JPH0525886B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel thermosetting resin composition having excellent heat resistance and fast curing properties. Various heat-resistant resins are available as insulating materials that meet the demands for larger capacity, smaller size, lighter weight, and higher reliability of electronic equipment, as well as thermal stability, longer life, and maintenance-free electrical equipment. Addition polymerization type imide resins such as bismaleimide resins or bismaleimide-aromatic diamine modified resins are well known as such heat-resistant resins. However, although the bismaleimide resin has excellent heat resistance, it has a high melting point, a slow curing speed, and is poorly soluble in general-purpose organic solvents such as methyl ethyl ketone and tetrahydrofuran. It has the disadvantage of being soluble only in high melting point polar organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide. Furthermore, when preparing a bismaleimide resin varnish using these polar organic solvents and impregnating it into a base material to form a prepreg, the B-staged prepreg is then heated and compressed to produce a laminate. Since it is extremely difficult to completely remove the solvent from the drying and manufacturing process of laminates, the solvent remains and causes voids in the laminate, reducing its quality and performance. This caused the foil to swell or peel, which was not satisfactory. Furthermore, the polar organic solvents described above are permeable through the skin and highly toxic, so their use is undesirable from the standpoint of environmental health and safety. On the other hand, in recent years, for the purpose of saving energy and improving workability, attempts have been made to produce impregnated varnishes or solvent-free varnishes using general-purpose organic solvents with low boiling points, and a combination of bismaleimide resin and epoxy resin has been adopted. However, these two have poor compatibility, and bismaleimide precipitates, and high temperatures are required to obtain a uniform liquid, resulting in a short pot life, which limits the scope of their application. The present invention is directed to N-(alkenylphenyl)maleimide derivatives, dimers thereof, or multimers thereof (hereinafter referred to as N-(alkenylphenyl) A thermosetting resin composition containing an aliphatic maleimide having an ether bond, an amino compound, and an epoxy resin, which has a low melting point, excellent solubility in organic solvents, and rapid dissolution. A curable composition is provided. The thermosetting resin composition of the present invention has the following formula: A: General formula () (In the formula, R ₁ to _{R 6} are the same or different, and each is a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 10 carbon atoms, or a phenyl group, or Alkyl group having 1 to 10 carbon atoms, halogen atom, R ₇ O- group, R ₇ CO- group, R ₇ COO-
is a phenyl group substituted with a group, a hydroxyl group or a cyano group, and each of R ₄ , R ₅ and R ₆ may be the same or different when a plurality of them are present, and X is a hydrogen atom, halogen atom,
Carboxyl group, hydroxyl group, R ₇ O− group, R ₇ CO−
group, R ₇ COO- group, or cyano group, and when multiple Xs exist, they may be the same or different, and m ₁ , m ₂ and m ₃ are each 0 to 4; So, m ₁ + m ₂ + m ₃ = 5,
Also, R ₇ is an optionally branched alkyl group having 1 to 10 carbon atoms or a phenyl group,
Or the number of carbon atoms that may be branched is 1
-5 alkyl group or phenyl group substituted with a halogen atom, and when multiple R _7s are present, they may be the same or different) N-(alkenylphenyl) represented by At least one maleimide compound selected from the group consisting of maleimide derivatives, dimers thereof, and multimers thereof, B: at least one aliphatic maleimide having an ether bond, C: at least one amino compound, and D: at least one type , and the proportions of component A and component B used are 2 to 99% by weight of component A and 1 to 98% by weight of component B, based on the total weight of both components, and the amount of component C used is The amount is such that the ratio of the total number of amino groups in component C to the total number of maleimide groups in components A and B is 1 or less, and the amount of component D used is 50% by weight of the total weight of the composition.
It is characterized by the following: The N-(alkenylphenyl)maleimide used in the composition of the present invention has significantly better solubility in solvents than ordinary maleimide compounds, and has not been conventionally used in compositions containing maleimide compounds. N-methyl-2-hydrolidone, N,N
- Even if polar organic solvents such as dimethylformamide are not used, the purpose can be sufficiently achieved using ordinary general-purpose organic solvents with relatively low boiling points, and because it has fast curing properties, B-stage at relatively low temperatures can be achieved. This not only improves work efficiency but also makes it easier to remove solvents from products such as laminates, which greatly improves product quality. On the other hand, aliphatic maleimide having an ether bond has the advantage of providing a highly flexible cured product since there is no benzene ring in the molecule, and since it has an ether bond, it is compatible with the resin of the present invention and various base materials. It is also expected to improve adhesive ability. Examples of the N-(alkenylphenyl)maleimide derivative represented by the general formula () which is component A of the present invention include N-(o-vinylphenyl)maleimide, N-(m-vinylphenyl)maleimide,
N-(p-vinylphenyl)maleimide, N-(o
-isopropenylphenyl)maleimide, N-
(m-isopropenylphenyl)maleimide, N
-(p-isopropenylphenyl)maleimide,
N-(vinyltolyl)maleimide (including all isomers), N-(isopropenyltolyl)maleimide (including all isomers), N-(P-α-ethylvinylphenyl)maleimide, N-(p −α
-phenylvinylphenyl)maleimide, N-
(o-vinylphenyl)dichloromaleimide, N
-(m-vinylphenyl)dichloromaleimide,
N-(p-vinylphenyl)dichloromaleimide,
N-(p-isopropenylphenyl) dichloromaleimide, N-(m-isopropenylphenyl)
Dichloromaleimide, N-(o-isopropenylphenyl)dichloromaleimide, N-(4-vinyl-2-hydroxyphenyl)maleimide, N-
(4-vinyl-3-hydroxyphenyl)maleimide, N-(4-isopropenyl-2-acetoxyphenyl)maleimide, N-(4-isopropenyl-3-acetoxyphenyl)maleimide, N
-(4-vinyl-3-cyanophenyl)maleimide, N-(4-vinyl-2-cyanophenyl)maleimide, N-(4-isopropenyl-3-cyanophenyl)maleimide, N-(4-isopropenyl-2-cyanophenyl) ) maleimide, N,
N'-(1-vinyl-2,4-phenylene)bismaleimide, N,N'-(1-vinyl-3,5-phenylene)bismaleimide, N,N'-(1-isopropenyl-2,4 -phenylene)bismaleimide, N,N'-(1-isopropenyl-3,5-phenylene)bismaleimide, N-(p-vinylphenyl)-di-t-butylmaleimide, N-(p-
isopropenylphenyl)diisopropylmaleimide, N-[p-α-(p'-cyanophenyl)vinylphenyl]maleimide, N-[p-α-(m'-
chlorophenyl) vinylphenyl] maleimide,
2-isopropenyl-4-N-maleimido-4'-
Chlorobiphenyl, 2-vinyl-4-N-maleimido-4'-methylbiphenyl, 3-isopropenyl-4-N-maleimido-3'-methoxybiphenyl, 3-vinyl-3-N-maleimido-4'-hydroxybiphenyl , 3-isopropenyl-4-N
-maleimido-4'-acetylbisphenyl, 2-
Examples include N-maleimido-4-isopropenyl-4'-cyanobiphenyl, N-(p-isopropenylphenyl)-p-chlorophenylmaleimide, and the like. The present invention includes the above N-(alkenyl phenyl)
Maleimide dimers and multimers thereof can be used. An example of a dimer of N-(alkenylphenyl)maleimide is the formula N-(p-isopropenylphenyl) represented by
Mention may be made of maleimide dimers. There are no particular restrictions on the polymer of N-(alkenylphenyl)maleimide, but in practice, the molecular weight is 1.
