JPH0352769B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition that provides a cured product with excellent moldability, heat resistance, adhesiveness, etc. B. A prepolymer obtained by heat-reacting polyfunctional maleimide, trialkenyl isocyanurate, and polyfunctional amine containing two or more cyanato groups, and B. a polyfunctional cyanate ester containing two or more cyanato groups in the molecule, and the cyanic acid. This is a curable resin composition containing an ester prepolymer or a prepolymer of the cyanate ester and an amine as an essential component. Conventionally, cured products of trialkenyl isocyanurate were brittle and difficult to use alone, despite their excellent heat resistance and chemical resistance, and were used to modify vinyl resins such as methyl methacrylate, styrene, and unsaturated polyester. It is used as a drug. In addition, curable resin compositions containing polyfunctional cyanate esters and polyfunctional maleimides as essential components have excellent heat resistance, chemical resistance, adhesiveness, moisture resistance, etc. It was somewhat insufficient in terms of higher moisture resistance, and when used for casting etc., it was insufficient in terms of surface gloss. Curable resin compositions containing polyfunctional cyanate esters, polyfunctional maleimides, and trialkenyl isocyanurates as essential components have excellent heat resistance, chemical resistance, adhesiveness, moisture resistance, etc. However, it is difficult to use as a uniform composition when used as a highly concentrated solution due to poor solvent solubility, and when used as a solvent-free liquid resin, it has a non-uniform composition with no transparency. The drawback is that it can only be used as an object. In addition, the method of heating and mixing polyfunctional maleimides and polyfunctional amines and then mixing them with epoxy resin is usually difficult because the melt reaction between polyfunctional maleimides and polyfunctional amines is rapid. , it was necessary to react in a solvent, and it was difficult to make it solvent-free. Furthermore, polyfunctional maleimide, polyfunctional amine,
In a mixture of trialkenyl isocyanurate and polyfunctional cyanate ester, the polyfunctional amine easily reacts with polyfunctional maleimide or polyfunctional cyanate ester, resulting in poor storage stability. The reaction between polyfunctional maleimides and polyfunctional amines is rapid, and the reaction between polyfunctional cyanate ester and polyfunctional amine forms an imine carbonate bond, so that the cured product is Heat resistance and storage stability of uncured compositions are poor. The present inventors have conducted intensive research to solve the above-mentioned drawbacks, and as a result, we have developed a prepolymer and a polyfunctional prepolymer obtained by heat-reacting polyfunctional maleimides, trialkenyl isocyanurates, and polyfunctional amines. By combining it with cyanate esters, we succeeded in obtaining a heat-resistant resin composition that has excellent heat resistance, moisture resistance, chemical resistance, electrical properties, mechanical strength, etc., and has good workability in processing. , led to the present invention. The present invention will be explained below. A preferred polyfunctional maleimide in component A of the present invention is represented by the following general formula (2): (In the formula, R is an aromatic or alicyclic organic group with a valence of 2 or more and usually 5 or less, X ¹ and X ² are hydrogen, halogen,
or an alkyl group, and n is usually an integer of 2 to 5. ) is a compound represented by Maleimides represented by the above formula are produced by a method known per se, in which maleic anhydride and polyamines containing 2 to 5 amino groups are reacted to prepare maleamic acid, and then maleamic acid is cyclized by dehydration. be able to. The polyamines used are preferably aromatic polyamines 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. Also,
It is desirable that the polyamines be primary amines in terms of reactivity, but secondary amines can also be used.
