JP2833433B2 - Epoxy resin composition for laminate and method for producing laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition for a laminate and a method for producing a laminate using the composition.

[0002]

2. Description of the Related Art In recent years, electronic devices have been increasingly integrated with component parts, and accordingly, finer and denser circuits and smaller diameters of through holes of printed circuit boards used in electronic devices have been developed. Is progressing. In order to cope with such a situation, it is necessary to improve the insulation properties, particularly the migration resistance, of the laminated board serving as the substrate of the printed circuit board. Conventionally, in order to improve migration resistance, it has been proposed to incorporate a metal ion scavenger in a resin to trap free metal ions that cause migration. Further, in the epoxy resin laminate, chloride ions are liberated, so that it has been proposed to incorporate a chloride ion scavenger into the resin. However, these ion scavengers have poor compatibility with the resin, or the heat resistance is lowered by incorporating the ion scavenger into the resin. On the other hand, the higher the softening temperature of the novolak epoxy resin blended as one component of the epoxy resin is, the higher the heat resistance is. Therefore, a novolak epoxy resin having a softening temperature exceeding 80 ° C. is usually used for manufacturing a laminate. However, when a prepreg manufactured by impregnating and drying a sheet-like substrate with an epoxy resin composition containing such a novolak epoxy resin is stored for a long period of time, the degree of curing of the prepreg advances, and voids occur in the manufactured laminate. It was easy. The presence of voids lowers the heat resistance of the laminate.

[0003]

A first problem to be solved by the present invention is to focus on free chlorine ions in an epoxy resin laminate and reduce it to improve migration resistance. A second problem is to improve the migration resistance without lowering the laminate properties when using a resin composition containing a metal ion scavenger. A third object is to obtain a resin composition which has a small decrease in heat resistance and a long usable life (life) of a prepreg while improving migration resistance.

[0004] As the diameter of the through-hole becomes smaller and the distance between the through-holes becomes smaller, it becomes necessary to further improve the migration resistance. Drills are easy to bend and misalign. If there is a portion where the hole interval becomes narrower than the set value due to misalignment, the effect of improving the migration resistance is reduced by half.
A fourth problem to be solved by the present invention is to enable drilling of an epoxy resin laminate made of glass woven fabric as a base material with high positional accuracy.

[0005]

In order to solve the first problem, the epoxy resin composition for a laminate according to the present invention is prepared by pre-reacting the following components (A) to (C) in the presence of a catalyst. It is obtained by blending dicyandiamide (curing agent) with the product. The components (A) and (B) are selected so that the amount of hydrolyzable chlorine in the preliminary reaction product is 100 ppm or less, and the amount of dicyandiamide is based on the epoxy equivalent of the preliminary reaction product. 0.45-0.
It is characterized by being 6 equivalents. (A) Novolak epoxy resin (B) Diglycidyl ether of polyhydric phenol or its alkyl or halogen derivative (C) Polyhydric phenol or its alkyl or halogen derivative Epoxy resin for laminated board to solve the second problem The composition is
In addition to the above components (A) to (C), (D) a chelating agent having a reactive functional group is preliminarily reacted together. In order to solve the third problem, the softening temperature of the (A) novolak epoxy resin is preferably limited to 50 to 80C.

A method for producing a laminated board according to the present invention is a method for heating and pressing a prepreg obtained by impregnating and drying a thermosetting resin on a sheet-like substrate, wherein the thermosetting resin is the epoxy resin composition for a laminated board. It is characterized by being. Further, in order to solve the fourth problem, in the method for manufacturing a laminate according to the present invention, the sheet-shaped substrate is a glass woven fabric, and glass fibers constituting the glass woven fabric are subjected to embrittlement treatment. Characterized in that: The embrittlement treatment is preferably a treatment for forming a porous gel film on the glass fiber surface.

