JPS6358184B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a heat-resistant resin composition. More specifically, a cyanate ester-based resin composition (a) consisting of a polyfunctional cyanate ester, the cyanate ester prepolymer, the above a and b the polyfunctional aleymide, the maleimide prepolymer, or c an epoxy resin. This is a heat-resistant resin composition comprising 1 to 30% by weight of the total composition of an acid anhydride () as a type of curing agent and a catalytic amount of a curing catalyst. Cyanate ester resin composition of the present invention ()
1928-1928 (component a), 46-
41112 (composition of a+c), No. 54-30440 (composition of a+b), No. 52-31279 (composition of a+b+c), and others, and as curing catalysts for these, imidazoles, third Known examples include class amines, phenols, organic metal salts, metal chelate compounds, and inorganic metal salts. However, there is no example of using acid anhydrides as a curing agent. The present invention has good workability, processability, etc., and the cured product has excellent heat resistance, moisture resistance, chemical resistance, and impact resistance. The present invention relates to a curable resin composition useful for, etc. As the cyanate ester resin, a polyfunctional cyanate ester, the cyanate ester prepolymer, b a polyfunctional aleimide, the maleimide prepolymer, or c an epoxy compound having two or more epoxy groups in the molecule (= epoxy resin ) from a alone,
Examples include mixtures or preliminary reactions of a and b, or a, b, and c. The components of the curable resin composition of the present invention will be explained below. The polyfunctional cyanate ester of component a of the present invention is a compound having at least two or more cyanate groups in the molecule. Preferred are organic cyanate esters represented by the following general formula. Formula R(-O-C≡N) _n (wherein R is a residue having an aromatic nucleus derived from an aromatic hydrocarbon selected from the group consisting of benzene, biphenyl, and naphthalene; two or more benzene rings but

[Formula] (R ₁ and R ₂ may be the same or different, hydrogen or an alkyl group having 1 to 4 carbon atoms),
-O-, -CH ₂ OCH ₂ -, -S-,

