JPH0160064B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel curable resin composition that provides a cured product with excellent electrical properties, adhesion, adhesion, heat resistance, mechanical properties, chemical resistance, etc. It is useful for adhesives, paints, and various other uses. Conventionally, cyanate ester-based curable resin compositions containing cyanate esters as an essential component and appropriately modified with maleimide, epoxy resins, etc. have been disclosed in Japanese Patent Publication No. 1928-1928 (component a), No. 46 −
41112 (composition of a+c), No. 54-30440 (composition of a+b), No. 52-31279 (composition of a+b+c), and others. Although it had excellent chemical properties, it was only a step up in terms of adhesion and adhesion. In addition, a modified butadiene-acrylonitrile copolymer with an acryloyl group and/or methacryloyl group introduced into the side chain and/or terminal,
Curing shrinkage during molding was large, and there were also problems with heat resistance. As a result of various researches aimed at improving the insufficiencies of cyanate ester resin compositions, the present invention has been developed using modified butadiene in which acryloyl groups and/or methacryloyl groups have been introduced into the side chains and/or terminals.
It was discovered that the cured product obtained by using an acrylonitrile copolymer has excellent mechanical strength, chemical resistance, and electrical properties, as well as excellent adhesion and adhesion, and based on this, the product was completed. This is what I did. 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, or a. and b. a polyfunctional maleimide, the maleimide prepolymer, or the maleimide In a cyanate ester-based curable resin composition consisting of a prepolymer of and an amine or c. an epoxy resin,
A curable product made by blending a modified butadiene-acrylonitrile copolymer with an acryloyl group or methacryloyl group introduced into the side chain or terminal in an amount that makes up less than 50% by weight of the composition, particularly in the range of 10 to 45% by weight. It is a resin composition that has greatly improved flexibility and adhesion compared to cyanate ester resin compositions, and has an acryloyl group and/or methacryloyl group introduced into the side chain and/or terminal. Compared to modified butadiene-acrylonitrile copolymers, this composition has greatly improved heat resistance, electrical properties, and chemical resistance. The configuration of the present invention will be explained below. First, the cyanate ester-based curable resin composition of the present invention is a known curable resin composition as described above, and has a cyanate group (-O-C≡
A compound having two or more N) or a prepolymer thereof alone, or a resin composition containing these components as essential components. The polyfunctional 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) [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-dicyana-tonaphthalene, 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-cyana-
tophenyl)propane, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, tris(4-cyanatophenyl)phosphite, tris(4-cyanatophenyl) phenyl) phosphate, and cyanic acid esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, Tokuko Sho 41-1928,
Special Publication 18468, Special Publication 4791, Special Publication 4791, Special Publication 1977-
Cyanic acid esters described in Japanese Patent Publication No. 11712, Japanese Patent Publication No. 46-41112, Japanese Patent Publication No. 47-26853, and Japanese Patent Publication No. 51-63149 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 paraphenylenediamine, meta or paraxylylenediamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylenediamine,
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 prepolymers with amines, can be used in 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. 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 amines that can be used in the prepolymer with the cyanate ester described above, melamines having an s-triazine ring, and polyamines obtained by reacting aniline with formalin and linking benzene rings with methylene bonds. etc. 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. Next, the modified butadiene-acrylonitrile copolymer having an acryloyl group and/or methacryloyl group introduced into the side chain and/or terminal of the present invention is one in which the copolymerization ratio of butadiene/acrylonitrile is 90/10 to 60/40. is preferred, and a butadiene-acrylonitrile copolymer having a number average molecular weight of 500 to 6,000, preferably 700 to 4,000 and containing a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group, etc. at the molecular terminal and/or side chain, and the following general formula. [In the formula, R ³ is a hydrogen atom or a methyl group, Y is a halogen, a hydroxyl group, or an organic compound containing a functional group selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an isocyanate group, and an acryloyl group Alternatively, the methacryloyl group is one that is bonded to each other via an ether bond, ester bond, urea bond or amide bond,
l is an integer from 1 to 3. ] Manufactured by reacting with. The production method may be any known method. For example, a compound represented by the formula (3) with a hydroxyl group, a carboxyl group, or an epoxy group at the end, and a compound having a hydroxyl group, carboxyl group, epoxy group, etc. at the molecular end and/or side chain. A method of reacting a hydroxyl group-containing butadiene-acrylonitrile copolymer with a (meth)acrylic acid halide or (meth)acrylic acid epoxy ester (e.g., glycidyl acrylate, glycidyl methacrylate) in a stoichiometric manner. , when using a halide, a tertiary compound such as dimethylaniline, pyridine, etc.
A method of reacting a butadiene-acrylonitrile copolymer containing a carboxyl group with an acrylate or methacrylate containing a hydroxyl group or an epoxy group; A method of reacting a butadiene-acrylonitrile copolymer containing an epoxy group with a butadiene-acrylonitrile copolymer containing a hydroxyl group. A method of reacting an acrylate or methacrylate; a method of reacting an isocyanate group-containing butadiene-acrylonitrile copolymer with a hydroxyl group-containing acrylate or methacrylate, and the like. Examples of the polyisocyanate compound that can be used in the above reaction include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, etc., and examples of the polyhydric alcohol used to form the hydroxyl group-containing (meth)acrylate include ethylene glycol. , propylene glycol, 1,4-butadiol,