[0007]

An epoxy resin composition for a laminate obtained by pre-reacting the components (A) to (C) in the presence of a catalyst is known. Has a molecular structure chemically bonded through the interposition of When the prepreg obtained by impregnating and drying such an epoxy resin composition on a sheet-like substrate is heated and pressed, the dispersion of the curing reaction is small,
To produce a laminate having excellent heat resistance, chemical resistance, and electrical properties and a high glass transition temperature, as compared to a case where a laminate is produced using a composition obtained by simply mixing the components (A) to (C). Can be. Migration phenomenon of printed circuit board
When the laminate, which is the substrate, absorbs moisture, ions in the resin elute and a small current flows between adjacent circuits with a potential difference, promoting the ionization of the copper that constitutes the circuit and causing the copper ions to migrate between the circuits. This is a phenomenon that causes a short circuit between circuits. Since the production of epoxy resin uses epichlorohydrin as a raw material, hydrolyzable chlorine remains as a by-product in the produced resin. Therefore, the epoxy resin laminate contains hydrolyzable chlorine which ionizes and causes migration. In the present invention, the components (A) and (B) are selected so that the amount of hydrolyzable chlorine in the preliminary reaction product is 100 ppm or less, and the amount of hydrolyzable chlorine contained in the laminate is reduced. doing. In addition, the amount of hydrolyzable chlorine in the laminate is reduced by setting the dicyandiamide to be added to the preliminary reaction product to 0.6 equivalent or less with respect to the epoxy equivalent. When the amount of dicyandiamide is reduced as described above, a reaction between the secondary hydroxyl group generated by the opening of the epoxy group and the epoxy group occurs in addition to the curing reaction using dicyandiamide as a nucleus. Hydrolyzable chlorine that can be incorporated into the chain and ionizes can be reduced. 100 ppm of hydrolyzable chlorine in the preliminary reaction product
Even in the following amounts, the compounding equivalent of dicyandiamide is set to 0.1.
Unless it is not more than 6 equivalents, the above reaction for incorporating hydrolyzable chlorine into the molecular chain of the cured resin is unlikely to occur, the amount of hydrolyzable chlorine in the laminate cannot be reduced, and the extraction conductivity can be lowered. Can not. However, if the amount of dicyandiamide is too small, the resin does not sufficiently cure at the time of molding the laminate, and the glass transition temperature and the adhesive strength decrease.
It must be at least 0.45 with respect to the epoxy equivalent. When the chelating agent having a reactive functional group is preliminarily reacted together with the components (A) to (C), the chelating agent is incorporated into the molecular skeleton of the prereaction product. The compatibility between the chelating agent and the resin is improved, and no decrease in heat resistance is observed. Further, the hydrolyzable chlorine in the preliminary reaction product is 100 ppm or less,
(A) The softening temperature of the novolak epoxy resin is 50 to 80.
When the temperature is limited to ° C., the heat resistance is hardly reduced and the life of the prepreg can be extended. When the softening temperature of the novolak epoxy resin is lower than 50 ° C., the number of binuclear bodies in the novolak epoxy resin is large, and the glass transition temperature of the laminate tends to decrease. When the softening temperature of the novolak epoxy resin exceeds 80 ° C., the polymer region of the molecular weight distribution of the pre-reaction product increases, and the life of the prepreg becomes short. Softening temperature of novolak epoxy resin is 50-80
Even in the range of ° C., unless the hydrolyzable chlorine in the preliminary reaction product is 100 ppm or less, the amount of a curing accelerator such as an imidazole compound must be increased, which adversely affects the life of the prepreg.

[0008] If the glass fibers constituting the glass woven fabric are embrittled in advance, when drilling holes for plating through holes in the laminated board, the displacement of the drill hardly occurs. Since the position accuracy of the drilling process is increased and the through hole interval can be maintained accurately, there is no portion where the through hole interval becomes narrow due to the misalignment of the drill, and the migration resistance does not decrease. The embrittlement treatment of the glass fiber may be a treatment of weakening the strength of the glass fiber by heating the glass woven fabric at 400 to 500 ° C. However, if a treatment technique for forming a porous gel film on the surface of the glass fiber is adopted. Since the strength is not reduced to the core of the glass fiber, it is preferable for maintaining the strength of the laminated plate.

