JPH0152419B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a resin composition that provides a resin with excellent physical properties such as impact resistance, flexibility, and heat resistance, and has practical properties that can be used in various applications such as paints, varnishes, adhesives, laminates, and molded products. It's expensive. The cyanate ester-based curable resin composition () of the present invention is disclosed in Japanese Patent Publication No. 41-1928 (component a),
46-41112 (composition of a + c), 54-30440 (a
+b composition) Publication No. 52-31279 (a+b+c
compositions) and others, and are used in various applications such as laminated products due to their excellent heat resistance and electrical properties. The present inventor has discovered that compositions of this cyanate ester-based curable resin composition () and acrylonitrile-butadiene rubber, polyisoprene rubber, etc., have improved impact resistance and flexibility, which are disadvantages of cyanate ester-based resin compositions. They discovered that they could provide a well-balanced composition with improved heat resistance and less deterioration in heat resistance, etc., and filed a patent application. after that,
As a result of extensive research, we discovered that by using an acrylonitrile-butadiene-isoprene terpolymer, we could obtain a well-balanced composition with less deterioration in heat resistance than in these earlier applications.
The invention has been completed. That is, the present invention provides a. a. a polyfunctional cyanate ester, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine; In a cyanate ester curable resin composition () consisting of a prepolymer of maleimide and an amine or c. an epoxy resin, an acrylonitrile-butadiene-isoprene terpolymer () is added to
This is a curable resin composition containing less than 50% by weight, particularly in the range of 5 to 40% by weight. The present invention significantly improves the impact resistance and flexibility of cyanate ester-based curable resin compositions (), and also improves the acrylonitrile-butadiene-isoprene terpolymer (). This is a composition with greatly improved heat resistance and electrical properties. The configuration of the present invention will be explained below. First, in the acrylonitrile-butadiene-isoprene terpolymer () of the present invention, the acrylonitrile component is 15 to 55 wt%, and the balance is 45 to 55 wt%.
It is usually synthesized by a random copolymerization method, with 85 wt% of butadiene and isoprene, and the ratio is appropriately selected. The polymerization method usually uses acrylonitrile, butadiene, and isoprene monomers,
It is produced by charging water, a surfactant, and a redox catalyst into a reaction vessel, conducting emulsion polymerization, and then separating and obtaining the polymer by salting out or the like. In the present invention, such terpolymers that are liquid at room temperature (Mooney viscosity 0) to those having a Mooney viscosity of 200 can be used. Next, the cyanate ester-based curable resin composition () of the present invention is a known composition as described above, and is a compound having two or more cyanate groups (-O-C≡N) in the molecule, or The prepolymer alone or a resin composition containing these components as essential components. The multifunctional cyanate ester, which is an essential component, 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)m...( 1) [In the formula, m is an integer of 2 or more and usually 5 or less, and is an aromatic organic group, and the cyanate ester group is bonded to the aromatic ring of the organic group R] It is a compound that 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. 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 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 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(3-chloro-4-aminophenyl)methane, bis(4-aminophenyl)phenylmethane, 3,4-diaminophenyl)-4'-aminophenylmethane, 1,1-bis(4-aminophenyl)-1- phenylethane, etc. Of course, the above-mentioned polyfunctional cyanate ester,
The prepolymers, and the prepolymers with amines, can be used in the form of mixtures. Components that can be combined with the polyfunctional cyanate ester to obtain the cyanate ester resin composition of the present invention include maleimides having two or more maleimide groups, and monofunctional or polyfunctional hydroxy compounds ( esters of meth)acrylic acid,
Epoxy ester of (meth)acrylic acid, (meth)
(meth) such as alkenyl esters of acrylic acid
Esters of acrylic acid and prepolymers thereof; polyallyl compounds such as diallyl phthalate, divinylbenzene, diallylbenzene, trialkenyl isocyanurate, etc. and prepolymers thereof; dicyclopentadiene and prepolymers thereof; epoxy resins; phenolic resins; polyvinyl formal, polyvinyl Polyvinyl acetal resins such as acetal and polyvinyl butyral;
Acrylic resin with OH group or COOH group,
Silicone resins, alkyd resins, etc. may also be used as appropriate. Here, maleimides are represented by the following general formula (2) [Wherein, R is a divalent, usually pentavalent or less aromatic or alicyclic organic group, and X ¹ and X ² are hydrogen, halogen,
or an alkyl group, where m is 2 or more and usually 5 or less. ] 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 polyamine used be an aromatic amine 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. Also,
