JPH0352770B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel thermosetting resin composition,
For details, see A. A reaction product of an epoxy compound having two or more epoxy groups in the molecule and a polyhydric phenol containing two or more phenolic hydroxyl groups in the molecule, B. A reaction product with two or more cyanato groups in the molecule. a polyfunctional cyanate ester containing, the cyanate ester prepolymer, or a prepolymer of the cyanate ester and an amine, and C. a polyfunctional maleimide containing two or more N-maleimide groups in the molecule;
This is a thermosetting resin composition containing the maleimide prepolymer or the prepolymer of maleimide and amine as an essential component. Conventionally, a curable resin composition prepared by mixing components B and C of the present invention with an epoxy resin was disclosed in Japanese Patent Publication No. 52-
It is known as Publication No. 31279, and it is possible to obtain a cured product with excellent heat resistance and various other properties. However, this curable resin composition was insufficient in terms of workability, processability, and especially solvent solubility. As a result of extensive research in order to eliminate the above drawbacks, the present inventors used a reaction product of an epoxy resin and a polyhydric phenol containing two or more phenolic hydroxyl groups in the molecule as an epoxy resin, and By adding a cyanate ester component and a maleimide component and pre-reacting if desired, it has excellent processability and workability, and the cured product has excellent heat resistance, electrical properties,
The inventors succeeded in obtaining a thermosetting resin composition with excellent mechanical properties, moisture resistance, etc., leading to the present invention. The present invention will be explained below. The epoxy compound having two or more epoxy groups in the molecule of component A of the present invention may be any known epoxy resin, but typical examples include glycidyl ether type, glycidyl ester type, glycidyl amine type, chain type, etc. Examples include aliphatic epoxide type and alicyclic epoxide type. In particular, glycidyl ether type epoxy resins include glycidyl ethers of bisphenol A (bisphenol A type), polyhalogenated bisphenol A
Typical examples include glycidyl ether of phenol novolak type, which is easily available and exhibits performance suitable for the purpose of the present invention. In addition, the combined use of monoepoxy compounds such as phenyl glycidyl ether, butyl glycidyl ether, etc.
This is preferable since it has the effect of improving workability. As polyhydric phenols containing two or more phenolic hydroxyl groups in the molecule to be reacted with the above epoxy compounds, compounds represented by the following formula are (In the formula, R ₁ and R ₂ are hydrocarbon groups having 1 to 6 carbon atoms,
-, -O-, -S-, -SO ₂ -, or O=P(O), X is a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and p, q, r are 0 or integers of 1 to 4; s, t, and u are integers of 0 to 3; s, t,
The sum of u is 2 or more, l is an integer of 1 to 4, m is 0 or 1, and n is an integer of 0 to 4. ) is preferred. Such compounds include 4,
4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, tri(4-hydroxyphenyl)methane, 1,1,1-tri(4-hydroxyphenyl)ethane, 2,2-bis(4 -hydroxyphenyl)propane, 2,2-bis(4-
Hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, bis(4-hydroxyphenyl)thioether, bis(4-hydroxyphenyl) Ether, bis(4-hydroxyphenyl) sulfone, tris(4-hydroxyphenyl) phosphite, tris(4-hydroxyphenyl) phosphate, phloroglycine, 4,6
-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptene-2,4,6-dimethyl-
2,4,6-tri(4-hydroxyphenyl)heptane, 1,3,5-tri(4-hydroxyphenyl)benzene; Alkyl phenol novolak resins such as phenol novolak resins and cresol novolak resins; low Examples include molecular weight polyP-vinylphenol and phenol-modified xylene resin. Component A of the present invention is prepared by reacting the above epoxy compound with a polyhydric phenol containing two or more phenolic hydroxyl groups in the molecule. The equivalent ratio used is epoxy group: hydroxyl group = 1:0.05 to 2, preferably 1:0.1 to 1.No solvent or dissolved in a solvent such as methyl ethyl ketone, methyl cellosolve, methyl isobutyl ketone, dioxane, etc., and usually, It is carried out at 20 to 300°C, preferably 80 to 250°C, for a period of 1 minute to 20 hours. Suitable polyfunctional cyanate esters as component B of the curable resin composition of the present invention have the following general formula (1) R(OCN)m...(1) (m in the formula is 2 or more, usually is an integer less than or equal to 5,
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. Furthermore, the polyfunctional cyanate esters described above can also be used in the form of prepolymers with amines. Preferred amines 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(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- Specific examples include diaminophenyl-4-aminophenylmethane, 1,1-bis(4-aminophenyl)-1-phenylethane, and benzoguanamine. Of course, the above-mentioned polyfunctional cyanate ester,
