RESIN COMPOSITION FOR METAL-CLAD LAMINATES, PREPREG, AND METAL-CLAD LAMINATE

Abstract

A resin composition for a metal-clad laminate plate includes a block copolymer comprising a butadiene block having a molar ratio of a 1,2-bonding structure to a 1,4-bonding structure of 80:20 to 100:0 and a styrene block. Further, the resin composition for the metal-clad laminate plate includes polybutadiene having a molar ratio of a 1,2-bonding structure to a 1,4-bonding structure of 80:20 to 100:0.

Claims

1. A resin composition for a metal-clad laminate plate comprising (A) a block copolymer comprising a butadiene block having a molar ratio of a 1,2-bonding structure to a 1,4-bonding structure of 80:20 to 100:0 and a styrene block.

2. A resin composition for a metal-clad laminate plate comprising (A) a styrene-butadiene-styrene block copolymer (SBS) having a molar ratio of a 1,2-bonding structure to a 1,4-bonding structure in a butadiene block of 80:20 to 100:0.

3. A resin composition for a metal-clad laminate plate, comprising: (A) a block copolymer comprising a butadiene block having a molar ratio of a 1,2-bonding structure to a 1,4-bonding structure of 80:20 to 100:0 and a styrene block, and (B) polybutadiene having a molar ratio of a 1,2-bonding structure to a 1,4-bonding structure of 80:20 to 100:0.

4. A resin composition for a metal-clad laminate plate, comprising: (A) a styrene-butadiene-styrene block copolymer (SBS) having a molar ratio of a 1,2-bonding structure to a 1,4-bonding structure in a butadiene block of 80:20 to 100:0, and (B) polybutadiene having a molar ratio of a 1,2-bonding structure to a 1,4-bonding structure of 80:20 to 100:0.

5. The resin composition for the metal-clad laminate plate according to claim 1, wherein a weight ratio of the styrene block to the butadiene block in the component (A) is 10:90 to 80:20.

6. The resin composition for the metal-clad laminate plate according to claim 1, wherein a weight average molecular weight (Mw) of the component (A) is 2,000 to 100,000.

7. The resin composition for the metal-clad laminate plate according to claim 1, wherein a molecular weight distribution (Mw/Mn) of the component (A) is 1.00 to 3.00.

8. The resin composition for the metal-clad laminate plate according to claim 3, wherein a weight average molecular weight (Mn) of the component (B) is 500 to 5,000.

9. The resin composition for the metal-clad laminate plate according to claim 3, wherein a content ratio of the component (A) to the component (B) is component (A): component (B)=5:95 to 95:5 in terms of weight ratio.

10. The resin composition for the metal-clad laminate plate according to claim 1, further comprising a crosslinking agent.

11. The resin composition for the metal-clad laminate plate according to claim 1, further comprising a flame retardant.

12. A prepreg wherein the resin composition for the metal-clad laminate plate according to claim 1 is impregnated in a base material.

13. A metal-clad laminate plate produced by laminating the prepreg according to claim 12 and a metal foil by hot press molding.

Description

EXAMPLES

[0058] Hereinafter, the present invention will be described in detail by way of Examples, but the present invention is not limited to the scope of Examples.

Component (A): Production of Styrene-Butadiene-Styrene Block Copolymer (SBS)

Production Example 1

[0059] Into a 500 mL flask, 151.95 g of tetrahydrofuran (hereinafter, abbreviated as THF) and 19.65 g of hexane were added. After the mixture was cooled to −40° C., 2.28 g of n-butyllithium (a hexane solution with a concentration of 15.1% by weight) was added and stirred for 10 minutes, then 11.99 g of styrene was added dropwise, and the reaction was continued for 30 minutes. The solution was measured by gas chromatography (hereinafter, abbreviated as GC) and the disappearance of monomers was confirmed. Then, a mixed solution of 21.44 g of 1,3-butadiene, 23.43 g of THF, and 7.80 g of hexane was added dropwise, and the reaction was continued. After the solution was measured by GC and the disappearance of monomers was confirmed, 12.05 g of styrene was added dropwise, and after 30 minutes, 0.51 g of methanol was added to terminate the reaction.

[0060] The copolymer obtained was analyzed by gel permeation chromatography (mobile phase: THF, polystyrene standards), and it was confirmed that the weight average molecular weight (Mw) was 24,300 and the molecular weight distribution (Mw/Mn) was 1.28. The copolymer obtained was a copolymer having a composition ratio of PS/PB/PS=25/50/25% by weight. Note that PS means the styrene block and PB means the butadiene block. The same applies hereinafter.

