JPH0322420B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a curable resin composition that has excellent heat resistance, adhesiveness, mechanical strength, chemical resistance, etc. and is particularly useful as a heat-resistant adhesive. a polyfunctional cyanate ester, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine; or a and b; a polyfunctional maleimide having two or more maleimide groups in the molecule; This is a curable resin composition comprising a polymer or a prepolymer of the maleimide and amine, and c-polybenzimidazole as essential components.
Polybenzimidazole is an excellent adhesive known as a heat-resistant adhesive, but it has a high melting point and
When used, high temperatures were required, and workability and processability were poor. On the other hand, cyanate ester resin (a) or cyanate-maleimide resin (a)
+b) is known as a heat-resistant resin and has excellent workability and processability, but when used as an adhesive resin, it has the disadvantage of poor flexibility etc. if used as is. Furthermore, conventional methods for imparting flexibility have had drawbacks such as increased deterioration at high temperatures and poor chemical resistance. The present invention was completed as a result of intensive research aimed at developing a resin particularly useful as an adhesive without deteriorating the properties of the cyanate ester resin or cyanate ester-maleimide resin. The constituent components and other components of the present invention will be explained below. First, polybenzimidazole as component c of the present invention is a known polybenzimidazole produced by, for example, polycondensing an aromatic primary tetraamine with a derivative such as diphenyl ester of an aromatic dicarboxylic acid or an aromatic diacid chloride. It is a resin. 3,3',4,4'-tetraminobiphenyl (2,3,3'-diaminobenzidine) as aromatic primary tetramine
When isophthalic acid diphenyl ester is used as the diphenyl ester of an aromatic dicarboxylic acid, a polymer having a molecular weight of several tens of thousands is represented by the following formula (2). Next, a cyanate ester resin or a+b cyanate ester-maleimide resin of the present invention will be explained. A preferred compound as the multifunctional cyanate ester of component a is one represented by the following general formula (2). R(-O-C≡N)m...(2) [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] 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-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(3,5-dichloro-4-cyanatophenyl)propane, 2,
2-bis(3,5-dipromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)
Ether, bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl) phosphate, and cyanate ester obtained by reaction of novolak with cyanogen halide, etc. It is.
In addition to these, Tokuko Sho 41-1928, Tokko Sho 43-18468,
Tokuko 1979-4791, Tokuko 11712 to Tokko 45, Tokuko 46 to
41112, JP 47-26853 and JP 51-63149
Cyanic acid esters described in et al. can also be used. Alternatively, the polyfunctional cyanate ester described above can be polymerized 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 triptylphosphine. It can be used as a prepolymer. These prepolymers generally have a sym-triazine ring in the molecule, which is formed by trimerization of the cyanide group in the cyanate ester. In the present invention, it is preferable to use the prepolymer having a number average molecular weight of 400 to 6,000. The polyfunctional maleimide as component b of the present invention is represented by the following general formula (3). [Wherein, R is a divalent, usually a pentavalent 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 can be produced by a method known per se, in which maleic anhydride and a polyamine having 2 to 5 amino groups are reacted to prepare maleamic acid, and then the maleamic acid is cyclodehydrated. . The polyamines used are preferably 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. 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 meta or paraphenylene diamine, meta or para xylylene diamine, 1,4- or 1,3-cyclohexane diamine, hexahydroxylylene diamine, 4,
4'-Diaminebiphenyl, bis(4-aminophenyl)mene, 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-dipromo-4-aminophenyl)propane, bis(4-chlorophenyl)methane,
-aminophenyl) phenylmethane, 3,4-diaminophenyl-4'-aminophenylmethane,
These include 1,1-bis(4-aminophenyl)-1-phenylethane, melamines having an s-triazine ring, and 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 or a prepolymer with the above-mentioned polyamine instead of being used in the form of a so-called monomer. In the present invention, other components other than the above-mentioned components include epoxy resins, esters of (meth)acrylic acid such as esters of (meth)acrylic acid, epoxy esters of (meth)acrylic acid, and alkenyl esters of (meth)acrylic acid. and prepolymers thereof; diallyl phthalate. Divinylbenzene.
Diallylbenzene. Polyallyl compounds such as trialkenyl isocyanurate and their prepolymers: Dicyclopentanediene and its prepolymers: Phenol resins: Polyvinyl acetal resins such as polyvinyl formal, polyvinyl acetal, and polyvinyl petyral; OH groups or
Acrylic resin with COOH group, silicone resin,
Alkyd resin; polyptadiene. Putadiene
Acrylonitrile copolymer, polychloroprene,
Liquid-elastic materials such as putadiene-styrene copolymer, polyisoprene, butyl rubber, natural rubber, etc.
