JPS621608B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition that provides a cured product with excellent heat resistance, and in particular, a heat-resistant resin composition that provides a varnish with improved workability and stability, and a molded product with excellent curability and physical properties after curing. The present invention relates to a curable resin composition. Maleimide resins are known as resins with excellent heat resistance, and are used as polymaleimide resins, which are homopolymers of maleimide compounds, and polymaleimide polyamine resins, which are polymerized with amines. This maleimide resin generally has sufficiently satisfactory performance in terms of heat resistance. However, the compound before curing has a high melting point and is hardly soluble in general-purpose organic solvents commonly used in the production of varnishes and laminates. Therefore, these compounds have the disadvantage that they must be dissolved in a polar solvent with a high boiling point and high hygroscopicity. Therefore, N-methyl-2-
Pyrrolidone, N/N-dimethylacetamide,
Impregnating varnishes are made using polar solvents such as N-N-dimethylformamide, but these solvents are not only expensive, but also penetrate and absorb more easily than the skin, and are toxic. Because it is strong, it is not suitable for work. Moreover, when producing a laminate using a varnish using these solvents, the solvent tends to remain in the product obtained by heating and curing, which is a major factor in reducing the performance of the product. Further, when a normal maleimide resin is used for manufacturing a copper-clad laminate, the adhesion between the copper foil and the base material is not necessarily good, and the processability such as punching is not satisfactory. On the other hand, epoxy resins are generally used in various electrical insulating materials, molded products, etc. because they provide cured products with excellent electrical properties, mechanical properties, dimensional stability, and chemical resistance when cured using various curing agents. It is widely used as adhesives and paints. However, despite these excellent properties, conventional epoxy resins are insufficient in terms of heat resistance, and various methods have been investigated to further improve heat resistance. . Attempts have been made to blend a maleimide compound into an epoxy resin in order to take advantage of the characteristics of both resins and at the same time compensate for their shortcomings to obtain a practical resin with excellent various performances. However, N・N′−
Generally known maleimide compounds such as (methylene-di-p-phenyl)bismaleimide have extremely poor compatibility with epoxy resins, and for example, when a varnish is made using a solvent, separation of the varnish may occur. However, when an attempt was made to use it for casting without a solvent, the maleimide compound precipitated as crystals, making it extremely difficult to obtain a uniform and stable composition suitable for practical use. The present inventors have conducted repeated studies with the aim of finding a maleimide compound that has excellent compatibility with epoxy resins, has a relatively low melting point, can be used as a solvent-free composition, and has high solubility in various solvents. As a result, N-(alkenyl phenyl) maleimide derivatives, dimers and multimers thereof are suitable for the above-mentioned purpose, and furthermore, the blend with epoxy resin has excellent curability and the physical properties of the cured product are satisfactory. We have discovered that this is the case, and have completed the present invention. That is, the present invention provides (1)(A) General formula () (In the formula, R ¹ to ^{R 3} each independently represent hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.) N-(alkenylphenyl)maleimide derivatives, dimers and multimers thereof and (B) one or more epoxy compounds having at least one epoxy bond in the molecule. Furthermore, the present invention provides (2)(A) an N-(alkenylphenyl)maleimide derivative represented by the above general formula (), Part 2
(B) one or more epoxy compounds having at least one epoxy bond in the molecule;
and (C) General formula () Q-(NH ₂ ) _o () (wherein, Q consists of 1 to 150 carbon atoms, hydrogen,
refers to an n-valent organic group that can include oxygen, sulfur, halogen, nitrogen, phosphorus, silicon,
This is a curable resin composition containing three components of an amino compound represented by (n is an integer of 1 or more), or a reactant of any two of the above three components and the remaining one component. The N-(alkenylphenyl)maleimide derivatives, their dimers and multimers, and their respective amine-modified products used in the composition of the present invention have significantly higher solubility in solvents than ordinary maleimide compounds. It has excellent compatibility with epoxy compounds. Therefore,
As already mentioned above, stable and uniform compositions with epoxy compounds could hardly be obtained with conventional maleimide compounds, but with the above N-
This was successfully obtained by using an (alkenyl phenyl)maleimide compound as a maleimide component. Moreover, the composition of the present invention can be applied to N-methyl-2-pyrrolidone, N-methyl-2-pyrrolidone, which has been used in conventional compositions containing maleimide compounds.
