JPH06279601A - Prepreg and laminate using thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide the subject prepreg excellent in heat resistance, etc., by compounding a specific epoxy-modified polybutadiene, 1,2-polybutadiene and a radical polymerization initiator in a specified ratio, impregnating a sheet-like substrate with the produced vanish, and subsequently drying the impregnated sheet-like substrate. CONSTITUTION:The objective prepreg is characterized by impregnating a sheet- like substrate with a varnish and subsequently drying the impregnated sheet-like substrate, the varnish being produced by compounding (A) an epoxy-modified polybutadiene of formula: A-B-C, [A is group of formula I (R is aromatic ring- containing organic group; X is 1-4); B is group of formula II (y is 5-100; z is 0-10; y>z; w is 1-300)], (B) 1,2-polybutadiene solid at room temperature preferably in an A:B of 70:30 to 30-70, and (C) 0.1-10 pts.wt. of a radical polymerization initiator (e.g. benzoylperoxide).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a prepreg and a laminated board using a thermosetting resin composition.

[0002]

2. Description of the Related Art Phenolic resins, epoxy resins, polyimide resins and the like have been conventionally known as laminated materials for multilayer printed circuit boards. However, due to the increasing demand for high-speed arithmetic processing of large-scale computers in recent years, there is an increasing need for improvement in signal transmission speed. Therefore, there is a strong demand for printed circuit boards with excellent electrical characteristics. In particular, a printed circuit board having a low dielectric constant is required in order to reduce the signal transmission delay time and the rotation width. As such a low dielectric constant laminated material, tetrafluoroethylene resin (PTFE) polybutadiene resin and the like have been developed.
However, since PTFE is a thermoplastic resin, it has problems in dimensional stability and through-hole reliability during multi-layer adhesion. Therefore, when it is applied to a multilayer printed board, it has a wiring density similar to that of an epoxy resin, and has little merit as a low dielectric constant material. Further, since PTFE does not have a suitable solvent, the adhesion method by heat melting and pressure bonding is generally adopted, but it has a drawback that the melting temperature is very high. As described above, the PTFE has many difficulties in workability and moldability as compared with the conventional method, and it is necessary to greatly change the manufacturing method.

[0003]

The conventional polybutadiene resin is a varnish, and a relatively low molecular weight polymer having good impregnability into a base material and good curability remains tacky in the prepreg stage, and is wound up. , Work such as stacking often interferes. In addition, when laminated, there was a problem with the strength of the bonded copper foil beer, mechanical strength, flame retardancy, heat resistance, and the like. The tackiness has conventionally been improved by using a high molecular weight polymer as described in JP-A-55-9613. However, at the same time, problems such as brittleness and cracks occurred. In addition, the disadvantages in laminated plate properties such as heat resistance, flame retardancy, and copper foil adhesion were based on the essence of polybutadiene resin, as well as the advantage of low dielectric constant. In the present invention, the polybutadiene resin is modified in order to overcome the shortening while utilizing the above advantages.

The object of the present invention is excellent in mechanical strength and heat resistance and can be applied to a multilayer printed circuit board. An object of the present invention is to provide a prepreg and a laminated board using a thermosetting resin composition having a small relative dielectric constant and excellent moldability and dimensional stability.

[0005]

The first invention is (a) the following general formula [I]:

[0006]

[Chemical 3]

An epoxy-modified polybutadiene, represented by: (b) 1,2-polybutadiene, which is solid at room temperature,
The radical polymerization initiator (c) is an essential component, and the mixing ratio (weight) of the component (a) and the component (B) is 8
A prepreg obtained by impregnating a sheet-like base material with a varnish of 0:20 to 20:80 and drying.

A second aspect of the present invention is a laminated board in which a prepreg obtained by impregnating a base material with a thermosetting resin composition and drying is laminated and adhered, wherein the thermosetting resin composition is (a) the following general formula: [I]

[0009]

[Chemical 4]

An epoxy-modified polybutadiene, represented by: (b) 1,2-polybutadiene, which is solid at room temperature,
The radical polymerization initiator (c) is an essential component, and the mixing ratio (weight) of the component (a) and the component (B) is 8
It relates to a laminated board characterized by being 0:20 to 20:80.

Specific examples of the glycidyl ether type epoxy resin used for modification 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 [I], are as follows. Cyglycidyl 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 , Phenol novolac type epoxy resin, orthocresol novolac type epoxy resin. These may be used alone or in combination of two or more, if desired.

Further, 1,2-in the resin composition of the present invention
As the polybutadiene component, 1,2-polybutadiene homopolymer, cyclized 1,2-polybutadiene, 1,
It is possible to use various polymers such as 2-polybutadiene glycol, 1,2-polybutadiene carboxylic acid and the like, which have 1,2-polybutadiene having a double bond in the side chain as a basic component, and copolymers. .

The compounding ratio (weight) with the epoxy modified polybutadiene is selected in the range of 80:20 to 20:80. If the former ratio is higher than this, the relative permittivity of the thermosetting resin becomes high, and Dimensional stability is also reduced. If the amount is too small, the flow of the synthetic resin is deteriorated during molding, and voids and scratches are likely to occur. The cured resin is brittle and easily cracks. Further, the effect of the bisphenol A type which is a carbon skeleton with good heat resistance and the novolac type becomes insignificant, and the adhesiveness with the copper foil is also reduced. A particularly preferable ratio of both components is 70:30 to 30:70.

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, binane 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), benzoguanamine, methylguanamine, tetramethylbutanediamine, phthalic anhydride, trimellitic anhydride, pyropyrolic acid 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 compounding amount is 0.1 to 3 with respect to 100 parts by weight of epoxy-modified polybutadiene.
It is suitable to use 0 part by weight, preferably 0.3 to 10 parts by weight.

