JP2906945B2 - Manufacturing method of laminated board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate (CEM-3) formed by heating and pressing a glass woven fabric impregnated with an epoxy resin as a surface layer and a glass nonwoven fabric impregnated with an epoxy resin containing an inorganic filler as a core material layer. More particularly, the present invention relates to a method for producing a laminated board suitable for use in a printed wiring board.

[0002]

2. Description of the Related Art In recent years, as electronic devices have become lighter, thinner, shorter, and have higher densities, CEM-3 laminates have been rapidly growing as materials for printed wiring boards used by incorporating them. Among them,
With respect to thinner and higher-density printed wiring board materials, there is a strong demand for improved moisture-resistant insulation properties and improved migration resistance between through holes of the printed wiring board. The conventional CEM-3 laminate has a resin composition obtained by mixing a liquid epoxy resin, a novolak epoxy resin, bisphenol A, and a brominated epoxy resin as an epoxy resin impregnating a glass woven fabric of a surface layer, and blending dicyandiamide as a curing agent. Things are used. This resin composition contains 200 to 300 ppm of hydrolyzable chlorine. On the other hand, the glass nonwoven fabric used as the core material has been subjected to an epoxysilane treatment as a treatment with a coupling agent.

[0003]

However, the conventional C
When used for a printed wiring board, the EM-3 laminate has insufficient moisture-resistant insulation properties and migration resistance between through holes. The problem to be solved by the present invention is:
In the EM-3 laminate, the coupling agent treatment of the epoxy resin impregnating the glass woven fabric of the surface layer and the glass nonwoven fabric of the core material layer is devised to improve the moisture resistance insulation property and the migration resistance between the through holes. It is.

[0004]

In order to solve the above-mentioned problems, in a method for manufacturing a CEM-3 laminate according to the present invention, a glass nonwoven fabric is subjected to cationic silane treatment as a treatment with a coupling agent. Use And the epoxy resin impregnated in the glass woven fabric is the following (A)
To (C) a reaction product in the presence of a catalyst in the presence of a catalyst, and dicyandiamide (curing agent) mixed therein, wherein the components (A) and (B) have a hydrolyzable chlorine in the preliminary reaction product of 100 ppm or less. Is selected. (A) novolak epoxy resin (B) glycidyl ether of polyhydric phenol or its alkyl or halogen derivative (C) polyhydric phenol or its alkyl or halogen derivative The cationic silane treatment applied to the glass nonwoven fabric is performed by using the cationic silane glass fiber itself. It is desirable to carry out both the treatment of the above and the incorporation of cationic silane into the binder that binds the glass fibers together. The CEM-3 laminate to be manufactured may be one in which a metal foil is integrated on at least one surface.

[0005]

The epoxy resin for electrical insulation contains hydrolyzable chlorine during the production process. This hydrolyzable chlorine has an adverse effect on electrical insulation. Therefore, it is necessary to reduce hydrolyzable chlorine as much as possible. Conventionally, the epoxy resin impregnating the glass woven fabric of the surface layer is a composition in which two or three types of epoxy resins are mixed, and the hydrolyzable chlorine content is 200 to 300 ppm. This chlorine remains as an unreacted material in the laminate formed by heating and pressing. A laminated board obtained by impregnating the composition with a glass woven fabric and pressing under pressure is likely to have a dense portion and a sparse portion of resin cross-linking, which is coupled with a problem of ionization of a large amount of hydrolyzable chlorine. Thus, it is presumed that this promotes migration in the surface layer. Therefore, the epoxy resin impregnated into the glass woven fabric of the surface layer is preliminarily reacted to make the molecular weight uniform, and the hydrolyzable chlorine content is reduced to a small amount of 100 ppm or less, so that the heat-pressed laminate is formed. There are no dense and rough portions due to cross-linking of the resin of the plate (it becomes uniform), and the amount of hydrolyzable chlorine is small, so that migration resistance can be improved.

On the other hand, as a coupling agent treatment of the glass nonwoven fabric of the core material layer, a treatment with epoxysilane has been conventionally performed, but in the method according to the present invention, a treatment with cationic silane is employed. Epoxysilane has a weak adhesive strength between the glass fiber and the epoxy resin as the matrix resin and the binder resin connecting the glass fibers to each other because the epoxy group (oxirane ring) loses reactivity with the resin due to the action of water. Become. In such a state, moisture easily penetrates into the interface between the resin and the glass fiber, so that the moisture-resistant insulation properties are reduced and the migration resistance between the walls of the adjacent through holes is deteriorated, but water is present in cationic silane. Even so, the reactivity with the resin is ensured. As described above, it is possible to improve the moisture-proof insulation property and the migration-proof property only by devising both the surface layer and the core material layer of the CEM-3 laminate.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments. Cationic silane used in Examples as a coupling agent used for treatment of a glass nonwoven fabric is represented by the following chemical formula (1).
Styryl aminosilane (“AZ-6” manufactured by Nippon Unicar)
131 ") and (Chemical Formula 2) phenylaminosilane (" Y-9138 "manufactured by Nippon Unicar). The epoxy silane of Chemical Formula 3 ("A-187" manufactured by Nippon Unicar) was used in the comparative example and the conventional example.