The prepolymers, and the prepolymers with amines, can be used in the form of mixtures. A preferred polyfunctional maleimide as component C of the present invention is represented by the following general formula (2). (In the formula, R is an aromatic or alicyclic organic group having a valence of 2 or more and usually 5 or less; X, X 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 the amines exemplified as those used for preparing the preliminary reactant in component B, melamines having a sym-triazine ring, and melamines having a benzene ring by reacting aniline with formalin. These include polyamines linked with methylene bonds. In the present invention, the above-mentioned transferable maleimide can also be used in the form of a prepolymer, or a prepolymer with the above-mentioned amine, instead of being used in the form of a so-called monomer. The curable resin composition of the present invention is prepared by mixing or preliminarily reacting the above A, B, and C. The preparation methods include simply mixing; mixing as a solution of a solvent such as methyl ethyl ketone, methyl cellosolve, and methyl isobutyl ketone; pre-reacting components B and C, and mixing component A with this; A and C Any method may be used, such as a method of preliminarily reacting the components and mixing component B; or a method of further preliminarily reacting after mixing, and the usage ratio of each component is not particularly limited. Although the curable resin composition of the present invention itself is cured by heating, a thermosetting catalyst or curing agent is usually used to accelerate curing. These 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, imidazoles exemplified by 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and 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, resilcin, catechol, phloroglycin; 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 and curing catalysts for epoxy resins. 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 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 resins such as rosin, silica, copal, oil-modified rosin, esters of (meth)acrylic acid of monofunctional or polyfunctional hydroxy compounds, and (meth)acrylic acid. Esters of (meth)acrylic acid, such as epoxy esters of acids, alkenyl esters of (meth)acrylic acid, and prepolymers thereof; diallyl phthalate, divinylbenzene, diallylbenzene,
Polyallyl compounds such as trialkenyl isocyanurate and their prepolymers; dicyclopentadiene and their prepolymers; phenolic resins;
polyvinyl formal, polyvinyl acetal,
Polyvinyl acetal resin such as polyvinyl butyral; Phenoxy resin; OH group or COOH
Acrylic resins with groups; silicone resins; alkyd resins; petroleum resins; low molecular weight liquid to high molecular weight such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber, natural rubber, etc. elastic rubber; polyethylene,
Polypropylene, polybutene, poly-4-methylpentene-1, polystyrene, polyvinyl chloride,
Polyvinylphenol, AS resin, ABS resin,
Vinyl compound polymers such as MBS resin, poly-4-fluorinated ethylene, fluorinated ethylene-propylene copolymer, 4-fluorinated ethylene-6-fluorinated ethylene copolymer, vinylidene fluoride; polycarbonate, polyphenylene fluoride, etc. High molecular weight polymers such as nylene ether, polysulfone, polyester, nylon, polyimide, polyadiimide, polyesterimide, polyphenylene sulfide, and low molecular weight prepolymers or oligomers thereof are exemplified and used as appropriate. In addition, as reinforcing agents and fillers, various glass cloths such as cloth, roving cloth, chopped pine, surfacing pine, quartz glass cloth, carbon fiber cloth, other inorganic fibers such as asbestos, rock wool, slag wool, and wholly aromatic fibers can be used. Nylon cloth, blended cloth of glass fiber and fully aromatic nylon fiber, synthetic fiber cloth such as acrylic, vinylon, polyester, nylon, polyimide, cotton cloth, linen cloth, felt, kraft paper, cotton paper, paper-glass blended paper, semi-woven fabric Carbon fiber cloth, etc., and the fiber chips that make up these cloths and papers; glass powder, glass bulbs, silica, alumina, silica alumina, aluminum hydroxide, asbestos, calcium carbonate, calcium silicate, wollastonite, carbon black. , kaolin clay, calcined kaolin, mica, talc, aluminum, copper, iron, iron oxide, synthetic mica, natural mica,
Examples include semiconductors, boron nitride, other ceramics, and various other materials. In addition to these, there are various additives known as resin additives, such as dyes, pigments, thickeners, lubricants, coupling agents, and flame retardants.
They may be used in appropriate combinations as desired. The curing temperature of the curable resin composition of the present invention described in detail above varies depending on the presence or absence of a curing agent and catalyst, the types of composition components, etc., but is usually 100 to 300°C.
It should be selected within the range. Also, molded products, laminated products,
It is preferable to apply pressure when constructing adhesive structures, etc., and generally speaking, the pressure is appropriately selected in the range of 0.1 to 500 kg/cm ² . The thermosetting resin composition of the present invention can be applied to paint powders, paints, cast products, molded products, laminates, tapes, sheets,
Used for various purposes such as film. 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 Novolac type epoxy resin (product name: ECN-
1273, epoxy equivalent 225, manufactured by Ciba Geigy Co., Ltd.)