It is particularly desirable for the polyvalent amines to be primary amines in terms of reactivity, but secondary amines can also be used. Suitable amines include amines that can be used in the prepolymer with the cyanate ester described above;
These include 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 maleimide can also be used in the form of a prepolymer instead of in the form of a so-called monomer. The curable resin composition of the present invention using the above-described components can be produced by various methods such as simply mixing, pre-reacting, and mixing pre-reacted materials and unreacted materials and further pre-reacting. It is manufactured by The resin composition of the present invention obtained as described above can vary from a solvent-free liquid at room temperature to a solid depending on the components used and the ratio of amounts used. The usage ratio of the acrylonitrile-butadiene-isoprene terpolymer () is as described above. Heat resistance has both aspects of improving electrical characteristics, and from this point of view, there are no particular limitations. However, the main purpose of the present invention is to improve component (), and from this point of view, in the present invention, component () usually accounts for less than 50% by weight of the composition, preferably 5 to 5% by weight. It is used in an amount of 40% by weight, particularly in the range of 5 to 30% by weight. Furthermore, 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 catalysts include 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-cyanoethyl-2ethyl-4-methyl imidazoles exemplified by imidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-guanaminoethyl-2-methylimidazole, as well as 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-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, N,N,N',N'-tetramethylbutanediamine, N-methylpiperidine, etc. Tertiary amines; Phenols such as phenol, cresol, xylenol, resorcin, catechol, phloroglucin; lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, Organic metal salts such as cobalt naphthenate and iron acetylacetonate; inorganic metal salts such as SnCl ₄ , ZnCl ₂ , AlCl ₃ ; benzoyl peroxide, lauroyl peroxide, caprylyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, jeter Peroxides such as sharybutyl sieperphthalate; maleic anhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride,
trimellitic anhydride, hexahydrophthalic anhydride,
Acid anhydrides such as hexahydro trimellitic anhydride and hexahydropyromellitic anhydride are mentioned. The amount of catalyst added is sufficient within the range of catalyst amounts in a general sense, for example 10
It may be used in an amount of % by weight or less. Although the crosslinking and reticulation reaction mechanism of the curable resin composition of the present invention described in detail above has not been proven, the reaction of the cyanato groups of multifunctional cyanate esters and the multifunctional The reaction of the maleimide group of the maleimides is estimated as follows. (1) Reaction of polyfunctional cyanate ester. (2) Reaction of polyfunctional maleimide. Furthermore, the reaction mechanisms of epoxy groups in epoxy resins with hydroxyl groups, carboxyl groups, amino groups, acid anhydride groups, etc. are known. From the above, in the composition of the present invention, in addition to the reactions that are presumed to occur in a composition comprising a known polyfunctional cyanate ester, a polyfunctional maleimide, and an epoxy resin, It is assumed that there is a possibility that the reaction between the nitrile groups and unsaturated double bonds of the newly added acrylonitrile-butadiene-isoprene terpolymer () and the cyanato groups and maleimide groups may occur. . However, it is not conceivable that all of the components react in proportion to the amount of functional groups as assumed above and form the cured product of the present invention. That is, since different functional groups have different reaction temperatures, rates, selectivities, types of catalysts, etc., the reactions of the functional groups in each of the above-mentioned components in the present invention mainly depend on the different components. It is thought that this contributes to the improvement of the affinity (compatibility) between the particles and realizes a finer dispersion state. 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, 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 1 to 500 kg/cm ² . 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 invention; fibrous reinforcement; fillers;
Various known additives such as dyes and pigments; thickeners; lubricants; and flame retardants are included, and may be used in appropriate combinations as desired. The curable resin composition of the present invention described in detail above has the advantage that it has a relatively fast curing speed and can be cured under relatively mild conditions.
Excellent workability and productivity can be obtained when used in various applications, and the cured resin obtained by curing this composition has excellent impact resistance, flexibility, adhesion or adhesion, and heat resistance. It has a desirable combination of various properties such as electrical properties and chemical resistance.
