JPH0231743B2 - JUSHISOSEIBUTSU - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition, and particularly to a thermosetting resin composition suitable for manufacturing printed wiring boards. With the recent development of the electronic industry, printed circuit boards have come to be used in various fields. For printed circuit boards, for example, the resin used is epoxy resin, unsaturated polyester resin, phenolic resin, etc., and the base material is glass products such as glass cloth, glass fiber nonwoven fabric, glass mat, paper, or cotton cloth. In general, paper phenol laminates are most commonly used in the consumer sector, and glass epoxy laminates are most commonly used in industrial applications.
Glass epoxy laminates are excellent printed circuit boards, with excellent heat resistance, electrical insulation, chemical resistance, through-hole properties, and solder resistance, which are all required for printed circuit boards, but they have relatively low dielectric constant and dielectric loss tangent. Because of its large value, it is unsuitable for use in high frequency or microwave equipment. On the other hand, polyphenylene ether has a very low dielectric constant and dielectric loss tangent, and although it is a thermoplastic resin, it has a high heat deformation temperature, and has excellent dimensional stability, chemical resistance, water resistance, etc. It is evaluated as an extremely useful material for printed circuit boards for devices. However, when using this without any base material, there are many defects in terms of strength and dimensional stability that make it unsuitable for use as an industrial printed circuit board, so a base material such as glass cloth is used. There was an attempt to make it a base. However, since polyphenylene ether is a thermoplastic resin and has extremely low polarity, it can be used as a composite material consisting of a normal thermosetting resin and a glass base material by combining glass and resin with a type of silane coupling agent. It turned out to be extremely difficult to cross-link chemically through . As is generally known in the past, for example, in laminated plates made of glass cloth, epoxy resin, etc., a silane coupling agent is interposed at the interface, thereby forming a chemical bond between inorganic and organic materials that is normally impossible. It is possible to create a printed circuit board.
In the process of copper plating on the walls of through-holes, serious defects such as those caused by infiltration of plating liquid from this interface are prevented from occurring, but defects cannot be prevented in this way with laminates made of polyphenylene ether and glass cloth. It was impossible. Furthermore, the weak bonding force between the two makes it difficult to make the wall of the hole smooth during the drilling process, and the through-hole plating cannot be made smooth, causing problems with the electrical performance of the final product. . For these reasons, today there are materials that have low dielectric constants and dielectric loss tangents for use in high-frequency and microwave equipment, and have sufficient heat resistance, solder resistance, chemical resistance, strength, and flame retardancy for printed circuit boards. Moreover, there is a strong demand for the development of inexpensive materials. As a result of intensive research to develop a material for printed circuit boards that takes advantage of the characteristics of polyphenylene ether and epoxy resin, the present inventor discovered that polyphenylene ether contains styrene, which has a phenolic hydroxyl group that can react with epoxy groups. It has been found that a mixed resin composition of a graft polymer grafted with a compound of the above-mentioned type and an epoxy resin forms an extremely excellent resin for printed circuit boards. The gist of the present invention is to provide polyphenylene ether with
A resin composition characterized by being made by mixing an epoxy resin with a graft copolymer obtained by grafting a styrene compound having a phenolic hydroxyl group in the molecule, and its purpose is to provide excellent use in printed circuit boards. The present invention provides a resin composition having excellent performance. The polyphenylene ether used in the present invention is, for example, Japanese Patent Publication No. 36-18692, 42-3195, 42-
It is obtained by oxidative polymerization of phenolic monomers by a method such as that described in Japanese Patent No. 4673, etc., and has a cyclic structure shown in the following formula. (R ₁ , R ₂ , R ₃ , and R ₄ represent hydrogen, halogen, hydrocarbon, or an alkyl group having 1 to 4 carbon atoms) In the present invention, a styrene compound having a phenolic hydroxyl group is, for example, hydroxy Monomers or mixtures of monomers such as styrene, chlorohydroxystyrene, dichlorohydroxystyrene, bromohydroxystyrene, tetrabromohydroxystyrene, aminohydroxystyrene, hydroxy α-methylstyrene, and homopolymers or copolymers made of these monomers , or at least one or more of these monomers,
Examples include copolymers formed using monomers copolymerizable with these. The graft compound used in the present invention can be obtained by grafting a styrene compound monomer onto polyphenylene ether by the method described in, for example, Japanese Patent Publication No. 47-47862, or
-118945, by grafting a styrene compound polymer having a phenolic hydroxyl group to polyphenylene ether. Moreover, the polymer of P-hydroxystyrene or this halogen compound used in the present invention is obtained by thermally polymerizing the monomer thereof,