Even without using polar organic solvents such as N-dimethyl-formamide and N/N-dimethylacetamide,
Since the purpose can be sufficiently achieved using a general-purpose solvent with a relatively low boiling point, not only work efficiency but also the solvent can be easily removed from the product, making it possible to greatly improve the quality of the product. Ta. Further, the above N- used in the composition of the present invention
In addition to the unsaturated bonds of the maleimide group, (alkenyl phenyl) maleimide compounds have unsaturated bonds due to the alkenyl group or its polymer, which form strong bonds with the epoxy compound or curing agent and harden. By increasing the crosslink density of the product, it is possible to provide a molded product with excellent heat resistance and mechanical strength at high temperatures. The composition of the present invention not only has the enhanced heat resistance of ordinary maleimide compounds, but also fully retains the excellent properties of epoxy resins, which require precision and high reliability. It has promising properties as a material for the electronic field. The N-(alkenylphenyl)maleimide derivative used in the composition of the present invention is at least one compound selected from the group consisting of compounds represented by the above general formula (), dimers and multimers thereof. Examples of N-(alkenylphenyl)maleimide derivatives represented by the general formula () are:
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-(m-α-ethylvinylphenyl)maleimide, N-(p-α・β-dimethylvinylphenyl)maleimide, N-(p-
α・β-dimethylvinylphenyl)maleimide,
N-(p-α-methyl-β-isopropenylphenyl)maleimide, N-(m-α-methyl-β-
isopropenylphenyl)maleimide, N-(p
-α-isopropylvinylphenyl)maleimide, N-(p-α-isobutylvinylphenyl)
Examples include maleimide. The present invention includes the above N-(alkenyl phenyl)
Dimers of maleimides and multimers thereof can be used, and an example of a dimer of N-(alkenylphenyl)maleimides is: Examples include linear dimers of N-(p-isopropenylphenyl)maleimide represented by the formulas () and (). Also, N-(alkenylphenyl)
There are no particular restrictions on the maleimide multimer, but those with a molecular weight of 10,000 or less are preferred. In the composition of the present invention, one of the epoxy compounds having at least one epoxy bond in the molecule
A species or two or more species may be used. Specific examples of the epoxy compound used in the present invention include bisphenol A type epoxy resin,
Bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, triglycidyl cyanurate, triglycidyl isocyanurate and hydantoin epoxy, such as heterocyclic epoxy resin, hydrogenated Bisphenol A type epoxy resin, aliphatic epoxy resin such as propylene glycol diglycidyl ether and pentaerythritol polyglycidyl ether, epoxy resin obtained by reaction of aliphatic or aromatic carboxylic acid with epichlorohydrin, spiro ring-containing epoxy resins, such as glycidyl ether type epoxy resins which are reaction products of orthoaryl phenol novolac compounds and epichlorohydrin. The composition ratio of the epoxy compound to the maleimide compound used in the composition of the present invention is in the range of 3:97 to 97:3, preferably in the range of 5:95 to 95:5. If the amount of the epoxy compound used is less than the above range, the excellent mechanical properties of the epoxy compound, good adhesion to glass cloth, copper foil, etc., dimensional stability, favorable electrical properties, etc. will hardly be observed. However, only a relatively brittle cured product is obtained, and the effects of the present invention are lost.
On the other hand, if the amount of the epoxy compound used exceeds the above range, the effect of the maleimide component used in the present invention will not be recognized, and in particular, the heat resistance of the cured product will be significantly reduced. In the composition of the present invention, the epoxy compound curing agent is not necessarily an essential component, but can be used together with the epoxy compound if necessary. In this case, there are no particular restrictions on the amount used.