It is preferably less than 10,000. In the present invention, the above compounds can be used alone or in combination of two or more. These N-(alkenylphenyl)maleimide derivatives, for example, JP-A-129266-1982,
It can be produced by the method described in JP-A No. 131566 and JP-A No. 56-145272. The aliphatic maleimide having an ether bond, which is component B of the present invention, has a maleimide residue having the formula R ₈ -O-R ₈ '-, -R ₈ (-O-R ₈ ') _a --, -R ₈ (- O-R ₈ ′) _a --(-O-R ₈ ″) _b --, −R ₈ (-O-R ₈ ′) _a --(-O-R ₈ ″) _b --(-O-
R ₈ ) _b ---, (In the formula, R ₈ , R ₈ ′, R ₈ ″, R ₈ and R ₉ may be the same or different, and each represents a linear or branched chain having 1 to 10 carbon atoms. ~trivalent aliphatic hydrocarbon group or one substituted with an alkoxy group, hydroxyl group, or halogen, and a, b, c, x, y, and z represent a number of 1 or more) Examples of such aliphatic maleimides include compounds having an aliphatic ether group having the structure: N-2,2'-hydroxyethoxyethylmaleimide, N-1-methoxymethylpropylmaleimide, N- 1-ethoxymethylpropylmaleimide, N-1-methoxymethylbutylmaleimide, N,N'-3,6-dioxaoctane-1,
8-bismaleimide, N,N'-4,7-dioxadecane-1,10-bismaleimide, N,N'-
3,6,9-trioxaundecane-1,11-bismaleimide, N,N'-4,9-dioxadodecane-1,12-bismaleimide, N,N'-4,
7,10-trioxatridecane-1,13-bismaleimide, N,N'-7-methyl-4,10-dioxatridecane-1,13-bismaleimide, N,
N'-3,6,9,12-tetraoxatetradecane-1,14-bismaleimide, N,N'-3,6,
9,12,15-pentaoxaheptadecane, 1,17
- bismaleimide, bis(3-N-maleimidopropyl)polytetrahydrofuran, as well as e.g. (In the formula, a is 2.6, 5.6 or 33.1.) (In the formula, the sum of a and c is approximately 3.5, and b is approximately 13.5 to 45.5.) (In the formula, the sum of x, y and z is about 5.3.). Furthermore, compounds in which the hydrogen atom bonded to the unsaturated carbon atom in the maleimide group of the above aliphatic maleimide is appropriately substituted with a chlorine atom, bromine atom, methyl group, ethyl group, phenyl group, etc. may also be used. In addition to using aliphatic maleimide alone, it is also possible to use a mixture of two or more types. In the composition of the present invention, N-
The proportion of both the (alkenyl phenyl) maleimide and the aliphatic maleimide used is 2 to 99% by weight, preferably 5 to 95% by weight, based on the total amount of both components.
Weight%. If the amount of the former is less than the above range, the heat resistance of the cured product obtained will decrease, and if it exceeds the above range, the curability and flexibility of the composition will deteriorate. The amino compound used for the purpose of imparting a homogeneous and dense structure and imparting toughness and mechanical strength to the cured product according to the present invention has the following formula: Z-(NH ₂ ) _l (wherein Z is the number of carbon atoms 1 Consisting of ~150 pieces, hydrogen,
is an l-valent organic group that can contain atoms of oxygen, sulfur, halogen, nitrogen, phosphorus, and silicon;
is an integer of 1 or more), typical examples of which are ethyleneamine, propylamine, hexylamine, aniline, p-(m
- or o-) toluidine, p- (m or o-)
Methoxyaniline, p-(m or o-)chloroaniline, 3,5-dichloroaniline, p-(m
or o-)hydroxyaniline, p-(m or o-)carboxyaniline, p-(m or o-)
-) vinylaniline, p-(m or o-)allylaniline, p-isopropenylaniline, 2-
Methyl-4-isopropenylaniline, 4-aminopyridine, 2-(4'-hydroxyphenyl)-2
-(4″-aminophenyl)propane, 2-(4′-hydroxyphenyl)-2-(3″-methyl-4″-aminophenyl)propane, benzylamine, 1-aminonaphthalene, 2-aminonaphthalene, ethylenediamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, 2,2,4-trimethylhexamethylene diamine, p- (or m-) phenylene diamine, 1,4-diaminocyclohexane,
2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(4'-aminophenyl)propane, 4,4'-diaminodiphenyl ether,
4,4'-diaminodiphenyl sulfide, 4,
4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodicyclohexylmethane, p-(or m-)xylene diamine, bis(4-aminophenyl)diphenylsilane, bis(4-aminophenyl) ) Methylphosphine oxide, bis(3-chloro-4-aminophenyl)methane, 2,2-bis(4′,4″-
aminophenoxyphenyl)propane, 1,4-
Bis(p-aminophenoxy)benzene, 1,4
-diaminonaphthalene, 2,4-diaminopyridine, 4-methyl-2,4-bis(p-aminophenyl)pentane, 4-methyl-2,4-bis(p
-aminophenyl)-1-pentene, 4-methyl-2,4-bis(p-aminophenyl)-2-pentene, tris(4-aminophenyl) phosphate, tris(4-aminophenyl) thiophosphate, 2,4,6-tris (4'-aminophenoxy)-s-triazine, 5 (or 6)-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, or vinylanilines, or three amounts of isopropenylanilines. polyamines obtained by the reaction of aromatic amines (e.g., aniline, toluidine) and aldehydes (e.g., formaldehyde, paraform, acetaldehyde), especially polyamines obtained by the reaction of aniline with formaldehyde. (phenylenemethylene)polyamine (e.g. MDA-
150 (trade name, manufactured by Mitsui Toatsu Chemical Co., Ltd.) and alicyclic polyamines obtained by hydrogenating the polyamine. These amino compounds can be used alone or as a mixture of two or more. The amount of these amino compounds used in the composition of the present invention is determined by the ratio of the total number of amino groups in the amino compound to the total number of maleimide groups in the maleimide component of the N-(alkenylphenyl)maleimide derivatives and aliphatic maleimide (described below). It is preferable that the formula () is 1 or less, and the range of 0.01 to 1 is more preferable: (ma・na/Ma)/(mi・ni/Mi) () (where mi, ni and Mi each represent maleimide The amount of the compound used, the average value of the number of maleimide groups in the molecule, and the average molecular weight are shown, and ma, na, and Ma are the amount of the amino compound used, the average value of the number of amino groups in the molecule, and the average molecular weight, respectively.) Amino compound If the amount used exceeds the above range, the heat resistance of the cured product will decrease, while if it falls below the above range, the adhesion will decrease and the mechanical strength of the cured product will tend to decrease.Thermosetting resin of the present invention The composition is component A and component B.
It may be a simple mixture of Component C and Component C, or it may be a composition containing at least a portion of these prepolymers. Prepolymer is a preliminary reaction obtained by reacting any two components selected from A (N-alkenyl phenyl)maleimide, B aliphatic maleimide, and C amino compound or three components A, B, and C. There are no restrictions on the specific reaction method, but the reaction temperature is in the range of 0 to 200°C,
The reaction time ranges from 5 minutes to 10 hours by directly and uniformly mixing each component without a solvent, or by using a solvent to react each component as a homogeneous solution or suspension. In addition, the epoxy resin used for the purpose of improving adhesive strength and adjusting viscosity in the present invention may be any known solid or liquid product, and typical examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, Resins, heterocyclic epoxy resins such as halogenated bisphenol A type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, cycloaliphatic epoxy resins, triglycidyl cyanurate, triglycidyl isocyanurate or hydantoin epoxy. , hydrogenated bisphenol A type epoxy resin,
Aliphatic epoxy resins such as propylene glycol diglycidyl ether and pentaerythritol polyglycidyl ether, epoxy resins obtained by the reaction of aliphatic or aromatic carboxylic acids with epichlorohydrin, spiro ring-containing epoxy resins, orthoaryl phenol novolaks Glycidyl ether type epoxy resin which is a reaction product of a compound and epichlorohydrin, p,p'-N,N,N',N'-tetraglycidylaminodiphenylmethane, which is represented by the following structural formula. Or triglycidyl-p-aminophenol represented by the following structural formula Epoxy resins obtained by the reaction of aliphatic or aromatic amines with epichlorohydrin, such as
and epoxy resins in which a part of the above epoxy resins is ring-opening polymerized, and further epoxidized or epoxy-modified resins (for example, acrylic resins having epoxy groups, 1,2-polybutadiene or alkyd resins, epoxy-modified silicone resins), etc. can be mentioned. In the present invention, epoxy resins can be used alone or in combination of two or more, and of course, a portion of a functional so-called reactive diluent may be included. The amount of epoxy resin used is preferably 50% or less of the total weight of the composition so as not to impair the heat resistance of the cured product obtained from the composition of the present invention. A catalyst is not necessarily required for the curing reaction of the thermosetting resin composition of the present invention, but one or more catalysts may be used depending on the situation. In this case, the amount used is within a range that does not interfere with the excellent effects of the composition of the present invention and improves its performance, and is actually 5% or less based on the total weight of the composition. Catalysts used for purposes such as improving workability and adjusting effect rate depending on the application form of the composition include boron trifluoride monoethylamine complex,
Boron trifluoride amine complexes such as boron trifluoride piperidine complex; tertiary amines such as triethylamine, N,N-dimethylbenzylamine, hexamethylenetetramine, N,N-dimethylaniline; quaternary amines such as tetramethylammonium bromide; grade ammonium salt, triphenylborate,
Borate compounds such as tricresylborate, N
- imidazole compounds such as methylimidazole and N-phenylimidazole, zinc acetate, sodium acetate, titanium acetylacetonate, sodium methylate, aluminum chloride, zinc chloride,
Metal compounds such as tin chloride, manganese naphthenate, cobalt naphthenate, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, benzophenonetetracarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, Examples include acid anhydrides such as maleic anhydride, peroxides such as dicumyl peroxide, t-butyl perbenzoate, and methyl ethyl ketone peroxide, and azo compounds such as azobisisobutyronitrile. The composition of the present invention is a solvent-free type in which a homogeneous mixture can be obtained by utilizing characteristics such as containing aliphatic maleimide, which is a low-melting liquid maleimide, and the homogeneous mixture can be simply heated for curing. However, since it is easily soluble in organic solvents, it can also be used in the form of a solution. In the case of a solution, there are no restrictions on the organic solvent used, but specific preferred examples include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, hydrocarbons such as n-hexane and cyclohexane, diethyl ether,
Ethyl cellosolve, methyl cellosolve, 1,4-
Ethers such as dioxane and tetrahydrofuran, chlorine compounds such as methylene chloride, chloroform, trichloroethane, carbon tetrachloride, benzene,
Aromatic hydrocarbons such as xylene and mesitylene,
Examples include alcohols such as methanol, ethanol, isopropyl alcohol, phenol, and cresol, nitriles such as acetonitrile, and esters such as methyl acetate, ethyl acetate, and 2-ethoxyethyl acetate. Also, N,N-dimethylformamide, N-methyl-2
- Of course, a solution-like composition can be obtained by using pyrrolidone or the like, but since these solvents have the drawbacks mentioned above, it is preferable to refrain from using them for purposes other than special purposes. The curable resin composition of the present invention may contain powder, granular or fibrous reinforcing agents, fillers, thickeners, mold release agents, etc., as necessary, to the extent that the effects of the present invention are not inhibited.
Coupling agents such as vinyltriethoxysilane, flame retardants, flame retardants, pigments and coloring agents, and other auxiliary agents can be added. The effective resin composition of the present invention has a wide range of uses, including impregnation, prepreg, coating and laminating varnishes, molding powders, paints, adhesives, sealants, and rubber agents. Curing conditions for forming a cured product vary depending on the composition and the form of the cured product. Generally, the compositions of the invention are applied to a substrate as an adhesive layer or coating, or as a powder,
The pellets are further impregnated with a base material such as glass cloth, molded or laminated, and then heated and cured. The curing temperature is generally in the range of 0 to 350°C, preferably 50 to 300°C. Curing time depends on the form of the cured product, but generally it takes 30 seconds to 20 seconds.
It is sufficient to select a time that is sufficient for the resin component to be completely cured. Further, when used for manufacturing molded products, laminate products, adhesive structures, etc., it is desirable to apply pressure during heat curing, and the applied pressure may range from 1 to 150 kg/cm ² . The composition of the present invention may be cured using visible light, ultraviolet rays, X-rays,
It is also possible to use electromagnetic waves such as gamma rays. There are no particular restrictions on the specific mode of carrying out the present invention, but examples of the mode include impregnating varnish,
Examples of preparing prepregs and laminates are shown below. A homogeneous liquid comprising an N-(alkenylphenyl)maleimide, a lipophilic maleimide, an amino compound, and an epoxy resin or a homogeneous solution containing an organic solvent is prepared. When a solvent is used, the concentration of the composition of the invention in the solution is preferably in the range of 10 to 80% by weight. A curing catalyst, a silane coupling agent, a flame retardant, etc. are added to this homogeneous liquid or solution as necessary, and the mixture is uniformly mixed to form a varnish. After impregnating glass cloth with the varnish, air dry it for a certain period of time and then heat it at 50 to 200℃.
A prepreg is obtained by pre-curing in an oven. Prepreg is often used in its original form as various insulating materials, such as prepreg mica tape. The prepreg obtained from the varnish prepared from the composition of the present invention does not cause separation of components or foaming.
Moreover, it has favorable dryness to the touch, can be stored stably for a long period of time even at room temperature, and maintains its flexibility. Next, for example, after stacking multiple prepreg sheets made of glass cloth, copper foil is layered on one or both sides of the prepreg sheets, and a compression molding machine is applied at a temperature of 100 to 300℃ and a pressure of 100 to 150℃.
A laminate for a wiring board can be obtained by pressure molding at kg/cm ² . EXAMPLES The present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. Note that parts and percentages in the examples are by weight unless otherwise specified. Further, various measurement methods in Examples are as follows. Soldering heat resistance: According to JIS C-6481, the temperature of the solder bath was set to 300°C, and the time required until blistering or peeling occurred on the copper foil surface was measured. Copper foil peel strength: According to JIS C-6481. Bending strength: Based on JIS CC-6481. Production Example 1 Production of 4-methyl-2,4-bis(p-N-maleimidophenyl)-1-pentene: 108 parts of maleic anhydride was dissolved in 500 parts of acetone, and this solution was maintained at 20°C. 4-methyl-2,
4-di(p-aminophenyl)-1-pentene 133
portion was gradually added with stirring. After the addition was completed, the reaction solution was continued to be stirred at a temperature of 20° C. for 2.5 hours. The reaction solution was a yellow slurry. Next, 1.25 parts of cobalt acetate tetrahydrate, 25 parts of triethylamine, and 123 parts of acetic anhydride were added to this slurry reaction solution,
This reaction solution was heated to 60°C. Then add the reaction solution
Stirring was continued for 3 hours while maintaining the temperature at 60°C. Next, the reaction solution was cooled to room temperature, 25 parts of methanol was added, and the mixture was gradually dropped into 1500 parts of thoroughly stirred water to obtain a precipitate. This precipitate was separated and poured into water, and after adjusting the pH to 8.5 by adding an aqueous sodium carbonate solution, the precipitate was thoroughly washed with water several times, and finally washed and purified with 100 parts of methanol. Temperature 50℃,
Dry under reduced pressure to obtain 4-methyl-2,4-bis(p
194 parts of -N-maleimidophenyl)-1-pentene (melting point 148-150°C) were obtained. Note that N-p-isopropenylphenylmaleimide, 4-methyl-2,4-bis(p-N-maleimidophenyl)-2-pentene, and N(p-isopropenylphenyl)maleimide oligomer are the starting materials, respectively. p-isopropenylaniline, 4-methyl-2,4-di(p-aminophenyl)-2-pentene and p-isopropenylaniline oligomer (composition: 3.2% monomer, dimer
76.9%, trimer 8.2%, tetramer or more 11.7%). Examples 1 to 7 N-(alkenylphenyl)maleimide of the type and amount shown in Table 1, aliphatic maleimide having an ether bond of the type and amount shown in Table 1, amino compound of the type and amount shown in Table 1, Table 1 An impregnated varnish was prepared by dissolving an epoxy resin of the kind and amount shown in Table 1 and a catalyst of the kind and amount shown in Table 1 in a solvent of the kind and amount shown in Table 1. Next, a glass cloth (thickness 0.18 mm) treated with aminosilane was impregnated, and after air drying,
A prepreg was obtained by drying at 150°C for 9 minutes. Layer nine sheets of this prepreg, place one sheet of copper foil on top,
At 180℃ using a heat press with a press pressure of 75Kg/ ^cm2 .
A copper clad laminate was obtained by compression for 30 minutes. This laminate was then after-cured in an oven at 200°C for 8 hours. Comparative Example 1 70 parts of N,N'-(methylenedi-p-phenylene)bismaleimide and 30 parts of N,N'-4,7-diosadecane-1,10-bismaleimide were mixed with N,N'-
An impregnating varnish was prepared by dissolving it in 100 parts of dimethylformamide, and copper-clad laminates were obtained in the same manner as in Examples 1 to 7. Note that N,N'-(methylenedi-p-phenylene) bismaleimide precipitated on the surface of the resin-containing glass cloth after air drying, and a good prepreg could not be obtained. The solder heat resistance, copper foil peel strength, and bending strength of the copper-clad laminates obtained in Examples 1 to 7 and Comparative Example 1 were measured, and the results are shown in Table 1. The symbols in the table represent the following compounds. N-(alkenylphenyl)maleimides BM-A N-p-isopropenylphenylmaleimide BM-B 4-methyl-2,4-bis(p-N-
maleimidophenyl)-1-pentene BM-C 4-methyl-2,4-bis(p-N-
maleimidophenyl)-2-pentene BM-D N-(p-isopropenylphenyl)
Maleimide oligomer (composition: monomer 3.1%,
Dimer 76.5%, trimer 8.3%, tetramer or more 12.1
%) BM-E N-(p-vinylphenyl)maleimide BM-F N-(p-isopropenylphenyl)
Dichlormaleimide aliphatic maleimide ABM-A N,N-4,7-dioxadecane-
1,10-Bismaleimide ABM-D In the following formula, a≒2.6 (bismaleimide of diefamine D-230) ABM-E In the following formula, a≒5.6 (bismaleimide of diefamine D-400) ABM-F In the following formula, a≒ 33.1 (Bismaleimide of diefamine D-2000) Amino compound AM-B 4,4'-diaminodiphenyl ether AM-C 4,4-diaminodiphenylmethane AM-D MDA-150 (compound represented by the following formula) Epoxy resin Epicoat 828: Trade name of bisphenol epoxy resin manufactured by Ciel Chemical Co., Ltd. DEN431: Trade name of novolac type epoxy resin manufactured by Dow Chemical Company Note (*) In Examples 3, 5, 6 and 7, N-
The (alkenylphenyl)maleimide and/or aliphatic maleimide and the amino compound are not a mere mixture but a prepolymer of the two or three components. That is, in Example 3, ABM-A and AM-D
Example 5 is a prepolmer of ABM-D.
and AM-C, and Examples 6 and 7 are three-component prepolymers.

[Table] 50 parts of N-(p-isopropenylphenyl)maleimide oligomer, 25 parts of N,N'-4,7-dioxadecane-1,10-bismaleimide and 15 parts of
After thoroughly mixing MDA-150, a melt reaction was performed at 120°C for 20 minutes to produce a prepolymer. Next, 90 parts of this prepolymer, 10 parts of Epicote 828, 3.3 parts of trimellitic anhydride, 120 parts of natural graphite, and 2.5 parts of calcium stearate were kneaded in a pressure kneader at a temperature of 100° C. for 30 minutes. This composition was then molded under pressure for 1 hour at a mold temperature of 200° C. and a pressure of 120 kg/cm ² . This molded product is JIS K-
The bending strength measured according to 6911 is 18.7Kg/at 25℃.
mm ² , 16.0Kg/after heating for 500 hours at 250℃
mm ² and showed satisfactory heat deterioration resistance.

Claims (1)

[Claims] 1 A: General formula () (In the formula, R ₁ to _{R 6} are the same or different, and each is a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 10 carbon atoms, or a phenyl group, or Alkyl group having 1 to 10 carbon atoms, halogen atom, R ₇ O- group, R ₇ CO- group, R ₇ COO-
is a phenyl group substituted with a group, a hydroxyl group or a cyano group, and each of R ₄ , R ₅ and R ₆ may be the same or different when a plurality of them are present, and X is a hydrogen atom, halogen atom,
Carboxyl group, hydroxyl group, R ₇ O− group, R ₇ CO−
group, R ₇ COO- group, or cyano group, and when multiple Xs exist, they may be the same or different, and m ₁ , m ₂ and m ₃ are each 0 to 4; So, m ₁ + m ₂ + m ₃ = 5,
Also, R ₇ is an optionally branched alkyl group having 1 to 10 carbon atoms or a phenyl group,
Or the number of carbon atoms that may be branched is 1
-5 alkyl group or phenyl group substituted with a halogen atom, and when multiple R _7s are present, they may be the same or different) N-(alkenylphenyl) represented by At least one maleimide compound selected from the group consisting of maleimide derivatives, dimers thereof, and multimers thereof, B: at least one aliphatic maleimide having an ether bond, C: at least one amino compound, and D: at least one type , and the proportions of component A and component B used are 2 to 99% by weight of component A and 1 to 98% by weight of component B, based on the total weight of both components, and the amount of component C used is The amount is such that the ratio of the total number of amino groups in component C to the total number of maleimide groups in components A and B is 1 or less, and the amount of component D used is 50% by weight of the total weight of the composition.
A thermosetting resin composition characterized by: 2. The thermosetting resin composition according to claim 1, which contains at least a portion of any two-component or three-component prepolymer of the A component, B component, and C component.