Suitable amines 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, 2,2bis(4-amino-3
-chlorophenyl)propane, bis(4-amino-3-chlorophenyl)methane, 2,2-bis(4-amino-3,5-dibromophenyl)propane, bis(4-aminophenyl)phenylmethane, 3,4-diamino Phenyl-4'-aminophenylmethane, 1,1-bis(4-aminophenyl)-1-phenylethane, and melamines with an s-triazine ring, aniline and formalin are reacted to bond the benzene ring with methylene. Polyamines etc. bound with The trialkenyl isocyanurate in component A of the present invention has the following general formula: [R in the formula is an alkenyl group having 2 to 4 carbon atoms] This is a compound represented by the following formula. Preferred examples of R (alkenyl group) include vinyl group, allyl group, crotyl group, metaallyl group, chlorpropenyl group, butadienyl group, and the like. Prepolymerization of these trialkenyl isocyanurates using organic peroxides, ultraviolet rays, heat, etc. can also be suitably used. Furthermore, from the viewpoint of flexibility and other aspects, a vinyl compound such as acrylic acid ester, styrene, diallyl phthalate, etc. may be used in combination as a reactive diluent. The polyfunctional amine in component A of the present invention is a polyfunctional amine having two or more primary amino groups ( _-NH2 ) in a divalent or higher organic group having two or more carbon atoms. Suitable examples include benzoguanamine, melamine, guanamine, 4,4'-diaminocyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, metaphenylenediamine, paraphenylenediamine, dichlorodiaminomethane, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, benzidine, 4,4'-diaminophenyl oxide, 4,4'-diaminodiphenyl sulfide, 4,4'- Diaminophenyl sulfone, bis(4-aminophenyl)diphenylsilane, bis(4-aminophenyl)methylphosphine oxide, bis(3-aminophenyl)methylphosphine oxide, bis(4-aminophenyl)phenylphosphine oxide, 1,5 -diaminonaphthalene, metaxylylene diamine, paraxylylene diamine, hexamethylene diamine, 1,
3,5-pentatriamine, 3,5-diamino-
Examples include 1,2,4-triazole. Suitable polyfunctional cyanate esters as component B of the present invention have the following general formula (2) R(OCN) _n ...(2) (m in the formula is an integer of 2 or more and usually 5 or less). can be,
R is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group. 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) phosphate, and cyanic acid esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, Tokuko Sho 41-1928, Sho 43-18468, Sho 44-4791, Sho 44-4791,
Cyanic acid esters described in JP-A No. 45-11712, No. 46-41112, No. 47-26853, and JP-A No. 51-63149 can also be used. Alternatively, the above-mentioned polyfunctional cyanate ester can be used as a prepolymer obtained by polymerizing it in the presence of a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, or a phosphate ester such as tributylphosphine. I can do it. These prepolymers generally have a sym-triazine ring in the molecule, which is formed by trimerization of the cyanide groups in the cyanate ester. In the present invention, it is preferable to use the prepolymer having a number average molecular weight of 300 to 6,000. A in the curable resin composition of the present invention refers to the amount of polyfunctional amine per 1 mol of polyfunctional maleimide.
0.009 to 0.3 mol, preferably 0.011 to 0.11 mol, by heating and reacting trialkenyl isocyanurate with 5 to 40 wt parts, preferably 10 to 35 wt parts, with respect to 100 wt parts of polyfunctional maleimide. adjust. The conditions for the heating reaction depend on the ratio of the amounts used of the three components above, but are usually 80 to 200℃, 0.5
to 24 hours, the three components are suitably selected from a range in which they become a uniform liquid and do not gel, and if desired, a radical polymerization inhibitor such as hydroquinone, tert-butylcatechol, or hydroquinone monomethyl ether is added. Here,
If the amount of polyfunctional amine is more than 0.3 mol per 1 mol of polyfunctional maleimide, excess unreacted polyfunctional amine remains and reacts with the polyfunctional cyanate ester of component B, forming an imine carbonate bond. This is undesirable because it forms a compound that deteriorates the heat resistance and also reduces the storage stability of the uncured resin composition. If the trialkenyl isocyanurate is less than 5 parts by weight, the melting reaction is difficult to occur, and if it exceeds 40 parts by weight, the heat resistance of the cured product decreases, which is not preferable. Although there is no particular limitation on the ratio of the amounts used of both components A and B in the curable resin composition of the present invention, a range of A:B = 1:99 to 90:10 is usually suitable; Preferably, the ratio is 10:90 to 80:20. The method