constant temperature bath at ℃ for 20 minutes to obtain a tack-free prepreg. 10 sheets of the prepreg are piled up, pressure 40 to 50 kgf / c
It was heated at m ^{2 at} a temperature of 130 ° C. for 30 minutes, further heated to 170 ° C. and 240 ° C., and subjected to an adhesive curing reaction in a press for 2 hours to prepare a laminated plate.

Example 2 A varnish obtained by using an acrylic acid ester of poly (p-hydroxystyrene) bromide and an epoxy-modified polybutadiene modified with a phenol novolak type epoxy in the same manner as in Example 1 was used as a radical polymerization agent with benzoyl peroxide and epoxy. 2-Methylimidazole as a curing agent was added to each of the resin amounts of 5% and 2% to obtain an impregnating varnish. This is impregnated into 50 μm thick quartz glass,
I got a tack-free prepreg. This prepreg was used in the same manner as in Example 1 to obtain a laminated plate.

Comparative Example 1 The epoxy-modified polybutadiene modified with diglycidyl ether bisphenol A used in Example 1 was heated and dissolved in xylene at 80 ° C. for 30 minutes, and dicumyl peroxide was used as a radical polymerization initiator and 4,4 as an epoxy curing agent. ′ -Diaminodiphenylethane was added at 5% and 1% respectively to obtain an impregnating varnish. This was used in the same manner as in Example 1 to obtain a laminated plate.

Comparative Example 2 A PTFE laminated plate (K6098 manufactured by Sumitomo 3M) is given as a comparative example.

Although the conventional PTFE laminate shown in Comparative Example 2 has a small dielectric constant, it has a large thermal expansion coefficient, so that the wiring density cannot be increased so much that it cannot be used for a multilayer printed wiring board. The present invention shown in Examples 1 and 2 has a small coefficient of thermal expansion, has dimensional stability applicable to a multilayer printed wiring board, and is a polyimide-based laminate material currently used for a multilayer printed wiring board. Compared to 48), it is a laminated material with a low dielectric constant and high flame retardancy that can significantly reduce the signal transmission time.

〔The invention's effect〕

By using the thermosetting resin composition, the laminate material using the resin composition of the present invention has excellent dimensional stability and enables dramatic high-density wiring as compared with the PTFE laminate. In addition, compared with the polymide-based materials (relative permittivity 4.7) that are currently applied to multilayer printed wiring boards for large-scale computers, it is expected that the relative permittivity will be 3.5 or less, which is a significant improvement in signal transmission speed.

As described above, according to the present invention, it is possible to manufacture a low dielectric constant laminated material suitable for a multilayer printed wiring board which is excellent in flame retardancy and heat resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location H05K 1/03 7011-4E (72) Inventor Akio Takahashi 4026 Kujicho, Hitachi City, Ibaraki Japan Hitachi Research Laboratory (72) Inventor Motoyo Wajima 4026 Kuji-machi, Hitachi City, Ibaraki Prefecture Hitachi Research Laboratory, Hitachi, Ltd. (56) Reference JP-A-61-243844 (JP, A)

Claims (5)

[Claims] (A) The following general formula [I]: (Wherein A is hydrogen, an alkyl group, and a halogen group, R is alkenyl or alkenoyl having 2 to 4 carbon atoms, m is 1 to 4 and n is a number of 1 to 100). And a block polymer represented by the following general formula [II] (B-C-B [II] where B is a copolymer of glycidyl ether type epoxy). And C has a double bond in the side chain and 0 to 10 in the main carbon chain.
It is a polybutadiene low polymer (molecular weight 300 to 5000) in which individual hydroxyl groups are bonded. And an epoxy-modified polybutadiene which is) is an essential component. 2. A thermosetting resin composition according to claim 1, wherein the compounding ratio (weight) of the prepolymer and the epoxy-modified polybutadiene or its derivative is 90:10 to 10:90. . 3. The thermosetting resin composition according to claim 1, which comprises (a) the prepolymer, (b) epoxy-modified polybutadiene, and (c) a radical polymerization initiator as essential components. object. 4. A method according to claim 1, wherein (a) the prepolymer, (b) epoxy modified polybutadiene, (c) radical polymerization initiator and (d) epoxy curing agent are essential components. The thermosetting resin composition described. 5. The thermosetting resin composition according to claim 1, wherein R in the prepolymer is an allyl group, a butenyl group, a vinyl group, a methanoyl group or an acrynoyl group.