JP2533747B2 - Laminated board and manufacturing method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated board suitable for a multilayer printed circuit board excellent in flame retardancy and heat resistance and electrical characteristics, and a method for producing the same.

[0002]

2. Description of the Related Art 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. But in recent years
Along with high-speed arithmetic processing of large-scale computers, printed circuit boards with excellent electrical characteristics are required to improve signal transmission speed. In particular, a printed circuit board having a low dielectric constant is required to reduce the signal transmission delay time and the circuit thickness. As such a flame-retardant low dielectric constant laminated material, a tetrafluoroethylene resin (PTFE) laminated plate or the like has been developed.

[0003]

However, since the resin is thermoplastic and the glass transition temperature is low, the PTFE laminated plate has a problem that the coefficient of thermal expansion is large at a high temperature and the dimensional stability is not sufficient. There is a concern about the reliability of through holes after chemical bonding, and when applied to a multilayer printed circuit board, the wiring density is about the same as that of epoxy resin, and there is not much advantage as a low dielectric constant material. Further, since PTFE does not have a suitable solvent, a 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, PTFE has many difficulties in workability and moldability as compared with the conventional method, and it is necessary to significantly change the manufacturing method.

The object of the present invention is to use a flame-retardant laminated material capable of high-density wiring comparable to that of a polyimide transfer laminated material, as a material replacing the conventional polyimide-based multilayer printed wiring board used in a large-scale computer. A laminated plate and a method for manufacturing the same are provided.

[0005]

[MEANS FOR SOLVING THE PROBLEMS] The present invention will be outlined. First, the first one relates to a thermosetting resin composition.
(A) The following general formula

[0006]

Embedded image

(Wherein A is hydrogen, another organic group, and a halogen group, R is an alkenyl or unsaturated carboxyl group, m is 1 to 4, and n is a number of 1 to 100). A prepolymer composed of a poly (p-hydroxystyrene) derivative represented by (b) a block polymer represented by the following general formula (II) (wherein B is a glycidyl ether epoxy copolymer and C is a side chain). Has a double bond in the chain and is the main carbon chain

[0008]

Embedded image Polybutadiene low polymer having 0-10 hydroxyl groups in B—C—B (II)
The epoxy-modified polybutadiene (having a molecular weight of 300 to 5000) is an essential component. A second aspect of the present invention relates to a laminated board obtained by laminating and molding a prepreg obtained by impregnating a base material with the thermosetting resin composition and drying, and the third aspect relates to a method for producing the laminated board.

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 vinyl ethers, isobutenyl ethers, allyl ethers of poly (p-hydroxystyrene), acrylic acid esters, methacrylic acid esters, epoxymethacrylates and their compounds. There is bromide. One or more of these may be used 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 above general formula [II], a specific example of the glycidyl ether type epoxy resin used for modification will be given. , Glycidyl ether bisphenol A, diglycidyl ether 2,
2'-dibromobisphenol A, diglycidyl ether 2,2 ', 4,4'-tetrabromobisphenol A, diglycidyl ether 2,2'-dimethylbisphenol A, diglycidyl ether 2,2,4-trimethylbisphenol A, There are phenol novolac type epoxy resin and orthocresol novolac 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 to copper foil, mechanical strength, etc. are improved. Further, the above resin compositions (a), (b), (c)
In addition, by further adding an epoxy curing agent, the above-mentioned 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, epoxy methacrylate and its derivative and epoxy-modified polybutadiene is 90:10.
It is selected in the range of 10:90. If the content of the former is higher than this, the relative permittivity of the thermosetting resin will be high, and if it is too low, it will be flame retardant, heat resistant, and adhesive to copper foil. The effect of alkenyl ethers of poly (p-hydroxystyrene), acrylates, methacrylates and their derivatives on such laminate properties becomes insignificant. A particularly preferable compounding ratio of both components is 70:30 to 30:70.

Next, a general method for manufacturing a laminated board according to the present invention will be described.

First, a varnish is prepared by dissolving a poly (p-hydroxystyrene) derivative and an 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, N-methylpyrrolidone, dimethyl sulfoxide, trichloroethylene, 1,1,2-trichloroethane. And the like, 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 peroxyphthalate,
Dibenzyl oxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, t-butylhydroperoxide, di-
t-butyl peroxide, 2,5-dimethyl-2,5-
Di- (t-butylperoxy) hexyne (3), diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, pinane hydroxide, 2,
Examples include 5-dimethylhexane-2,5-dihydroperoxide and cumene hydroperoxide. These are preferably 0.1 to 1 with respect to 100 parts by weight of the resin composition.
Add 0 parts by weight.

Typical examples of epoxy curing agents include 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'-diaminophenyloxide, 4,4'-diaminophenylsulfone, bis (4-aminophenyl) methylphosphine oxide, bis (4-aminophenyl) phenylphosphine oxide, bis ( 4-aminophenyl) methylamine, 1,5-diaminonaphthalene, m-xylylenediamine, 1,1'-bis (p-aminophenyl) furatan, 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-methyl Phenyl)
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-oxadiazolyl), 4,4'-diaminodiphenyl ether, 4,
4'-bis (p-aminophenyl) -2,2'-dithiazole, m-bis (4-p-aminophenyl-2-thiazolyl) benzene, 4,4'-diaminobenzanilide, 4,4'-diamino Phenylbenzoate, N,
N'-bis (4-aminobenzyl) -p-phenylenediamine, 4,4'-methylenebis (2-dichloroaniline), benzoquanamine, methylguanamine, tetramethylbutanediamine, phthalic anhydride, trimellitic anhydride, pyropyrohydrate Mellitic acid, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate), maleic anhydride, 2-methylimidazole,
2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, etc.,
At least one kind is used. The blending amount is 0.1 with respect to 100 parts by weight of epoxy-modified polybutadiene.
It is suitable to use in the range of -30 parts by weight, preferably 0.3-10 parts by weight.