It also has excellent moisture resistance. Thus, the composition of the present invention can be used in various paints, electrically insulating varnishes, adhesives,
It is useful as a laminated material suitable for furniture, building materials, exterior materials, electrical insulation materials, etc., or as various molding resins. The present invention will be explained in more detail below using Examples and Comparative Examples. Example 1 900 g of 2,2-bis(4-cyanatophenyl)propane and 100 g of bis(4-maleimidophenyl)methane were reacted at 150°C for 150 minutes, and this was mixed with acrylonitrile-butadiene-isoprene ternary containing 34 wt% of acrylonitrile component. 200 g of a copolymer (trade name Nipol DN 1201; manufactured by Nippon Zeon Co., Ltd.) was added and dissolved in methyl ethyl ketone. In this solution, 0.4 g of zinc octylate and 0.2 g of triethylenediamine were uniformly dissolved and mixed as a catalyst, and a glass woven fabric was also impregnated with this solution and dried to obtain a B-stage prepreg. Six sheets of this prepreg were stacked, electrolytic copper foil with a thickness of 35 μm was layered on both sides, and lamination molding was performed at 175° C. and 40 kg/cm ² for 120 minutes to obtain a double-sided copper-clad laminate. This laminate has a copper foil peel strength of 1.90 kg/cm, no abnormality in solder heat resistance (after floating at 350°C for 3 minutes), and a glass transition temperature of 220°C. 1-trichlorethylene, methyl ethyl ketone, 10% HCl, 10%
No abnormalities were observed even after immersion in NaCl for 10 minutes. Example 2 700g of 1,4-dicyanatobenzene and bis(4
−maleimidophenyl) ether and 300 g at 150°C.
200 g of glycidyl methacrylate and 200 g of the same acrylonitrile-butadiene-isoprene terpolymer as in Example 1 were added and mixed, and methyl ethyl ketone and N,
Heat and heat the mixed solvent with N-dimethylformamide.
The mixture was uniformly dissolved and mixed with stirring, and 0.5 g of zinc octylate, 1.0 g of N,N-dimethylbenzylamine, and 0.2 g of benzoyl peroxide were uniformly dissolved and mixed in this solution as catalysts. This solution was applied to a length of 10 mm on the longitudinal ends of multiple stainless steel plates with a length of 125 mm, a width of 25 mm, and a thickness of 1 mm. After heating and drying to form a B-stage, the coated parts were overlapped and heated to 120 °C at 170 °C. It was further heated and cured at 260°C for 60 minutes. Table 1 shows the test results for the adhesive portion of this stainless steel plate. Comparative Example 1 In Example 2, in addition to the acrylonitrile-butadiene-isoprene terpolymer, acrylonitrile-butadiene copolymer (trade name, Nipol
1042; manufactured by Memoto Zeon Co., Ltd.) A resin solution was prepared and bonding was performed in the same manner except that 200 g of the resin solution was used. The results are shown in Table 1.

[Table] Example 3 A resin solution obtained in exactly the same manner as in Example 2 was continuously impregnated into a fully aromatic polyamide fiber cloth (trade name: Nomex; manufactured by Dupont), and this was continuously impregnated at 140°C. The seeds were dried and hardened to obtain long seeds.
The performance of this sheet is shown in Table 2. Example 4 After preliminarily reacting 700 g of 2,2-bis(4-cyanatophenyl)propane at 150°C for 150 minutes, this was dissolved in methyl ethyl ketone to produce the same acrylonitrile-butadiene-isoprene terpolymer as in Example 1. After adding 300 g of Nipol DN 1201 (trade name: Nipol DN 1201, manufactured by Nippon Zeon Co., Ltd.) and uniformly dissolving and mixing, 0.1 g of zinc octylate and 1 g of dicumyl peroxide were added as catalysts to form a varnish. This varnish is continuously impregnated into a glass woven fabric and dried to form a B-stage prepreg, and then heated to 140°C.
A long sheet was obtained by curing. The performance of this sheet is shown in Table 2. Comparative Example 2 In Example 3, a long sheet was obtained in exactly the same manner as in Comparative Example 1, except that the resin composition solution used was obtained in the same manner as in Comparative Example 1. The performance of this sheet is shown in Table 2.

【table】

Claims (1)

[Claims] 1 a. 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, the maleimide prepolymer, or A prepolymer of the maleimide and an amine or
c. In a cyanate ester-based curable resin composition () consisting of an epoxy resin, acrylonitrile-butadiene-isoprene terpolymer () is blended in an amount such that the component () is less than 50% by weight of the composition. A curable resin composition made of 2 Based on the sum of the cyanate ester-based curable resin composition () and the terpolymer () in the curable resin composition, the component () is 5 to 40%
The curable resin composition according to claim 1, which is obtained by blending in a range of % by weight.