Rubbers, polyimide polymers, etc. can be used as appropriate. The resin composition of the present invention itself has the property of becoming a heat-resistant resin by being bonded and reticulated by heating, but in order to promote crosslinking and reticulation, it is usually used in the form of a catalyst. Such a catalyst is
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-
Imidazoles exemplified by cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole, and further,
Trimellitic acid adducts of these imidazoles, etc.; 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, Tertiary amines such as N-methylmorpholine, triethanolamine, triethylenediamine, N,N,N',N'-tetramethylbutanediamine, N-methylpiperidine; phenol, cresol, xylenol, resorcin, catechol, phloroglucin Phenols such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate,
Organic metal salts such as diptyltin maleate, manganese nathenate, cobalt naphthenate, iron acetylacetone; inorganic metal salts such as SnCl ₂ , ZnCl ₃ , AlCl ₃ ; benzoyl peroxide, lauroyl peroxide, capryl peroxide, acetyl peroxide, Peroxides such as parachlorobenzoyl peroxide, tertiary butyl phthalate; maleic anhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydro trimellitic anhydride, hexahydro anhydride Examples include acid anhydrides such as pyromellitic acid, and azo compounds such as azopisnitrile.
The amount of the catalyst to be added is sufficient within the general range of the catalyst amount, for example, it may be used in an amount of 10% by weight or less based on the total composition. The curable resin composition of the present invention is prepared by a method using a conventional solvent or a method in which powders of each component are mixed without a solvent under conditions in which components a or a+b are melted. The temperature for curing the curable resin composition of the present invention may vary depending on the presence or absence of a curing agent or catalyst, the salts of the composition components, etc., but is generally selected within the range of 100 to 300°C. When used in the production of molded products, laminates, adhesive structures, etc., it is preferable to apply pressure during heat curing, and generally speaking, the pressure is appropriately selected within the range of 0.1 to 500 kg/cm ² . Various additives can be added to the composition of the present invention as desired, as long as the original properties of the composition are not impaired. Examples of these additives include various known additives such as fiber reinforcing base materials, fillers, dyes and pigments, lubricants, coupling agents, and flame retardants. The present invention will be specifically explained below using Examples and Comparative Examples. Example 1 2,2-bis(4-anatophenyl)propane
Polybenzimidazole (trade name,
1000 g of Imidite (manufactured by Whittaker) were added, and these were dissolved in a mixed solvent of N,N-dimethylformamide and N,N-dimethylacetamide. To this was added 0.1 g of zinc octylate as a catalyst, and the mixture was stirred and mixed uniformly. This was applied to stainless steel, heated and dried to bring the resin to B-Stage, then stainless steel was placed on top of this and heated to 175°C while applying a pressure of 5 kg/cm ^2.
It was allowed to cure for 3 hours. The measurement results of this adhesive layer are
Shown in the table. Example 2 2,2-bis(4-anatophenyl)propane
500g and bis(4-maleimidophenyl)methane
500g was pre-reacted at 150°C for 45 minutes. To this was added 400 g of polybenzimidazole (thermal softening temperature: about 360°C) synthesized from 3,3',4,4'-tetraaminobiphenyl and isophthalic acid diphenyl ester and mixed uniformly with a roll at 80°C. This was applied to stainless steel in the same manner as in Example 1, and another sheet of stainless steel was placed on top and cured at 175° C. for 2 hours and then at 240° C. for 4 hours while applying a pressure of 5 kg/cm ² . The measurement results of this adhesive layer are shown in Table 1. Note that polybenzimidazole alone has a heat softening temperature of about 360°C, so it has poor processability, and bonding requires high temperature (360°C or higher) and high pressure. Comparative Example 1 0.1 g of zinc octylate catalyst was added to the prepolymer of 2,2-bis(4-cyanatophenyl)propane and bis(4-maleimidophenyl)methane obtained in Example 2, and stainless steel was prepared in the same manner as above. Glued the steel. The test results are shown in Table 1. Comparative Example 2 200 g of polyvinyl butyral (degree of polymerization 2000) was added to 1000 g of the 2,2-bis(4-cyanatophenyl)propane prepolymer obtained in Example 1,
After dissolving this in methyl ethyl ketone and making it homogeneous, it was applied to stainless steel, heated and dried.
- After setting it to Stage, place stainless steel on top and 5
It was cured at 175°C for 2 hours and at 200°C for 1 hour under a pressure of Kg/cm ² . The measurement results of this adhesive layer are shown in Table 1.

【table】

[Table] See whether it is true or not.

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 the a and b molecules described above. A curable resin composition comprising a polyfunctional maleimide having two or more maleimide groups therein, a prepolymer of the maleimide, or a prepolymer of the maleimide and an amine, and polybenzimidazole as essential components.