JPH0222314A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the tittle resin composition useful as varnish, etc., having excellent compatibility, workability and stability, capable of forming cured material of high heat resistance and impact resistance, containing components of a specific maleimide derivative, allyl compound, amine compound, etc., in an arbitrary form. CONSTITUTION:Three components of (A) a maleimide derivative shown by formula I (D is 2-200C n-functional organic group containing one or more carbon- carbon double bonds; R<1>-R<3> are H, 1-20C hydrocarbon or halogen; m<1> and m<2> are positive integer and m<1>+m<2>=5; n is positive integer) or maleimide compound [e.g., N-(p-isopropenylphenyl)maleimide] such as dimer or polymer of the derivative, (B) an allyl compound (e.g., diallyl phthalate) containing at least one allyl group in the molecule and (C) an amine compound (e.g., 4,4'- diaminodiphenylmethane) shown by formula II (Q is 1-150C m-functional organic group; m is positive integer) are blended or a reaction product of any two of the components is blended with the rest of one component to give the aimed resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition that provides a cured product with excellent heat resistance, and this composition particularly provides a face with improved workability and stability, as well as curability and physical properties after curing (! We provide molded products that are

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 maleimide compounds together with aminos. This maleimide resin generally has sufficiently satisfactory performance in terms of heat resistance, but the compound before curing has a high melting point (and most of the general-purpose organic solvents commonly used in the production of varnishes and laminates do not have a high melting point). It dissolves easily, has a high boiling point,
However, since it has the disadvantage of being soluble only in highly hygroscopic polar solvents, N-methyl-2-pyrrolidone,
Impregnating varnishes have to be made using polar solvents such as N,N-dimethylacetamide and N,N-dimethylformamide, and therefore, not only are these solvents expensive, but they also have difficulty penetrating and absorbing into the skin. It is highly toxic and undesirable for work.

Moreover, when producing laminates from varnishes using these solvents, the solvent tends to remain in the product obtained by heating and curing, which is a major factor in reducing performance.

Furthermore, it is known that allyl compounds having an allyl group in the molecule form resins with very excellent properties through polymerization. Allyl polymers obtained from allyl compounds have particularly excellent electrical properties, heat resistance, and mechanical properties, and if maleimide resins can be produced by copolymerizing allyl compounds, they will have even higher performance than the same components alone. It was previously expected that enhanced polymers would be obtained.

However, known maleimide resins have extremely low solubility in or compatibility with allyl compounds (for this reason, it has been difficult to obtain a cured product with the expected performance even if the two are mixed and cured. This is because the mutual solubility of the two is poor, making it difficult to proceed with uniform copolymerization.
Therefore, a cured product having excellent physical properties cannot be obtained.

The present inventors have conducted repeated studies with the aim of finding a maleimide compound that has excellent compatibility with allyl compounds and high solubility in commonly used general-purpose organic solvents. By using a maleimide compound having a double bond in its moiety, the above objectives can be easily achieved,
Furthermore, the inventors have discovered that the cured product containing the maleimide compound and allyl compound has excellent physical properties, leading to the completion of the present invention.

In particular, when a liquid allyl compound is used, since the maleimide compound of the present invention is easily dissolved therein, a uniform mixed solution of both resins can be obtained without a solvent, and this can be advantageously used in many applications.

That is, the present invention provides [where D is an n-valent organic group having 2 to 200 carbon atoms containing at least one carbon-carbon double bond;
R3 is each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, and may be the same or different from each other, ml and 1m" are positive integers, and m'+m"=5
and when ml is 2 or more, R1 may be the same or different from each other, and n is a positive integer], dimers and multimers thereof; Both are maleimide compounds.

(B) one or more allyl compounds having at least one allyl group in the molecule, and (C) general formula (n) Q-(NHi)m...(If) (where Q
is an m-valent organic group having 1N150 carbon atoms which may contain hydrogen, oxygen, sulfur, halogen, nitrogen, phosphorus or silicon atoms, where m is a positive integer) The compound contains three components, or any two of the above three components.
This is a thermosetting resin composition characterized by containing reactants of the components and one remaining component.