[0061] The reaction liquid was washed twice with water, and then the solvent was distilled off. This was reprecipitated in methanol, filtered off, and dried in vacuo to obtain a white powder. The 1,2-bonding structure in the butadiene block calculated by .sup.1H-NMR was 93 mol %.

Production Example 2

[0062] Into a 500 mL flask, 149.37 g of THF and 17.53 g of hexane were added. After the mixture was cooled to −40° C., 5.21 g of n-butyllithium (a hexane solution with a concentration of 15.1% by weight) was added and stirred for 10 minutes, then 10.47 g of styrene was added dropwise, and the reaction was continued for 30 minutes. The solution was measured by gas chromatography (hereinafter, abbreviated as GC) and the disappearance of monomers was confirmed. Then, a mixed solution of 49.28 g of 1,3-butadiene and 49.28 g of THF was added dropwise and the reaction was continued. After the solution was measured by GC and the disappearance of monomers was confirmed, 10.66 g of styrene was added dropwise, and after 30 minutes, 1.12 g of methanol was added to terminate the reaction.

[0063] The copolymer obtained was analyzed by gel permeation chromatography (mobile phase: THF, polystyrene standards), and it was confirmed that the weight average molecular weight (Mw) was 14,200 and the molecular weight distribution (Mw/Mn) was 1.18. The copolymer obtained was a copolymer having a composition ratio of PS/PB/PS=15/70/15% by weight.

[0064] The reaction liquid was washed twice with water, and then the solvent was distilled off. This was reprecipitated in methanol, filtered off, and dried in vacuo to obtain a colorless and transparent viscous liquid. The 1,2-bonding structure in the butadiene block calculated by .sup.1H-NMR was 94 mol %.

Production Example 3

[0065] Into a 500 mL flask, 155.90 g of cyclohexane and 20.10 g of THF were added. The mixture was warmed to 30° C., 1.95 g of n-butyllithium (a hexane solution with a concentration of 15.1% by weight) was added and stirred for 10 minutes, then 7.64 g of styrene was added dropwise, and the reaction was continued for 30 minutes. The solution was measured by gas chromatography (hereinafter, abbreviated as GC) and the disappearance of monomers was confirmed. Then, a mixed solution of 35.07 g of 1,3-butadiene and 35.07 g of cyclohexane was added dropwise and the reaction was continued. After the solution was measured by GC and the disappearance of monomers was confirmed, 7.78 g of styrene was added dropwise, and after 30 minutes, 0.40 g of methanol was added to terminate the reaction.

[0066] The copolymer obtained was analyzed by gel permeation chromatography (mobile phase: THF, polystyrene standards), and it was confirmed that the weight average molecular weight (Mw) was 17,400 and the molecular weight distribution (Mw/Mn) was 1.07. The copolymer obtained was a copolymer having a composition ratio of PS/PB/PS=15/70/15% by weight.

[0067] The reaction liquid was washed twice with water, and then the solvent was distilled off. This was reprecipitated in methanol, filtered off, and dried in vacuo to obtain a colorless and transparent viscous liquid. The 1,2-bonding structure in the butadiene block calculated by .sup.1H-NMR was 89 mol %.

Production Example 4

[0068] Into a 5,000 mL flask, 1,212 g of THF and 132 g of hexane were added. After the mixture was cooled to −40° C., 98.58 g of n-butyllithium (a hexane solution with a concentration of 15.1% by weight) was added and stirred for 10 minutes, then 60.50 g of styrene was added dropwise, and the reaction was continued for 15 minutes. The solution was measured by gas chromatography (hereinafter, abbreviated as GC) and the disappearance of monomers was confirmed. Then, a mixed solution of 481.88 g of butadiene, 432.12 g of THF, and 48.08 g of hexane was added dropwise and the reaction was continued. After the solution was measured by GC and the disappearance of monomers was confirmed, 61.13 g of styrene was added dropwise, and after 30 minutes, 16.02 g of methanol was added to terminate the reaction.

[0069] The copolymer obtained was analyzed by gel permeation chromatography (mobile phase: THF, polystyrene standards), and it was confirmed that the weight average molecular weight (Mw) was 4,742 and the molecular weight distribution (Mw/Mn) was 1.12. The copolymer obtained was a copolymer having a composition ratio of PS/PB/PS=10/80/10% by weight.

[0070] The reaction liquid was washed twice with water, and the solvent was distilled off to obtain a white viscous liquid. The 1,2-bonding structure in the butadiene unit calculated by .sup.1H-NMR was 91%.