However, the amount used should not be so great as to interfere with the excellent effects exhibited by the maleimide compound and the epoxy compound, respectively, but should be limited to a range that improves the performance of the composition of the invention. Curing agents used as necessary include boron trifluoride amine complexes such as boron trifluoride monoethylamine complexes and boron trifluoride piperidine complexes, triethylamine, benzylmethylamine, hexamethylenetetramine, N.N-
Tertiary amines such as dimethylaniline, quaternary ammonium salts such as tetramethylammonium bromide, borate compounds such as triphenyl borate, tricresyl borate, N-methylimidazole, N-ethylimidazole, N-
Imidazole compounds such as phenylimidazole and N-vinylimidazole, zinc acetate, sodium acetate, cobalt naphthenate, titanium acetylacetonate, iron acetylacetonate, nickel acetylacetonate, sodium methylate,
Metal compounds such as sodium ethylate and tetrabutoxy titanate, amide compounds obtained from amine compounds and carboxylic acid compounds, urea compounds, melamine compounds, dicyandiamide, bisphenol A, bisphenol F, bisphenol S, pyrocarol, resorcinol, catechol , phenolic compounds such as hydroquinone and various phenolic resins obtained by the reaction of phenol with aldehydes or ketones, methylene-di-P-phenylene-diisocyanate, sulfone-di-m-phenylene-diisocyanate,
Isocyanate compounds such as tolylene diisocyanate, cyanate compounds such as methylene-di-p-phenylene-dicyanate, oxy-di-P-phenylene-dicyanate, sulfone-di-m-phenylene-dicyanate, phthalic anhydride,
Hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, nadic anhydride, methyl-nadic anhydride, chlorendic anhydride, dodecyl succinic anhydride, methyl succinic anhydride , acid anhydrides such as benzophenonetetracarboxylic anhydride, pyromellitic anhydride, maleic anhydride, dicumyl peroxide, t-butyl perbenzoate, methyl ethyl ketone peroxide, azobisisobutyronitrile, etc. . In the second invention of the present invention, in addition to the maleimide compound and the epoxy compound, compounds of the general formula () Q-(NH ₂ ) _o () (wherein Q is hydrogen having 1 to 150 carbon atoms, oxygen,
An n-valent organic group that can contain sulfur, halogen, nitrogen, phosphorus, and silicon, where n is an integer of 1 or more, is used. Examples of amino compounds represented by the general formula () include aniline, toluidines, xylidines, vinylanilines, isopropenylanilines, phenylenecyamines, diaminocyclohexane, 2,4-diaminotoluene, 4,4 '-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(4'-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfate Ido,
4,4'-diaminodiphenylsulfone, 4,4'-
Diaminodicyclohexylmethane, m-xylylenediamine, P-xylylenediamine, bis(4
-aminophenyl)diphenylsilane, bis(4
-aminophenyl)methylphosphine oxide,
Bis(4-aminophenyl)methylphosphine oxide, tris(4-aminophenyl)thiophosphate, tris(4-aminophenyl) phosphate, 1,5-diaminonaphthalene, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylene Diamine, nonamethylene diamine, 4-methyl-2,4-bis(P-aminophenyl)pentene-1, 4-methyl-2,4-bis(P-aminophenyl)pentene-2, and isopropenyl of trimer or higher Anilines can be obtained by reacting polymers, vinylaniline polymers, aromatic amines (e.g., aniline, toluidines, xylidines, anisidines) with aldehydes, ketones (e.g., formaldehyde, acetaldehyde, acetone). Examples include poly(phenylmethylene) polyamines obtained by the reaction of aniline and formaldehyde. As mentioned above, the type of amino compound may be aliphatic, alicyclic, or aromatic.
Furthermore, it may be substituted with various substituents.
Furthermore, the molecule may contain oxygen, halogen, sulfur, phosphorus, silicon, and other various metal atoms. The amount of the amino compound used in the composition of the present invention is not particularly limited, but the N-
The weight ratio to the (alkenyl phenyl)maleimide component is in the range of 3:97 to 97:3, preferably
It is in the range of 5:95 to 95:5. If the amount of the amino compound used is less than the above range, the effects expected when the amino compound is coexisting, for example, excellent solubility in a solvent having a composition consisting of an N-(alkenylphenyl)maleimide component and an epoxy compound. , the effect of further increasing the impact resistance of the cured product is hardly recognized. On the other hand, if the amount of the amino compound used is greater than the above range, the heat resistance of the resulting cured product will be significantly reduced, and when used in insulation varnishes, copper-clad laminates, etc., there is a risk of accelerating copper corrosion. When impregnating and laminating with glass cloth, etc., there are drawbacks such as a large flow of resin. The optimum amount of the amino compound to be used varies depending on the amount of maleimide groups and double bonds other than maleimide groups in the maleimide component and the amount of epoxy groups present in the epoxy compound. The composition of the present invention may contain a maleimide compound of the general formula (), an epoxy compound, and an amino compound of the general formula (), or may contain a reactant of any two of these three components and the remainder. It is also possible to consist of components. That is, after the maleimide compound of the general formula () and the amino compound of the general formula () are reacted in advance, a curable composition can be prepared together with the epoxy resin. There are no particular restrictions on the mixing ratio of both components when reacting a maleimide compound and an amino compound, but preferably the ratio of the total number of amino groups in the amino compound to the total number of maleimide groups in the maleimide component (formula ()) is 1 or less. , more preferably in the range of 1 to 0.01. (ma・na/Ma)/(mi・ni/Mi)
1() (where mi, ni and Mi represent the amount of maleimide compound used, the average number of maleimide groups in the molecule, and the average molecular weight, respectively, and ma, na and Ma
represent the amount of the amine component used, the average number of amino groups in the molecule, and the average molecular weight, respectively. ) The reaction between a maleimide compound and an amino compound is generally carried out by directly mixing the two components without a solvent and homogenizing them by heating, or by using a solvent to react as a homogeneous solution or suspension of both components. However, there are no restrictions on the specific reaction method. The reaction is usually carried out at a temperature of 50 to 200°C for a period of 0 to 20 hours. Furthermore, catalysts, additives, etc. may be used as necessary. Alternatively, the epoxy compound and the amino compound of the general formula () may be mixed and reacted in advance, and then a curable composition may be prepared together with the maleimide compound of the general formula (). In the reaction between an epoxy compound and an amino compound, the amino compound acts as a curing agent and increases its molecular weight, resulting in a product that is insoluble and infusible in solvents. is used as a prepolymer with a range of from 50 to 8000 together with maleimide compounds and other compounds. Furthermore, a composition comprising a product obtained by reacting a part of an epoxy compound and an amino compound as described above as a constituent component and containing other epoxy compounds, amino compounds, and maleimide compounds, or a composition of the general formula () The composition may contain an amino compound and a reaction product obtained by reacting a maleimide compound and an epoxy compound in advance. The composition of the present invention can be applied to either a solvent-free method in which the composition is simply mixed and homogenized and heated, or a method using a solvent. When using a solvent, there are no particular limitations on the solvent used, but examples of preferred solvents include 1,4-dioxane, tetrahydrofuran, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexane, chloroform, methylene chloride, trichloroethane, benzene toluene, xylenes, acetonitrile, 2-
Methoxyethanol, 2-ethoxyethanol,
Examples include 2-n-butoxyethanol and 2-ethoxyethyl acetate. Also, N/N-dimethylformamide, N/N-dimethylacetamide, N-methyl-2-pyrrolidone,
A uniformly dissolved composition can be obtained using dimethyl sulfoxide, hexamethylphosphoramidate, etc., but these solvents have major drawbacks as mentioned above, so they should not be used unless there are special purposes or restrictions. It is preferable to refrain from using it. The concentration of the total resin when using a solvent varies depending on the purpose and conditions in which the composition is actually used, but is preferably in the range of 5 to 80% for ordinary impregnated varnishes.
For example, when used in the manufacture of laminates, if the total resin concentration is lower than 5%, it will be difficult to impregnate the glass cloth with the required amount of resin, and the impregnation process will have to be repeated or carried out for a long time. , workability is significantly reduced. On the other hand, it is practically difficult to increase the concentration of the total resin content to 80% or more due to constraints such as solubility and compatibility, but even if it is possible, the viscosity of the solution will increase significantly and it will cause defoaming before curing. This makes it difficult and causes problems in work. Particularly preferred total resin concentrations range from 10 to 70% by weight. Furthermore, the composition of the present invention can also be used in the form of an emulsion or a suspension. The composition of the present invention includes the above-mentioned N-(alkenylphenyl)maleimide compound, epoxy compound, and optionally an amino compound,
In addition to these arbitrary two-component reactants, the following components can be added. (1) Powdered reinforcing agents, fillers and thickeners, e.g.