[0008]

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[0009]

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[0010]

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In the preliminary reaction of the epoxy resin composition impregnating the glass woven fabric of the surface layer, the component (A) is a phenol novolak epoxy resin, a cresol novolak epoxy resin, or the like. The component (B) is bisphenol A,
Diglycidyl ethers of polyhydric phenols such as brominated bisphenol A and bisphenol F, or alkyl or halogen derivatives thereof. The component (C) is a polyhydric phenol such as bisphenol A, brominated bisphenol A, bisphenol F, or an alkyl or halogen derivative thereof. The pre-reaction process of the components (A), (B) and (C) is known, and the components (A),
Melting and mixing the epoxy resin (B) at 100 ° C.
By mixing the component (C) and stirring at about 120 ° C., a transparent molten mixture is obtained. Add the catalyst to this and add 14
Perform the reaction at 0 ° C. The reaction is carried out, if necessary, after dilution with a solvent. The end point of the reaction is determined to be a predetermined point by measuring the change over time of the epoxy equivalent. The catalyst used for this preliminary reaction is
Alkaline hydroxides and halides, tertiary amines such as trimethylamine and triethylamine and their hydrochlorides, quaternary ammonium salts such as tetramethylammonium chloride and tetramethylammonium bromide, imidazole, 2-ethyl-4-methylimidazole and the like Acidic phosphorus compounds such as imidazoles and triphenylphosphonium.

Example 1 In a four-necked flask equipped with a stirrer, a condenser, a nitrogen gas introducing device and a thermometer, a cresol novolak type epoxy resin (“E-180” manufactured by Yuka Shell Epoxy, epoxy equivalent 210 g / eq) was used. , Hydrolyzable chlorine 200ppm) 2
00 g, bisphenol A type epoxy resin (“Ep-828” manufactured by Yuka Shell Epoxy, epoxy equivalent: 187 g /
eq, hydrolyzable chlorine 30 ppm), and 600 g of bisphenol A were reacted at 140 ° C. for 3 hours in the presence of 0.08 g of 2-ethyl 4-methylimidazole (2E4MEZ) to obtain a pre-reacted product A (epoxy equivalent 405).
g / eq, hydrolyzable chlorine 60 ppm). Preliminary reactant A
Was added with 0.5 equivalent of dicyandiamide (DICY), 2E4MEZ (curing accelerator) was added, and the gel time at 170 ° C. was 4 minutes (resin composition A). Resin composition A
To a glass woven cloth (G7195 / AS manufactured by Asahi Schwebel)
633AV ”) to obtain a woven glass prepreg. On the other hand, a glass nonwoven fabric produced by bonding glass fibers treated with “AZ-6131” with a binder blended with “Y-9138” is impregnated with an epoxy resin containing an inorganic filler (aluminum hydroxide and talc) and dried. A non-woven prepreg was obtained. One glass woven prepreg is used for each surface layer, the glass nonwoven prepreg is used for the core material layer, and a copper foil is placed on the outermost surface. The copper foil is placed at a temperature of 160 ° C. and a pressure of 40 kgf /. 60 minutes heating and pressure molding at cm ^2, and to produce double-sided copper clad laminate of 1.6 thick mm.

Example 2 A four-necked flask equipped with a stirrer, a condenser, a nitrogen gas introducing device and a thermometer was charged with a cresol novolak type epoxy resin (“E-180” manufactured by Yuka Shell Epoxy, epoxy equivalent 210 g / eq). , Hydrolyzable chlorine 200ppm) 2
00 g, bisphenol A type epoxy resin (“Ep-828” manufactured by Yuka Shell Epoxy, epoxy equivalent: 187 g /
eq, hydrolyzable chlorine (80 ppm), and 600 g of bisphenol A were reacted at 140 ° C. for 3 hours in the presence of 0.08 g of 2E4MEZ to obtain a preliminary reaction product B (epoxy equivalent: 415 g / eq, hydrolyzable chlorine: 100 pp).
m). Add 0.5 equivalents of DICY to Pre-Reaction B,
2E4MEZ was added to set the gel time at 170 ° C. to 4 minutes (resin composition B). The resin composition B was impregnated and dried in the same glass woven fabric as in Example 1 to obtain a glass woven prepreg. Using the glass woven fabric prepreg and the glass nonwoven fabric prepreg of Example 1, the same procedure as in Example 1 was followed.
A 6 mm double-sided copper clad laminate was produced.

