JP2000043042A - Polyphenylene ether resin prepreg - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a prepreg and the laminate which has a base material of an organic fiber, characterized by small moisture absorption, a small tangent of loss angle, an excellent dielectric property, and an excellent heat resistance. SOLUTION: A base material formed from a polybenzazole fiber is combined with a curable polyphenylene ether resin composition so as to manufacture a prepreg, and then a curable composite material and a laminate by means of the prepreg. The form of the liquid crystal polyester fiber is preferably a woven fabric and/or a nonwoven fabric.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg and a laminate used mainly for manufacturing a printed wiring board.

[0002]

2. Description of the Related Art In recent years, in the field of electronic equipment for communication, consumer use, industrial use, and the like, there has been a remarkable trend toward miniaturization and higher density of mounting methods, and accordingly, materials are more excellent. Heat resistance, dimensional stability, and electrical properties are being demanded. For example, as a printed wiring board, a glass cloth-base copper-clad laminate manufactured using a prepreg having a glass cloth as a base material has been conventionally and generally used. However, in recent years, printed wiring boards using prepregs based on organic fibers have been proposed due to demands for weight reduction, low dielectric constant, laser workability, and the like. A typical example of the organic fiber is aramid (wholly aromatic polyamide) fiber. However, since the aramid fiber itself has a large hygroscopic property and a large dielectric loss tangent, the obtained laminated board has a large hygroscopic property and There is a problem that the dielectric loss tangent is large.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and uses an organic fiber as a base material, has a small hygroscopic property, a small dielectric loss tangent, has excellent dielectric properties, and has excellent heat resistance. It is an object to provide a prepreg and a laminate.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present application provides the following inventions. (1) A prepreg obtained by combining a substrate formed of polybenzazole fibers with a curable polyphenylene ether-based resin composition.

Here, it is a preferred embodiment that the form of the polybenzazole fiber is a woven fabric and / or a nonwoven fabric. (2) A cured composite material obtained by curing the prepreg according to (1). (3) A laminate comprising the prepreg according to (1) and a metal foil. (4) A cured laminate comprising the cured composite material of (2) and a metal foil.

Hereinafter, the present invention will be described in detail. The curable polyphenylene ether-based resin composition used in the present invention is a composition containing a polyphenylene ether-based resin (including a modified product) as a component. Preferred examples of the above polyphenylene ether-based resin include poly (2,6-dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2,6-dimethylphenol, and poly (2,6
-Dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,2-dimethylphenol
It was obtained by polymerization in the presence of a copolymer of 3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and 2-methyl-6-phenylphenol, and a copolymer of 2,6-dimethylphenol and a polyfunctional phenol compound. Polyfunctional polyphenylene ether resin, for example, JP-A-63-301
And copolymers containing units of the general formulas (A) and (B) as disclosed in JP-A-222 and JP-A-1-297428.

With respect to the molecular weight of the polyphenylene ether resin described above, the viscosity number ηsp / c measured at 30 ° C. in a 0.5 g / dl chloroform solution is 0.1 to 1.
Those in the range of 0 can be used favorably. Further, the polyphenylene ether-based resin referred to in the present invention also includes modified products. Examples of such modified products include polyphenylene ether resins containing unsaturated groups (Japanese Patent Application Laid-Open No. Sho 64-64).
-69628, JP-A-1-113425, JP-A-1
And the reaction products of polyphenylene ether resins with unsaturated carboxylic acids and / or acid anhydrides.

Next, as the resin to be blended in addition to the above-mentioned polyphenylene-based resin, any resin may be used as long as it does not impair the physical properties of the substrate as a material for a printed substrate, which is the object of the present invention. Specific examples of such a resin include a phenol resin, an epoxy resin, diallyl phthalate, divinylbenzene, a polyfunctional acryloyl compound, a polyfunctional methacryloyl compound, a polyfunctional maleimide, a polyfunctional methacryloyl compound, a polyfunctional methacryloyl compound. Crosslinkable polymers such as maleimide, polyfunctional cyanate ester, polyfunctional isocyanate, unsaturated polyester, triallyl isocyanurate, triallyl cyanurate, polybutadiene, styrene-butadiene / styrene-butadiene-styrene, and various thermoplastic resins And various thermosetting resins. These are generally blended for the purpose of improving the physical properties of a substrate produced by laminating and molding a prepreg.

Preferred examples of the resin composition used in the present invention include polyphenylene ether and triallyl isocyanurate and / or triallyl cyanurate, polyphenylene ether and epoxy resin, polyphenylene ether and styrene butadiene block copolymer and triallyl isocyanurate. and/
Or triallyl cyanurate, polyphenylene ether containing unsaturated group and triallyl isocyanurate and / or triallyl cyanurate, polyphenylene ether containing unsaturated group and triallyl isocyanurate and / or triallyl cyanurate and epoxy resin, polyphenylene Reaction product of ether resin with unsaturated carboxylic acid and / or acid anhydride and reaction product of triallyl isocyanurate and / or triallyl cyanurate, reaction product of polyphenylene ether resin with unsaturated carboxylic acid and / or acid anhydride Reaction products of epoxy resins, polyphenylene ether resins with unsaturated carboxylic acids and / or acid anhydrides, and triallyl isocyanurate and / or triallyl cyanurate and epoxy resins. Carboxymethyl resins. The amount of each component in these systems is selected according to the purpose.

