JP2003119371A - Resin composition for production of metal-clad laminated board, prepreg, laminate, metal-clad laminated board and multilayer printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene ether resin-based highly multilayered printed wiring board excellent in connecting reliability of through hole and to provide their relating materials. SOLUTION: This resin composition for production of a metal-clad laminated board includes (A) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid, (B) triallyl isocyanurate or triallyl cyanurate, (C) silicone resin particles or silicone rubber particles covered with silicone resin and (D) silica particles as the essential components in a ratio of 50-60 pts.wt. of the component (A) and 40-50 pts.wt. of the component (B), 1-10 pts.wt. of the component (C) and 5-40 pts.wt. of the component (D), respectively per 100 pts.wt. of the sum of the components (A) and (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for producing a metal-clad laminate, which provides a highly multilayer printed wiring board having particularly excellent connection reliability of through holes, and a prepreg, a laminate, and a metal-clad laminate produced therefrom. The present invention relates to boards and multilayer printed wiring boards.

[0002]

2. Description of the Related Art In recent years, the speed and integration of LSIs have increased and the capacity of memories has increased, and along with this, various electronic components have been rapidly reduced in size, weight and thickness. Along with this, excellent heat resistance, dimensional stability, and electrical characteristics are required in terms of materials. Thermosetting resins such as phenolic resins, epoxy resins, and polyimide resins have been conventionally used for printed wiring boards. Although these resins have various performances in a well-balanced manner, they have the drawback of not having sufficient dielectric properties in the high frequency region. As a new material for solving this problem, polyphenylene ether has recently attracted attention and its application to copper clad laminates has been attempted.

For example, JP-A-61-287739, JP-B-7-37567, JP-A-64-69628, JP-A-64-69629, JP-A-1-113425,
Japanese Unexamined Patent Publication (Kokai) No. 1-113426 discloses a resin composition containing polyphenylene ether and a laminate using the resin composition.

Further, Japanese Examined Patent Publication No. S64-3223 and Japanese Patent Laid-Open No. Hei 2
JP-A-135216 and JP-A-2-166115 disclose a resin composition in which a polyphenylene ether and an epoxy resin are combined.

A resin composition containing polyphenylene ether can be used in various electronic devices as a double-sided printed wiring board or a multilayer printed wiring board. Particularly, in a high multilayer printed wiring board, the through hole has excellent connection reliability. Is required to be added. The connection reliability of the through hole is evaluated by performing a low temperature / high temperature thermal cycle test for accelerated evaluation. However, in a high multilayer printed wiring board, barrel cracks and corner cracks are generated in the through hole during the thermal cycle test, and sufficient It has been difficult to obtain a reliable resin composition.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a polyphenylene ether resin-based high multi-layer printed wiring board excellent in connection reliability of through holes and its related materials. To provide.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that in a polyphenylene ether resin composition, "silicone resin particles and / or particulate silicone rubber are used as silicone." By blending “resin-coated particles” and “silica particles”,
The present invention has been completed by finding that the above problems can be solved.

That is, the resin composition for producing a metal-clad laminate of the present invention comprises (A) a reaction product of polyphenylene ether and an unsaturated carboxylic acid and / or acid anhydride, (B) triallyl isocyanurate and / or Alternatively, triallyl cyanurate, (C) silicone resin particles or silicone rubber particles whose surface is coated with a silicone resin and (D) silica particles are used as essential components, and the total amount of the components (A) and (B) is 100 parts by weight. Then, 50 to 60 parts by weight of the component (A), 40 to 50 parts by weight of the component (B), and 1 to 1 of the component (C).
It is characterized by containing 10 parts by weight and the component (D) at a ratio of 5 to 40 parts by weight, respectively. Yet another invention is
A prepreg, a laminated board, a metal-clad laminated board, and a multilayer printed wiring board manufactured by using the resin composition.

The present invention will be described in detail below.