Example 1

[0071] Polybutadiene (manufactured by Nippon Soda Co., Ltd., B-3000), the styrene-butadiene-styrene block copolymer obtained in Production Example 1, and dicumyl peroxide (manufactured by Aldrich) were mixed in an amount shown in Table 1 and dissolved in methyl ethyl ketone (hereinafter, referred to as MEK, manufactured by FUJIFILM Wako Pure Chemical Corporation) to obtain a varnish.

Example 2

[0072] A varnish was obtained in the same manner as in Example 1, except for using the styrene-butadiene-styrene block copolymer obtained in Production Example 4 instead of the styrene-butadiene-styrene block copolymer obtained in Production Example 1.

Comparative Example 1

[0073] A varnish was obtained in the same manner as in Example 1, except for using Kraton D1192 (manufactured by Kraton, styrene-butadiene-styrene block copolymer) instead of the styrene-butadiene-styrene block copolymer obtained in Production Example 1.

(Method for Fabricating Sample for Solder Heat-Resistance Test)

[0074] 4 pieces of glass fiber cloth which were cut into 3 cm squares were sufficiently impregnated with the varnish and heated in an oven at 150° C. for 10 minutes to fabricate prepregs. The rough surface of a copper foil having a thickness of 18 μm was applied to both surfaces of the obtained prepregs. Thereafter, this was sandwiched by polytetrafluoroethylene plates and hot-pressed using a press at 230° C. under conditions of 3-4 MPa for 2 hours to obtain an evaluation substrate (copper-clad laminate plate).

(Solder Heat-Resistance Test)

[0075] The solder heat-resistance test was measured in accordance with JIS C 6481. The solder heat resistance was evaluated by immersing the copper-clad laminate plate in solder at 260° C. for 2 minutes and observing the peeling of the copper foil. When no peeling occurred, it was evaluated as “o,” and when peeling occurred, it was evaluated as “x.” The results are shown in Table 1.

(Method for Fabricating Sample for Measuring Glass Transition Temperature Tg and Electrical Characteristics)

[0076] 10 pieces of glass fiber cloth which were cut into cm squares were sufficiently impregnated with the varnish and heated in an oven at 150° C. for 10 minutes to fabricate prepregs. 10 pieces of the prepregs obtained were laminated, and this was sandwiched by polytetrafluoroethylene plates and hot-pressed using a press at 230° C. under conditions of 3-4 MPa for 2 hours to obtain an evaluation substrate (laminate plate).

(Measurement of Glass Transition Temperature Tg)

[0077] The Tg of the laminate plate was measured by using a dynamic viscoelasticity apparatus “RSA-G2” manufactured by TA Instruments. At this time, dynamic viscoelasticity measurement (DMA) was carried out with a bending module using a 30 mm dual cantilever as a jig at a frequency of 1 Hz, and the temperature at which the tanδ was maximum when the temperature was raised from −50° C. to 270° C. at a temperature rising rate of 5° C./min was determined as Tg. The results are shown in Table 1.

(Heat Resistance Evaluation)

[0078] Dynamic viscoelasticity measurement (DMA) was carried out using a dynamic viscoelasticity apparatus “RSA-G2” manufactured by TA Instruments with a bending module using a 30 mm dual cantilever as a jig at a frequency of 1 Hz, and when two cycles of measurements from −50° C. to 270° C. at a temperature rising rate of 5° C./min were carried out, the difference of Tg between the first cycle and the second cycle, ATg was evaluated. The temperature at which the tanδ was maximum was determined as Tg. The results are shown in Table 1.

(Dielectric Characteristics)

[0079] The relative dielectric constants (Dk) and dielectric loss tangents (Df) of the evaluation substrates at 10 GHz were measured by the resonant cavity perturbation method. Specifically, the relative dielectric constants and dielectric loss tangents of the test substrates at 10 GHz were measured using a network analyzer (MS46122B, manufactured by Anritsu Corporation). The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Example Example Comparative 1 2 Example 1 Composition B-3000 50 50 50 (parts by Polymer 50 weight) synthesized in Production Example 1 Polymer 50 synthesized in Production Example 4 Kraton D1192 50 DCP 2 2 2 Evaluation Solder heat ∘ ∘ ∘ resistance Tg (First 74.3 28.9 14.1 cycle) (° C.) Tg (Second 81.2 40.8 10.1 cycle) (° C.) ΔTg 6.9 11.9 −4.1 Relative 2.95 3.64 3.39 dielectric constant(Dk) Dielectric 0.0051 0.0050 0.0051 loss tangent(Df)

[0080] These test results revealed that the Tg of the laminate plate produced using the composition of the present invention has excellent heat resistance that is higher than that of Comparative Example.