The maleimide compound used in the composition of the present invention is a compound having one or more carbon-carbon unsaturated bonds in a part other than the maleimide group in the molecule, and has a structure represented by general formula (1). Maleimide derivatives represented by the general formula (1) include N-(0-vinylphenyl ) Maleimide, N-(m-vinylphenyl)maleimide, N(
p-vinylphenyl)maleimide, N-(0-isopropenylphenyl)maleimide, N-(m-isopropenylphenyl)maleimide, N-(p-isopropenylphenyl)maleimide, N-(vinyltolyl)maleimide (o+, (including all m- or p-isomers),
N-(isopropenyltolyl)maleimide (o+, m-
or p-), N-(p-α-ethylvinylphenyl)maleimide, N-(m-α-ethylvinylphenyl)maleimide, N-(p-α, β-
dimethylvinylphenyl)maleimide, N-(m-α
, β-dimethylvinylphenyl)maleimide, N-(p
-a-methyl-β-isopropylvinylphenyl)maleimide, N-(m-α-methyl-β-isopropylphenyl)maleimide, N-(p-α-isobutylvinylphenyl)maleimide, N-(m-α-in butylvinylphenyl)maleimide, N-(p-1-cyclohexerphenyl)maleimide, N-(m-1-cyclohexerphenyl)maleimide, N-(0-vinylphenyl)-3,4-dichloromaleimide , N-(m-vinylphenyl)-3,4-dichloromaleimide, N-(p-
vinylphenyl)-3,4-dichloromaleimide, N-
(p-isopropenylphenyl)-3,4-dichloromaleimide, N -(m-impropenylphenyl)-3
,4-dichloromaleimide, N-(o-isopropenylphenyl)-3,4-dichloromaleimide, N-(p-
isopropenylphenyl)-3,4-dibromomaleimide, N-(p-impropenylphenyl)-3,4-dibromomaleimide, N,N'-(1-vinyl-2,4-
phenylene) bismaleimide, N, N'-(1-vinyl-3,5-phenylene) bismaleimide, N, N'-(
1-Ipropenyl-2,4-phenylene)bismaleimide, N,N'-(1-isopropenyl-3,5-phenylene)bismaleimide, N-<p-vinylphenyl)
-3,4-di-monobutylmaleimide, N-(p-isopropenylphenyl)-3,4-diisopropylmaleimide, N-[4-α-methyl-β-(m-chlorophenyl)vinylphenyl 1maleimide, N -(m-impropenylphenyl)-3(p-chlorophenyl)maleimide, 2-impropenyl-4-N-may-mide-4
゛-Chlorobiphenyl, 4-impropenyl-2-N-
Maleimido-4°-methylbiphenyl, 2,4.6-
Tris(N-maleimido)styrene, 3.4.5-tris(N-maleimido)styrene, 1-isopropenyl-
2,4,6-)lis(N-maleimido)benzene, 4,
4゛-bis(N-maleimide) cis-styreneben, 4.4゛-bis(N-maleimide) trans-stilbene, 1.3-bis(p-N-maleimidophenyl)propene-1% 1.4- Bis(p-N-maleimidophenyl)butene-1,1,3-bis(p-N-maleimidophenyl)=3-methyl-butene-1,2,4-bis(
p-N-maleimidophenyl)-pentene-2,2,4
-bis(p-N-maleimidophenyl)-pentene-1
14-Methyl-2,4-bis(p-N-maleimidophenyl)pentene-2,4,6-dimethyl-2.4.6-
Dolisu(p-N-maleimidophenyl)hebutene-1
,4,6-dimethyl-2.4,6-tris(p-N-maleimidophenyl)butene-2,4,6,8-trismethyl-2,4,6,8-tetrakis(p-N-maleimidophenyl) ) nonene-1゜4,6.8-trimethyl-
Examples include 2,4,6,8-tetrakis(p-N-maleimidophenyl)nonene-2.

Allyl compounds having at least one allyl group in the molecule used in the composition of the present invention include all known allyl compounds.