1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, neopentyl glycol, xylylene glycol and other divalent to tetravalent aliphatic, alicyclic or aromatic alcohols having 2 to 15 carbon atoms, or Examples include one or a combination of two or more ether-type polyhydric alcohols having about 4 to 20 carbon atoms, such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol. Other examples include diethanolamine and adducts of active hydrogen-containing compounds such as polyhydric alcohols and amines exemplified above and alkylene oxides such as ethylene oxide. Examples of polyepoxy compounds that can be used to form the epoxy group-containing (meth)acrylate include divalent to hexavalent polyepoxy compounds such as glycerin diglycidyl ether, phthalic acid diglycidyl ether, and bisphenol A-type diglycidyl ether. Examples include epoxy compounds having 1 to 20 atoms. As the compound used in formula (3), (meth)acrylate is most suitable, but amide group-containing (meth)acrylate can also be advantageously used.
These may be used alone or in combination. The usage ratio of the resin components of the above-mentioned curable resin composition of the present invention is not particularly limited, but when adhesiveness and adhesion are important as a heat-resistant resin, the curable resin composition A modified butadiene-acrylonitrile copolymer containing 90 to 50 wt% of a component mainly composed of cyanate esters and/or maleimides, which are preferred components of the It is best to use 10 to 50 wt% of the polymer, more preferably 20 to 45 wt%, and conversely, by using the former component in the range of 10 to 50 wt%, the heat resistance of the latter can be improved. can. 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-penzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1
-cyanoethyl-2-methylimidazole, 1-
Imidazoles exemplified by cyanoethyl-2ethyl-4methylimidazole, 1-cyanoethyl-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole, and trimellites of these imidazoles Acid adducts, etc.
N,N-dimethylbenzenamine, 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,
Tertiary amines such as N-methylpiperidine; phenols such as phenol, cresol, xylenol, resorcinol, phloroglucin; lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate,
Organometallic salts such as iron acetylacetonate; SnCl ₄ ,
Inorganic metal salts such as ZnCl ₂ and AlCl ₂ ; peroxides such as benzoyl peroxide, lauroyl peroxide, caprylyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, tertiary butyl diperphthalate, and even azobisnitrile Examples include: In addition, those generally known as curing agents or catalysts for epoxy resins, such as acid anhydrides such as pyromellitic anhydride and phthalic anhydride, can also be used in combination. Moreover, those used as cross-curing agents for rubber can also be used in combination. 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 known natural or synthetic resins for imparting new properties to the composition of the present invention; fibrous reinforcing materials; fillers; dyes and pigments; thickeners; lubricants; flame retardants, etc. Various additives are included and used in appropriate combinations as desired. The temperature for curing the 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 is usually 90 to 300°C, preferably 100°C.
It is sufficient if the temperature is selected within the range of ~270°C. When used for manufacturing 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 200 kg/cm ³ .
Moreover, ultraviolet rays or the like can be used for curing. The cured resin obtained by curing the 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, as well as chemical resistance. It is also excellent. Although the crosslinking and network formation 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 polyfunctional cyanate esters and the polyfunctional The reaction of the maleimide group of maleimides is estimated as follows. (1) Reaction of polyfunctional cyanate ester. (2) Reaction of polyfunctional maleimides. Also, regarding the epoxy group of epoxy resin,
The reaction mechanism with hydroxyl groups, carboxyl groups, amino groups, acid anhydride groups, etc. is 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 presumed that there is a possibility that a reaction between the (meth)acrylate group of the butadiene-acrylonitrile copolymer having a (meth)acrylate group newly added as a component and the cyanato group or maleimide group may occur. However, it is not conceivable that all the components react in proportion to the amount of functional groups as estimated above to produce 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. This will be explained in detail below using Examples and Comparative Examples. Note that parts represent parts by weight. Example 1 700 parts of 2,2-bis(4-cyanatophenyl)propane and 300 parts of bis(4-maleimidophenyl)methane were pre-reacted at 150°C for 120 minutes.
850 parts and 150 parts of acryloyl group-containing butadiene-acrylonitrile copolymer (trade name: VTBNX, manufactured by Ube Industries, Ltd.) were melt-mixed and placed in a mold.
Under pressure of 20Kg/ ^cm3 , 175℃, 120 minutes, then 260℃
The mixture was cured by heating at ℃ for 60 minutes to obtain a cast plate with a thickness of 2 mm. This was cut into 50 x 50 ^mm2 , dried at 110°C for 60 minutes, allowed to cool in a desiccator, weighed, heated in an open air at 300°C, and the loss on heating was measured. The results are shown in Figure 1. Comparative Examples 1-2 2,2-bis(4-
To 850 parts of a preliminary reaction mixture of cyanatophenyl)propane and bis(4-maleimidophenyl)methane,
Modified polybutadiene (trade name: BF-1000,
(manufactured by Nippon Soda Co., Ltd.) 150 parts (Comparative Example 1), modified with hydantoin type epoxy resin (trade name;
CY350, manufactured by Ciba Geigy Corporation) 150 parts (Comparative Example 2)
were added, and cast-cured in the same manner as in Example 1. This was similarly heated in an open air at 300°C, and the loss on heating was measured. The results are shown in Figure 1. Example 2 Acryloyl of Example 1 was added to 750 parts of a resin composition prepared by pre-reacting 900 parts of 2,2-bis(4-cyanatophenyl)propane and 100 parts of bis(4-maleimidophenyl)methane at 150°C for 60 minutes. 250 parts of group-containing butadiene-acrylonitrile copolymer and 120 parts of
After pre-reacting for 30 minutes while mixing at ℃, it was applied to a mild steel plate, pre-dried for 5 minutes at 130℃, adhered to the adherend according to JIS K6850, and pre-dried for 5 minutes at 130℃. , at 175℃ under a pressure of 0.9Kg/ ^cm2
It was heated and cured for 120 minutes. This tensile test piece
The specimen was left open at 260°C and the deterioration of tensile shear strength was measured. The results are shown in Table 1. Comparative Example 3 In Example 2, acryloyl group-containing butadiene-acrylonitrile copolymer (trade name;
Hydantoin-type epoxy resin-modified butadiene (CY-350) instead of VTBNX (manufactured by Ube Industries, Ltd.)
Glue in the same manner except using 250 parts and heat at 260℃.
It was placed in the open and the deterioration of tensile shear strength was measured. The results are shown in Table 1.

