JPS648667B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a heat-resistant resin composition with improved electrical properties, particularly dielectric constant and dielectric loss tangent, and more specifically, a curable heat-resistant resin composition made by mixing a cyanate ester-maleimide resin with a fluororesin. be. Fluororesins have excellent lubricity, heat resistance, chemical resistance, and even electrical properties. However, there are no suitable solvents for fluorocarbon resins, and the workability is poor in achieving sufficient adhesion with metals and reinforcing agents, making them extremely expensive. or,
Cyanate ester-maleimide resin compositions have excellent electrical properties, adhesion, strength, hardness, heat resistance, chemical resistance, and other various aspects. In terms of tangent, it was inferior to fluororesins, polyolefins, etc. The present inventors have conducted extensive studies on improving the dielectric constant and dielectric loss tangent of cyanate ester-maleimide resin compositions, and have found that fluorine-based resins are effective and that the compositions have excellent workability. thing,
Furthermore, the present invention was completed by discovering that the characteristics of cyanate ester resin compositions can be fully utilized in terms of strength and hardness. The present invention will be explained below. The cyanate ester-maleimide resin of the present invention is a heat-resistant curable resin composition known from Japanese Patent Publications No. 54-30440, Japanese Patent Publication No. 52-31279, and others. First, the polyfunctional cyanate ester which is component a is an organic compound having two or more cyanate ester groups, and a suitable cyanate ester has the following general formula R(-O-C≡N) _n ...( 1) [In the formula, m is an integer of 2 or more and usually 5 or less, R is an aromatic organic group, and the cyanate ester group is bonded to the aromatic ring of the organic group R] It is a compound represented by 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-dyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(3 ,5-dichloro-4-cyanatophenyl)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)
These include phosphates and cyanate esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, Tokuko Sho 41-1928, Tokko Sho
Cyanic acid esters described in Japanese Patent Publication No. 44-4791, Japanese Patent Publication No. 45-11712, Japanese Patent Publication No. 46-41112, and Japanese Patent Application Laid-Open 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. Furthermore, the polyfunctional cyanate esters mentioned above can also be used in the form of prepolymers with amines. Examples of amines that can be suitably used include meta or paraphenylene diamine, meta or para xylylene diamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylene diamine,
4,4'-diaminobiphenyl, bis(4-aminophenyl)methane, bis(4-aminophenyl)
Ether, bis(4-aminophenyl) sulfone, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-aminophenyl)cyclohexane, 2,2- Bis(4-aminophenyl)propane, 2,2-bis(4-amino-3-
methylphenyl)propane, 2,2-bis(3,
5-dibromo-4-aminophenyl)propane,
bis(4-aminophenyl)phenylmethane,
3,4-diaminophenyl-4'-aminophenylmethane, 1,1-bis(4-aminophenyl)-
1-phenylethane and the like. Of course, the above-mentioned polyfunctional cyanate ester,
The prepolymers, and the prepolymers with amines, can be used in the form of mixtures. Moreover, the polyfunctional maleimide of component b is a compound having two or more N-maleimide groups in the molecule. The polyfunctional maleimide suitably used in the present invention has the following general formula: [Wherein, R is a divalent or trivalent aromatic or alicyclic organic group, X ₁ and X ₂ are hydrogen, halogen, or an alkyl group, and n is 2 or 3. ] It is a compound represented by Maleimide represented by the above formula is prepared by reacting maleic anhydride with divalent or trivalent amine,
It can then be produced by a method known per se in which maleamic acid is cyclodehydrated. It is preferable that the polyvalent amines used are aromatic amines in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, alicyclic amines may be used alone or in combination. It's okay. Furthermore, it is particularly desirable that the polyvalent amines be primary amines in terms of reactivity, but secondary amines can also be used. Suitable amines include those exemplified in the production of the prepolymer of polyfunctional cyanate ester and amine, and melamine having an s-triazine ring;
Examples include polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds. In the present invention, the above-mentioned polyfunctional maleimide can be used in the form of a prepolymer instead of in the form of a so-called monomer, and furthermore, it can be used in the form of a prepolymer with the amine used in the synthesis of the polyfunctional maleimide. It can also be suitably used in the form of The fluororesins of the present invention include polytetrafluoroethylene resins, tetrafluoroethylene-hexafluoropropylene copolymer resins, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resins, and tetrafluoroethylene-ethylene copolymer resins. It is a fluororesin with excellent dielectric properties, such as resins, and its molecular weight ranges from those for ordinary molding to those with a relatively low molecular weight for fluororesins, usually less than 100,000 used as additives. It may be either. Although the above-mentioned components may be mixed by any conventionally known method, it is preferable to mix the fluororesin more uniformly. The amount added to the composition depends on the use, but is usually 85 wt% or less, preferably in the range of 70 to 5 wt%. The fluororesin component
If it exceeds 85wt%, it is unfavorable in terms of strength, hardness, and workability. The heat-resistant resin composition of the present invention as described above not only has excellent physical properties such as electrical properties, heat resistance, chemical resistance, strength, and adhesiveness, but also has superior properties compared to conventional cyanate ester resin compositions. It has workability equivalent to that of Moreover, various reinforcing agents, fillers, pigments, dyes, modifying resins, monomers, etc. can be added and mixed as necessary within the allowable range of desired physical properties, making it extremely practical. The present invention will be explained below with reference to Examples. Example 1 900 g of 2,2-bis(4-cyanatophenyl)propane and 100 g of bis(4-maleimidophenyl)methane were pre-reacted at 150°C for 200 minutes, and this was mixed with N,N-dimethylformamide and methyl ethyl ketone. Dissolved in solvent. Add finely powdered polytetrafluoroethylene (Lupron L-2,
Daikin Industries) 450g, zinc octylate 1.0g,
0.5 g of triethylenediamine was added and mixed uniformly. This solution (varnish) was applied to a glass nonwoven fabric, and then heated and dried to obtain a B-stage prepreg.
10 sheets of this prepreg were stacked and electrolytic copper foil with a thickness of 35μ was layered on top and bottom, and the pressure was gradually increased at a temperature of 175℃45
Lamination molding was carried out for 120 minutes at Kg/cm ² to obtain a double-sided copper-clad laminate. The test results for this laminate are shown in Table 1. Example 2 445g of 1,4-dicyanatobenzene at 140℃
A pre-reaction was carried out for 120 minutes, 5 g of bis(4-aminophenyl)methane was added thereto, and a pre-reaction was further carried out for 12 minutes. Add to this, 400g of bis(4-maleimidophenyl)methane, and epoxy resin (product name:
Add 50g of ECN-1273 (manufactured by Chipa Geigy),
After dissolving in a mixed solvent of N,N-dimethylformamide and methyl ethyl ketone, 100 g of tetrafluoroethylene-hexafluoropropylene copolymer powder (Neoflon; manufactured by Daikin Industries, Ltd.) was added and mixed uniformly. . Add 0.2g of zinc octylate as a catalyst to this solution.
Add 0.2g of triethylenediamine, mix and dissolve, impregnate glass nonwoven fabric with this, and dry.
Stage prepreg is used, and 6 sheets of this prepreg are stacked and electrolytic copper foil with a thickness of 35μ is layered on top and bottom, and the temperature is 175.
℃, gradually increase the pressure to a final pressure of 40Kg/ ^cm2 for 90 minutes,
Further, lamination molding was performed at 230° C. for 4 hours to obtain a double-sided copper-clad laminate. The test results for this laminate are shown in Table 1.