Examples of typical allyl compounds used in the present invention include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, allyl benzoate, triallyl trimellitate, triallyl trimesate, tetralyl pyromellitate, allyl acetate, and malonic acid. Diallyl, diallyl succinate, diallyl maleate, allyl acrylate, allyl methacrylate, allyl p-chlorobenzoate, diallyl 4-methylphthalate, triallyl isocyanurate, triallyl cyanurate, hexaallylmelamine, 2,4-bis(
There are allyl ethers of diallylamino)-6-phenyl-sym-triazine and phenols, and allyl phenols and derivatives thereof obtained by heat-treating these at high temperatures to cause so-called Claisen rearrangement.

Raw material phenols for forming allyl ethers of phenol and allyl phenols include phenol, p
-Cresol, m-cresol, 0-cresol, resorcin, hydroquinone, catechol, p-chlorophenol, m-chlorophenol, pyrogallol, phloroglucin, p-nitrophenol, m-nitrophenol, p-amiphenol, m-aminophenol ,p-
Aminophenol, 2,2-bis(p-hydroxyphenyl)propane, 2-(p-hydroxyphenyl)-2
-(p-aminophenyl)propane, bis(p-hydroxyphenyl)ether, bis(p-hydroxyphenyl)sulfide, bis(p-hydroxyphenyl)sulfone, bis(p-hydroxyphenyl)ketone, 1.5
-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and the like. Allyl ethers of phenols are usually obtained by condensing allyl halides and various phenols in the presence of a dehydrochlorinating agent. Furthermore, allylphenols are obtained by heating allyl ether of phenols to usually 180° C. or higher to cause Claisen rearrangement.

Furthermore, low molecular weight polymers of the allyl compounds described above having residual double bonds (oligomers or prepolymers) can also be used as the allyl compound component of the present invention.

Examples include diallyl phthalate prepolymer, diallyl isophthalate prepolymer, triallyl isocyanurate prepolymer, etc. All of the compounds already listed as allyl compounds can form prepolymers; can also be used in the present invention.

Such prepolymers of allyl compounds can be easily produced by known methods, and many of them are commercially available.
Taking the prepolymer of triallyl isocyanurate as an example, triallyl isocyanurate is dissolved in carbon tetrachloride or other organic solvent, a small amount of radical catalyst is added, heated, reacted for a certain period of time, cooled, and a precipitant is added. It is obtained as a white powder. The prepolymer thus obtained usually has a bromine number of 50 to 100 and a molecular weight of 1.
It is a compound of about 500 to 4,000.

The above allyl compounds can be used in the present invention alone or as a mixture of two or more.

The weight-based composition ratio of the allyl compound to the maleimide compound used in the composition of the present invention varies depending on the purpose of use and the type of allyl compound and maleimide compound or amino compound, but is usually 3:97 to 97:
3, preferably 5:95 to 95:5. If the amount of the allyl compound used is less than the above range, the viscosity of the mixture will be very high (the viscosity cannot be lowered without using a large amount of solvent, which is not only disadvantageous in practice but also reduces the properties of the cured product. If the allyl compound is used in an amount exceeding the above range, it is possible to lower the viscosity, but the polymerizability is significantly reduced and a sufficient curing rate cannot be obtained even if the curing conditions are tightened.Therefore, using a large amount of polymerization catalyst It becomes necessary to cure the cured product, resulting in deterioration of the properties of the cured product.

In the present invention, an amino compound represented by general formula (II) is used in addition to the maleimide compound and allyl compound described above. By using this amino compound, the effect of further enhancing the excellent compatibility, solubility in general-purpose solvents, impact resistance of the cured product, etc. possessed by the above-mentioned composition comprising the maleimide compound and allyl compound can be obtained.

Examples of amino compounds represented by general formula (II) include aniline, toluidines, xylidines, vinylanilines, impropenylanilines, phenylenediamines, diaminocyclohexanes, 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°-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-diaminotoluene, ethylenediamine, trimethylenediamine, tetramethylene diamine, hexamethylene diamine, nonamethylene diamine, 4-methyl-2,4-bis(p-aminophenyl)pentene-1,4-methyl-2,4-(1)-aminophenyl)pentene-2, and Polymers of isopropenylanilines or vinylanilines, aromatic amines (e.g. aniline, toluidine,
Examples include polyamines obtained by the reaction of xylidines, anisidines) with aldehydes and ketones (e.g. formaldehyde, acetaldehyde, acetone), particularly poly(phenylenemethylene) polyamines obtained by the reaction of aniline with formaldehyde. can. The above poly(phenylene methylene) polyamine is
Industrially manufactured as a raw material for polyurethane, MD
It is commercially available as A-150 (manufactured by Mitsui Toatsu Chemical Co., Ltd.).