[0009]

EXAMPLES In the epoxy resin composition for a laminate according to the present invention, the component (A) is phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, or the like. The component (B) is a diglycidyl ether of a polyhydric phenol such as bisphenol A, brominated bisphenol A, and bisphenol F, or an alkyl or halogen derivative thereof. The component (C) is a polyphenol such as bisphenol A, brominated bisphenol A, bisphenol F, or
It is an alkyl or halogen derivative thereof. (A),
The preliminary reaction process of the components (B) and (C) is known,
Epoxy resins (A) and (B) having different skeletons
The mixture is melt-mixed at 0 ° C, the component (C) is blended, and the mixture is stirred at about 120 ° C to obtain a transparent molten mixture. A catalyst is added thereto and the reaction is carried out at 140 ° 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. Catalysts used in this preliminary reaction include 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 And imidazoles such as 2-ethyl-4-methylimidazole, and acidic phosphorus compounds such as triphenylphosphonium. The chelating agent is 2,
2'-dipyridyl, 8-quinolinol, cuperon, salicylic acid, m-aminophenol, iminodiacetic acid and the like can be used, and these contain a functional group such as a hydroxyl group or an amino group that reacts with an epoxy resin. It is not particularly limited as long as it is one.

The porous gel film on the surface of the glass fiber can be formed by shrinking the metal alkoxide compound on the surface of the glass fiber. The laminate manufactured by the method according to the present invention includes a double-sided or single-sided copper-clad laminate and a laminate for a multilayer circuit board. Further, the sheet-like substrate impregnated with the resin varnish may be used in combination with a glass woven fabric and a glass nonwoven fabric.

(Embodiment 1) Claims 1, 3 and 5 and 6
In a four-necked flask equipped with a stirrer, cooling tube, nitrogen gas introduction device and thermometer, 200 g of cresol novolak type epoxy resin ("E-180" made by Yuka Shell Epoxy, epoxy equivalent 210 g)
/ Eq, hydrolyzable chlorine 200 ppm, softening temperature 70
℃) bisphenol A type epoxy resin 600g ("Ep-828" made by Yuka Shell Epoxy, epoxy equivalent 187g /
eq, hydrolyzable chlorine 30 ppm) 200 g of bisphenol A was charged, and 2-ethyl 4-methylimidazole (2E4
The reaction was carried out at 140 ° C. for 3 hours in the presence of 0.08 g of MEZ) to obtain a pre-reaction product A (epoxy equivalent: 415 g / e).
q, 75 ppm hydrolyzable chlorine). Add 0 to pre-reactant A.
55 equivalents of dicyandiamide (DICY) were added and 2
E4MEZ (curing accelerator) was added to set the gel time at 170 ° C. to 4 minutes (resin composition A). The resin composition A was coated on a glass woven fabric having a porous gel coating on the surface of a glass fiber ("G7195 / AS633AV" manufactured by Asahi Schwebel).
The prepreg was impregnated and dried to obtain a prepreg, and a copper foil was laminated on both surfaces of the prepregs, and formed by heating and pressing by a conventional method to obtain a 1.6 mm-thick double-sided copper-clad laminate. .

The amount of hydrolyzable chlorine is measured by dissolving the pre-reacted product in methyl ethyl ketone, adding ethylene glycol monobutyl ether, alkaline ethylene glycol monobutyl ether and glacial acetic acid.
The titration was performed using a 01N silver nitrate standard solution. The measurement of the softening temperature of the novolak epoxy resin is performed according to JIS K25
31. The same applies to the following examples and comparative examples.

(Embodiment 2) Claims 1 and 3 and claims 5 and 6
In a four-necked flask equipped with a stirrer, cooling tube, nitrogen gas introduction device and thermometer, 200 g of cresol novolak type epoxy resin ("E-180" made by Yuka Shell Epoxy, epoxy equivalent 210 g)
/ Eq, hydrolyzable chlorine 200 ppm, softening temperature 70
℃) bisphenol A type epoxy resin 600g ("Ep-828" made by Yuka Shell Epoxy, epoxy equivalent 187g /
eq, hydrolyzable chlorine 80 ppm) 200 g of bisphenol A was added, and 140 ° C. in the presence of 0.08 g of 2E4MEZ
For 3 hours to obtain a preliminary reaction product B (epoxy equivalent: 415 g / eq, hydrolyzable chlorine: 90 ppm). To Prereaction B was added 0.58 equivalents of DICY and 2E4ME
Z 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 prepreg, and was heated and pressed using the prepreg in the same manner as in Example 1 to a thickness of 1.6.
A copper-clad laminate of mm was obtained.

