JPH01237132A - Manufacture of heat-curable resin copper-clad laminate - Google Patents

Abstract

PURPOSE:To increase soldering heat resistance and copper foil peeling strength by laminating prepregs with lowered volatile content and copper foils constituted of applied and dried resin composed of phenol resin and polyvinyl butyral resin as main components and heat pressurizing. CONSTITUTION:A base constituted of Aramid fiber paper is immersed with varnish composed of heat-curable resin and dried, and one or a plurality of prepregs with volatile content controlled to 1.5% or less and copper foils constituted of a resin bonding agent composed of phenol resin and polyvinyl butyral resin as main components and dried are laminated and heat pressurized to manufacture a heat-curable resin copper-clad laminate. As the heat-curable resin, epoxy resin, phenol resin, polyester resin or the like is used, and not specifically limited to any one of them. As the Aramid fiber paper, Kevlar fiber paper or Technola fiber paper is used. If the ratio of volatile content in the Aramid fiber paper prepreg is 1.5% or more, the effect of increasing soldering heat resistance is small. Drying for lowering the volatile content in prepregs is desirable at the high temperature for a long time in the range that curing reaction of resin is not developed: usually approximately at 80 deg.C-120 deg.C for 2-20minutes.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a copper-clad N temporary aramid fiber paper base having excellent heat resistance and copper foil peeling strength.

[Prior Art] Conventionally, aramid fiber paper laminates have been partially used as substrates for surface mounting due to their low thermal expansion, but they have the drawback of insufficient solder heat resistance, and an improvement has been desired.

In addition, the aramid fibers of the base material easily absorbed resin, and since there was little resin on the surface of the base material, the adhesion to the W4 foil was poor.

[Purpose of the invention]

In order to solve the drawback of low soldering heat resistance 9 copper foil peeling strength of conventional thermosetting resin laminates based on aramid fiber paper, the present inventors reduced the volatile components in the prepreg and developed a method using phenolic resin. The present inventors have discovered that the soldering heat resistance and copper foil peel strength can be significantly improved by using a resin consisting of polyvinyl butyral and polyvinyl butyral in a copper foil adhesive, and have completed the present invention.

[Structure of the Invention] The present invention impregnates a base material made of aramid fiber 1 fiber with a varnish made of thermosetting resin and dries it to reduce the volatile component to 1.5%.
A thermosetting resin characterized by laminating one or more sheets of prepreg controlled as follows and copper foil coated and dried with a resin adhesive mainly composed of phenol resin and polyvinyl butyral resin and then heated and pressed. The present invention relates to a method for manufacturing a copper-clad laminate.

The thermosetting resin referred to in the present invention includes epoxy resin, phenol resin, polyimide resin, polyester resin, etc., and is not limited to any of them.

For the aramid fiber paper, we used Kevlar fiber paper with a structure of polyparaphenylene terephthalamide (PPT^) and Technora 0 with a structure of polyparaphenylene-3゜4-diphenyl ether terephthalamide. There is Technora fiber paper.

The copper foil adhesive used in the present invention is a resin mainly composed of phenol resin and polyvinyl butyral resin, but epoxy resin, melamine resin, and other additives may be added.

In the present invention, the value of volatile components is calculated by drying the prepreg at 200° C. for 19 minutes, determining the weight before and after drying, and using the following formula.

The prepreg used in the present invention has a volatile component content of 1.5% or less, preferably 0.6% or less.

One of the features of the present invention is that the proportion of volatile components in the aramid fiber paper prepreg is 1.5% by weight or less,
At 1.5% or more, the effect of improving soldering heat resistance is small;
．． When it is 6% or less, the effect of improving soldering heat resistance becomes more significant and becomes equivalent to that of a normal glass epoxy laminate.

In order to reduce the volatile components of the prepreg, drying is preferably carried out at a high temperature for a long period of time within a range where the curing reaction of the resin does not progress, but it is usually 80°C to 120°C for about 12 to 20 minutes.

Possible methods for reducing the volatile components of prepreg include drying the prepreg again, storing the prepreg in a low humidity environment after impregnating it with varnish and drying it, and molding the prepreg under vacuum.

Another feature of the present invention is the use of a copper foil adhesive whose main components are phenolic resin and polyvinyl butyral resin.

