JPS6131244A - Manufacture of epoxy resin laminated board - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to 2.1 a method for manufacturing a glass epoxy laminate for printed wiring boards having small surface irregularities and excellent drill workability.

[Conventional methods and their problems]

The goal of electronic equipment is to reduce size, high reliability, and lower prices through high-density wiring, and the printed wiring boards used for this purpose have also been improved and developed to meet these demands. It is being said. In particular, there are concerns about reducing surface irregularities (smoothing), improving drilling workability (especially when drilling small holes), and improving thermal conductivity.

Conventionally, a method for reducing surface irregularities has been to increase the amount of resin impregnated into prepreg.

Although this method is known, it tends to cause a lot of resin flow during lamination molding, and the prepreg is likely to shift, which is problematic in practice. Regarding the drillability of small holes, Q, 3m was applied to a glass epoxy laminate with a thickness of 1.6fi.
When drilling a hole of φ, it is possible to drill only one piece by selecting the drilling conditions, but it is difficult to drill just one piece under normal conditions. There was a problem with the three-ply structure, which caused problems such as drill breakage.

[Means for solving problems]

As a result of intensive studies to solve the above problems, the present inventors have found that by using a prepreg containing a specific inorganic filler in a specific range, the surface unevenness is small and the drillability is excellent. They also discovered that a glass epoxy laminate could be obtained and completed the present invention.

That is, the present invention uses calcium silicate 80 to 99 wt.
%, white carbon 1 to 20 wt% inorganic filler (A) mixed with an epoxy resin composition (B), a glass woven fabric (C) is impregnated or coated with a varnish, and dried. ) 15-25 wt%, said (B) 35
It is characterized by stacking one or more sheets of B-stage prepreg having a composition ratio of ~45 wt% and (C) 35 to 45 wt%, and layering metal foil on one or both sides of the prepreg as necessary. This is a method for manufacturing epoxy resin laminates for printed wiring boards.

The configuration of the present invention will be explained below.

The calcium silicate of the inorganic filler (A) of the present invention is C
It is a substance represented by the chemical formula @5303, and commercially available products include wollastonite (Nagase Sangyo ■) and Kemolit (
A phase biochemical @I) etc. are exemplified. White carbon refers to anhydrous vapor-grown silica, hydrated fine powder silicic acid, and calcium silicate, and is generally used as a thixotropic agent and reinforcing agent for plastics, a thixotropic agent for paints, etc. . The usage ratio of calcium silicate and white carbon in the inorganic filler (A) is 80~
99wt% and the latter 1 to 20wt%. If the amount of white carbon used is less than 1wt%, misalignment will easily occur during lamination molding, making it difficult to obtain a good laminate. If it exceeds this, the impregnating properties of the glass woven fabric will be insufficient, which is not preferable.

The epoxy resin composition of the present invention is not particularly limited and can be any composition that has been conventionally used for laminated boards. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, Talesol novolank type epoxy resin, halogenated bisphenol A type epoxy resin, halogenated phenol novolak. These include type epoxy resins, polyglycol epoxy resins, alicyclic epoxy resins, etc., and these can be used alone or as a mixture of two or more. Examples of curing agents include dicyandiamide, diaminodiphenylmethane, diaminodichlorodiphenylmethane, xylylene diamine, phthalic anhydride, chlorendic anhydride, polyamide resins, novolac resins, and curing catalysts or curing accelerators. , benzyldimethylamine, dimethylamino, methylphenol, imidazoles, imidazole-acid anhydride adduct,
Examples include quaternary ammonium salts, which may be used alone or in combination of two or more.

As the glass woven fabric (C) of the present invention, JIS R341
This is a treated glass cloth specified in No. 6, and generally, an alkali-free glass cloth treated with a silane coupling agent is used.

The prepreg of the present invention is prepared using the above components.

A composition of an inorganic filler and an epoxy resin composition is preferably impregnated or coated on a glass woven fabric once to achieve the above composition ratio, that is, inorganic filler (A) 15-25-
B-s with a composition ratio of 1%, epoxy resin composition CB) 35 to 45 wt%, glass woven fabric (C): 35 to 45 wt%
A varnish with a composition that will yield a prepreg of 100% of the total weight is prepared by sufficiently mixing with a conventional mixing means, impregnated or applied onto a glass woven fabric, and dried to obtain the prepreg of the present invention.

If the inorganic filler (^) in the prepreg is less than 15 wt%, the prepreg tends to shift during lamination molding, and 25
If it exceeds wt%, drill workability tends to decrease, which is not preferable. Further, if the glass woven fabric (C) is less than 35 wt%, the mechanical properties will be insufficient, and if it exceeds 45 wt%, drill workability tends to deteriorate, which is not preferable. Further, if the content of the epoxy resin composition (B) is less than 35 wt%, lamination molding becomes difficult, and if it exceeds 45 wt%, misalignment tends to occur during lamination molding, which is not preferable.

One or more sheets of prepreg prepared by the above manufacturing method are used, and if desired, metal foil (for example, electrolytic steel foil) is layered and sandwiched between end plates, and then laminated under normal lamination molding conditions, temperature 100 to 200 °C, pressure. 5~100kl! /'
The laminate of the present invention is produced by lamination molding at cd for 0.5 to 5 hours.