(Embodiment 3) Claims 1, 3 and 5, 6
In a four-necked flask equipped with a stirrer, cooling tube, nitrogen gas introducing device and thermometer, 200 g of phenol novolak type epoxy resin ("E-154" made by Yuka Shell Epoxy, epoxy equivalent 176 g)
/ Eq, hydrolyzable chlorine 200 ppm, softening temperature 65
℃) Bisphenol A type epoxy resin 500g ("Ep-828" made by Yuka Shell Epoxy, epoxy equivalent 187g /
eq, hydrolyzable chlorine 80 ppm) 300 g of tetrabromobisphenol A was charged, and reacted at 140 ° C. for 4 hours in the presence of 0.08 g of triphenylphosphonium to obtain a pre-reaction product C (epoxy equivalent: 370 g / eq, water Degradable chlorine 90p
pm). 0.45 equivalent of DICY was added to the pre-reaction product C, and 2E4MEZ was added to set the gel time at 170 ° C. to 4 minutes (resin composition C). The resin composition C was impregnated in the same glass woven fabric as in Example 1 and dried to obtain a prepreg. The prepreg was heated and pressed in the same manner as in Example 1 to form a 1.6 mm thick copper. A laminated laminate was obtained.

(Embodiment 4) Claims 2 and 3 and Claims 5 and 6
In a four-necked flask equipped with a stirrer, cooling tube, nitrogen gas introducing device and thermometer, 200 g of phenol novolak type epoxy resin ("E-154" made by Yuka Shell Epoxy, epoxy equivalent 176 g)
/ Eq, hydrolyzable chlorine 200 ppm, softening temperature 65
℃) Bisphenol A type epoxy resin 500g ("Ep-828" made by Yuka Shell Epoxy, epoxy equivalent 187g /
eq, 80 ppm of hydrolyzable chlorine) 300 g of tetrabromobisphenol A, 10 g of 2,2'-dipyridyl, and 140 ° C. in the presence of 0.04 g of 2E4MEZ
For 3 hours to obtain a preliminary reaction product D (epoxy equivalent: 380 g / eq, hydrolyzable chlorine: 100 ppm). To Prereaction D was added 0.45 equivalent of DICY and 2E4M
EZ was added to set the gel time at 170 ° C. to 4 minutes (resin composition D). The resin composition D was impregnated in the same glass woven fabric as in Example 1 and dried to obtain a prepreg. The prepreg was heated and pressed in the same manner as in Example 1 to obtain a prepreg having a thickness of 1.
A 6 mm copper clad laminate was obtained.

(Embodiment 5) Claims 1, 3 and 5 and 6
The resin composition A was impregnated into a normal glass woven fabric not subjected to embrittlement treatment and dried to obtain a prepreg. The prepreg was heated and pressed in the same manner as in Example 1 to obtain a prepreg. 1.6
A copper-clad laminate of mm was obtained.

Example 6 A four-necked flask equipped with a stirrer, a condenser, a nitrogen gas introducing device and a thermometer was charged with 200 g of a cresol novolak type epoxy resin ("E-180" manufactured by Yuka Shell Epoxy, epoxy equivalent) 210g
/ Eq, hydrolyzable chlorine 200 ppm, softening temperature 80
℃) bisphenol A type epoxy resin 600g ("Ep-828" made by Yuka Shell Epoxy, epoxy equivalent 187g /
eq, hydrolyzable chlorine 30 ppm) 200 g of bisphenol A was added, and 140 ° C. in the presence of 0.08 g of 2E4MEZ
For 3 hours to obtain a pre-reaction product E (epoxy equivalent: 425 g / eq, hydrolyzable chlorine: 75 ppm). To Prereaction E was added 0.55 equivalents of DICY and 2E4ME
Z was added to set the gel time at 170 ° C. to 4 minutes (resin composition E). The resin composition E was impregnated into the same glass woven fabric as in Example 1 and dried to obtain a prepreg. The prepreg was heated and pressed in the same manner as in Example 1 to have a thickness of 1.6.
A copper-clad laminate of mm was obtained.