of mixing and adjusting both components A and B of the curable resin composition of the present invention includes a method of simply mixing both components A and B, a method of dissolving them in a solvent or dispersing them uniformly, and a method of mixing the components A and B by dissolving them in a solvent or dispersing them uniformly. This can be done by pre-reacting for 0 to 24 hours at °C. The curable resin composition of the present invention itself has the property of becoming a heat-resistant resin by bonding and reticulating when heated, but it may also contain a catalyst for the purpose of promoting cross-linking and reticulating. . Such catalysts include 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole,
2-Phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole , 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and imidazoles exemplified by 1-guanaminoethyl-2-methylimidazole,
Furthermore, adducts of carboxylic acids or their anhydrides to 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-n-butylamine, pyridine,
Quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, N,N,N',
Tertiary amines such as N'-tetramethylbutanediamine and N-methylpiperidine; phenol,
Phenols such as xylenol, cresol, resorcin, catechol, phlologlycin; lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate,
Organometallic salts such as iron acetylacetonate; SnCl ₄ ,
Inorganic metal salts such as _ZnCl2 , _AlCl3 ; peroxides such as benzoyl peroxide, lauroyl peroxide, caprylic peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate; Acid anhydrides such as maleic anhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydro trimellitic anhydride, hexahydropyromellitic anhydride; Examples include compounds. The amount of these catalysts to be added is sufficient within the range of catalytic amounts in a general sense, and may be used, for example, in an amount of 5 wt% or less based on the total composition. 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 may be generally selected within the range of 100 to 250°C. This composition is used for various purposes, but when used for manufacturing molded products, laminated products, adhesive structures, etc., it is preferable to apply pressure during heat curing, and generally speaking,
It is suitably selected within the range of 500 Kg/cm ² , preferably 5 to 150 Kg/cm ² . The curable resin composition of the present invention may contain various additives as desired, as long as the original properties of the composition are not impaired. These additives include natural or synthetic thermosetting or thermoplastic resins and their low molecular weight products, fibrous reinforcing agents, fillers, dyes, pigments, thickeners, lubricants, coupling agents, flame retardants, etc. Various known additives are included and can be used in appropriate combinations as desired. Examples of thermoplastic resins or low molecular weight compounds thereof include polyvinyl acetal resins such as polyvinyl formal, polyvinyl acetal, and polyvinyl butyral; thermoplastic polyurethane resins; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene. Non-crosslinked (non-vulcanized) rubbers such as copolymers, polyisoprene, butyl rubber, and natural rubber;
polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, polyvinyl chloride,
Vinylidene chloride resin, polystyrene, polyvinyltoluene, polyvinylphenol, AS resin,
ABS resin, MBS resin, poly-4-fluorinated ethylene, fluorinated ethylene-propylene copolymer, 4-
Fluorinated ethylene-6-fluorinated ethylene copolymer,
Vinyl compound polymers such as vinylidene fluoride;
polycarbonate, polyester carbonate,
Resins such as polyphenylene ether, polysulfone, polyester, polyethersulfone, polyamide, polyadimide, polyester imide, polyphenylene sulfide, and low polymers of these thermoplastic resins with a molecular weight of 10,000 or less,
Usually, one thousand to several thousand low molecular weight polymers (prepolymers) can be mentioned. The present invention will be explained in more detail below using Examples and Comparative Examples. In addition, parts in Examples and Comparative Examples are parts by weight unless otherwise specified. Example 1 and Comparative Example 1 100 parts (0.28 mol) of bis(4-maleimidophenyl)methane, 5 parts (0.025 mol) of bis(4-aminophenyl)methane and 20 parts of triallylisocyanurate were mixed, and the mixture was heated at 145°C. A heating reaction was performed for 2 hours to obtain a prepolymer. Add 2,2-bis(4-cyanaphenyl)propane to this prepolymer.
67 parts of a prepolymer pre-reacted at 150°C for 1 hour was added, mixed at 120°C for 1 hour, and then cooled to obtain a brown transparent resin liquid with a viscosity of 3400PS (at 30°C). Pour this resin liquid into a mold and heat it at 150℃ for 2 hours at 180℃.