As the polyphenylene ether in the reaction product of the polyphenylene ether (A) used in the present invention with the unsaturated carboxylic acid and / or acid anhydride, for example, poly (phenylene ether obtained by homopolymerization of 2,6-dimethylphenol 2,6-Dimethyl-1,4-phenylene ether), poly (2,6-dimethyl-1,4-phenylene ether) styrene graft copolymer, 2,6-dimethylphenol and 2-methyl-6-phenyl Copolymer of phenol, 2,6-dimethylphenol and 2,3,6-
Copolymer of trimethylphenol, polyfunctional polyphenylene ether obtained by polymerization in the presence of 2,6-dimethylphenol and a polyfunctional phenol compound, the presence of aniline or an aliphatic secondary amine substituted with 2,6-dimethylphenol Nitrogen-containing polyphenylene ether obtained by polymerization under the following may be mentioned.

Regarding the molecular weight of the polyphenylene ether described above, one having a viscosity number ηsp / C measured in a chloroform solution of 30 g at 0.5 g / dl in the range of 0.1 to 1.0 can be preferably used.

The unsaturated carboxylic acid in the reaction product of the polyphenylene ether (A) used in the present invention with the unsaturated carboxylic acid and / or acid anhydride is a double bond and at least one carboxylic acid group or It is a compound having a dicarboxylic acid anhydride group in its molecular structure, and is preferably maleic anhydride, maleic acid, fumaric acid, or itaconic acid. These may be used alone or in combination of two or more. The modification reaction of the component (A) may be carried out by a conventional method described in the above-mentioned publicly known publications.

The amount of the reaction product (A) blended in the present invention is the total amount of the component (A) and the following component (B): [(A)
+ (B)] It is desirable to add 50 to 60 parts by weight to 100 parts by weight. If the amount of component (A) is less than 50 parts by weight, the impact resistance of the cured product will decrease, and if it exceeds 60 parts by weight, the chemical resistance of the cured product will decrease.

The (B) triallyl isocyanurate or triallyl cyanurate used in the present invention is used alone or as a mixture of two or more as a crosslinking agent. By using triallyl isocyanurate or triallyl cyanurate, a cured product having excellent dielectric properties and heat resistance can be obtained. The blending amount of the component (B) is [(A) +
(B)] It is desirable to add 40 to 50 parts by weight to 100 parts by weight.

In order to crosslink (A) the reaction product of polyphenylene ether and unsaturated carboxylic acid with (B) triallyl isocyanurate or triallyl cyanurate, a curing accelerator can be used. Examples of the agent include radical initiators, and examples thereof include ordinary peroxides such as Perhexin 25B (trade name, manufactured by NOF CORPORATION).

The silicone resin particles of component (C) used in the present invention include MSP-1500 and MSP-3000.
(Manufactured by Nikko Rica Co., Ltd.) and the like, and as the silicone rubber particles whose surface is coated with a silicone resin, KMP-600, KMP-603, KMP-60.
4, KMP-605, KMP-594, KMP-597
(Trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and these can be used alone or in combination of two or more kinds.

In the present invention, the average particle size of the silicone resin particles of component (C) or the silicone rubber particles whose surface is coated with a silicone resin is preferably 10 μm or less. If it exceeds 10 μm, various problems may occur when forming fine wiring, for example, problems such as deterioration in adhesion with a metal foil.

In the present invention, the blending ratio of the component (C) is
It is added in a ratio of 1 to 10 parts by weight with respect to 100 parts by weight of [(A) + (B)]. If this ratio is less than 1 part by weight, sufficient through-hole connection reliability of the high multilayer printed board cannot be obtained, and if it exceeds 10 parts by weight, the adhesion to the metal foil and the moisture absorption resistance are deteriorated. Therefore, it is preferable to set it within the above range.

As the (D) silica particles used in the present invention, pulverized silica, fused silica or a mixture thereof can be used. Specifically, for example, FUSELEX E
-2, Adma Fine SO-C5, PLV-3
(Trade name, manufactured by Tatsumori Co., Ltd.) and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

In the present invention, the average particle diameter of the (D) silica particles is preferably 10 μm or less. 10 μm
If it exceeds the range, various problems may occur during formation of fine wiring, for example, problems such as deterioration in adhesion with the metal foil.