In order to accelerate the curing reaction, the polyphenylene ether resin used in the present invention may contain a usual radical initiator or a usual curing agent for an epoxy resin. Further, fillers and additives can be blended and used in an amount that does not impair the original properties for the purpose of imparting desired performance according to the application. Examples of the filler include carbon black, silica, alumina, and titanium. Examples include barium acid, talc, mica, glass beads, glass hollow spheres, and the like. As additives, antioxidants,
Heat stabilizer, antistatic agent, ultraviolet absorber, plasticizer, pigment,
Dyes (including fluorescent agents), coloring agents, and the like can be given.
For the purpose of further improving flame retardancy, bromine, chlorine,
A phosphorus-based or silicon-based flame retardant or a flame retardant auxiliary such as antimony trioxide or antimony pentoxide can be used in combination.

The substrate used in the present invention is formed from polybenzazole fibers. The polybenzazole fiber referred to here is a fiber made of polybenzazole, and the polybenzazole (PBZ) is a polybenzoxazole (P
BO) homopolymer, polybenzothiazole (PBT) homopolymer, and random, sequence or block copolymers of PBO and PBT.

Examples of the form of the polybenzazole fiber used in the present invention include woven and / or nonwoven fabric of polybenzazole fiber such as roving cloth, cloth, chopped mat, and surfacing mat.
Among these forms, woven fabric,
And a nonwoven fabric is preferable from a viewpoint of workability. In the present invention, a woven fabric and a nonwoven fabric may be laminated in order to combine these two features. In addition, the substrate of the present invention,
Glasses, aramids, aromatic polyesters, cloths or microfibrils of natural cellulosic fibers may be mixed and used. Examples of the method for producing a nonwoven fabric of polybenzazole fibers used in the present invention include a dry method using chopped fibers and a papermaking method.

[0013] The proportion of the substrate in the prepreg of the present invention is 10-80% by weight, more preferably 20-70% by weight.
When the proportion of the base material is less than 10% by weight, the dimensional stability and strength after curing are insufficient, and when the proportion exceeds 80% by weight, the amount of resin in the prepreg becomes extremely small, so that the adhesiveness between the prepregs is reduced. And the adhesion to other materials typified by metal foil is inferior.

The method of combining the resin composition of the present invention with a substrate is not particularly limited. A melting method in which the resin composition is melted and impregnated into the substrate, and a method in which the resin composition is dissolved in a solvent A wet method of obtaining a prepreg by impregnating the base material and then drying the solvent can be employed. Molding and curing temperature: 8
0-300 ° C, time: 1 minute-10 hours, pressure: 0.1-
500 kg / cm 2 range, more preferably, temperature: 15
0-250 ° C, time: 1 minute-5 hours, pressure: 1-100
It is performed in the range of kg / cm2.

The metal foil used for the laminate of the present invention includes, for example, copper foil, aluminum foil and the like. The thickness is not particularly limited, but is preferably 3-200 microns, more preferably 5-105 microns. The prepreg of the present invention can obtain a copper-clad laminate by laminating and curing a copper foil on both sides. Also, the prepreg can be used as a so-called prepreg for a build-up method in which a prepreg is laminated on the upper and lower sides of a printed wiring board, a via hole is formed by laser irradiation, and then plated to form a connection and pattern of the via hole. In this case, a prepreg may be previously laminated on one side of a metal foil, that is, a so-called resin-coated copper foil may be used. Further, when prepreg is laminated on the outer layer of the printed wiring board, copper foil can be laminated on the outermost layer at the same time. At this time, the outermost copper foil can be used when forming a via with a laser. Further, the prepreg of the present invention is formed with a hole by laser or mechanical punching, and then filled with a conductive paste, and then a copper foil is laminated on both surfaces thereof and cured to form a core material. This core material is patterned to form a printed wiring board, and then the filler-containing prepreg prepared in the same manner can be used for a multilayer wiring board to be subsequently laminated.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described by way of examples to further clarify the present invention.

[0017]

REFERENCE EXAMPLE 1 Poly (2,4) having a viscosity number ηsp / c of 0/44 as measured with a chloroform solution of 0.5 g / dl at 30 ° C.
6-dimethyl-1,4-phenylene ether): 100
Parts by weight, maleic anhydride: 1.5 parts by weight, and 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane (Perhexa 25B manufactured by NOF Corporation): 1.
0 parts by weight were dry-blended at room temperature, and then heated at a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm.
It was extruded by a screw extruder. This reaction product is referred to as polymer A. The viscosity number ηsp / C of each polymer described in the following Reference Examples and Examples was measured by the same method as in Reference Example 1.

