JPH025779B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a curable resin composition formed by mixing a cyanato resin with a polyamide resin, and more specifically, a polyfunctional cyanate ester having two or more cyanato groups in the molecule, and the cyanate ester prepolymer. Alternatively, a prepolymer of the cyanate ester and an amine, or a polyfunctional maleimide having two or more N-maleimide groups in the molecule, the maleimide prepolymer, or a prepolymer of the maleimide and an amine as essential components. A curable resin composition obtained by mixing a curable resin composition (A) and a polyamide resin (B), in a preferred embodiment, the polyamide resin (B) is obtained from a dimer acid and a polyamine. It is a polyamide resin with excellent adhesive properties such as interlayer adhesive strength, and water resistance. Conventionally, resins whose main component is cyanate resin (component a above) have excellent heat resistance and electrical properties, but they have insufficient adhesion and flexibility, and cyanate ester-maleimide resins (component a) A resin containing components a and b) had better heat resistance and water resistance than cyanato resin, but had insufficient adhesion and flexibility. The present invention aims to improve the deficiencies of the cyanato resins or cyanate ester-maleimide resins described above, and improves heat resistance, flexibility, adhesiveness,
It is a curable resin composition with excellent moisture resistance, chemical resistance, electrical properties, etc. The present invention will be explained below. First, the curable resin composition (A) of the present invention is composed of component a, and components a and b, as described above.
First, a suitable polyfunctional cyanate ester as component a has the following general formula (1) R-(O-C≡N) _n ...(1) [m in the formula is 2 or more, usually 5 is the following integer, 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-dicyanatophenyl)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
43-18468, Special Publication 44-4791, Special Publication 45-11712,
Special Publication No. 46-41112, Special Publication No. 47-26853, and Special Publication No. 1983
Cyanic acid esters described in 51-63149 and the like 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 described 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-cyclohexane diamine, 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, bis(4-amino-
3-chlorophenyl)methane, 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. A preferred polyfunctional maleimide as component b of the present invention is represented by the following general formula (2): [Wherein, R is a divalent, usually 5 or less, aromatic or alicyclic organic group, X ¹ and X ² are hydrogen, halogen, or an alkyl group, and m is 2 or more and usually 5 or less It is. ] It is a compound represented by The maleimide represented by the above formula has maleic anhydride and an amino group of 2 to 2.
It can be produced by a method known per se, in which maleamic acid is prepared by reacting with a polyamine having five polyamines, and then the maleamic acid is cyclized by dehydration. It is preferable that the polyamines 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. good. 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 amines used in the form of a prepolymer with the above-mentioned component a, melamines having an s-triazine ring, and melamines having benzene rings linked with methylene bonds by reacting aniline with formalin. Polyamines, etc. In the present invention, the above-mentioned polyfunctional maleimide can be used in the form of a prepolymer, or a prepolymer with the above-mentioned amine, instead of being used in the form of a so-called monomer. As the polyamide resin of component B of the present invention, common polyamide resins such as nylon 6, nylon 66, nylon 610, nylon 11, nylon 12,
and copolymerized nylons, but it is particularly preferable to use dimer acid, which is a dimer of unsaturated fatty acids having 18 to 22 carbon atoms, as the dibasic acid. The composition ratio of component A and component B in the present invention is not particularly limited. However, in heat-resistant applications, the A component is 80wt%.
Above, it is preferable that the B component be 0.1 to 20 wt%.