After curing at 240°C for 2 hours, the mixture was cured at 240°C for 20 hours to obtain a cast plate with a thickness of 4 mm. The test results for this casting board are shown in Table 1. Further, the above resin liquid was mixed with N,N-dimethylformamide to form a brown transparent solution at room temperature with a concentration of 55%, and to 182 parts of this solution, 0.05 part of zinc octylate and 0.1 part of dicumyl peroxide were added as a catalyst. The mixture was added and mixed, impregnated into a glass woven fabric with a thickness of 0.2 mm, and heated and dried to form a B-stage prepreg. Electrolytic copper foil with a thickness of 35μ was layered on both sides of eight sheets of this prepreg, and the mixture was heated at a temperature of 180℃ and a pressure of 50Kg/ ^cm2. Lamination molding was carried out for 120 minutes, and post-curing was further carried out at 240°C for 24 hours. The test results of the obtained copper-clad laminates are shown in Table 1. Example 2 Bis(3-chloro-4-maleimidophenyl)
1 part benzoguanamine to 100 parts (0.23 mol) methane
part (0.0053 mol), triallyl isocyanurate
30 parts and 0.1 part of hydroquinone were mixed and reacted by heating at 160°C for 1 hour to obtain a prepolymer. To this prepolymer, 150 parts of a prepolymer prepared by pre-reacting 2,2-bis(4-cyanatophenyl)propane at 150°C for 1 hour was added, and after mixing at 140°C for 1 hour, it was cooled to give a brown transparent viscosity of 12,000 PS ( A resin liquid was obtained at a temperature of 30°C. A casting plate was obtained in the same manner as in Example 1 except that this resin liquid was used. The test results for this casting board are shown in Table 1. Further, a copper-clad laminate was obtained and tested in the same manner as in Example 1, except that the above resin liquid was mixed with N,N-dimethylformamide to form a brown transparent solution at room temperature with a concentration of 55%. The test results are shown in Table 1. Comparative Example 1 A preliminary reaction similar to Example 1 was attempted except that triallyl isocyanurate was not used. but,
A homogeneous reaction solution could not be obtained at a reaction temperature of 145°C, so when the reaction temperature was increased to 160°C, gelation occurred after 15 minutes, making it impossible to obtain a prepolymer. Comparative Example 2 The same method as in Example 1 was attempted except that bis(4-aminophenyl)methane was not used. At a pre-reaction temperature of 145°C, rapid gelation occurred after 45 minutes, so the pre-reaction temperature was set to 120°C and a heating reaction was carried out for 2 hours. After the preliminary reaction, 2,2-
Bis(4-cyanatophenyl)propane at 150℃
After adding 67 parts of prepolymer pre-reacted for 1 hour at 120 DEG C. and mixing for 1 hour, the mixture was cooled to give a yellowish brown, opaque paste-like resin that was close to a solid state. Comparative Example 3 100 parts of bis(4-maleimidophenyl)methane, 67 parts of 2,2-bis(4-cyanatophenyl)propane and 20 parts of triallylisocyanurate were mixed, reacted by heating at 145°C for 2 hours, and cooled. A yellow-brown opaque resin liquid with a viscosity of 31,000 PS (30°C) was obtained. A cast plate and a copper-clad laminate were obtained in the same manner except that this resin liquid was used. In the case of making a varnish, since the resin liquid is non-uniform, it is necessary to stir and mix the resin liquid and impregnate it immediately when impregnating the glass woven fabric. The test results are shown in Table 1. Comparative Example 4 In Example 1, 2,2-bis(4-cyanatophenyl) was prepared without pre-reacting the mixture of bis(4-maleimidophenyl)methane, bis(4-aminophenyl)methane and triallylisocyanurate. Propane pre-reacted at 150°C for 1 hour was added and mixed at 120°C for 1 hour, but the resin liquid did not become homogeneous and transparent, and a large amount of bis(4-maleimidophenyl)methane was precipitated into an almost solid state. It became a mixture of shapes. A cast plate was obtained using this mixture in the same manner as in Example 1, except that the casting temperature was 120° C. under heating.
The results are shown in Table 1. In addition, an attempt was made to produce prepreg in the same manner as in Example 1, but only a very non-uniform varnish was obtained.
Moreover, due to this non-uniformity, the flow was abnormally large, making it impossible to produce a good prepreg. 【table】

Claims (1)

[Scope of Claims] 1. A. A prepolymer obtained by heat-reacting a polyfunctional maleimide, trialkenyl isocyanurate, and a polyfunctional amine containing two or more N-maleimide groups in the molecule, and B. A cyanato group in the molecule. A curable resin composition comprising as an essential component a polyfunctional cyanate ester containing two or more of the above, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine.