JPH0352771B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel thermosetting resin composition, and specifically, a reaction product of an epoxy compound having two or more epoxy groups in the molecule of A and a diamine, and a reaction product of a diamine with two or more cyanato groups in the molecule of B. A polyfunctional cyanate ester containing the above, a prepolymer of the cyanate ester or a prepolymer of the cyanate ester and an amine, a polyfunctional maleimide containing two or more N-maleimide groups in the C molecule, and a polyfunctional maleimide containing two or more N-maleimide groups in the C molecule. It is a thermosetting resin composition containing a remide prepolymer or a prepolymer of the maleimide and an amine as an essential component. Conventionally, a curable resin composition prepared by mixing the B and C components of the present invention with an epoxy resin has been disclosed in Japanese Patent Publication No. 1986-
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-mentioned drawbacks, the present inventors used a reaction product of an epoxy resin and a diamine as the epoxy resin, added a cyonic acid ester component and a maleimide component to this, and conducted a preliminary reaction as desired. By doing so, it is possible to obtain a thermosetting resin composition that is easily dissolved in a low boiling point solvent, has excellent processability and workability, and has excellent heat resistance, electrical properties, mechanical properties, moisture resistance, etc. of the cured product. This was successful and led 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 representative 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. The diamine to be reacted with the above epoxy compound may be any primary organic diamine represented by R(NH ₂ ) ₂ (R in the formula is an organic group having two or more carbon atoms), and is not particularly limited. . Such diamines include meta or paraphenylene diamine, meta or para xylylene diamine, 1,4
- or 1,3-cyclohexanediamine, hexahydroxylylenediamine, 4,4-diaminobiphenyl, bis(4-aminophenyl)methane, bis(4-aminophenyl)ether, bis(4-aminophenyl)sulfone, bis(4-aminophenyl) -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
-diaminophenyl-4-aminophenylmethane, 1,1-bis(4-aminophenyl)-1-
Specific examples include phenylethane and benzoguanamine. The above epoxy compound and diamine are reacted to prepare component A of the present invention. The equivalent ratio used is epoxy group:amino group=1:0.05-1, preferably
1:0.1:0.8, either without solvent or dissolved in a solvent such as methyl ethyl ketone, methyl cellosolve, methyl sobutyl ketone, and usually at 20 to 250°C.
Preferably, it is carried out at a temperature of 50 to 200°C for a period of 1 minute to 10 hours. Suitable polyfunctional cyanate esters as component B of the curable resin composition of the present invention have the following general formula (1) R ₁ (OCN)m...(1) (m in the formula is 2 or more. , usually an integer greater than or equal to 5,
R ₁ 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-dicyanatona)talene, 1,3,6-tricyanatonahetalene, 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 obtained by reaction of novolak with cyanogen halides. These include esters. In addition to these, special public interest
1928, 43-18468, 44-4791, 45-11712,
No. 46-41112, No. 47-26853 and JP-A No. 1973-
Cyanic acid esters described in 63149 and the like 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. Examples of amines that can be suitably used include those exemplified as those used in the reaction with the epoxy resin described above. 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 with a valence of 2 or more and usually 5 or less, X ¹ and X ² 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 listed above for use in the preparation of component A, and sym
-Melamines with a triazine ring, polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds, etc. 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 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 solvents such as methyl ethyl ketone, methyl cellosolve, and methyl isobutyl keto; B and C
Any method may be used, such as pre-reacting the components and mixing the A component therein; pre-reacting the A and C components and mixing the B component; or further pre-reacting the components after mixing. The usage ratio is not particularly limited. The curable resin composition of the present invention itself is cured by heating, but a thermosetting catalyst or curing agent is usually used to accelerate curing. These include:
2-Methylimidazole, 2-indecylimidazole, 2-heptadecylimidazole, 2-phenylmidazole, 2-ethyl-4-methylimidazole, 1-benzol-2-methylimidazole, 1-propyl-2-methylimidazole ,1
-cyanoethyl-2-methylimidazole, 1-
Cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-
Cyanoethyl-2-phenylimidazole, 1-
Imidazoles exemplified by cyanoethyl-2-ethyl-4-methylimidazole and 1-guanaminoethyl-2-methylimidazole;
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,
Tertiary amines such as triethylenediamine, N,N,N',N'-tetramethylbutanediamine, N-methylpiperidine; Phenols such as phenol, xylenol, cresol, resorcinol, catechol, phloroglycine; Lead naphthenate ,
Organometallic salts such as lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacecentate; SnCl ₄ , ZnC ₂ ,
Inorganic metal salts such as AlCll ₃ ; peroxides such as benzoyl peroxide, lauroyl peroxide, caprylic peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate; maleic anhydride ,
Acid anhydrides such as phthalic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydro trimellitic anhydride, and hexahydropyromellitic anhydride; furthermore, azo compounds such as azobisisobutylnitrile and epoxy Examples include resin curing catalysts. 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, gelatin, 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,
Parylyl 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 ether, polysulfone,
High molecular weight polymers such as polyester, nylon, polyimide, polyadimide, polyesterimide, polyphenylene sulfide, and low molecular weight prepolymers or oligomers thereof are exemplified and used as appropriate. In addition, as reinforcing materials 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 manufacturing adhesive structures and the like, 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 used as a composition with a catalyst, an inorganic filler, etc., as necessary, to form electric insulating paint powder for automobile starter motors and generator motors; for coating metal plates, etc. It is used for various purposes such as paints, cast products, molded products, laminates, tapes, sheets, and films. 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 1 576 parts of bisphenol A type epoxy resin (trade name: Epicote 828, manufactured by Yuka Ciel Epoxy Co., Ltd., epoxy equivalent: 192) and bis(4-aminophenyl)
A prepolymer was obtained by reacting 198 parts of methane (equivalent ratio 1:0.67) for 50 minutes while melting at 110°C (hereinafter referred to as (a)
). Add 1074 parts of bis(4-maleimidophenyl)methane to this (a) and pre-react at 110°C for 11 minutes.
Furthermore, 1074 parts of 2,2-bis(4-cyanatophenyl)propane was added and mixed uniformly to obtain a curable resin composition. This curable resin composition was soluble in methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, and dioxane at a solid content of 65 wt% or more. 100 parts of this curable resin composition, 50 parts of powdered graphite carbon, 0.3 part of di-tert-butyl peroxide and 0.1 part of zinc octylate were added and kneaded uniformly with a hot roll at 80°C to obtain a molding material. This molding material was compressed at 170℃ and 300Kg/ ^cm2 for 2 minutes, and then cured in an oven at 230℃ for 12 hours.
A good molded product was obtained. The test results for this molded article are shown in Table 1. Example 2 Novolac type epoxy resin (product name: ECN-
1273, epoxy equivalent 225, manufactured by Ciba Geigy Co., Ltd.)
2250 parts and 198 parts of bis(4-aminophenyl)methane
(equivalent ratio 1:0.2) was reacted for 50 minutes in a melted state at 110°C to obtain a prepolymer (hereinafter referred to as (b)). 2,880 parts of bis(4-maleimidophenyl) ether was added to this (b), and a preliminary reaction was carried out at 110°C for 12 minutes. 2,780 parts of 2,2-bis(4-cyanatophenyl)propane was added to this and mixed uniformly to obtain a curable resin composition. This curable resin composition was soluble in methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, and dioxane at a solid content of 65 wt% or more. To 1000 parts of this curable resin composition, 0.2 parts of zinc octylate and 0.3 parts of triethylenediamine were added and dissolved in methyl ethyl ketone. This solution was impregnated into a 0.2 mm thick glass woven cloth and dried to form a B-stage prepreg. Eight sheets of this prepreg were stacked and 35μ electrolytic copper foil was placed on both sides.
Temperature 180℃, pressure 30Kg/ ^cm2 for 180 minutes, then 200 minutes
Lamination molding was carried out for 120 minutes at 40 Kg/cm ² at ℃ to obtain a copper-clad laminate. The test results for this board are shown in Table 2. Example 3 In Example-2, the prepolymer (b) was preliminarily reacted with 2,880 parts of bis(4-maleimidophenyl) ether and 2,780 parts of 2,2-bis(4-cyanatophenyl)propane at 160°C for 2 hours. The prepolymer was added and mixed uniformly to obtain a curable resin composition. This curable resin composition was soluble in methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, and dioxane at a solid content of 65 wt% or more. To 1000 parts of this curable resin composition, 0.2 parts of zinc octerate and 0.3 parts of triethylenediamine were added and dissolved in methyl ethyl ketone. This solution was impregnated into a glass woven fabric with a thickness of 0.2 mm and dried to obtain a B-stage prepreg. Eight sheets of this prepreg were stacked, 35μ electrolytic copper foil was placed on both sides, and the temperature was 180℃ and the pressure was 30Kg/ ^cm2 . 180 minutes, then 200℃,
Lamination molding was carried out for 120 minutes at 40 kg/cm ² to obtain a copper-clad laminate.
The test results for this board are shown in Table 2. Example 4 250 parts of bisphenol A type epoxy resin (trade name: Epicote 828, epoxy equivalent: 192, manufactured by Yuka Ciel Epoxy Co., Ltd.) and bis(4-aminophenyl)
A prepolymer was obtained by reacting 100 parts of ether (equivalence ratio 1:0.77) for 50 minutes in the melt at 100°C (hereinafter referred to as
(c)). 540 parts of bis(4-maleimidophenyl) ether was added to this (c), and a preliminary reaction was carried out at 110°C for 10 minutes. 361 parts of 2,2-bis(4-cyanatophenyl)propane was added to this and mixed uniformly to obtain a curable resin composition. This curable resin composition was soluble in methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, and dioxane at a solid content of 60 wt % or more. To 1000 parts of this curable resin composition, 0.2 parts of zinc octylate and 0.3 parts of triethylenediamine were added and dissolved in methyl ethyl ketone. This is impregnated into a 0.2 mm thick glass woven cloth and dried to form a B-stage prepreg. Eight sheets of this prepreg are stacked, 35μ electrolytic copper foil is placed on both sides, and the temperature is
180℃, pressure 30Kg/ ^cm2 for 180 minutes, then 200℃,
Lamination molding was carried out for 120 minutes at 40 kg/cm ² to obtain a copper-clad laminate.
The test results for this board are shown in Table 2. Comparative Example 1 In Example 3, bis(4-maleimidophenyl)ether and 2,2-bis(4-cyanatophenyl)propane were prepared without pre-reacting the novolak type epoxy resin and bis(4-aminophenyl)methane. When compounded, the gelation time at 160°C was 0 seconds, making it impossible to produce prepreg. Comparative example 2 Polyano bismaleide resin (product name:
Kerimid 601 (manufactured by Rhône-Poulenc) 700 parts and novolac type epoxy resin (trade name: ECN-1273,
Epoxy equivalent: 225, Ciba Geigy Co., Ltd. 300 parts was dissolved and mixed in N-methylpyrrolidone, and the thickness was 0.2 mm.
The results are shown in Table 2 in the same manner as in Example 2, except that a prepreg was prepared by impregnating and drying a glass woven fabric. Comparative Example 3 100 parts of bis(4-aminophenyl)methane, 1000 parts of bisphenol A type epoxy resin (trade name: Epicote 1001, manufactured by Yuka Ciel Epoxy Co., Ltd.) and 20 parts of 2-ethylimidazole were dissolved in methyl ethyl ketone, This was impregnated into a 0.2 mm thick glass woven fabric and dried to form a prepreg, which was then stacked in 8 layers, with 35μ electrolytic copper foil placed on both sides, heated at 175°C.
Lamination molding was performed for 90 minutes at a pressure of 30 kg/cm ² to obtain a copper-clad laminate. The test results for this board are shown in Table 2.

[Table] Ivy.

【table】

Claims (1)

[Scope of Claims] 1. A reaction product of an epoxy compound having two or more epoxy groups in the molecule and a diamine, B a polyfunctional cyanate ester having two or more cyanato groups in the molecule, and the cyanic acid. An ester prepolymer or a prepolymer of the cyanate ester and an amine, a polyfunctional maleimide containing two or more N-maleimide groups in the C molecule, the maleimide prepolymer, or a prepolymer of the maleimide and an amine are essential. A thermosetting resin composition as an ingredient.