Alumina, diatomaceous earth powder, magnesia, kaolin, magnesium carbonate, basic magnesium silicate, calcined clay, finely powdered silica, carbon black, etc.Fiber reinforcing agents and fillers such as glass fiber, rock wool, ceramic fiber, asbestos and These include inorganic fibers such as carbon fiber, paper, pulp, wood flour, linters, and polyamide fibers. The amount of these powder or fibrous reinforcing agents and fillers used varies depending on the purpose, but as a laminated material or molding material, it can be used up to 4 times the weight of the resin solid content. (2) Coupling agents, such as vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, n -(trimethoxysilylpropyl)ethylenediamine, n-(di-methoxymethyl-silylpropyl)ethylenediamine, γ-chloropropyltrimethoxysilane,
Vinyltrichlorosilane, β-3,4-epoxycyclohexylethyltrimethoxysilane,
Examples include γ-mercaptopropyltriethoxysilane. The amount of coupling agent used is usually in the range of 0.001 to 10.0%, preferably in the range of 0.01 to 5%, based on the weight of the total resin. (3) Flame retardants, flame retardants, tetrabromo bisphenol A, tetrabromo phthalic anhydride, brominated epoxy resins (epoxides of brominated bisphenol A, brominated novolac, etc. and other halides), decabromodiphenyl ether, Hexabromobenzene, tetrabromo terephthalic acid, chlorinated paraffin, Diels-Alder adduct of hexachlorocyclopentadiene, red phosphorus, tricresicle phosphate, phosphonic acid esters, phosphinate esters, phosphoroamidates, trioxide antimony, and ranges from 1 to 70%, preferably from 5 to 40%, based on the weight of the total resin. (4) Various natural and semi-synthetic products can be blended for the purpose of improving the properties of resins in adhesive layers, resin molded products, coatings, etc. Such resins include, for example, drying oils, semi-drying oils, oleoresins, rosins, silica resins, oil-modified rosins, phenolic resins, alkyd resins, urea resins, melamine resins, polyester resins, polyvinyl butyral resins, vinyl acetate resins, chlorinated resins, etc. Examples include one or a combination of two or more of vinyl resin, acrylic resin, and silicone resin. The amount of these resins used is within a range that does not impair the inherent properties of the composition of the present invention, that is, 30% by weight or less of the total resin amount. Curing conditions for producing a cured product from the curable resin composition of the present invention vary depending on the type of catalyst or resin actually used, and also vary depending on the form of the composition. Generally, the composition of the present invention is applied to a substrate as an adhesive or coating, or formed or laminated as a powder, pellet, or impregnated into a substrate, and then cured by heating. The curing temperature is generally in the range of 0 to 300°C, preferably 100 to 250°C. The heating time for curing is particularly affected by the form, but generally a time sufficient for the resin component to be completely cured may be selected within the range of 30 seconds to 10 hours. Furthermore, 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 100 kg/m ² . Although there are no particular restrictions on the manner in which the composition of the present invention is actually used, examples of the preparation of impregnating varnishes and laminates are as follows. A homogeneous solution of an organic solvent containing an N-(alkenylphenyl)maleimide compound, an epoxy compound, an optionally used amino compound, or each reactant is prepared. At this time, it is preferable that the concentration of the total resin content in the solution is within the range of 10 to 70%. Other curing agents, silane coupling agents, flame retardants, etc. are added to the solution obtained in this manner as necessary, and the mixture is uniformly blended to form a varnish. Impregnate a sheet reinforcing material such as glass cloth, glass paper, glass nonwoven fabric, asbestos paper, etc. with the impregnating varnish obtained in the above procedure, air dry for a certain period of time as necessary, and then heat in an oven at 60 to 160℃. Dry inside to obtain pre-prebs. A prepreg obtained from a uniform varnish prepared according to the composition of the present invention does not cause separation of components or foaming even during drying, and has preferable dryness to the touch. The prepreg sheet thus obtained can be stably stored at room temperature for a long period of time. After layering multiple prepreg sheets, if necessary, layer copper foil on one or both sides.
Temperature 100 to 250℃, pressure 1 to 100kg/compression molding machine
Pressure molding is performed at cm ² for a certain period of time. During this compression molding, the molten resin exhibits appropriate flow characteristics and uniform impregnation of the resin is promoted. In this way, the resin is cured and a good laminate or copper-clad laminate is obtained. The present invention will be further explained below with reference to Examples. Example 1 4-methyl-2,4-bis(p-N-maleimidophenyl)pentene-138.5g and DEN-431
(Novolak epoxy resin manufactured by Dow Chemical Company)