[Table] Example 3 870 parts of 1,4-dicyanatobenzene was added with bis(4
- Add 130 parts of maleimidophenyl) ether to 150 parts.
200 parts of an epoxy resin (trade name: Araldite ECN-1273, manufactured by Ciba Geigy Corporation) was added to the pre-reacted product for 120 minutes at ℃, and further 300 parts of the acryloyl group-containing butadiene-acrylonitrile copolymer used in Example 1. and dissolved them in methyl ethyl ketone. Furthermore, 0.4 parts of zinc octylate, 0.2 parts of triethylenediamine, and 0.5 parts of dicumyl peroxide were added as a catalyst, and the mixture was stirred and mixed uniformly.The mixture was then impregnated into a glass woven fabric and dried to produce a B-stage prepreg. Layer 8 sheets of this prepreg and layer 35μ electrolytic copper foil on both sides.
175℃, 40Kg/ ^cm2 for 120 minutes, then 220℃, 50 minutes
Press molding was carried out at Kg/cm ² for 120 minutes. The test results for this laminate are shown in Table 2.

【table】

[Table] Example 4 After preliminarily reacting 700 parts of 2,2-bis(4-cyanatophenyl)propane at 160°C for 180 minutes, 300 parts of the same terminal acrylic-containing butadiene-acrylonitrile copolymer as in Example 1 was added. and 120
Pre-reaction was carried out for 10 minutes with mixing at °C. To this, 0.1 part of zinc octylate and 0.1 part of di-t-butyl peroxide were added as catalysts and mixed uniformly. A deterioration test was carried out by bonding mild steel plates in the same manner as in Example 2, except that this mixture was used. The initial tensile shear strength was 250 Kg/cm ² , and after 50 hours at 260°C, the tensile shear strength was 133
It was Kg/ ^cm2 .

[Brief explanation of drawings]

Figure 1 shows the loss of weight on heating of the test piece after it was heated in an open environment at 300°C for a predetermined period of time.

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, 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, a modified butadiene-acrylonitrile copolymer having an acryloyl group or a methacryloyl group introduced into the side chain or end, the component being less than 50% by weight of the composition. A curable resin composition containing the following amounts. 2. A patent claim obtained by blending the components in a range of 10 to 45% by weight based on the sum of the cyanate ester-based curable resin composition and the modified butadiene-acrylonitrile copolymer in the curable resin composition. The curable resin composition according to item 1.