The blending ratio of the (D) silica particles is
It is added in a proportion of 5 to 40 parts by weight with respect to 100 parts by weight of [(A) + (B)]. If this ratio is less than 5 parts by weight, sufficient through-hole connection reliability of the high-layer printed board cannot be obtained, and if it exceeds 40 parts by weight, the adhesion to the metal foil and the melt fluidity of the composition are deteriorated. Therefore, it is preferable to set it within the above range.

In addition to the above-mentioned essential components (A), (B), (C), and (D), the resin composition of the present invention may be appropriately blended with fillers and additives depending on the intended use. Can be used. Examples of the filler include carbon black, titanium oxide, barium titanate, glass beads, glass hollow spheres and the like. Examples of the additives include antioxidants, heat stabilizers, antistatic agents, plasticizers, pigments, dyes, colorants and the like. Specific additives are:
Examples thereof include antimony trioxide, SAYTEX 8010 (trade name, manufactured by Albemarle Asano Co., Ltd.), and these can be used alone or in combination of two or more.

Further, in addition to the components (A) and (B), one type or two types of thermoplastic resins or thermosetting resins are used.
It is also possible to mix more than one kind. Examples of thermoplastic resins include GPPS (General Purpose Polystyrene), HIPS
(Impact-resistant polystyrene), polybutadiene, styrene-butadiene block copolymer and the like can be mentioned. Examples of the thermosetting resin include epoxy resin and the like, and these can be used alone or in combination of two or more kinds.

As the method for mixing the above (A) to (D) and other components, a solution mixing method in which all the components are uniformly dissolved or dispersed in a solvent, or a melt blending method performed by heating with an extruder or the like. Etc. can be used. Examples of the solvent used in the solution mixing method include aromatic solvents such as benzene, toluene, xylene, and tetrahydrofuran, and these can be used alone or in combination of two or more.

Next, the prepreg and the laminated board product of the present invention will be described.

The prepreg of the present invention can be obtained by applying the resin composition for metal-clad lamination of the present invention to a base material by a conventional method, impregnating and drying it. As the base material, glass, woven fabric of fibers such as polyimide, non-woven fabric, paper and the like can be used, impregnated with this,
Dry to make a prepreg. As the material of the glass, D glass, S glass, quartz glass and the like can be used in addition to E glass which is usually used.

The proportion of the base material in the prepreg is preferably 20 to 80% by weight of the whole prepreg.
If the proportion of the base material is less than 20% by weight, the dimensional stability and the strength of the prepreg after curing are insufficient, and if it exceeds 80% by weight, the dielectric properties of the laminate are poor, which is not preferable. Further, in the prepreg of the present invention, a coupling agent such as a silane coupling agent or a titanate coupling agent can be used if necessary.

The method for producing the prepreg of the present invention includes, for example, adding other components as necessary to the components (A) to (D) of the present invention, and further adding the above components to the aromatic solvent and the ketone solvent. Examples include a method of uniformly dissolving or dispersing, impregnating the base material, and then drying. Further, the components (A) to (D) may be melted and impregnated into the base material. The impregnation is performed by dipping, coating or the like. The impregnation can be repeated a plurality of times as necessary, and the impregnation can be repeated using a plurality of impregnation tanks having different resin concentrations.

The laminated board of the present invention can be obtained by thermoforming the prepreg thus obtained. The method of heat molding is not particularly limited, and for example, a plurality of prepregs may be superposed and heat-pressed to obtain a laminate having a predetermined thickness. Furthermore, a thicker laminated board can be obtained by combining the obtained laminated board and prepreg.