【formula】

【formula】 【formula】

[Formula] and

A residue having an aromatic nucleus derived from a compound bonded by a bridge selected from the group consisting of [Formula]; aroma obtained by removing the phenolic hydroxyl group from a novolak type or resol type phenolic resin skeleton The residue is selected from a residue having a nucleus; a residue having an aromatic nucleus obtained by removing the terminal hydroxyl group of a polycarbonate skeleton derived from bisphenol. These aromatic nuclei may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, chloro, or bromine substituent. m is 2
~10, and the cyanate group is always bonded directly to the aromatic nucleus. ) Specific examples of such compounds 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-cyanatophenyl)
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) phosphate, and the like. In addition to these, cyanate esters described in Japanese Patent Publication No. 46-4112 or Japanese Patent Publication No. 44-4791 can be used. In addition, the molecular weight of these cyanate esters has a triazine ring formed by trimerization of the cyanate group.
400-6000 prepolymers are also used. This prepolymer can contain the above-mentioned cyanate esters, for example, mineral acids, Lewis acids, and other acids; sodium hydroxide;
It can be obtained by polymerization using a base such as sodium alcoholate or tertiary amines; or a salt such as sodium carbonate or lithium chloride as a catalyst. Polyfunctional cyanate esters can also be used in the form of mixtures of monomers and prepolymers. For example, many of the commercially available cyanate esters from bisphenol A and cyanogen halides may be in the form of mixtures of cyanate ester monomers and prepolymers; such raw materials It can be fully used for the purpose of the present invention. As the component b used in the present invention, polyfunctional maleimide, other generally known imide monomers, and prepolymers may be used. However, in the present invention, polyfunctional maleimide represented by the following general formula derived from maleic anhydride and polyamine, and the maleimide prepolymer are preferred. General formula; (In the formula, 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 more and usually 5 or less. ). The maleimide represented by the above formula can be produced by a method known per se, in which maleic anhydride and polyamine are reacted to prepare maleamic acid, and then the maleamic acid is cyclodehydrated. It is preferable that the polyamines used are aromatic amines in terms of 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. Further, it is particularly desirable that the polyamines be primary amines in terms of reactivity, but secondary amines can also be used. These maleimides can be used alone or in combination of two or more. Moreover, those obtained by heating without a catalyst or in the presence of a catalyst to form a prepolymer can also be suitably used. Furthermore, the above-mentioned polyfunctional cyanate ester and polyfunctional maleimide each modified with an amine can also be used. Amides used as raw materials for polyfunctional maleimide or as modifiers include metaphenylenediamine, meta- or para-xylylenediamine, 1,4-cyclohexanediamine, hexahydroxylylenediamine, 4,4'-bis Aminophenylmethane, 4,4'-bisaminophenyl sulfone, bis(4-amino-3-methylphenyl)methane (MDT), bis(4-amino-3,
5-dimethylphenyl)methane (MDX), 4,
4'-bisaminophenylcyclohexane, 4,
4'-bisaminophenyl ether, 2,2-bis(4'-aminophenyl)propane, 2,2-bis(4-amino-3-methylphenyl)methane, α,
Examples include α-bis(4-aminophenyl)phenylmethane, melamine, and a compound in which the benzene ring of aniline obtained from aniline and formalin is bonded with --CH ₂ --. The epoxy compound having two or more epoxy groups in the molecule of c above, which is used as necessary in the present invention, has a wide range of properties, from liquids with relatively low viscosity to solids with relatively high melting point. However, any of these can be used for the purpose of the present invention. These epoxy compounds, especially bis-epoxy compounds, are those produced by reacting the corresponding polyhydric phenol with epihalohydrin such as epichlorohydrin in the presence of a base such as alkali hydroxide, and diamines and epihalohydrin. It is also possible to use a bisepoxy compound produced by this method. Epoxy compounds which are easily available and suitable for the purpose of the present invention include epoxy compounds derived from bisphenol A or the chloride of bisphenol A, or bromine-substituted derivatives of epihalohydrin, and epoxy compounds derived from epihalohydrin, and epoxy compounds derived from bisphenol A, the chloride of bisphenol A, and epihalohydrin, and epoxy compounds derived from epihalohydrin, and epoxy compounds derived from bisphenol A or the chloride of bisphenol A, and epihalohydrin; These include epoxy compounds derived from condensates and epihalohydrin, and epoxy compounds derived from hydroxyl group-containing silicone resins. As mentioned above, the three components a, b, and c do not need to be separate compounds, and can be used, for example, in the form of a compound containing a maleimide group and an epoxy group in the same molecule. In the present invention, an acid anhydride is used in combination with another curing catalyst as a catalyst for curing the above-mentioned resin component. Examples of acid anhydrides include _C4 to _C25 acid anhydrides. Specifically, maleic anhydride, methylmaleic anhydride, propionic anhydride, dimethylmaleic anhydride, phthalic anhydride, 4-bromphthalic anhydride,
Examples include diphthalic anhydride, lauric anhydride, diphenyl acetic anhydride, and the like. Further examples include hydrogenated acid anhydrides. The amount of acid anhydride used is 1 to 30%, preferably 1 to 20% by weight, based on the cyanate ester resin composition. Further, as the curing catalyst used in combination with the above peroxide of the present invention, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-ethyl-4
-Methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl 2-
Imidazoles exemplified by methylimidazole, and trimellitic acid adducts of these imidazoles; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, N,N-dimethyl -p-anisidine, p-halogeno-N,N-dimethylaniline, 2-N-ethylanilinoethanol, tri-
Tertiary amines such as o-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, N,N,N',N'-tetramethylbutanediamine, N-methylpiperidine; phenol, cresol , xylenol, resordin, phloroglucin, and other phenols: lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate,
Examples include organic metal compounds such as dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetonate; inorganic metal compounds such as SnCl ₄ , ZnCl ₂ , and AlCl ₃ . The curable resin composition described above includes natural and synthetic resins, natural and synthetic inorganic or organic fillers, double reinforcing materials, pigments, etc., to the extent that their original properties are not impaired.
A dye or the like may also be added. The above-described curable resin composition of the present invention can be obtained in a variety of properties, from liquid to solid at room temperature, depending on the component compounds used and preliminary reaction conditions. Depending on the purpose of use, solvent-free liquids, solutions, and even solids can be used. The curing conditions for the curable resin composition of the present invention vary depending on the resin component ratio, etc., but are usually in the range of 5 minutes to 20 hours at a temperature of 100 to 250°C. The composition of the present invention is useful as a laminate, a casting resin, an insulating paint, an adhesive, a varnish, etc., especially a laminate, a casting resin. Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. Example 1 (1) Preparation of composition (a) 10 g of bis(4-maleimidophenyl)methane was added to 90 g of 2,2-bis(4-cyanatophenyl)propane and pre-reacted at 150°C for 120 minutes to obtain a uniform resin composition. I got something. This resin composition is referred to as A. (b) Add 20 g of a novolak type epoxy resin (ECN-1273, manufactured by Ciba Geigy) to the above resin composition at 150°C and mix uniformly to obtain a resin composition B. (c) 60 g of 2,2-bis(4-cyanatophenyl)propane and 40 g of bis(4-cyanatophenyl) ether were preliminarily reacted at 150°C for 190 minutes. This resin composition is designated as C. (d) 20g of 1,4-dicyanatobenzene and bis(4
-maleimidophenyl) propane 64 g, 4-maleimidophenyl-3',4'-dimaleimidophenylmethane and 4-maleimidophenyl-2',
Mixture with 4'-dimaleimidophenylmethane16
A resin composition obtained by pre-reacting g at 160°C for 60 minutes is designated as D. After dissolving the above resin composition in N,N-dimethylformamide, an acid anhydride is added and the gelation time is increased.
Measured at 180℃. The results are shown in Table 1. From Table 1 the effect of the curing agent is clear.