Solvents used when the resin is used as a varnish include xylene, toluene, methyl ethyl ketone, acetone, N, N-dimethylformamide,
N-methyl-2-pyrrolidone, dimethyl sulfoxide,
There are trichloroethylene, 1,1,2-trichloroethane and the like, and any solvent can be used without limitation as long as it can uniformly mix the above component polymers. Then, the sheet-like base material is impregnated with the obtained impregnating varnish and applied at room temperature to 170
Dry at ℃ to obtain a tack-free prepreg. The setting of the drying temperature at this time depends on the solvent used, the radical polymerization agent, the curing agent, and the like. The required number of prepregs obtained at the end are piled up, preferably 1 to 100 kgf / at 100 to 250 ° C.
A heat curing reaction is performed under a pressure of cm ² to obtain a laminated plate.

As the sheet-like base material, almost all those generally used can be used. As the inorganic fibers, there are 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 , AlO _3, etc. . Further, as the organic fiber, there is aramid fiber or the like containing a polymer compound having an aromatic polyamideimide skeleton as a component.

[0018]

【Example】

Example 1 Epoxy-modified polybutadiene which was modified with diglycidyl ether bisphenol A and 1,2-polybutadiene (molecular weight 1.5 × 10 ⁵ , side chain vinyl group content 90% or more) in xylene at 80 ° C. for 30 minutes The mixture was heated and dissolved to obtain a varnish having a polymer compounding ratio of 4: 6 (weight ratio) and a solid content of 25%. Furthermore, as a radical polymerization initiator, 5 parts by weight of dicumyl peroxide was added to the entire resin composition.
A glass cloth of 50 μm (sheet-like substrate)
And then 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, heated at a pressure of 40 to 50 kgf / cm ² and a temperature of 130 ° C. for 30 minutes, further heated to 170 ° C. to 240 ° C., and subjected to an adhesive curing reaction in a press for 2 hours to prepare a laminated plate. did. Example 2 In addition to the resin composition and radical polymerization initiator of Example 1, 7 parts by weight of 4,4′-diaminodiphenylmethane as an epoxy curing agent and 100 parts by weight of epoxy modified polybutadiene were added. A laminate was obtained in the same manner.

Example 3 A phenol novolac type epoxy modified polybutadiene and 1,2-polybutadiene were used in the same manner as in Example 1 to obtain a laminate.

Example 4 Two hydroxyl groups are added to the polybutadiene chain. Example 1 diglycidyl ether bisphenol A type epoxy modified polybutadiene and 1,2-polybutadiene were prepared.
To obtain a laminated plate.

Example 5 Brominated diglycidyl ether bisphenol A epoxy-modified polybutadiene (bromine content 30%), 1,2
-Polybutadiene was used as in Example 1 to obtain a laminate.

Comparative Example 1 A 1,2-polybutadiene as used in Example 1 and a varnish obtained by dissolving dicumyl peroxide in xylene were used in the same manner as in Example 1 to try to make a laminate. But,
A large number of cracks were generated and the laminated plate was not formed.

Comparative Example 2 A laminate was obtained by using a varnish obtained by dissolving diglycidyl ether bisphenol A type epoxy resin and 4,4'-diaminodiphenylmethane in methyl ethyl ketone in the same manner as in Example 1.

The main characteristics of the laminates obtained from the above Examples and Comparative Examples and the heat resistance of the cured resin are shown in the table.

As can be seen from Comparative Example 1, 1,2-polybutadiene has a large number of cracks and does not form a laminate. Further, as can be seen from Comparative Example 2, the dielectric constant of epoxy resin is too high, and the wiring density cannot be increased. However, the laminate obtained by adding the epoxy-modified polybutadiene to the 1,2-polybutadiene of the present invention has improved moldability, flexibility, and copper foil adhesiveness. The addition of an epoxy curing agent further improved the above properties and also lowered the dielectric constant. For example, comparing Comparative Example 2 with Example 3, the signal transmission speed is improved by about 20% because the dielectric constant is changed from 5.0 to 3.3. Further, flame retardancy was also improved by adding the brominated epoxy-modified polybutadiene, as shown in Example 5, to the polybutadiene resin.

[0026]

[Table 1]

[0027]

By using the thermosetting resin composition of the present invention, it is possible to obtain a prepreg multilayer printed circuit board having not only heat resistance and adhesiveness but also excellent electrical characteristics.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location H05K 1/03 D 7011-4E (72) Inventor Akio Takahashi 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Co., Ltd. Hitachi Research Laboratory, Hitachi, Ltd. (72) Ritsuro Tada, 4026 Kuji Town, Hitachi City, Hitachi, Ibaraki Prefecture Hitate Works, Ltd. Hitachi Research Laboratory (72) Inventor Toshikazu Narahara 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Hitachi Research Laboratory, Hitachi, Ltd.

Claims (2)

[Claims] (A) The following general formula [I]: The epoxy-modified polybutadiene represented by the formula (b), 1,2-polybutadiene which is solid at room temperature, and (c) the radical polymerization initiator are essential components, and the component (a) and the component (B) are blended. Ratio (weight) is 80: 20-2
A prepreg obtained by impregnating a sheet-shaped substrate with a varnish of 0:80 and drying. 2. A laminated board having a prepreg obtained by impregnating a base material with a thermosetting resin composition and drying the laminated prepreg, wherein the thermosetting resin composition comprises (a) the following general formula [I]: Chemical 2] The epoxy-modified polybutadiene represented by the formula (b), 1,2-polybutadiene which is solid at room temperature, and (c) the radical polymerization initiator are essential components, and the component (a) and the component (B) are blended. Ratio (weight) is 80: 20-2
Laminated board characterized by being 0:80.