For example, it is sold by Maruzen Sekiyu Co., Ltd. under the trade name Resin M or Resin MB. The epoxy resin used in the present invention is not particularly limited, but those having at least two epoxy groups in the molecule are used. Specifically, bisphenol epoxy resins, novolak epoxy resins, nitrogen-containing epoxy resins, and these epoxy resins are used. Examples include halogen compounds, and these can be used alone or in combination. Moreover, this composition is a thermosetting resin composition, and it is also possible to mix and use a curing agent or a curing accelerator for a commonly used epoxy resin. Specific curing agents or curing accelerators include, for example, aliphatic amines, aromatic amines, acid anhydrides, and boron trifluoride complexes. Although the grafting rate of the graft compound used in the present invention is not particularly limited, it is necessary to have at least one phenolic hydroxyl group per one polyphenylene ether molecular chain. Furthermore, the mixing ratio of the epoxy resin and the graft polymer of polyphenylene ether in the composition of the present invention is not particularly limited and can be adjusted freely. When the hydroxyl equivalent of is less than 1, it is effective to further mix a curing agent to maintain various physical properties of the final cured product. Furthermore, in the present invention, it is possible to use a solvent, and examples of solvents that can be used include toluene,
Examples include chloroform and percrene. The present invention will be explained in detail below using examples. However, the present invention is not limited to the following examples. First, two types of graft copolymers were synthesized as follows. [Graft copolymer A] [η] is 0.50 dl/g (chloroform, measured at 30°C)
poly(2,6-dimethylphenylene-1,4-
ether), 50 parts of tetrabromo P-hydroxystyrene, 3 parts of lauryl peroxide and 3 parts of dicumyl peroxide were added into an autoclave and mixed well, and then 0.5 parts of sodium dodecylbenzenesulfonate and polyvinyl were added to 500 parts of water. A mixed solution containing 5 parts of alcohol was charged into a nitrogen atmosphere while stirring. After the addition, the reaction was carried out at 90°C for 6 hours while stirring, and then at 130°C for 10 hours. The reaction product was filtered, washed with water, and dried to obtain a product. [Graft copolymer B] [η] is 0.50 dl/g (chloroform, measured at 30°C)
poly(2,6-dimethylphenylene-1,4-
ether), 50 parts of brominated polyP-hydroxystyrene (Marzen Resin MB), and 10 parts of tetramethylthiuram monosulfide were melt-kneaded under reduced pressure in a 30 mmφ vented extruder to obtain a graft reaction product. Residence time in the extruder was 10 minutes. Next, a resin varnish was prepared using the above two types of graft copolymers in the following manner. Example 1 100 parts of brominated bisphenol epoxy resin (AER-711 manufactured by Asahi Kasei Corporation), 40 parts of graft copolymer A, and 7 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane, A resin varnish was prepared by dissolving it in 250 parts of chloroform. Next, impregnate a glass cloth with a thickness of 0.18 mm with this varnish, and then
A prepreg with a resin content of 45% was obtained by drying at 140°C. Next, 8 sheets of this prepreg were stacked, and copper foil with a thickness of 35μ was layered on both sides to give a temperature of 40Kg/cm ² at 175℃.
Compression molding was performed for 60 minutes to obtain a double-sided copper-clad laminate. Example 2 A resin varnish was prepared in the same manner as in Example 1 except that graft copolymer B was used, and a double-sided copper-clad laminate was obtained using this resin varnish. Example 3 90 parts of bisphenol epoxy resin (AER661, manufactured by Asahi Kasei Corporation), 10 parts of epoxy novolac resin (DEN438, manufactured by Dow Chemical Company), 40 parts of graft copolymer A, 3,3'-dichloro-4・7 parts of 4'-diaminodiphenylmethane and 250 parts of chloroform
A resin varnish was prepared by dissolving the resin in the following parts. Using this, a double-sided copper-clad laminate was obtained in the same manner as in Example 1. Example 4 A resin varnish was prepared in the same manner as in Example 3 except that graft copolymer B was used, and a double-sided copper-clad laminate was obtained using this resin varnish. Comparative Example 1 100 parts of brominated bisphenol epoxy resin (AER-711 manufactured by Asahi Kasei Corporation), 2.5 parts of dicyandiamide, and 0.2 parts of benzyldimethylamine.
A resin varnish was prepared by dissolving it in a mixed solvent of 25 parts of MEK, 20 parts of dimethylformamide, and 20 parts of methyl cellosolve. Using this, a double-sided copper-clad laminate was obtained in the same manner as in Example 1. Comparative Example 2 90 parts of bisphenol epoxy resin (AER661, manufactured by Asahi Kasei Corporation), 10 parts of epoxy novolac resin (DEN-438, manufactured by Dow Chemical), 2.5 parts of dicyandiamide, and 0.2 parts of benzyldimethylamine.
A resin varnish was prepared by dissolving it in a mixed solvent of 25 parts of MEK, 20 parts of dimethylformamide, and 20 parts of methyl cellosolve. Using this, a double-sided copper-clad laminate was obtained in the same manner as in Example 1. Comparative example 3 [η] is 0.50 dl/g (chloroform, measured at 30°C)
poly(2,6-dimethylphenylene-1,4-
ether) in chloroform to a concentration of 40
% varnish was made. This varnish has a thickness of 0.18mm.
A glass cloth was impregnated with the resin and dried at 100°C for 20 minutes to remove volatile substances, creating a resin-impregnated cloth.
Next, stack 8 of these, layer copper foil with a thickness of 35μ on both sides, fit a frame with a thickness of 1.6mm, and heat at 270℃, 50kg/
cm ² for 12 minutes to obtain a copper-clad polyphenylene ether laminate with a thickness of 1.6 mm. The performance of the double-sided copper-clad laminates obtained in the above Examples and Comparative Examples was tested. The results are shown in the table below.

[Table] Test method: Copper foil peel strength, water absorption rate, dielectric constant, dielectric loss tangent, insulation resistance, and soldering heat resistance were in accordance with JIS-C-6481. The method of expressing test conditions was based on MEMA. That is, A: Acceptance state C-96/20/65: Stored at 20℃, 65%RH for 96 hours D-2/100: Boiled at 100℃ for 2 hours E-24/: Stored at 50℃ for 48 hours, etc. It is.

Claims (1)

[Claims] 1. General formula (R ₁ , R ₂ , R ₃ , and R ₄ each represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.) The polyphenylene ether has a phenolic hydroxyl group in the molecule. A resin composition characterized in that it is made by mixing a graft copolymer obtained by grafting a styrene-based compound with an epoxy resin. 2. The resin composition according to claim 1, wherein the compound having a phenolic hydroxyl group in the molecule is a monomer or polymer of P-hydroxystyrene or its halogen compound.