JPS59209828A - Manufacture of laminate - Google Patents

Abstract

PURPOSE:To produce continuously a laminate using an unsaturated resin wherein the interlaminer strength of glass substrates is improved, by impregnating glass substrates with a blended resin liquid of an unsaturated polyester resin and an epoxy resin, and passing the resin-impregnated glass substrates together with other substrates between rolls to be formed into a laminate substrate. CONSTITUTION:Substrates 1 including at least one glass substrate are fed from each roll 2 and are dipped in each resin impregnating tank 3. Then a plurality of resin-impregnated substrates 4 that have been impregnated with the blended resin liquid are passed between rolls 5, 5 to be formed into a laminate substrate 6. Then a copper foil 8 is laminated to the laminate substrate 6, and the obtained laminate is cured by heating in a curing oven 10, then is cooled by a cooler and is cut by a cutter 12 to obtain a laminate (A) lined with copper. The weight ratio of the unsaturated resin/epoxy resin of the blended resin liquid is preferably 9/10-50/50.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to method J for manufacturing a laminate for printed wiring boards using a continuous molding method.

[Background technology]

Continuous molding methods have recently been attracting attention when molding laminates that serve as insulating substrates for printed wiring boards. In other words, in the past, a long substrate was continuously impregnated with thermosetting resin varnish and dried, and then this resin-impregnated base material was cut to a predetermined size, and then multiple sheets were stacked and coated with copper foil, etc. Previously, laminates were formed by stacking metal foils and heating and pressing the laminate between hot platens.1 However, this method required forming in batches, making it impossible to perform continuous forming, and production slowed. It is extremely inefficient. Therefore, after impregnating a long base material with a thermosetting resin liquid, multiple sheets of this resin-impregnated base material are passed between rolls and stacked to form a long laminated base material, and a long metal foil is attached to this base material. The thermosetting resin is cured by stacking the sheets and heating them continuously in a medium furnace, thereby continuously forming a laminate with high production efficiency. However, in this continuous method, the resin is cured by heating in a Shinya furnace without pressing as in the past, so resins that generate scum during curing, such as resins for fine fibers, are not suitable, such as unsaturated polyesters. Unsaturated resins such as resins and vinyl ester resins are often used. When a glass substrate such as glass cloth or glass paper is used as a substrate, there is a problem that the adhesion between the glass substrate and the unsaturated resin is poor and delamination occurs between the substrates. Therefore, the use of Evo+Si resin, which has good adhesion to glass, is being considered in place of unsaturated resins, but Evo+Si resin has a slow reaction rate and cannot be used in a continuous manner, making it impossible to increase the reaction rate. There is a problem that the advantages of the molding method are not fully realized. Furthermore, when using t or -tn fast-curing evolvable resin, there is a problem in the hot life of the resin and the resulting laminate has insufficient performance such as heat resistance and electrical properties.

[Purpose of the invention]

The present invention has been made in view of the above points, and is a laminate that can improve the interlayer adhesion of a glass substrate while using an unsaturated 4N resin! The purpose is to provide the J construction method.

[Disclosure of the invention]

However, the manufacturing method for laminates related to "Unexploded" AK involves continuously feeding a plurality of base materials including at least one glass base material.
Each of these base materials is impregnated with a Presito resin solution prepared by blending an unsaturated resin with a cured epoxy resin, and the multiple resin-impregnated base materials are stacked and laminated by passing between the two layers. This method is characterized by forming a base material and then curing each resin of this laminated base material. \
At least one of the plurality of base materials (1) is a glass film.
Use glass substrates such as glass or glass paper. Usually all glass base materials are used, but even if paper base materials are included, it is still considered yokomi. This base material +1+ is used by being wound around a roll (2). In addition, unsaturated resins such as unsaturated polyester resins and vinyl ester resins are used as the resin to be impregnated into the base material (1), but they can also be used as refueling agents and fillers such as Te5bzOa, Afz(OH)3°CaCOs, etc.
Even if polybutadiene or the like is blended as a modifier, a blended resin solution is prepared by blending an epoxy resin with this resin, but the epoxy resin is not particularly limited. It is preferable that the polymer has a low molecular weight and is a solvent-free liquid.

