JPS6346098B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the production of laminates with particularly excellent electrical properties by using cyanate ester resin prepreg obtained from fluorine fiber cloth as a reinforcing base material. In a method for producing laminates such as foil-clad laminates, insulated metal laminates, or multilayer boards, a fluorine fiber cloth is impregnated with a cyanate ester resin composition as a prepreg for laminate molding, and B-staged. This is a method for manufacturing laminates, characterized by using prepreg obtained by the process. Glass fiber woven fabrics and nonwoven fabrics are mainly used as reinforcing base materials for laminates using heat-resistant resins. However, in the case of glass fiber cloth, there was a drawback that the electrical properties, particularly the values of dielectric constant and dielectric loss tangent, were larger than those of heat-resistant resin alone. The present invention was invented as a result of studies on a method for manufacturing laminates that does not have the above-mentioned drawbacks. By using fluorine fiber cloth as a reinforcing base material impregnated with a cyanate ester resin composition, the electrical properties are improved. It was discovered and completed that it was possible to obtain a laminate that not only greatly improved the width but also had excellent adhesion to the base material. The configuration of the present invention will be explained below. The laminates of the present invention include films or metal foil-clad films using only one prepreg, rigid laminates, metal foil-clad laminates, and multilayer plates. The fluorine fiber cloth used as a base material in the prepreg of the present invention is a fluororesin fiber cloth such as polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene copolymer, etc., which has excellent electrical properties. The cyanate ester resin composition of the present invention to be impregnated or applied onto the fluorine fiber cloth is a resin composition containing a polyfunctional cyanate ester and the cyanate ester prepolymer as an essential component. First, polyfunctional cyanate ester has the general formula (1) R(-O-C≡N)m...(1) [In the formula, m is an integer of 1 or more, preferably 2 or more and usually 5 or less. and R is an aromatic organic group, and the cyanate ester group is bonded to the aromatic ring of the organic group R. Specific examples include 1,3- or 1,4-dicyanatobenzene,
1,3,5-tricyanatobenzene, 1,3-,
1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis( 4-dianatophenyl)methane,
2,2-bis(4-dianatophenyl)propane, 2,2-bis(3,5-dichloro-4-dianatophenyl)propane, 2,2-bis(3,5
-dibromo-4-cyanatophenyl)propane,
Bis(4-cyanatophenyl) ether, bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, tris(4
-cyanatophenyl) phosphite, tris(4
-cyanatophenyl) phosphate, and cyanic acid esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, Tokuko 1928-1928, Tokuko 43-18468, Tokuko 44-
Cyanic acid esters described in Japanese Patent Publication No. 4791, Japanese Patent Publication No. 45-11712, Japanese Patent Publication No. 46-41112, Japanese Patent Publication No. 47-26853, and Japanese Patent Publication No. 51-63149 can also be used. Further, a prepolymer obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence of a catalyst such as a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, or a phosphate ester such as tributylphosphine. It can be used as These prepolymers are symylamines formed by trimerization of the cyanide groups in the cyanate ester.
- Generally has a triazine ring in the molecule.
In the present invention, it is preferable to use the prepolymer having an average molecular weight of 400 to 6,000. Further, the cyanate ester resin composition is made by combining the above-mentioned cyanate esters with other components. Such compositions include maleimides (Japanese Patent Publication No. 54-30440, Japanese Patent Publication No. 54-73900, etc.);
Epoxy compounds (Japanese Patent Publication No. 46-41112, etc.), maleimide-epoxies (Japanese Patent Publication No. 52-31279, etc.) are known, and in addition, unsaturated bonds such as diallylphthalate, dicyclopentadiene, acrylic ester, etc. Compounds having epoxy groups and unsaturated double bonds such as glycidyl methacrylate, and their polymers and copolymers, as well as their polymers, as well as polyimide resins, polyester resins, synthetic rubbers, and various coupling agents. There are one or more mixtures or pre-reactants selected from the group consisting of: These are also used in the present invention, and range from solvent-free liquids to solids at room temperature. The method of impregnating or applying the cyanate ester resin composition to the fluorine fiber cloth may be any conventional method, and usually it is impregnated in the form of a varnish dissolved in a solvent, or it is impregnated as it is in a solvent-free liquid form. Depends on how you do it. Also, after this impregnation or coating, it is B-staged, but this condition is usually
By heating at temperatures below 150°C. The laminate plates of the present invention are manufactured using the prepreg obtained as described above. The lamination molding method is performed under conventional lamination molding conditions for cyanate ester resin compositions, that is, a temperature of 100 to 300°C, preferably 120 to 250°C;
More preferably at 150-200°C, 1-500Kg/cm ² ,
Lamination molding is preferably carried out at 5 to 100 kg/cm ² for 0.1 to 10 hours, preferably 0.5 to 5 hours. Incidentally, the present invention also includes a method of producing a long continuous film or a metal foil-clad film, and in this case, the film is usually produced by continuous heating and pressing using a roll or the like. The laminates produced by the method of the present invention as described above have excellent electrical properties and adhesion, and can be used in applications where glass fiber cloth is insufficient. Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 150 g of 2,2-bis(4-maleimidophenyl)methane and 850 g of 2,2-bis(4-cyanatophenyl)propane were preliminarily reacted at 150°C for 300 minutes, and then cooled to 100°C. benzoyl peroxide 0.2
After reacting for an additional 90 minutes, this was dissolved in methyl ethyl ketone, and 0.3 g of zinc octylate was mixed as a catalyst. This is impregnated into a woven fabric using polytetrafluoroethylene fibers and dried to create B-stage prepreg. Five sheets of this prepreg are stacked one on top of the other.
A 35μ electrolytic copper foil was put in and press-molded at 175°C and 40Kg/cm ² for 160 minutes to obtain a good copper-clad laminate. The performance of this copper-clad laminate is shown in Table 1. Comparative Example 1 A copper-clad laminate was obtained in the same manner as in Example 1 except that a glass fiber woven fabric was used instead of the polytetrafluoroethylene fiber as a reinforcing material. The performance of this copper-clad laminate is shown in Table 1. Example 2 400 g of 2,2-bis(4-cyanatophenyl) ether and 100 g of bis(4-maleimidophenyl) ether were pre-reacted at 160°C for 150 minutes, and then reacted with methyl ethyl ketone and N.N- Dissolve in a mixed solvent with dimethylformamide and add epoxy resin (ECN-1273, manufactured by Ciba Geigy) to this.
Add 100 g of glycidyl methacrylate, add 0.2 g of zinc octylate, 0.2 g of triethylenediamine, and 0.1 g of benzoyl peroxide as catalysts, and dissolve and mix them uniformly. B-stage prepreg was made by impregnating woven fabric and drying it. Five sheets of this prepreg were stacked together, polypropylene films were placed on top and bottom as release films, and heated at 170°C.
A good laminate was obtained by press molding at 40 kg/cm ² for 120 minutes. The properties of this laminate are shown in Table 1.

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【table】

Claims (1)

[Claims] 1 Laminated board, metal foil clad laminate, insulated metal laminate,
Alternatively, in a method for manufacturing laminated boards such as multilayer boards, a fluorine fiber cloth is impregnated with a cyanate ester resin composition as a prepreg for laminated molding, and B
- A method for producing laminates characterized by using staged prepreg.