[Table] Example 3 80 g of 2,2-bis(4-cyanatophenyl)propane and bis(4-maleimidophenyl)methane
120g was preliminarily reacted at 160°C for 80 minutes. to this,
800 g of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer powder (PFA, manufactured by Mitsui Fluorochemical Co., Ltd.), zinc octylate as a catalyst
Add 0.02g and 0.2g of dicumyl peroxide,
The mixture was kneaded uniformly with heated rolls at 80°C to form a molding material. Put this molding material into a mold and heat it at 180℃, 100Kg/
After press molding at cm ² for 120 minutes and taking it out from the mold, it was further post-cured at 250° C. for 4 hours. The test results for this molded article are shown in Table 2. Example 4 300 g of 2,2-bis(4-cyanatophenyl)propane was preliminarily reacted at 160°C for 90 minutes. To this, bis(4-maleimidophenyl) ether 95
and 5 g of bis(4-aminophenyl) ether at 160°C for 30 minutes, 50 g of 1,4-dicyanatobenzene, and powder of tetrafluoroethylene-ethylene copolymer (Aphron).
COP (manufactured by Asahi Glass Co., Ltd.) 550g, and 0.03g of zinc octylate and dicumyl peroxide as a catalyst.
0.2 g was added and kneaded uniformly with a heated roll at 80°C to obtain a molding material. Put this molding material into a mold and heat it at 180℃, 60Kg/
After press molding at cm ² for 120 minutes and taking it out from the mold, it was further cured at 200° C. for 2 hours. The test results for this molded article are shown in Table 2.

【table】

Claims (1)

[Scope of Claims] 1 (a) a polyfunctional cyanate ester, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine, and (b) a polyfunctional maleimide, the maleimide prepolymer, or the maleimide A curable heat-resistant resin composition made by mixing a fluorine resin with a cyanate ester-maleimide resin whose essential components are a prepolymer of and an amine.