The lamination molding and curing are usually carried out simultaneously by using a hot press machine, but both may be carried out separately. That is, it is also possible to first laminate and mold to obtain a semi-cured laminate, and then treat with a heat treatment machine to completely cure. The conditions for heat and pressure molding are a temperature of 80 to 300 ° C. and a pressure of 0.1 to 5.
0 MPa, time range of 1 minute to 10 hours, more preferably, temperature 150 to 250 ° C., pressure 0.5 to 10 MPa,
The time is 10 minutes to 5 hours.

The metal-clad laminate of the present invention can be obtained by stacking the prepreg of the present invention and a metal foil, and heating and pressing. The metal foil used in the present invention may be an electrolytic copper foil, a copper foil such as a rolled copper foil, an aluminum foil or a composite foil obtained by stacking them. The thickness is not particularly limited,
For the printed board, those having a thickness of 5 to 105 μm can be used. The metal-clad laminate of the present invention is manufactured by stacking a predetermined number of the above-mentioned prepregs and a metal foil and heat-pressing.

In the multilayer board of the present invention, the metal-clad laminate obtained as described above is subjected to circuit formation and through-hole formation to overlap the inner layer board and prepreg, and further the surface layer is covered with a metal foil. It is obtained by heat-press molding after stacking. Further, a circuit and a through hole are formed on the surface metal foil to obtain a multilayer printed wiring board.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples. In the following Examples and Comparative Examples, "part" means "part by weight".

Example 1 [Synthesis of maleic anhydride-modified polyphenylene ether]
100 parts of poly (2,6-dimethyl-1,4-phenylene ether) having a viscosity number ηsp / C of 0.54 measured at 30 ° C. in a 0.5 g / dl chloroform solution, 2 parts of maleic anhydride, and perhexin. 25B (made by NOF CORPORATION,
After 1 part of product name) was dry blended at room temperature using a drum blender, it was extruded by a twin-screw extruder under the conditions of a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm to obtain a maleic anhydride-modified polyphenylene ether.

[Production Evaluation of Multilayer Printed Circuit Board] 50 parts of the above maleic anhydride-modified polyphenylene ether, triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd., trade name) 46
Part, GPPS (General-purpose polystyrene, weight average molecular weight 27
50,000) 4 parts, KMP- of coated silicone rubber particles
600 (trade name of Shin-Etsu Chemical Co., Ltd., average particle size 5 μm) 3 parts,
15 parts of silica particle FUSELEXE-2 (trade name of Tatsumori Co., average particle size 7 μm), 6 parts of Perhexin 25B (trade name of NOF CORPORATION, trade name) as a peroxide, and 4 parts of antimony trioxide as an additive And SAYTEX8010
20 parts (trade name, manufactured by Albemarle Asano Co., Ltd.) was dissolved or dispersed in toluene to prepare a resin varnish.

A resin varnish of the above type 2116 type (10
7 g / m ² ) and 2112 type (71 g / m ² ) glass cloth respectively coated, impregnated and dried to a thickness of 1
50 μm (58% by weight of resin) prepreg and thickness 110
A μm (resin 60% by weight) prepreg was prepared.

35 on both sides of a prepreg having a thickness of 150 μm
A copper foil with a thickness of μm is placed, and mirror plates are stacked on top and bottom of the foil.
An m-thick inner layer plate was prepared. This inner layer board and thickness 110 μm
The above prepregs were alternately combined, and 18 μm copper foils were superposed on the front and back sides and heat-pressed to obtain a 22-layer multilayer plate. Further, punching and through-hole plating were performed to prepare a test plate having a daisy chain with a through-hole diameter of 0.5 mm, a plating thickness of 20 μm and 3000 holes.

Separately, 10 pieces of prepreg having a thickness of 150 μm were superposed on each other and 18 μm of copper foil was superposed on the front and back sides of the prepreg and heat-pressed to form a 1.6 mm-thick copper clad laminate.

Example 2 50 parts of maleic anhydride-modified polyphenylene ether of Example 1 and triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.,
Brand name) 46 parts, GPPS (general-purpose polystyrene, weight average molecular weight 270,000) 4 parts, coated silicone rubber particles KMP-605 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 5)
μm) 3 parts, FUSELEX E-2 (trade name manufactured by Tatsumori, average particle size 7 μm) 15 parts, 6 parts of Perhexin 25B (trade name of NOF CORPORATION, trade name), 4 parts of antimony trioxide, and SAYTEX 8010 (Albemarle Asano). A resin varnish was prepared by dissolving or dispersing 20 parts (trade name, manufactured by Co., Ltd.) in toluene.

2116 type (10
7 g / m ² ) and 2112 type (71 g / m ² ) glass cloth respectively coated, impregnated and dried to a thickness of 1
50 μm (58% by weight of resin) prepreg and thickness 110
A μm (resin 60% by weight) prepreg was prepared.

Using the prepared prepreg, a 22-layer multilayer plate was molded in the same manner as in Example 1 to prepare a test plate having a daisy chain with a through hole diameter of 0.5 mm, a plating thickness of 20 μm and 3000 holes.

Separately, 10 pieces of prepreg having a thickness of 150 μm were superposed, 18 μm of copper foil was superposed on the front and back, and heat-pressed to form a copper-clad laminate having a thickness of 1.6 mm.

Example 3 50 parts of maleic anhydride-modified polyphenylene ether of Example 1 and triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.,
Trade name) 46 parts, GPPS (general-purpose polystyrene, weight average molecular weight 270,000) 4 parts, MSP-3000 of silicone rubber resin particles (Nikko Rica brand name, average particle size 3 μm) 3 parts, FUSELEX E-2 ( Tatsumori Co., Ltd. product name, average particle size 7 μm) 15 parts, Perhexin 25B (NOF CORPORATION, product name) 6 parts, antimony trioxide 4 parts, and SAYTEX 8010 (Albemarle Asano Co., product name) 20 parts A resin varnish was prepared by dissolving or dispersing in toluene.

A resin varnish of the above type 2116 type (10
7 g / m ² ) and 2112 type (71 g / m ² ) glass cloth respectively coated, impregnated and dried to a thickness of 15
0μm (58% by weight of resin) prepreg and thickness 110μ
m (60% by weight of resin) prepreg was prepared.

Using the prepared prepreg, a 22-layer multilayer plate was molded in the same manner as in Example 1, and the through hole diameter was 0.
A test plate having a daisy chain of 5 mm and a plating thickness of 20 μm and 3000 holes was prepared.

Separately, 10 pieces of prepreg having a thickness of 150 μm were superposed, 18 μm of copper foil was superposed on the front and back sides, and heat-pressed to form a copper clad laminate having a thickness of 1.6 mm.

Example 4 50 parts of maleic anhydride-modified polyphenylene ether of Example 1, triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.,
Brand name) 46 parts, GPPS (general-purpose polystyrene, weight average molecular weight 270,000) 4 parts, KMP-600 of coated silicone rubber particles (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 5)
μm) 3 parts, FUSELEX E-2 (trade name manufactured by Tatsumori, average particle size 7 μm) 30 parts, perhexin 25B (trade name, manufactured by NOF CORPORATION) 6 parts, antimony trioxide 4 parts, and SAYTEX 8010 (Albemarle Asano). A resin varnish was prepared by dissolving or dispersing 20 parts (trade name, manufactured by Co., Ltd.) in toluene.

2116 type (10
7 g / m ² ) and 2112 type (71 g / m ² ) glass cloth respectively coated, impregnated and dried to a thickness of 1
50 μm (58% by weight of resin) prepreg and thickness 110
A μm (resin 60% by weight) prepreg was prepared.

Using the prepared prepreg, a 22-layer multilayer plate was molded in the same manner as in Example 1, and the through hole diameter was 0.
A test plate having a daisy chain of 5 mm and a plating thickness of 20 μm and 3000 holes was prepared.

Separately, 10 pieces of prepreg having a thickness of 150 μm were superposed on each other, and 18 μm of copper foil was superposed on the front and back sides thereof, and heat-pressed to form a copper-clad laminate having a thickness of 1.6 mm.

Comparative Example 1 50 parts of maleic anhydride-modified polyphenylene ether of Example 1, triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.,
Brand name) 46 parts, GPPS (general-purpose polystyrene, weight average molecular weight 270,000) 4 parts, KMP-600 of coated silicone rubber particles (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 5)
μm) 3 parts, Perhexin 25B (manufactured by NOF Corporation, trade name) 6 parts, antimony trioxide 4 parts, and SAYTEX
8010 (Albemarle Asano Co., Ltd., trade name) 20
A part was dissolved or dispersed in toluene to prepare a resin varnish.

A resin varnish of the above type 2116 type (10
7 g / m ² ) and 2112 type (71 g / m ² ) glass cloth respectively coated, impregnated and dried to a thickness of 1
50 μm (58% by weight of resin) prepreg and thickness 110
A μm (resin 60% by weight) prepreg was prepared.

Using the prepared prepreg, a 22-layer multilayer plate was molded in the same manner as in Example 1, and the through hole diameter was 0.
A test plate having a daisy chain of 5 mm and a plating thickness of 20 μm and 3000 holes was prepared.

Separately, 10 pieces of prepreg having a thickness of 150 μm were superposed on each other and copper foil of 18 μm was placed on the front and back sides of the prepreg to heat-press and form a copper clad laminate having a thickness of 1.6 mm.

Comparative Example 2 50 parts of maleic anhydride-modified polyphenylene ether of Example 1 and triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.,
Brand name) 46 parts, GPPS (general-purpose polystyrene, weight average molecular weight 270,000) 4 parts, KMP-600 of coated silicone rubber particles (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 5)
μm) 3 parts, FUSELEX E-2 (trade name, manufactured by Tatsumori Co., Ltd., average particle size 7 μm) 3 parts, perhexin 25B (manufactured by NOF CORPORATION, trade name) 6 parts, antimony trioxide 4 parts, and SAYTEX 8010 (Albemarle Asano). A resin varnish was prepared by dissolving or dispersing 20 parts (trade name, manufactured by Co., Ltd.) in toluene.

2116 type (10
7 g / m ² ) and 2112 type (71 g / m ² ) glass cloth respectively coated, impregnated and dried to a thickness of 1
50 μm (58% by weight of resin) prepreg and thickness 110
A μm (resin 60% by weight) prepreg was prepared.

Using the prepared prepreg, a 22-layer multilayer plate was molded in the same manner as in Example 1, and the through hole diameter was 0.
A test plate having a daisy chain of 5 mm and a plating thickness of 20 μm and 3000 holes was prepared.

Separately, 10 pieces of prepreg having a thickness of 150 μm were superposed, 18 μm of copper foil was superposed on the front and back, and heat-pressed to form a copper-clad laminate having a thickness of 1.6 mm.

Comparative Example 3 50 parts of maleic anhydride-modified polyphenylene ether of Example 1 and triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.,
Brand name) 46 parts, GPPS (general-purpose polystyrene, weight average molecular weight 270,000) 4 parts, KMP-600 of coated silicone rubber particles (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 5)
μm) 3 parts, FUSELEX E-2 (trade name, manufactured by Tatsumori Co., Ltd., average particle size 7 μm) 50 parts, perhexin 25B (trade name, manufactured by NOF CORPORATION), 6 parts, antimony trioxide 4 parts, and SAYTEX 8010 (Albemarle Asano). A resin varnish was prepared by dissolving or dispersing 20 parts (trade name, manufactured by Co., Ltd.) in toluene.

2116 type (10
7 g / m ² ) and 2112 type (71 g / m ² ) glass cloth respectively coated, impregnated and dried to a thickness of 1
50 μm (58% by weight of resin) prepreg and thickness 110
A μm (resin 60% by weight) prepreg was prepared.

Using the prepared prepreg, a 22-layer multilayer plate was molded in the same manner as in Example 1, and the through hole diameter was 0.
A test plate having a daisy chain of 5 mm and a plating thickness of 20 μm and 3000 holes was prepared.