[0018]

REFERENCE EXAMPLE 2 <Polyphenylene ether resin containing unsaturated group> A poly (2,6-dimethyl-1,4-phenylene ether) having .eta.sp / C = 0.56 was used and disclosed in
Ηs according to the known method disclosed in US Pat.
An allyl group-substituted polyphenylene ether having ap / c of 0.62 (average substitution ratio: 14%) was synthesized. This allyl-substituted polyphenylene ether is referred to as polymer B.

[0019]

Example 1 50 parts by weight of polymer A (hereinafter all parts by weight), 46 parts of triallyl isocyanurate (TAIC), 30 parts of flame retardant SAYTEX8010 (manufactured by Albemare), 30 parts of peroxide PH25B (manufactured by NOF Corporation) ): A varnish was prepared by dissolving 35 parts of a resin composition consisting of 6 parts in 100 parts of toluene. Next, the varnish was impregnated with a PBO fiber nonwoven fabric, and the solvent was subsequently dried to prepare a prepreg. The resin content in this prepreg was 50%. A copper foil of 35 microns was applied to both sides of the prepreg and cured at 200 ° C. for 1 hour to prepare a double-sided copper-clad laminate. The double-sided copper-clad laminate has a dielectric constant of 3.0 (1 MHz) and a dielectric tangent of 0.003 (1 MH)
z), glass transition temperature 210 ° C. (measured by DMA),
Moisture absorption 0.4%, xy linear expansion coefficient 10pp each
m was excellent in dielectric properties and low hygroscopicity. The prepreg obtained above was coated on a copper foil and the solvent was dried to obtain a resin-coated copper foil. This material can be suitably used as a build-up material.

[0020]

Comparative Example 1 A prepreg was prepared in the same manner as in Example 1 except that an aramid nonwoven fabric was used instead of the PBO fiber nonwoven fabric, and then a copper-clad laminate was prepared. This copper clad laminate had a glass transition temperature of 210 ° C., a dielectric constant of 3.5, a dielectric loss tangent of 0.01, and a moisture absorption of 1.0%.

[0021]

Example 2 A copper-clad laminate was prepared in the same manner as in Example 1 except that Polymer B was used instead of Polymer A.
The obtained copper-clad laminate has a dielectric constant of 3.0 and a dielectric tangent of 0.4.
002, glass transition temperature 220 ° C., moisture absorption 0.35%,
The coefficient of linear expansion was 10 ppm.

[0022]

Example 3 Polyphenylene ether resin: 30 parts, TA
A prepreg was prepared in the same manner as in Example 1 using 35 parts of a resin composition consisting of 5 parts of IC, 60 parts of epoxy resin and 5 parts of curing agent, and cured at 180 ° C. for 90 minutes. The obtained copper-clad laminate has a glass transition temperature of 170 ° C.
Dielectric constant 3.2, dielectric loss tangent 0.008, moisture absorption 0.45
% And the linear expansion coefficient were 10 ppm.

[0023]

Example 4 Polyphenylene ether resin: 30 parts, styrene / butadiene block copolymer: 30 parts, TAI
Using a resin composition consisting of 35 parts of C: 35 parts and 5 parts of perhexaperoxide 25B, 35 parts of a resin composition was prepared in the same manner as in Example 1, and cured at 200 ° C. for 1 hour to obtain a copper-clad laminate. The obtained copper-clad laminate had a glass transition temperature of 180 ° C., a dielectric constant of 3.0, a dielectric loss tangent of 0.003, a water absorption of 0.4%, and a linear expansion coefficient of 12 ppm.

[0024]

Example 5 Polymer A: 50 parts, TAIC: 40 parts, hydrogenated styrene / butadiene copolymer: 10 parts, flame retardant SA
A prepreg was prepared in the same manner as in Example 1 using 35 parts of a resin composition consisting of 25 parts of YTEX8010 and 45 parts of silica, and then cured at 200 ° C. for 90 minutes to prepare a double-sided copper-clad laminate. The obtained copper-clad laminate had a glass transition temperature of 240 ° C., a dielectric constant of 2.9, a dielectric loss tangent of 0.0025,
The moisture absorption was 0.35% and the coefficient of linear expansion was 9 ppm.

[0025]

The laminate obtained from the prepreg of the present invention has good characteristics which have not been obtained conventionally in terms of low dielectric constant, low water absorption, high heat resistance and low coefficient of linear expansion. In particular, it has both low coefficient of linear expansion, high heat resistance, and low water absorption, and is therefore suitable as an excellent printed wiring board material, particularly a material in the field of semiconductor mounting. In addition, since it does not include a glass cloth, various types of laser processing are easy, so that a high-density mounting substrate can be manufactured.

Claims (4)

[Claims] 1. A prepreg comprising a substrate formed of polybenzazole fiber and a curable polyphenylene ether-based resin composition. 2. A cured composite material obtained by curing the prepreg according to claim 1. 3. A laminate comprising the prepreg according to claim 1 and a metal foil. 4. A cured laminate comprising the cured composite material of claim 2 and a metal foil.