90 parts (0.4 equivalents) and 10 parts (0.1 equivalents) of phenol novolak resin (average molecular weight 571, 5.5 hydroxyl groups).
A prepolymer was obtained by reacting for 80 minutes under melting conditions at 200°C (hereinafter referred to as (a)). To this (a), a prepolymer prepared by pre-reacting 40 parts of bis(4-maleimidophenyl)methane and 60 parts of 2,2-bis(4-cyanatophenyl)propane at 160°C for 60 minutes is uniformly mixed, To this were added 2.0 parts of di-tert-butyl peroxide and 0.7 parts of zinc octylate as catalysts, and 200 parts of wollastonite.
part was added and extrusion kneaded at 100 to 110°C to form pellets. The pellets were compression molded at 170° C. and 300 kg/cm ² for 3 minutes, and then post-cured in an oven at 200° C. for 30 minutes to obtain a molded article. The test results for this molded article are shown in Table 1. Example 2 In Example 1, 2,2-bis(4-
A prepolymer prepared by pre-reacting 60 parts of cyanatophenyl)propane at 160°C for 150 minutes and 40 parts of bis(4-maleimidophenyl)methane were added, and to this was added 2.0 parts of di-tert-butyl peroxide as a catalyst and 0.7 parts of zinc octylate. part, and wollastonite
The same procedure was followed except that 200 parts of the pellets were added and extrusion kneaded at 100 to 110°C to form pellets. The test results for this molded article are shown in Table 1. Example 3 Novolac type epoxy resin (product name: ECN-
1273, epoxy equivalent 225, manufactured by Ciba Geigy Co., Ltd.)
225 parts (1 equivalent) and 90 parts (0.8 equivalents) of 2,2-bis(4-hydroxyphenyl)propane (molecular weight 228) were reacted for 120 minutes in the melt at 160°C to obtain a prepolymer (hereinafter referred to as ( b)). To this (b), a prepolymer prepared by pre-reacting 126 parts of 2,2-bis(4-cyanatophenyl)propane and 190 parts of bis(4-maleimidophenyl)ether at 160°C for 60 minutes is mixed uniformly, This was supplemented with 6.3 parts of dicumyl peroxide and 1.0 part of iron acetylacetonate as a catalyst, and wollastonite 632.
part was added and extrusion kneaded at 100 to 110°C to form pellets. The pellets were compression molded at 170° C. and 300 kg/cm ² for 3 minutes, and then post-cured in an oven at 200° C. for 30 minutes to obtain a molded product. The test results for this molded article are shown in Table 1. Comparative Example 1 The procedure of Example 1 was repeated except that the phenol novolac resin was not used. The results are shown in Table 1. Comparative Example 2 In Example 1, 90 parts (0.4 equivalents) of a novolak type epoxy resin (trade name: ECN-1273, epoxy equivalent weight 225, manufactured by Ciba Geigy Co., Ltd.) and a phenol novolak resin (average molecular weight 571, 5.5 hydroxyl groups) were used. )
The same procedure was followed except that 10 parts (0.1 equivalent) was used without pre-reaction. The results are shown in Table 1. Comparative Example 3 The procedure of Example 3 was repeated except that 2,2-bis(4-hydroxyphenyl)propane was not used. The results are shown in Table 1. In Table 1, *1 and *2 are as follows, respectively. *1 After 100 hours of heat treatment (%) *2 Blocking property: Crush pellets and
The powders that passed through the mesh sieve were collected, and 7 g of each was placed in a 40 mm diameter glass container, and the containers were left in an oven at 40° C. for one week, and the containers were turned upside down to examine their blocking properties. ◎: Falls without forming lumps. ○: Forms lumps, but crumbles when touched lightly. ×: Forms a lump and does not crumble even when touched. 【table】

Claims (1)

[Scope of Claims] 1 A: A reaction product of an epoxy compound having two or more epoxy groups in the molecule and a polyhydric phenol containing two or more phenolic hydroxyl groups in the molecule, B: A reaction product with two or more cyanato groups in the molecule. a polyfunctional cyanate ester containing two or more N-maleimide groups, a prepolymer of the cyanate ester, or a prepolymer of the cyanate ester and an amine, and a polyfunctional maleimide containing two or more N-maleimide groups in the molecule; A thermosetting resin composition containing a maleimide prepolymer or a prepolymer of the maleimide and an amine as an essential component.