(Embodiment 7) Claims 1, 3 and 5 and 6
In a four-necked flask equipped with a stirrer, cooling tube, nitrogen gas introduction device and thermometer, 200 g of cresol novolak type epoxy resin ("E-180" made by Yuka Shell Epoxy, epoxy equivalent 210 g)
/ Eq, hydrolyzable chlorine 200 ppm, softening temperature 50
℃) bisphenol A type epoxy resin 600g ("Ep-828" made by Yuka Shell Epoxy, epoxy equivalent 187g /
eq, hydrolyzable chlorine 30 ppm) 200 g of bisphenol A was added, and 140 ° C. in the presence of 0.08 g of 2E4MEZ
For 3 hours to obtain a preliminary reaction product F (epoxy equivalent: 400 g / eq, hydrolyzable chlorine: 70 ppm). To Prereaction F was added 0.55 equivalents of DICY and 2E4ME
Z was added to set the gel time at 170 ° C. to 4 minutes (resin composition F). The resin composition F was impregnated and dried in the same glass woven fabric as in Example 1 to obtain a prepreg, and was heated and pressed using this prepreg in the same manner as in Example 1 to a thickness of 1.6.
A copper-clad laminate of mm was obtained.

EXAMPLE 8 200 g of a cresol novolak type epoxy resin (oil oil) was placed in a four-necked flask equipped with a stirrer, a cooling pipe, a nitrogen gas introducing device and a thermometer. Shell epoxy "E-180", epoxy equivalent 205g
/ Eq, hydrolyzable chlorine 200 ppm, softening temperature 45
℃) bisphenol A type epoxy resin 600g ("Ep-828" made by Yuka Shell Epoxy, epoxy equivalent 187g /
eq, hydrolyzable chlorine 30 ppm) 200 g of bisphenol A was added, and 140 ° C. in the presence of 0.08 g of 2E4MEZ
For 3 hours to obtain a preliminary reaction product G (epoxy equivalent: 400 g / eq, hydrolyzable chlorine: 70 ppm). To Prereaction G was added 0.55 equivalents of DICY and 2E4ME
Z was added to set the gel time at 170 ° C. to 4 minutes (resin composition G). The resin composition G was impregnated into the same glass woven fabric as in Example 1 and dried to obtain a prepreg. The prepreg was heated and pressed in the same manner as in Example 1 to have a thickness of 1.6.
A copper-clad laminate of mm was obtained.

Example 9 200 g of cresol novolac epoxy resin (oil oil) was placed in a four-necked flask equipped with a stirrer, a cooling pipe, a nitrogen gas introducing device and a thermometer. Shell epoxy "E-180", epoxy equivalent 205g
/ Eq, hydrolyzable chlorine 200 ppm, softening temperature 85
℃) bisphenol A type epoxy resin 600g ("Ep-828" made by Yuka Shell Epoxy, epoxy equivalent 187g /
eq, hydrolyzable chlorine 30 ppm) 200 g of bisphenol A was added, and 140 ° C. in the presence of 0.08 g of 2E4MEZ
For 3 hours to obtain a preliminary reaction product H (epoxy equivalent: 415 g / eq, hydrolyzable chlorine: 75 ppm). To Prereaction H was added 0.55 equivalents of DICY and 2E4ME
Z was added to set the gel time at 170 ° C. to 4 minutes (resin composition H). The resin composition H was impregnated into the same glass woven fabric as in Example 1 and dried to obtain a prepreg. The prepreg was heated and pressed in the same manner as in Example 1 to a thickness of 1.6.
A copper-clad laminate of mm was obtained.

Comparative Example 1 200 g of a cresol novolak type epoxy resin ("E-180" manufactured by Yuka Shell Epoxy, epoxy equivalent) was placed in a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen gas introducing device and a thermometer. 210g
/ Eq, hydrolyzable chlorine 200 ppm, softening temperature 70
℃) bisphenol A type epoxy resin 600g ("Ep-828" made by Yuka Shell Epoxy, epoxy equivalent 187g /
eq, hydrolyzable chlorine 120 ppm) 200 g of bisphenol A was added, and 140 ° C. in the presence of 0.08 g of 2E4MEZ
For 3 hours to obtain a preliminary reaction product I (epoxy equivalent: 415 g / eq, hydrolyzable chlorine: 130 ppm). To Prereaction I was added 0.55 equivalent of DICY and 2E4M
EZ was added and the gel time at 170 ° C. was set to 4 minutes (resin composition I). The resin composition I was impregnated and dried in the same glass woven fabric as in Example 1 to obtain a prepreg. The prepreg was heated and pressed in the same manner as in Example 1 to obtain a prepreg having a thickness of 1.
A 6 mm copper clad laminate was obtained.