〔Example〕

Hereinafter, a more specific explanation will be given by showing examples and comparative examples. In addition, "%" in Examples and Comparative Examples is "% by weight" unless otherwise specified.

Example-1 Bisphenol A type epoxy resin (trade name: Epicoat 1001, manufactured by Yuka Shell Epoxy ■) 70%, 2
-Ethyl-4-methylimidazole□, 2% and dicyandiamide 2.8% were dissolved in N,N-dimethylbormamide and added.

To this, 24.3% of calcium silicate and 2.7% of vapor-phase silica type white carbon (trade name: Aerosil, manufactured by Nippon Aerosil ■) were added and mixed thoroughly, and then acetone was added and the inorganic filler was added. Adjusted the revarnish.

Apply this varnish to a 0.18 m thick glass woven cloth for 1
Dry at 50℃, B-stage glass woven fabric 44%
, epoxy resin composition 40.9%, inorganic filler 15.1
% prepreg was obtained.

6 sheets of this prepreg were stacked, 18-thick copper foil was layered on both sides, and 2 sheets were heated at a temperature of 17oC and a pressure of 20kg/cj.
A double-sided copper-clad laminate with a thickness of 1.6 mm was obtained by time lamination molding. The properties of this laminate are shown in Table 1.

Example-2 Brominated bisphenol A type epoxy resin (trade name: Epicote 1045, manufactured by Yuka Shell Epoxy ■) 63%
, 6.5% of diaminodiphenylmethane, and 0.5% of penzyldimethylamine were dissolved in methyl ethyl ketone.

To this solution, add 2466% calcium silicate and wet method white carbon (product name: Nipsil, manufactured by Nippon Silica).
5.4% was added and thoroughly mixed to prepare an inorganic-filled varnish.

A glass woven fabric with a thickness of 0.18 tm was impregnated with this varnish and dried at 140°C.
1%, epoxy resin composition 41.3%, inorganic filler 17
．． A 7% prepreg was obtained.

6 sheets of this prepreg are stacked and the thickness is 18Lna on both sides.
layered with copper foil, temperature 180'C1 pressure 50 kg/1f
A double-sided copper-clad laminate having a thickness of 1.6 fins was obtained by lamination molding for 1.5 hours at fl.

The properties of this laminate are shown in Table 1.

Example-3 Bisphenol A type epoxy resin (product name: Epicoat 1001, manufactured by Yuka Shell Epoxy ■) 36%, phenol novolac type epoxy resin (product name: Epicoat 1)
54 (manufactured by Yuka Shell Epoxy ■) 6% and chlorendeic anhydride 18% were dissolved and mixed with acetone.

To this solution, 38% calcium silicate and 2% calcium silicate type white carbon (trade name: Fluorite, manufactured by Tokuyama Soda ■) were added and thoroughly mixed to prepare an inorganic filler varnish.゛This varnish has a thickness of 0.18
B.tm glass fabric was impregnated and dried at 120℃.
A prepreg containing 38% glass woven fabric, 37.2% epoxy resin composition, and 24.8% inorganic filler was obtained.

Three sheets of this prepreg were stacked, a copper foil with a thickness of 35 mm was layered on one side, and lamination molding was performed for 1 hour at a temperature of 150° C. and a pressure cuff of 0 kg/cj to obtain a single-sided copper-clad laminate with a thickness of 0.8 nm.

The properties of this laminate are shown in Table 1.

Comparative Example 1 A varnish made in the same manner as in Example 1 except that no inorganic filler was used as the impregnating varnish was used to obtain a prepreg of 60% glass woven fabric.

A double-sided copper-clad laminate was obtained in the same manner except that eight sheets of this prepreg were used. The properties of this laminate are shown in Table 1.

Comparative Example 2 A prepreg was obtained in the same manner as in Example 2 except that the white carbon in the inorganic filler was not used as the impregnating varnish, and laminated molding was carried out in the same manner as in Example 1 except that this prepreg was used.

A good laminate could not be obtained because the prepreg shifted during lamination molding.

Comparative Example 3 The same procedure as in Example 2 was carried out except that talc was used instead of calcium silicate in the inorganic filler used in the impregnated varnish.

The properties of the obtained laminate are shown in Table 1.

Table 1 [Operations and Effects of the Invention] As is clear from the above detailed description of the invention, Examples, and Comparative Examples, the manufacturing method of the present invention controls the fluidity of the resin so that the prepreg used is suitable for lamination molding. The resulting laminate has a smooth surface (small surface irregularities) and is extremely easy to drill. It can be seen that it is an excellent product and highly practical and can be used extremely suitably for manufacturing printed wiring boards.

Claims (1)

[Claims] A glass woven fabric (C
) is impregnated or applied and dried, said (A) 15~
25 wt%, the (B) 35-45 wt%, the (C) 35
An epoxy resin laminate for printed wiring boards, characterized in that one or more B-stage prepregs with a composition ratio of ~45 wt% are stacked, and if necessary, metal foil is stacked on one or both sides of the prepreg and laminated and molded. manufacturing method.