16.5 g was dissolved and homogenized in 45 g of tetrahydrofuran. A glass cloth (thickness: 0.18 mm) was impregnated with this varnish and further dried at 100°C for 20 minutes to obtain a prepreg. Stack nine of these prepreg sheets, place one copper foil on top, press at a pressure of 40 kg/cm ² , heat from 100°C to 180°C over 30 minutes, and then heat at 180°C for 1 hour. A copper-clad laminate was obtained by heating. Furthermore, this laminate was subjected to after-curing in an oven at 220°C for 10 hours. Table 1 shows the solder heat resistance and copper foil peel strength of the obtained laminate. Example 2 N-(p-isopropenylphenyl)maleimide oligomer (composition, monomer 2.7%, dimer 77.3
%, trimer 6.7%, tetramer or more 13.3%), 42.6 g of 4,4'-diaminodiphenylmethane, 22.5 g of Epicote-828 (bisphenol epoxy resin manufactured by Ciel Chemical Co., Ltd.), and 61.4 g of methyl ethyl ketone. dissolved in A glass cloth (thickness: 0.18 mm) was impregnated with this varnish and further dried at 95°C for 15 minutes to obtain a prepreg. Nine sheets of this prepreg sheet were stacked, one sheet of copper foil was placed on top of the sheets, and the sheets were pressed, crimped, and cured under the following conditions. The press pressure was set to 40 kg/cm ² , and the temperature was raised from 100 to 180°C in 30 minutes and maintained at 180°C for 1 hour. Table 1 shows the solder heat resistance and copper foil peel strength of the obtained laminate. Example 3 4-Methyl-2,4-bis(p-N-maleimidophenyl)pentene-1 89.5% and 4-methyl-2,4-bis(p-N-maleimidophenyl)pentene-2 10.5% 213 g of a linear dimer mixture of N-(p-isopropenylphenyl)maleimide consisting of It was allowed to react for a minute. After cooling the reactant, 44 g of powder obtained by crushing and DEN-431 11
g was dissolved in 45 g of dioxane to obtain a varnish. Using the varnish thus prepared, a laminate was prepared under the conditions of Example 1, and the solder heat resistance and copper foil peel strength were measured, and the results are shown in Table 1. Comparative Example 1 89.6 g of N.N'-(methylene-di-p-phenylene) bismaleimide and 24.8 g of 4,4'-diaminodiphenylmethane were thoroughly pulverized and mixed into a powder, which was further heated to 120°C and melted. It was allowed to react for a minute. After cooling and solidifying the reactant, 41 g of powder obtained by crushing the product and 10 g of DEN-431 were mixed with N.
A varnish was prepared by dissolving it in 45 g of N'-dimethylformamide. Apply this varnish to a glass cloth (thickness
0.18 mm) and further dried at 160°C for 20 minutes to obtain a prepreg. This prepreg sheet is 9
Stack one sheet of copper foil on top of that, pressing pressure 40
Kg/cm ² , the temperature was raised from 120°C to 180°C over 30 minutes, and further heated at 180°C for 1 hour to obtain a copper-clad laminate. Table 1 shows the solder heat resistance and copper foil peel strength of the obtained laminate. Comparative Example 2 N-
It was dissolved and homogenized in 45 g of methyl-2-pyrrolidone.
A copper-clad laminate was produced under the same conditions as Comparative Example 1, and the solder heat resistance and copper foil peel strength are shown in Table 1.

[Table] Example 4 N-(p-isopropenylphenyl)maleimide oligomer (composition: monomer 3.7%, dimer 83.3%
%, trimer 5.1%, tetramer or more 7.9%) and 3 g of Epicote 1001 (bisphenol epoxy resin manufactured by Ciel Chemical Co., Ltd.) were dissolved in 50 g of methyl ethyl ketone to prepare a varnish, and the stability of the varnish was determined by changing the viscosity. We investigated and obtained the results shown in Table 2. Comparative Example 3 Prepolymer 47 prepared from N·N′-(methylene-di-p-phenylene)bismaleimide and 4·4′-diaminodiphenylmethane as in Comparative Example 1.
g, 3g of Epicote 1001 to methyl ethyl ketone
Although it was mixed with 50g of the liquid, it was insoluble. When 50 g of N-methyl-2-pyrrolidone was used instead of methyl ethyl ketone and dissolved, a homogeneous solution was obtained.The stability of the varnish thus prepared was investigated by viscosity measurement, and the results are shown in Table 2. Got the results.

【table】

Claims (1)

[Claims] 1 (A) General formula () (In the formula, R ¹ to ^{R 3} each independently represent hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.) N-(alkenylphenyl)maleimide derivatives, dimers and multimers thereof A thermosetting resin composition characterized by containing at least one compound selected from the group consisting of: and (B) one or more epoxy compounds having at least one epoxy bond in the molecule. . 2 (A) General formula () (In the formula, R ¹ to ^{R 3} each independently represent hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.) N-(alkenylphenyl)maleimide derivatives, dimers and multimers thereof (B) one or more epoxy compounds having at least one epoxy bond in the molecule, and (C) the general formula () Q-(NH ₂ ) _o () (wherein, Q represents an n-valent organic group consisting of 1 to 150 carbon atoms and capable of containing hydrogen, oxygen, sulfur, halogen, nitrogen, phosphorus, and silicon, and n is 1
is an integer greater than or equal to ) A thermosetting resin composition comprising three components of an amino compound represented by the following formula, or a reactant of any two of the three components and a remaining component.