Comparative Example 2 0.63 equivalents of DICY were added to the pre-reacted product A, 2E4MEZ was added, and the gel time at 170 ° C. was 4 minutes (resin composition J). The resin composition J was impregnated into the same glass woven fabric as in Example 1 and dried to obtain a prepreg. The prepreg was heated and pressed in the same manner as in Example 1 to form a 1.6 mm thick copper. A laminated laminate was obtained.

(Comparative Example 3) 0.43 equivalent of DICY was added to the pre-reaction product A, 2E4MEZ was added, and the gelation time at 170 ° C was 4 minutes (resin composition K). The resin composition K was impregnated into the same glass woven fabric as in Example 1 and dried to obtain a prepreg. The prepreg was heated and pressed in the same manner as in Example 1 to form a 1.6 mm thick copper. A laminated laminate was obtained.

(Conventional Example 1) Cresol novolak type epoxy resin 200 g ("E-180" made by Yuka Shell Epoxy, epoxy equivalent 210 g)
/ Eq, hydrolyzable chlorine 200 ppm, softening temperature 90
℃) Bisphenol A type epoxy resin 300g ("E-1001" made by Yuka Shell Epoxy, epoxy equivalent 450g /
eq) 500 g of low brominated bisphenol A type epoxy resin ("E-5046" made by Yuka Shell Epoxy, epoxy equivalent: 4)
75 g / eq), and mixed with 0.50 equivalent of DICY.
Was added, and the gelation time at 170 ° C. was set to 4 minutes by adding 2E4MEZ (resin composition L, epoxy equivalent: 380 g /
eq, hydrolyzable chlorine 280 ppm). Resin composition L
Is impregnated into ordinary glass woven fabric that has not been embrittled and dried to obtain a prepreg. The prepreg is heated and pressed in the same manner as in Example 1 to form a copper-clad 1.6 mm thick sheet. A laminate was obtained.

(Conventional Example 2) 200 g of cresol novolak type epoxy resin ("E-180" made by Yuka Shell Epoxy, epoxy equivalent 210 g)
/ Eq, hydrolyzable chlorine 200 ppm, softening temperature 90
℃) Bisphenol A type epoxy resin 300g ("E-1001" made by Yuka Shell Epoxy, epoxy equivalent 450g /
eq) 500 g of low brominated bisphenol A type epoxy resin ("E-5046" made by Yuka Shell Epoxy, epoxy equivalent: 4)
75 g / eq) 10 g of 2,2′-dipyridyl was dissolved and mixed, and 0.50 equivalent of DICY was added thereto.
4 MEZ was added to set the gel time at 170 ° C. to 4 minutes (resin composition M, epoxy equivalent: 380 g / eq, hydrolyzable chlorine: 280 ppm). The resin composition M is impregnated into a normal glass woven fabric that has not been subjected to embrittlement treatment and dried to obtain a prepreg. The prepreg is heated and pressed in the same manner as in Example 1 to obtain a prepreg having a thickness of 1. A 6 mm copper clad laminate was obtained.