As mentioned above, the type of amino compound of general formula (II) may be aliphatic, alicyclic, or aromatic,
Furthermore, the molecule may be substituted with various substituents, and the molecule may contain oxygen, halogen, sulfur, phosphorus, or silicon atoms (of course, impurities originating from the manufacturing process of amino compounds) may contain various metal atoms.

Although there are no particular restrictions on the amount of the amino compound used in the composition of the present invention, the weight ratio of the amino compound to the maleimide component is preferably in the range of 3:97 to 97:3, more preferably 5:95 to 95:5. Good range. If the amount of the amino compound used is less than the above range, the above-mentioned effects obtained when using the amino compound will hardly be observed.

On the other hand, if the amount of the amine 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 glass cloth is used for impregnation and lamination molding, disadvantages such as excessive flow of the composition of the present invention occur. The optimum amount of the amino compound to be used varies depending on the amount of maleimide groups and biaxial bonds other than maleimide groups in the maleimide compound, and the amount of allyl groups present in the allyl compound, but it also depends on the viscosity of the mixed composition and the curing speed. It is preferable to specify factors that influence the workability of the composition of the present invention during practical use, such as:

The composition of the present invention uses the above-described maleimide compound, allyl compound, and amino compound of general formula (II), and is composed of the reactant of any two of these three components and the remaining component. It is also possible.

That is, the composition of the present invention can be prepared by reacting the maleimide compound and the amino compound in advance and then combining them with the allyl compound. There is no particular restriction on the mixing ratio of the same components when reacting a maleimide compound and an amino compound, but preferably the ratio of the number of amino groups to the total number of maleimide groups in the maleimide component (formula (II
It is appropriate that I) be 1 or less, more preferably in the range of 1 to 0°01. When this ratio exceeds 1, practical problems such as heat resistance of the cured product, corrosion of steel, and excessive flow tend to occur, and when this ratio is less than 0.01, both reactants may not be obtained substantially. many.

(In the formula, mi, ni and ML each represent the weight used, the average number of maleimide groups in the molecule, and the average molecular weight of the maleimide compound, and ma, na and Ma represent the weight used and the average number of maleimide groups in the molecule, respectively, of the amino compound. The reaction between the maleimide compound and the amino compound in this case shows the average number of amino groups and average molecular weight of
Generally, both components are directly mixed without a solvent and reacted by heating and homogenizing, or a solvent is used to react as a homogeneous solution or suspension of both components, but depending on the specific reaction method. No constraints 0 reaction 1 at temperatures between 50 and 200°C
It is usually carried out within a range of minutes to 20 hours, but it is also possible to use catalysts, additives, etc. as necessary.

Furthermore, the curable composition of the present invention can be prepared by mixing and reacting the maleimide compound and allyl compound in advance, and then using them together with the amino compound represented by general formula (II). The reactant of both components is preferably an oligomer with a relatively low molecular weight, and the composition of the present invention can be prepared by mixing the oligomer with an amino compound.

Furthermore, in the composition of the present invention, a prepolymer is prepared by reacting an allyl compound and an amino compound in advance using a catalyst or a solvent as necessary, and the resulting prepolymer and a maleimide compound are mixed. A composition can be prepared.

The composition of the present invention can be applied to a solvent-free method in which the components are simply mixed and homogenized. In particular, allyl compounds are often liquids with relatively low viscosity (in this case, the maleimide compound used in the present invention has excellent compatibility with allyl compounds, so it forms a uniform liquid with allyl compounds even at room temperature). Furthermore, even when an amino compound is used in addition to the above components, a uniform liquid composition can be obtained because the amino compound usually has good solubility.Also, depending on the type and composition of the allyl compound and maleimide compound, Although it is sometimes difficult to form a uniform liquid phase, it is usually possible to obtain a uniform liquid composition by only slight heating.

The liquid composition obtained in this way does not require a solvent during curing, and therefore has the advantage of not requiring an operation to remove the solvent and greatly simplifying the process. It can be directly used in fields such as

As mentioned above, the composition of the present invention allows a cured product with excellent performance to be obtained without using a solvent, but a solvent may be used if there is a particular need for reducing viscosity. When using a solvent, there is no particular restriction on the type of solvent used, but examples of preferred solvents include 1,4-dioxane, tetrahydrofuran, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, chloroform, methylene chloride, trichloroethane, benzene, Toluene, xylenes, acetonitrile, 2-methoxyethanol, 2
-ethoxyethanol, 2-n-butoxyethanol,
Examples include 2-ethoxyethyl acetate. A uniformly dissolved composition can also be obtained using N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoroamidate, etc.
As mentioned above, these solvents have major drawbacks, so it is preferable to refrain from using them unless there are special purposes or restrictions.

The concentration of the composition of the invention in solution when using a solvent is:
Although it varies depending on the actual use of the composition of the present invention, usage conditions, etc., the range is preferably from 5 to 90% in the case of ordinary impregnated varnish. For example, when used in the production of a glass cloth-based laminate, if the concentration is lower than 5%, it will be difficult to impregnate the glass cloth with a substantially required amount of the composition of the present invention; The impregnation process must be repeated or carried out for a long time, resulting in a significant decrease in workability. On the other hand, if the concentration is 90% or more, the purpose of using the solvent is often not achieved. Particularly preferred 1 degree is within the range of 10 to 80% 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 is easily cured even without a catalyst. especially,
While allyl compounds are known to be relatively stable, curing is accelerated when an allyl compound and a maleimide compound are allowed to coexist in a uniformly mixed system according to the present invention. This effect is even more remarkable due to the presence of the amino compound, and usually does not require a polymerization catalyst.

However, if you need Sarabanko to harden in a short time,
Radical polymerization catalysts, anionic polymerization catalysts, cationic polymerization catalysts, etc. can be used. In particular, the radical polymerization catalyst effectively acts on the curing of the composition of the present invention, making it possible to significantly shorten the curing time. All commonly known radical polymerization catalysts can be used, but representative examples include dicumyl peroxide, di-1
-butyl peroxide, benzoyl peroxide,
These include azobisisobutyronitrile, t-butylperoxybenzoate, methyl ethyl ketone peroxide, and the like. Furthermore, it is also effective to use carboxylic acid metal salts, which exhibit a polymerization promoting effect when used together with these peroxides. As anionic polymerization catalysts, secondary amines,
Tertiary amines, quaternary ammonium salts, quaternary phosphonium salts, alkali metal compounds, transition metal acetylacetonates, and the like can be used. Various boron trifluoride complexes are effective as cationic polymerization catalysts.

There is no particular restriction on the amount of catalysts used, but it ranges from o.ooi to 10% based on the weight of the entire composition, and usually 0.00% to 10%.
It is used in a range of 0.01 to 3%.

Furthermore, the following components can be added to the composition of the present invention.

■ Powdered reinforcing agents, fillers and thickeners, such as alumina,
Diatomaceous earth powder, magnesia, kaolin, magnesium carbonate, basic magnesium silicate, calcined clay, finely powdered silica, carbon black, etc., as well as fibrous reinforcing agents and fillers, such as glass fiber, rock wool, ceramic fiber, asbestos. and inorganic fibers such as carbon fiber, paper, valves, wood flour, linters, and polyamide fibers. The amount of these powder or fibrous reinforcing agents and fillers to be used varies depending on the use, but in the case of laminated materials and molding materials, it can usually be used in an amount up to 4 times the weight of the composition of the present invention.

■Coupling agents, such as λ, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-
methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, (trimethoxysilylpropyl)ethylenediamine, (dimethoxymethyl-silylpropyl)ethylenediamine, γ-chloropropyltrimethoxysilane, Vinyltrichlorosilane, β-(3
, 4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. Generally, the amount of the coupling agent used is within the range of 0.001 to 10.0%, preferably 0.01 to 5%, based on the weight of the composition of the present invention.