Separately, ten prepregs each having a thickness of 150 μm were superposed on each other and copper foils of 18 μm were superposed on the front and back sides thereof, and heat-pressed to form a copper-clad laminate having a thickness of 1.6 mm.

Comparative Example 4 50 parts of maleic anhydride-modified polyphenylene ether of Example 1 and triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.,
Brand name) 46 parts, GPPS (general-purpose polystyrene, weight average molecular weight 270,000) 4 parts, FUSELEX E-
2 (Tatsumori Co., Ltd. trade name, average particle size 7 μm) 15 parts, Perhexin 25B (NOF CORPORATION, trade name) 6 parts, antimony trioxide 4 parts, and SAYTEX 8010 (Albemarle Asano Co., trade name) 20 A part was dissolved or dispersed in toluene to prepare a resin varnish.

A resin varnish of the above type 2116 (10
7 g / m ² ) and 2112 type (71 g / m ² ) glass cloth respectively coated, impregnated and dried to a thickness of 1
50 μm (58% by weight of resin) prepreg and thickness 110
A μm (resin 60% by weight) prepreg was prepared.

Using the prepared prepreg, a 22-layer multilayer plate was molded in the same manner as in Example 1, and the through hole diameter was 0.
A test plate having a daisy chain of 5 mm and a plating thickness of 20 μm and 3000 holes was prepared.

Separately, 10 prepregs each having a thickness of 150 μm were stacked on each other, 18 μm of copper foil was stacked on the front and back, and heat-pressed to form a copper-clad laminate having a thickness of 1.6 mm.

Comparative Example 5 50 parts of maleic anhydride-modified polyphenylene ether of Example 1, triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.,
Brand name) 46 parts, GPPS (general-purpose polystyrene, weight average molecular weight 270,000) 4 parts, KMP-600 of coated silicone rubber particles (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 5)
μm) 15 parts, FUSELEX E-2 (trade name manufactured by Tatsumori Co., average particle size 7 μm) 15 parts, 6 parts perhexin 25B (trade name, manufactured by NOF CORPORATION), 4 parts antimony trioxide, and SAYTEX 8010 (Albemarle Asano). A resin varnish was prepared by dissolving or dispersing 20 parts (trade name, manufactured by Co., Ltd.) in toluene.

2116 type (10
7 g / m ² ) and 2112 type (71 g / m ² ) glass cloth respectively coated, impregnated and dried to a thickness of 1
50 μm (58% by weight of resin) prepreg and thickness 110
A μm (resin 60% by weight) prepreg was prepared.

Using the prepared prepreg, a 22-layer multilayer plate was molded in the same manner as in Example 1, and the through hole diameter was 0.
A test plate having a daisy chain of 5 mm and a plating thickness of 20 μm and 3000 holes was prepared.

Separately, 10 pieces of prepreg having a thickness of 150 μm were superposed, 18 μm of copper foil was superposed on the front and back, and heat-pressed to form a copper-clad laminate having a thickness of 1.6 mm.

Comparative Example 6 50 parts of maleic anhydride-modified polyphenylene ether of Example 1 and triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.,
Brand name) 46 parts, GPPS (general-purpose polystyrene, weight average molecular weight 270,000) 4 parts, Perhexin 25B
(Nippon Yushi Co., Ltd., trade name) 6 parts, antimony trioxide 4
Parts and 20 parts of SAYTEX 8010 (trade name, manufactured by Albemarle Asano Co., Ltd.) were dissolved or dispersed in 28 parts of toluene to prepare a resin varnish.

2116 type (10
7 g / m ² ) and 2112 type (71 g / m ² ) glass cloth respectively coated, impregnated and dried to a thickness of 1
50 μm (58% by weight of resin) prepreg and thickness 110
A μm (resin 60% by weight) prepreg was prepared.

Using the prepared prepreg, a 22-layer multilayer plate was molded in the same manner as in Example 1, and the through hole diameter was 0.
A test plate having a daisy chain of 5 mm and a plating thickness of 20 μm and 3000 holes was prepared.