The properties of the resin compositions of Examples are shown in Table 1, and the properties of the resin compositions of Comparative Examples and Conventional Examples are shown in Table 2. Table 3 shows the characteristics of the copper-clad laminate obtained in the examples, and Table 4 shows the characteristics of the copper-clad laminate obtained in the comparative example and the conventional example. The evaluation method of the characteristics is as follows. (1) Copper foil peel strength: based on JIS C-6481. (2) Extraction conductivity: 2 g of a sample obtained by pulverizing the laminate to about 200 mesh was immersed in 20 cc of pure water placed in a Teflon container, and the Teflon container was sealed and placed in an oven at 121 ° C. for 168 hours. Measure water conductivity. (3) Migration resistance: A copper-clad laminate was processed into a printed circuit board having the circuit pattern shown in FIG. 1 (hole diameter of through hole 0.3 mm, plating thickness 25 μm, hole wall interval 0.3 mm), 8
A voltage of 50 V was applied in a 5 ° C./85% RH atmosphere, and the time required for the resistance value between circuit patterns to be 10 ⁸ Ω or less was measured. (4) Displacement and position variation of hole positions: Three copper-clad laminates were stacked (a 1.5 mm-thick phenol resin laminate on the lower surface and a 0.2 mm-thick aluminum plate on the upper surface).
Using a 4 mm diameter drill (ST30 manufactured by Union Tool), measurement was performed after drilling 10,000 hits at a rotation speed of 70 krpm and a feed speed of 20 μm / rev. (5) Moisture and heat resistance: pressure cooker treatment (121
4 ° C.) 4 hours later, immersed in a solder bath at 260 ° C., and measured the time until blistering occurred on the surface. (6) Life of prepreg: The prepreg is stored in an oven at 40 ° C. for 10 days, and the change in the gelling time of the prepreg is measured, and the change is determined by Formula 1.

[0027]

(Equation 1)

(7) Glass transition temperature (Tg): Indicates the inflection temperature of the amount of expansion in the thickness direction of the laminate using thermomechanical analysis (TMA).

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

As is clear from Tables 3 and 4, the laminate using the resin composition according to the present invention can improve the migration resistance and has a high peel strength of the copper foil. It can be seen that the curing reaction has also proceeded sufficiently. Chelating agents having a reactive functional group (A)
When pre-reacted with the component (C), the migration resistance can be further improved without lowering the heat resistance. (A) When a novolak epoxy resin having a softening temperature of 50 to 80 ° C. is used, the life of the prepreg becomes longer and the heat resistance becomes excellent.
In addition, when a glass woven fabric made of glass fibers subjected to embrittlement treatment is used as the base material of the laminated plate, the positional accuracy of drilling is increased, and it is difficult to form a narrow space between the through holes. Become noticeable,
It is useful for high density printed circuit boards.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a circuit pattern of a printed circuit board for performing a migration resistance test.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-288318 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 59/14 C08G 59/44-59 / 46 B32B 17/04 C08J 5/24

Claims (6)

(57) [Claims] A dicyandiamide (curing agent) is blended with a pre-reaction product under the catalyst of the following components (A) to (C), and components (A) and (B) are contained in the pre-reaction product. The laminate is characterized in that the amount of hydrolyzable chlorine is selected to be 100 ppm or less, and the blending amount of dicyandiamide is 0.45 to 0.60 equivalent relative to the epoxy equivalent of the preliminary reaction product. Epoxy resin composition for use. (A) Novolak epoxy resin (B) Diglycidyl ether of polyhydric phenol or its alkyl or halogen derivative (C) Polyhydric phenol or its alkyl or halogen derivative 2. A dicyandiamide (curing agent) is blended with a pre-reaction product of the following components (A) to (D) in the presence of a catalyst, and components (A) and (B) are contained in the pre-reaction product. The laminate is characterized in that the hydrolyzable chlorine is selected to be in an amount of 100 ppm or less, and the blending amount of dicyandiamide is 0.45 to 0.6 equivalent with respect to the epoxy equivalent of the preliminary reaction product. Epoxy resin composition for use. (A) Novolak epoxy resin (B) Diglycidyl ether of polyhydric phenol or its alkyl or halogen derivative (C) Polyhydric phenol or its alkyl or halogen derivative (D) Chelating agent having reactive functional group 3. The epoxy resin composition for a laminate according to claim 1, wherein the softening temperature of the novolak epoxy resin (A) is 50 to 80 ° C. 4. A laminate according to claim 1, wherein said thermosetting resin is produced by heating and pressing a prepreg obtained by impregnating and drying a thermosetting resin in a sheet-like base material. For producing a laminated board, which is an epoxy resin composition for use in an automobile. 5. The method according to claim 4, wherein the sheet-like substrate is a glass woven fabric, and glass fibers constituting the glass woven fabric have been subjected to an embrittlement treatment. 6. The method for producing a laminate according to claim 5, wherein the embrittlement treatment is a treatment for forming a porous gel film on the glass fiber surface.