Phenol resins include resol type resins and novolac type resins, but in the present invention, it is preferable to use resol type resins. In addition, ammonia, barium hydroxide, magnesium oxide, etc. are preferable as reaction catalysts for resol type resins. used. The phenol resin can be used with a number average molecular weight in the range of 200 to 400, but preferably in the range of 250 to 350.

On the other hand, polyvinyl butyral has a polymerization degree of 500 to 50.
A range of 0.00 can be used, but a range of 800 to 4000 is preferred. The degree of butyralization is not particularly limited, but bf is preferably 55 to 70.
It is mole%.

Epoxy resin has an epoxy equivalent weight of 350 to '? 00 range can be used, preferably 100 to 5
The range is 00.

The blending ratio of the resins ranges from 30 parts by weight (solid content) to 80 parts by weight (solid content) for phenolic resin and 1 part by weight (solid content) to 1 part by weight (solid content) for polyvinyl resin. A blending range of from 5 parts by weight of epoxy resin to 1 part by weight (solid content) to 25 parts by weight (solid content) to 100 parts by weight (solid content) of the resin blended in can be used, but preferably from 40 parts by weight (solid content) to phenolic resin. 75 parts by weight (solid content) and polyvinyl butyral in a range of 60 parts by weight (solid content) to 25 parts by weight (solid content) to 100 parts by weight (solid content) of an epoxy resin and 5 parts by weight (solid content) to 25 parts by weight of an epoxy resin. Part by weight (solid content)
This is the blending range of

〔Effect of the invention〕

The method for manufacturing a thermosetting resin copper-clad laminate according to the present invention has the following features.

(1) By using a prepreg with lower volatile components than before, the soldering heat resistance has been significantly improved.

(11) By using the copper foil welding agent 4, the peeling strength of the copper foil was also significantly improved.

〔Example] Examples of the present invention and comparative examples (subordinate examples) are shown below.

EXAMPLE An epoxy resin was used here as the thermosetting resin.

Epoxy resin (oiled shells EP-1001) 100
dicyanamide 42-phenyl-4-methyl cellosolve board 15 methyl cellosolve 36 acetone
60 The above materials were mixed to obtain a uniform varnish. Aramid fiber paper was impregnated with this varnish and dried at 165°C to 175°C for 5 minutes to obtain an aramid fiber paper prepreg.

The above prepreg was further dried at 100°C for about 10 minutes,
A prepreg containing volatile components of 1.5% or less was obtained.

Further, all layers of this prepreg were arranged, and a copper foil with adhesive described below was layered thereon, and heat molded at 165° C., 60 kg/d, for 90 minutes to obtain a copper-clad laminate having a thickness of 1.6 ffl11O.

The composition of the copper foil adhesive is as follows.

and +4 Poly core ≠ Lupetiral (BX-1 manufactured by Block Chemical) 80 parts Methyl ethyl ketone 650 phenol resin (PR-51406 manufactured by Sumitomo Durez) Epoxy resin (
Oilified shells EP-tool) The above adhesive was applied to a thickness of 30 to 40 μl on the roughened surface of the copper foil, air-dried, and then dried in a dryer at 150° C. for 4 minutes to create an adhesive-coated copper foil.

Comparative Example 1 Prepreg was obtained in the same manner as in Example, and laminated as is without additional drying. wA foil was laminated without applying adhesive, and laminated under the same conditions as in Example 1 to obtain a copper-clad laminate. .

Comparative Example 2 A prepreg was obtained in the same manner as in the example, and at 100°C
After drying for 0 minutes, a prepreg containing volatile components of 1.5% or less was obtained. A plurality of sheets of this prepreg were laminated, and the copper foils were stacked without applying an adhesive to obtain a copper-clad laminate under the same conditions as in Example 1.

Regarding the copper-clad laminates obtained by each of the above, JI
Table 1 shows the measurement results of solder heat resistance and copper tensile peel strength using SC6481.

Table 1 Peeling strength and soldering heat resistance for copper foil As shown above,
The thermosetting resin copper-clad laminate according to the present invention is a laminate having extremely excellent peel strength for copper foil and solder heat resistance.

Claims (1)

[Claims] (1) One or more sheets of prepreg prepared by impregnating and drying a base material made of aramid fiber paper with a varnish made of a thermosetting resin and controlling the volatile components to 1.5% by weight or less;
A method for producing a thermosetting resin copper-clad laminate, which comprises laminating copper foil coated and dried in advance with a resin whose main components are phenol resin and polyvinyl butyral resin, and heating and pressurizing the laminated sheets.