In order to achieve flame retardancy, it is preferable to use brominated epoxy resin. A curing agent for the evo+shi resin is also blended into the blended resin liquid, and acid anhydrides are particularly preferred as this curing agent, and some amines such as aromatic amines can also be used. Examples include hesylhydrophthalic anhydride, methylnadic anhydride) diaminodiphenylsulfo, 71 cyanodiphenylmethane, 2-methyl-4-methylimitaryl, and the like. In addition, the blended resin contains curing accelerators such as Eboshi Juryoku, and curing accelerators include benzyldimethylamine, 2-ethyl-4-methyltribenol, etc. A third convex third ring can be used. The blending ratio of the unsaturated resin and the Eboshi resin in the Presito resin liquid is preferably such that the weight ratio of the unsaturated resin/Eboshi resin is 9515 to 10/9, particularly 9
A value of 0/10 to 50,150 is preferable. As shown in the attached drawing, a plurality of base materials f1+ are continuously fed out from the O-ru (2) and immersed in the resin gold V tank (3). The resin impregnation tank (3) is filled with the precipitate resin liquid described above. Then, in this way, the base material m is immersed in the resin impregnation tank (3) to impregnate the base material i1) with the blended resin liquid. The impregnation is preferably carried out so that the amount of resin is approximately 50 tib by weight. Next, multiple resin-impregnated base materials (4) impregnated with blended resin liquid are stacked and rolled +5) [
5) A plurality of resin-impregnated base materials (4) are pressed together while squeezing out excess blended resin liquid by passing the mixture between the resin-impregnated base materials (4), and a laminated base material ( In addition to 6), a long copper foil (
8), and overlap and press together using the three-layer O-ru f9) [9). The copper foil (8) can be laminated by passing the resin-impregnated base material (4) through the rolls (5) at the same time as the copper foil (8). The laminated base material (6) containing the three layers is introduced into a Shinia furnace (1O), and the unsaturated resin and ebo-shi resin in the laminated base material (6) are heated and cured under no pressure. After heat curing in the Shinia furnace (lO) in this way, the cooling machine (
A copper-clad laminate A is obtained by cooling with a cutter 04 and cutting with a cutter 04. If necessary, the laminate A is also after-cured.

Next, the present invention will be explained in detail with reference to Examples.Problem:/Silicol, synthesized from phthalic anhydride and maleic anhydride, heat distortion temperature 100'C, unsaturated laminate containing 30% by weight of styrene. 1% by weight of besidyl peroxide was added to the polyester resin as a curing initiator.

And for 100 parts by weight of this unsaturated polyester resin liquid, 100 parts by weight of Eboshi resin (Epic 0:/825; Dainippon Inshi Chemical Industry Co., Ltd.!!!),
A blended resin solution was prepared by mixing 10 parts by weight of a resin solution prepared by blending 80 parts by weight of phthalic anhydride and 1 part by weight of beradyl dimethylamine. On the other hand, the base material is a combination of 2 sheets of glass cloth (Nittobo Co., Ltd.!!! WE-18-BS) and 2 sheets of glass paper (Ep-4060 manufactured by Nippon Vilene Co., Ltd.). A copper-clad laminate having a thickness of 1.6 mm was obtained by using the same method as in Germany and molding according to the steps shown in the attached drawings. The curing conditions were 120° C. for 0 minutes, and the after curing conditions were 180° C. for 130 minutes.

Examples 2 to 5 The same procedure as above was carried out except that the blending ratio of unsaturated polyester resin and Eboshi resin was set as shown in the following table, and the blending ratio of Eboshi resin was set as shown in the following table. A copper-clad laminate was obtained.

Example 6 Example 1 except that the blending ratio of unsaturated polyester resin and Evo+Si resin and the blending of Epoxy resin were set as shown in the table below, and six sheets of glass cloth were used as the base material. A copper-clad laminate was obtained in the same manner as above.

Conventional Example A copper-clad laminate was obtained in the same manner as in Example 1, except that the epoxy resin was not used.

The properties of the copper-clad laminates obtained in Examples 1 to 6 and the conventional example are shown in the following table. In addition, in the following table, HHPA stands for sulfur phthalic anhydride, BDMA stands for benzyldimethylamine, HMA stands for methylnadic anhydride, DDM stands for diaminodiphenylmethane, and 2E4MZ stands for 2-ethyl-4-
Indicates methyl imitalyl.

(Left below) Based on my ex-husband's results, in all Examples 1 to 6, which used a blended resin liquid of unsaturated phase polyester resin and Eboshi oil, only the unsaturated phase polyester resin was impregnated. It has been confirmed that the adhesive strength between multiple layers can be significantly improved compared to the conventional example. In addition, the interlayer adhesion strength of Evo + Shikarasu laminate using the conventional method is 2.0 Kg/c
The InN copper foil peel strength is 2.0 Ky/am, and even when compared to this, those of Examples 1 to 0 are comparable.

〔Effect of the invention〕

As described above, according to the present invention, since the glass base material is impregnated with a blend resin liquid of unsaturated polyester resin and Eboshi resin, it is possible to make Eboshi resin glass. It is possible to improve interlayer adhesion due to the excellent adhesion of 1. Moreover, it can improve productivity, which is the advantage of continuous molding method, such as when molding is performed by impregnating only Eboshi resin into the base material. It is something that cannot be lost.

[Brief explanation of the drawing]

The attached drawings are schematic diagrams of the process of manufacturing a laminate according to the present invention. +1+\'i base material, (4) is a resin-impregnated base material, (5) is a roll, and (6) is a laminated base material. Agent Patent Attorney Ishi 1) Choshichi

Claims (1)

[Claims] (1) Continuously feed multiple substrates, including at least one glass substrate, and apply a blended resin solution prepared by blending an unsaturated resin with a curing agent-containing resin to each substrate. manufacturing a laminate, which is characterized by forming a laminated base material by impregnating a plurality of resin-impregnated base materials and passing the resin-impregnated base materials between layers, and then curing each resin of the laminated base material. Law.