JPS642611B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel curable resin composition containing polyfunctional cyanate esters, polyfunctional maleimides, and trialkenyl isocyanurates, which exhibits properties such as surface gloss, heat resistance, chemical resistance, adhesion, and moisture resistance. It gives a good cured product. Conventionally, single cured products of trialkenyl isocyanurate were brittle, and their excellent heat resistance and
Despite its chemical resistance, it is difficult to use, and is used as a modifier for vinyl yarn resins such as methyl methacrylate, styrene, and unsaturated polyester. 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 high moisture resistance, and when used for casting, etc., it was insufficient in terms of surface gloss. As a result of repeated research to improve the above-mentioned drawbacks, it was discovered that by using polyfunctional cyanate esters, polyfunctional maleimides, and trialkenyl isocyanurates in combination, a cured product with extremely excellent physical properties can be obtained. This is what we discovered and completed the present invention. That is, the present invention provides 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, a prepolymer of the maleimide, or a prepolymer of the maleimide and an amine. and c A curable resin composition comprising trialkenyl isocyanurate or the trialkenyl isocyanurate prepolymer as an essential component. The polyfunctional cyanate ester which is component a of the composition of the present invention 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) [m in the formula is an integer of 2 or more and usually 5 or less, and 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-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. These other Tokko 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 Publication No. 51-63149 can also be used. It can also be 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 a prepolymer. These prepolymers are formed by trimerization of cyanide groups in the cyanate ester.
Generally has a sym-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, 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. The polyfunctional maleimide as component b of the composition of the present invention is a compound having two or more N-maleimide groups represented by the following formula in the molecule, and the polyfunctional maleimide preferably used in the present invention is General formula below [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 Maleimides represented by the above formula are prepared by reacting maleic anhydride with divalent or trivalent amines to prepare maleamic acid,
It can then be produced by a method known per se in which maleamic acid is cyclodehydrated. The polyvalent amines used are preferably 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 trialkenyl isocyanurate as component c of the present invention has the general formula

[R in the formula is an alkenyl group having 2 to 4 carbon atoms]

It is a compound represented by Preferred examples of -R (alkenyl group) include vinyl, allyl, crotyl, metaallyl, chlorpropenyl, butadienyl, and the like. Also preferably used are those prepared by prepolymerizing these trialkenyl inucyanurates using organic peroxides, ultraviolet rays, heat, or the like. 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 usage ratio of each component in the curable resin composition of the present invention, which essentially includes the above a, b, and c, can be varied depending on the intended use. The composition may be prepared by any conventionally known method, such as simply mixing, pre-reacting after mixing, pre-reacting and mixing, or pre-reacting. . 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-2methylimidazole, 1-propyl-2-methylimidazole, 1
-cyanoethyl-2-methylimidazole, 1-
Imidazoles exemplified by cyanoethyl-2ethyl-4methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole, and further, these imidazoles such as trimellitic acid adducts; 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, phloroglucin, etc. Phenols; lead naphthenate, lead stearate, zinc naphthenate,
Organometallic compounds such as zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; inorganic metal compounds such as SnCl ₄ , ZnCl ₂ , AlCl ₃ ; benzoyl peroxide, lauroyl peroxide, Examples include peroxides such as caprylyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and tertiary butyl perphthalate. In addition, what is generally known as a curing agent or catalyst for epoxy resins can also be used in combination. 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 5% by weight or less based on the total composition. The 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 resins for imparting new properties to the composition of the present invention, such as epoxy resins; fibrous reinforcing materials, fillers; dyes and pigments; thickeners; lubricants; flame retardants, and various other known additions. These agents 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 may be generally selected within the range of 100 to 250°C. When used in the production of molded products, laminated products, adhesive structures, etc., it is preferable to apply pressure during heat curing;
Appropriately selected within the range of 10 to 500Kg/ ^cm2 . The cured resin obtained by curing the curable resin composition of the present invention described in detail above has a desirable combination of various properties such as adhesiveness, heat resistance, and electrical properties. It has excellent mechanical properties, especially impact resistance, as well as chemical resistance and moisture resistance. Thus, the composition of the present invention can be used for various purposes such as rust prevention, fire prevention, disaster prevention, and other various paints; electrical insulating varnishes, adhesives; laminated materials suitable for use in furniture, building materials, exterior materials, electrical insulation materials, etc.; Useful as a molding resin. The present invention will be explained in more detail below using Examples and Comparative Examples. Parts in Examples, Comparative Examples, and Reference Examples are based on weight. Examples 1 to 3 and Comparative Example 1 Compositions of the present invention and comparative compositions were prepared at the blending ratios shown in Table 1, and placed in a mold.
It was cured under the curing conditions shown in Table 1 to form a casting plate with a thickness of 4 mm and a diameter of 10 cm. In the case of Comparative Example 1, cracks often occurred when the casting plate was released from the mold. The test results for these casting plates are shown in Table 2. In addition, the composition components in Table 1 were prepared by the following method. A-1: 40 parts of 1,4-dicyanatobenzene, 48 parts of bis(4-maleimidophenyl)methane, 4-
maleimidophenyl-3′,4′-dimaleimidophenylmethane and 4-maleimidophenyl-2′,
Mixture with 4′-dimaleimidophenylmethane 12
Prepolymer A-2: 2,2-bis(4-cyanatophenyl) obtained by reacting 160°C for 1 hour
Prepolymer trialkenyl isocyanurate prepolymer prepared by mixing propane and bis(4-maleimidophenyl)methane in a ratio of 3:1 and reacting at 160°C for 110 minutes:
100 parts of triallylisocyanurate was dissolved in a mixed solution of 180 parts of carbon tetrachloride and 130 parts of benzene, and 0.3 parts of benzoyl peroxide was added to the solution, and after pre-reacting at 60°C for 50 minutes under a carbon dioxide gas flow,
The white precipitate obtained by rapidly cooling to 0°C and adding cold methanol was divided into three parts, washed with methanol, and then washed at 30°C for 2 mm.
Vacuum dried with Hg for 10 hours. (Yield: 94%) Epoxy resin: Novolac type epoxy resin (product name: ECN-1280, manufactured by Ciba Geigy)

【table】

[Table] Example 4 To 100 g of triallylisocyanurate prepolymer obtained in the same manner as in Examples 1 to 3, 900 g of 2,2-bis(4-cyanatophenyl)propane,
100g of bis(4-maleimidophenyl)methane
After adding the prepolymer obtained by reacting at 160°C for 2 hours and 200 g of novolac type epoxy resin (ECN-1280 manufactured by Ciba Geigy) and dissolving it in methyl ethyl ketone, zinc octylate was added as a catalyst.
B
−stage prepreg was manufactured. Multiple sheets of this prepreg are stacked on top of each other to create a thickness on both sides.
Insert 35μ copper foil and heat at 180℃ and pressure 50Kg/ ^cm2 .
Press molding was performed for 150 minutes. Table 3 shows the properties of the copper-clad laminate obtained. Comparative Example 2 A copper-clad laminate was obtained in the same manner as in Example 3 except that the triallylisocyanurate prepolymer was not used. The properties of this laminate were measured. 3rd result
Shown in the table.

【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, b. A polyfunctional maleimide, a prepolymer of the maleimide, or a prepolymer of the maleimide and an amine. A curable resin composition comprising a prepolymer and c trialkenyl isocyanurate or the trialkenyl isocyanurate prepolymer as essential components.