[Table] Example 2 Prepare 1000g of composition A of Example 1, add N,
Dissolved in N-dimethylformamide. This is added to bisphenol A type epoxy resin (Epicoat).
Add 200g of 1001 (manufactured by Ciel Chemical) and further 20g of acid anhydride represented by and the formula

After adding 3 g of acid anhydride represented by the formula and 0.1 g of zinc octylate and making it homogeneous,
After impregnating glass cloth, heating and drying it, B-
I got stage prepreg. Stack 6 of these, put 35μ electrolytic copper foil on the outside, and heat at 175℃ for 40 minutes.
Press molded for 120 minutes at Kg/cm ² and further heated to 180°C at 200℃.
A copper clad laminate was obtained by heating for a minute. The performance of this board is shown in Table 2. Comparative Example 1 A copper-clad laminate was obtained in the same manner as in Example 2, except that no acid anhydride was used. The performance of this board is shown in Table 2.

【table】

[Table] Example 3 To 500 g of the resin composition B obtained in Example 1, 300 g of pyromellitic anhydride and zinc octylate were added.
Add 0.04g and 0.5g of 2-ethylimidazole,
Put this in a mold, heat it at 160℃ for 150 minutes, and then
It was cured at 200°C for 5 hours and at 220°C for 4 hours. The performance of this sample is shown in Table 3.

【table】

Claims (1)

[Claims] 1. In a cyanate ester-based resin composition () consisting of a polyfunctional cyanate ester, the cyanate ester prepolymer, the polyfunctional aleimide of a and b, the maleimide prepolymer, or c an epoxy resin, curing is performed. A heat-resistant resin composition comprising 1 to 30% by weight of the total composition of an acid anhydride as a type of agent and a catalytic amount of a curing catalyst.