■Flame retardants, flame retardants, such as tetrabromobisphenol A, tetrabromophthalic anhydride, brominated epoxy resins (brominated bisphenol A, brominated novolak, etc. and other halogenated epoxides), decabromodiphenyl ether, Hexabromobenzene, tetrabromo terephthalic acid, chlorinated paraffin, Diels-Alder adduct of hexachlorocyclopentadiene, red phosphorus, tricresyl bosphate, phosphonates, phosphinates, phosphoroamidates, trioxide Such as antimony, it is usually used in an amount of 1 to 70%, preferably 5 to 40%, based on the weight of the composition of the present invention.

(2) In order to further improve the properties of the composition of the present invention in adhesive layers, molded articles, coating films, etc., various resin-based substances can be blended. Such substances include, for example, drying oils, semi-drying oils, oleoresins, rosins, shellacs, oil-modified rosins, niboxy resins, phenolic resins, alkyd resins, urea resins, melamine resins, polyester resins,
Examples include one or a combination of two or more of polyvinyl butyral resin, vinyl acetate resin, vinyl chloride resin, acrylic resin, and silicone resin. The preferred amount of these substances used is within a range that does not impair the inherent properties of the composition of the present invention, ie, generally not more than 30% by weight of the composition of the present invention.

Curing conditions for producing a cured product from the thermosetting resin composition of the present invention vary depending on the composition and also vary depending on the form of the cured product obtained. Generally, the composition of the present invention is applied to a substrate as an adhesive layer, a coating, or is formed or laminated as a powder, pellet, or impregnated into a substrate such as glass cloth, and then cured by heating. let The curing temperature is generally 0-300%, preferably 1
The temperature is preferably in the range of 00 to 250°C. The heating time for curing is particularly influenced by the form, but generally a time sufficient to completely cure the resin component may be selected within the range of 30 seconds to 10 hours.

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 be in the range of 1 to 100 kg/cI112.

Although there are no particular restrictions on the specific mode of implementing the present invention, preparation examples of impregnating varnish, prepreg, and laminate are shown below as examples of the mode.

A homogeneous liquid containing a maleimide compound, an allyl compound, an amino compound, or a reactant of any two of these three compounds and the remaining one, or a homogeneous solution further 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%. A curing catalyst, a silane coupling agent, a flame retardant, etc. are added to the homogeneous solution obtained in this way, if necessary, and the mixture is uniformly mixed to form a varnish.

Among the varnishes obtained as described above, especially solvent-free varnishes are used directly for impregnating coils for electrical equipment, etc., and are also impregnated into sheet-like reinforcing materials to form prepregs and cured molded products. Both solution type and solvent-free type varnishes are used for impregnating various sheet-like reinforcing materials, and examples include glass cloth, glass paper, glass nonwoven fabric, asbestos paper, and mica tape. After impregnating these materials with varnish, if necessary, they are air-dried for a certain period of time, and then precured in an oven at 60 to 160°C to obtain a prepreg. Prepreg is often used as a variety of insulating materials, such as prepreg mica tape. The prepreg obtained from the uniform varnish prepared by the composition of the present invention does not cause separation of components or foaming, and has preferable dryness to the touch. The prepreg sheet thus obtained can be stored stably for a long period of time even at room temperature, and its flexibility is maintained.

After stacking multiple sheets of glass cloth prepreg, if necessary, layer copper foil on one or both sides, and mold using a compression molding machine at a temperature of 100 to 250°C and a pressure of 1 to 100 kg/cm.
A laminate for a wiring board can be obtained by performing pressure molding.

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.

In addition, various measurement methods in Examples are as follows.

Thermogravimetric analysis: Measured using DTG-30M manufactured by Shimadzu Corporation in air at a heating rate of 5° C./ll1n.

Solder heat resistance test: According to JIS C6481, the solder bath temperature was set to 300°C, and the time (seconds) until bulging or peeling occurred on the copper foil surface was measured.

Copper foil peel strength: According to JIS C6481.

Volume resistivity: According to JIS (:6481).