Next, the sheet-like base material is impregnated and coated with the obtained impregnating varnish 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, stack the required number of prepregs at 1 to 100 kg at 100 to 250 ° C.
A heat curing reaction is performed under a pressure of f / 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 fiber, E glass, C glass, A glass, S glass, D glass YM- containing SiO ₂ , Al ₂ O _{3 and the} like as components.
There are various glass fibers such as 31-A glass and Q glass using quartz. Examples of the organic fibers include aramid fibers containing a polymer compound having an aromatic polyamideimide skeleton as a component.

[0019]

【Example】

Example 1 Poly (p-hydroxystyrene) bromide (Maruzen Oil Co., Ltd.)
And the epoxy-modified polybutadiene modified with diglycidyl ether bisphenol A are 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%. It was Furthermore, 5% and 1% of dicumyl peroxide as a radical polymerization initiator and 4,4'-diaminodiphenylmethane as an epoxy curing agent were added to the total resin, respectively. This varnish was applied on a glass cloth (E-glass) having a thickness of 50 μm and dried in a constant temperature bath at 110 ° C. for 20 minutes to obtain a tack-free prepreg. 10 sheets of the prepreg are stacked, pressure is 40 to 50 kgf / cm ² , temperature is 130 ° C., and 30
After heating for minutes, the temperature was further raised to 170 ° C. and 240 ° C., and an adhesive curing reaction was performed in the press for 2 hours to produce 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 novolac type epoxy in the same manner as in Example 1 was used as a radical polymerization agent and benzoylper. 2-Methylimidazole was added as an oxide and an epoxy curing agent in amounts of 5% and 2%, respectively, of the total amount of resin to obtain an impregnating varnish. This was impregnated into quartz glass having a thickness of 50 μm to obtain 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 as a radical polymerization initiator and an epoxy curing agent were used. As a result, 4,4'-diaminodiphenylmethane 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 As a comparative example, a PTFE laminated plate (K609 manufactured by Sumitomo 3M)
8) Give.

[0023]

[Table 1]

The conventional PTFE laminated plate shown in Comparative Example 2 has a small dielectric constant, but 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. It is a laminated material that has a low dielectric constant and is highly flame-retardant, which can significantly reduce the signal transmission time compared to 48).

[0025]

The laminate using the resin composition of the present invention has a PT due to the use of the thermosetting resin composition.
Compared with FE laminated board, it has excellent dimensional stability and enables dramatic high-density wiring. In addition, compared with the polyimide material (relative permittivity 4.7) that is currently applied to multilayer printed wiring boards for large-scale computers, it is expected that the relative permittivity is 3.5 or less, which is a significant improvement in signal transmission speed.

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

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location // C08J 5/24 CET C08J 5/24 CET (72) Inventor Akio Takahashi Kuji Town, Hitachi City, Ibaraki Prefecture 4026, Hitachi, Ltd., Hitachi Research Laboratory (72) Inventor, Motoyo Wajima, 4026, Kuji Town, Hitachi, Ibaraki Prefecture, Hitachi, Ltd. 4026, Hitachi, Ltd., within Hitachi Research Laboratory

Claims (2)

(57) [Claims] 1. A laminated board having a prepreg obtained by impregnating a synthetic resin on a substrate and drying the laminated prepreg, wherein the synthetic resin has the following general formula [I] (wherein A is hydrogen, an alkyl group, Yo [Chemical 1] And a halogen group, R is alkenyl or alkenoyl having 1 to 4 carbon atoms, m is 1 to 4 and n is 1 to 100.
Of a poly (p-hydroxystyrene) derivative represented by the formula (2) and (b) a block represented by the following general formula (II): B-C-B ... (II) Polymer (however, B is a glycidyl ether-based epoxy copolymer, C is a polybutadiene low polymer having a double bond in the side chain and 0 to 10 hydroxyl groups bonded to the main carbon chain (molecular weight 300-5000).)
And an epoxy-modified polybutadiene that is an essential component. 2. (a) The following general formula [I] (wherein A is hydrogen, an alkyl group, and a halogen group): And R is an alkenyl or alkenoyl group having 1 to 4 carbon atoms, m is 1 to 4, and n is a number of 1 to 100).
A prepolymer composed of a poly (p-hydroxystyrene) derivative represented by: and (b) a block polymer represented by the following general formula (II): BCB (II) (where B is Is a glycidyl ether epoxy copolymer, and C is a polybutadiene low polymer (molecular weight 300 to 5000) having a double bond in the side chain and having 0 to 10 hydroxyl groups bonded to the main carbon chain. ) The epoxy-modified polybutadiene which is) is impregnated into a sheet-shaped substrate with a varnish containing a resin composition as an essential component, and a step of laminating the prepreg and integrally molding the prepreg under pressure is performed. Laminated board manufacturing method.