Separately, 10 pieces of prepreg having a thickness of 150 μm were superposed on each other and copper foil of 18 μm was placed on the front and back sides of the prepreg to form a copper clad laminate having a thickness of 1.6 mm by heat and pressure molding.

The thermal shock tests of the 22-layer multilayer boards obtained in Examples 1 to 4 and Comparative Examples 1 to 6 and the copper foil peeling strength of the copper clad laminates were tested, and the results are shown in Tables 1 and 2. Indicated. In all cases, the present invention was excellent, and the effects of the present invention could be confirmed.

[0076]

[Table 1] * 1: The conduction resistance of 20 multi-layer test plates having a daisy chain of 0.5 mmφ and 3,000 holes was tested. The failure modes are mainly barrel cracks, and the others are corner cracks in the plated part. * 2: Measured according to JIS-C-8161, * 3: A 50 mm square sample in which the copper foil is entirely etched is prepared and 2 atm / After performing a pressure cooker test at 121 ° C. for 2 hours, the weight increase rate of the sample was measured.

[0077]

[Table 2] * 1: The conduction resistance of 20 multi-layer test plates having a daisy chain of 0.5 mmφ and 3,000 holes was tested. The failure modes are mainly barrel cracks, and the others are corner cracks in the plated part. * 2: Measured according to JIS-C-8161, * 3: A 50 mm square sample in which the copper foil is entirely etched is prepared and 2 atm / After performing a pressure cooker test at 121 ° C. for 2 hours, the weight increase rate of the sample was measured.

[0078]

According to the resin composition for producing a metal-clad laminate of the present invention, it is possible to obtain a high multilayer printed board having excellent connection reliability of through holes, which contributes to improvement of reliability in electronic equipment. be able to.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 3/36 C08K 3/36 5/3477 5/3477 H05K 1/03 610 H05K 1/03 610H 610R 630 630G 3/46 3/46 T // (C08L 71/12 C08L 83:04 83:04) (72) Inventor, Tetsuaki Suzuki, 5-14-25 Ryoke, Kawaguchi City, Saitama Toshiba Chemical Company Kawaguchi Factory F term (reference) 4F072 AA04 AA07 AB09 AB28 AB34 AD42 AE01 AE06 AE23 AF06 AF11 AF15 AF32 AG03 AG17 AG19 AH02 AH21 AK05 AK14 AL13 4F100 AA21A AB17B AB33B AG00A AK51A AK52A AK54A AK54J AL05B AL07A AN02A BA02 DE01A DG12A DH01A GB43 4J002 CH071 CP032 DJ017 EU196 FA082 FA087 FB262 FD010 FD146 GQ01 4J005 AA26 BD02 5E346 AA12 CC04 CC08 CC32 DD02 DD12 DD32 FF04 GG13 GG15 GG17 GG28 HH07

Claims (5)

[Claims] 1. A reaction product of (A) a polyphenylene ether and an unsaturated carboxylic acid and / or an acid anhydride, and (B).
Triallyl isocyanurate and / or triallyl cyanurate, (C) silicone resin particles or silicone rubber particles whose surface is coated with a silicone resin, and (D)
Silica particles as an essential component, 50 to 60 parts by weight of the component (A), 40 to 50 parts by weight of the component (B), and (C) to 100 parts by weight of the total of the components (A) and (B). Ingredient 1
10 to 10 parts by weight of the component (D) at a ratio of 5 to 40 parts by weight,
A resin composition for producing a metal-clad laminate, each of which is contained. 2. A prepreg comprising the resin composition for producing a laminated board according to claim 1 and a base material, wherein the content ratio of the base material is 20 to 80% by weight. 3. A laminate obtained by heat-press molding the prepreg according to claim 2. 4. A metal-clad laminate obtained by heating and pressing the prepreg according to claim 2 and a metal foil. 5. A multilayer printed wiring board obtained by heating and pressing the prepreg according to claim 2 and the metal-clad laminate according to claim 4.