Example 1 N-(p-impropenylphenyl)maleimide oligomer (composition, monomer 3.1%, 2fi form 76.5%, 3
8.3% of monomer, 12.1% of tetramer or more) 35 parts, diallyl phthalate 20 parts, triallyl incyanurate 30 parts,
When 5 parts of 4,4°-diaminodiphenylmethane were mixed, dissolved and homogenized, a reddish-brown transparent solvent-free varnish was obtained.

Apply this varnish to a smooth inner diameter of 20 mm on the bottom. ! 'S 5m
Heated to 70℃ in a fluororesin beaker of 20℃.
After holding for 30 minutes, the temperature was raised to 180℃ over 30 minutes.
It was held at ℃ for 1 hour to cure. Furthermore, after curing for 3 hours at 200°C, a reddish-brown transparent cured product was obtained.

A portion of the obtained cured product was taken, crushed, and subjected to thermogravimetric analysis (
As a result, the 5% weight dehumidification temperature was 428°C.

Comparative Examples 1 to 2 In the method described in Example 1, N,N'-(methylenedi-p-phenylene)bismaleimide or N,N'-m-phenylenebismaleimide was used as the maleimide component; The same procedure was carried out, but in each case, the maleimide component was insoluble and precipitated, and a uniform solvent-free varnish could not be obtained.

Examples 2 to 6 In addition to the ingredients and amounts used in Table 1, dioxane 1
10 parts were added and sufficiently stirred and mixed to prepare a solution type varnish. The varnishes of Examples 2 to 6 were applied to glass cloth (thickness 0
．． 18 mm) and further dried at 100° C. for 10 minutes to obtain a prepreg.

Stack nine of these prepreg sheets, layer copper foil on top and bottom,
2 at 180°C with a press pressure of 40 kg/cm”.
The product was heated and pressed for 0 minutes to obtain a double-sided copper-clad laminate. The thus obtained laminate was after-cured in an oven at 200° C. for 3 hours. Table 2 shows the results of various tests on the obtained laminate.

Examples 7 to 8 A resin composition consisting of the components and usage amounts shown in Table 3 was poured between two glass plates with a thickness of 1.5 mm, and heated at 110°C.
The resin plate was cured by heating at 170° C. for 1 hour and then for 8 hours at 170° C. to obtain a resin plate with a thickness of 1.5 mm. After observing the condition of the resin plate obtained in this way, a 1010x10 plate was cut out.
It was heated in an oven at 200°C or 250°C for 1000 hours, and the loss on heating was measured. The results are shown in Table-3.

Examples 9 to 11 A resin composition consisting of the components and usage amounts shown in Table 4 was cured at the same time as in Example 1 to obtain a brown transparent cured product. A part of the cured product was crushed and thermogravimetrically analyzed (heating rate 5°C/m1n).
) and the obtained 5% weight dehumidification temperature is shown in Table 4.

Table-1 [Note] a) Same as used in Example 1.

b) Guisodatsubu 100LI Manufactured by Osaka Soda Co., Ltd. Part name) Table 2 Table 3 [Note] a) Same as that used in Example 1.

bl A resin obtained by condensing O-allylphenol with paraformaldehyde in the presence of a hydrochloric acid catalyst.

Claims (1)

[Claims] (A) General formula (1) ▲ Includes mathematical formulas, chemical formulas, tables, etc. ▼ [Here, D is an n-valent compound having 2 to 200 carbon atoms and containing at least one carbon-carbon double bond. is an organic group with R^1
~R^3 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, and may be the same or different from each other, m^1 and m^2 are positive integers, and m^ 1
+m^2 = 5, and when m^1 is 2 or more, R' may be the same or different from each other, and n is a positive integer], dimers and multimers thereof; At least one maleimide compound selected from the group consisting of (B) one or more allyl compounds having at least one allyl group in the molecule, and (C) general formula (II) Q- (NH_2)m...(II) (here, Q is 1 carbon atom which may have each atom of hydrogen, oxygen, sulfur, halogen, nitrogen, phosphorus or silicon)
~150 m-valent organic groups, m is a positive integer), or any two of the above three components.
A thermosetting resin composition comprising a reactant of the components and a remaining component.