In a preferred embodiment, when a polyamide resin containing dimer acid as a dibasic acid is used as component B, the weight average molecular weight is 5,000 to 30,000, preferably 6,000 to 30,000.
20000, and the softening point is 250℃ or less, preferably
A temperature of 120-220℃ is best. In addition, in applications where adhesiveness and flexibility are more important than heat resistance, A component is 1 to 80 wt% and B component is 20 wt%.
A range of ~99wt% is suitable for use. In a preferred embodiment, when a polyamide resin containing dimer acid as a dibasic acid is used as component B, the weight average molecular weight is 1000 to 20000, preferably 3000 to 10000.
The softening point is 200°C or less, preferably 80 to 180°C. The method for preparing the curable resin composition of the present invention includes a method of dissolving or uniformly dispersing components A and B in a solvent, respectively, and mixing the components A and B without a solvent at room temperature or under heating, for example, Banbury. By a method of uniformly mixing using a mixer, Henschel mixer, roll, extruder, etc. Although the present invention is as described above, A of the present invention
Known reactive or non-reactive organic compounds, resins, rubbers, etc. that can be used as components;
Catalyst or curing agent; Fibrous reinforcement base material; Filler;
Dyes and pigments; lubricants; coupling agents; flame retardants (for example, JP-A-50-129700, etc.) may be used in appropriate combinations as desired. The temperature for curing the curable resin composition of the present invention varies depending on the presence or absence of a curing agent and catalyst, the types of composition components, etc., but it may be generally selected within the range of 100 to 300°C. When used in the production of molded products, laminated products, adhesive structures, etc., it is preferable to apply pressure during heat curing;
It is appropriately selected within the range of 0.1 to 500Kg/ ^cm2 . Hereinafter, this will be explained in detail using examples. Example 1 After preliminarily reacting 4875 g of 2,2-bis(4-cyanatophenyl)propane and 4875 g of bis(4-maleimidophenyl) ether at 150°C for 60 minutes,
Polyamide resin (product; Versamide 950, manufactured by Henkel Japan Co., Ltd., softening point 90-100℃, viscosity 4.5-9.5
Add 250g of Poise/160℃, disperse evenly,
A solid resin was obtained by cooling to room temperature. This solid resin was dissolved in methyl ethyl ketone, 2 g of dicumyl peroxide was added as a catalyst, impregnated into carbon cloth, and dried at 140° C. for 6 minutes to obtain a prepreg. 8 sheets of the obtained prepreg were stacked and the temperature was
Laminate molding at 170℃ for 2 hours at a pressure of 30Kg/ ^cm2 , and then after-cure in a dryer at 240℃ for 4 hours.
A carbon cloth laminate with a thickness of 3 mm was obtained. Table 1 shows the characteristic values of the obtained carbon cloth laminate. Example 2 When 950 g of 2,2-bis(4-cyanatophenyl)propane was pre-reacted at 150°C for 5 hours, the polyamide resin (trade name: Tomide #509, manufactured by Fuji Kasei Kogyo Co., Ltd., softening point 115 ± Add 50g of
The mixture was uniformly dispersed and cooled to room temperature to obtain a solid resin. This solid resin was dissolved in methyl ethyl ketone, and as catalysts, 40 ml of an MEK solution of zinc octylate (0.01 g/ml) and 40 ml of an MEK solution of dicumyl peroxide (0.05 g/ml) were added.
Stir evenly. Carbon cloth was impregnated with the obtained varnish and dried at 140°C for 6 minutes to obtain a prepreg. 8 sheets of the obtained prepreg were stacked and the temperature was
Lamination molding was carried out at 170° C. for 2 hours at a pressure of 30 kg/cm ² to obtain a carbon cloth laminate with a thickness of 3 mm. Table 1 shows the characteristic values of the obtained carbon cloth laminate.

【table】

【table】

Claims (1)

[Scope of Claims] 1 a A polyfunctional cyanate ester having two or more cyanato groups in the molecule, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine, or a and b in the molecule. A curable resin composition (A) containing a polyfunctional maleimide having two or more N-maleimide groups, a prepolymer of the maleimide, or a prepolymer of the maleimide and an amine as essential components, and a polyamide resin (B). A curable resin composition formed by mixing. 2. The composition according to claim 1, wherein the polyamide resin (B) is a polyamide resin obtained from a dimer acid and a polyamine.