Comparative Example 1 A four-necked flask equipped with a stirrer, a condenser, a nitrogen gas introducing device and a thermometer was charged with a phenol novolak type epoxy resin ("E-154" manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 176 g / eq.). , Hydrolyzable chlorine 200ppm) 2
00 g, bisphenol A type epoxy resin (“Ep-828” manufactured by Yuka Shell Epoxy, epoxy equivalent: 187 g /
eq, hydrolyzable chlorine (60 ppm), 500 g, and tetrabromobisphenol A, 300 g, are dissolved at 80 ° C., mixed and cooled. This is DICY27g and 2E4MEZ
3.6 g was blended to obtain a resin composition C (200 ppm of hydrolyzable chlorine). The resin composition C was impregnated and dried in the same glass woven fabric as in Example 1 to obtain a glass woven prepreg. Using the glass woven prepreg and the glass nonwoven prepreg of Example 1, a 1.6 mm double-sided copper-clad laminate was produced in the same manner as in Example 1 below.

Comparative Example 2 In Example 1, "A-187" was used instead of "AZ-6131" for the treatment of the glass fibers constituting the glass nonwoven fabric, and "Y-
The same procedure as in Example 1 was carried out except that "A-187" was used instead of "9138" to produce a 1.6 mm double-sided copper-clad laminate.

Comparative Example 3 A four-necked flask equipped with a stirrer, a condenser, a nitrogen gas introducing device and a thermometer was charged with a phenol novolak type epoxy resin (“E-154” manufactured by Yuka Shell Epoxy, epoxy equivalent 176 g / eq.). , Hydrolyzable chlorine 200ppm) 2
00 g, bisphenol A type epoxy resin (“Ep-828” manufactured by Yuka Shell Epoxy, epoxy equivalent: 187 g /
eq, 150 g of hydrolyzable chlorine) and 300 g of tetrabromobisphenol A were reacted at 140 ° C. for 3 hours in the presence of 0.08 g of triphenylphosphonium to obtain a preliminary reaction product D (epoxy equivalent: 370 g / e).
q, hydrolyzable chlorine 120 ppm). To the preliminary reaction product D, 0.5 equivalent of DICY was added, and 2E4MEZ was added to set the gel time at 170 ° C. to 4 minutes (resin composition D).
Impregnating resin composition D into the same glass woven fabric as in Example 1,
It dried and obtained the glass woven fabric prepreg. Using the glass woven prepreg and the glass nonwoven prepreg of Example 1, a 1.6 mm double-sided copper-clad laminate was produced in the same manner as in Example 1 below.

Conventional Example The glass woven prepreg of Comparative Example 1 was used for the surface layer, and the glass nonwoven fabric prepreg of Comparative Example 2 was used for the core material layer. A laminated board was manufactured.

Table 1 briefly summarizes the specifications of the above embodiment, comparative example, and conventional example.

[0019]

[Table 1]

The laminates in the above Examples, Comparative Examples and Conventional Examples were subjected to a pressure cooker treatment (121 ° C.-2 atm), and the relationship between the treatment time and the insulation resistance is shown in FIG. This indicates that the laminates of the examples have excellent moisture-resistant insulation properties. Further, copper plated through holes were provided on the laminates of the examples, comparative examples and conventional examples with a hole wall interval of 0.3 mm, and D between the through holes at 85 ° C.-85% RH.
The sample was subjected to a process of applying C100V. FIG. 2 shows the relationship between the processing time and the cumulative short-circuit occurrence rate between through holes in 50 samples. This indicates that the laminates of the examples have excellent migration resistance.

[0021]

As is apparent from FIGS. 1 and 2, according to the method of the present invention, it is possible to manufacture a CEM-3 laminate having excellent migration resistance and moisture-resistant insulation resistance. In particular, the migration resistance is 0% to 0% even after 1000 hours. This means that the value of industrial use will be very large as the density of through-hole substrates further increases in the future.

[Brief description of the drawings]

FIG. 1 is a curve diagram showing a relationship between a pressure cooker processing time of a laminate and a change in insulation resistance.

FIG. 2 is a curve diagram showing a relationship between a voltage application time between through holes and a cumulative short circuit occurrence rate.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-152138 (JP, A) JP-A-64-48832 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08J 5 / 08,5 / 24 B32B 27 / 04,27 / 38

Claims (3)

(57) [Claims] 1. A method of manufacturing a laminate, wherein a glass woven fabric impregnated with an epoxy resin is used as a surface layer, and a glass nonwoven fabric impregnated with an epoxy resin containing an inorganic filler is used as a core material layer in a heat-pressed laminate. The epoxy resin to be impregnated into the glass woven fabric is the following (A)-
The reaction product of the component (C) under the catalyst is a mixture of dicyandiamide (curing agent), and the components (A) and (B) contain 100 p of hydrolyzable chlorine in the preliminary reaction product.
pm or less. (A) novolak epoxy resin (B) glycidyl ether of polyhydric phenol or its alkyl or halogen derivative (C) polyhydric phenol or its alkyl or halogen derivative 2. The laminated board according to claim 1, wherein the cationic silane treatment applied to the glass nonwoven fabric comprises treating the glass fiber itself with the cationic silane and blending the cationic silane into a binder for binding the glass fibers. Manufacturing method. 3. The method according to claim 1, wherein a metal foil is integrated with at least one outermost surface.