JPH0343287B2 - - 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 that it dissolves only in high boiling point polar organic solvents, such as 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. It is extremely difficult to completely remove the solvent from the drying and manufacturing process of laminates, and the solvent remains, causing voids in the laminate and deteriorating its quality and performance. Especially in copper-clad laminates, it causes swelling of the copper foil, Otherwise, it caused peeling, etc., and was not satisfactory. Furthermore, the above-mentioned polar organic solvents are permeable through the human body 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) It is a thermosetting resin composition comprising an aliphatic maleimide having an ether bond and an amino compound as required, and has a low melting point and excellent solubility in organic solvents. Moreover, it provides a fast-curing composition. 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,
Each is a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 10 carbon atoms, or a phenyl group, or an optionally branched alkyl group having 1 to 10 carbon atoms, or a halogen atom , R ₇ O− group,

【formula】

[Formula] A phenyl group substituted with a hydroxyl group or a cyano group, 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 hydrogen Atom, halogen atom, carboxyl group, hydroxyl group, R ₇ O−
basis,

【formula】

[Formula] or a cyano group, when multiple Xs exist, they may be the same or different, m ₁ , m ₂ and m ₃ are each 0 to 4, m ₁ + m ₂ +
m ₃ =5, and R ₇ is an optionally branched alkyl group having 1 to 10 carbon atoms or a phenyl group, or an optionally branched alkyl group having 1 to 5 carbon atoms. a phenyl group substituted with a group or a halogen atom,
(When multiple R _7s are present, they may be the same or different); a dimer thereof; and a multimer thereof. and B: at least one aliphatic maleimide having an ether bond.The thermosetting resin composition of the present invention is characterized by containing at least one maleimide compound having an ether bond. It can be used as The N-(alkenylphenyl)maleimides used in the composition of the present invention have significantly better solubility in solvents than ordinary maleimide compounds,
Instead of using polar organic solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide, which were conventionally used in compositions containing maleimide compounds, ordinary general-purpose organic solvents with relatively low boiling points can be used. The purpose can be fully achieved by using the laminate, and since it has fast curing properties, it is possible to B-stage at a relatively low temperature, which not only improves workability but also makes it easier to remove solvents from products such as laminates, which improves the quality of the product. can be significantly improved. 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 enyl, 3-isopropenyl-4-N
-maleimido-4'-acetylbiphenyl, 2-N
-maleimido-4-isopropenyl-4'-cyanobiphenyl, N-(p-isopropenylphenyl)
-p-chlorophenylmaleimide and the like can be mentioned. 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 Examples include dimers of N-(p-isopropenylphenyl)maleimide represented by the formulas () and (). Also N-(alkenylphenyl)
There are no particular restrictions on the maleimide multimer, but
Substantially, those having a molecular weight of 10,000 or less are preferred. In the present invention, the above compounds can be used alone or in combination of two or more. These N-(alkenylphenyl)maleimide derivatives are, for example, JP-A No. 55-129266, JP-A No. 56-Sho.
It can be produced by the method described in JP-A No. 131566 and JP-A No. 56-145272. The aliphatic maleimide 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 ′} −)
−) _c , (In the formula, R ₈ , R ₈ ′, R ₈ ″, R ₈ and R ₉ may be the same or different and are linear or branched mono- to trivalent fatty acids having 1 to 10 carbon atoms. group hydrocarbon group or one substituted with an alkoxy group, hydroxy group or halogen, a, b,
c, x, y and z represent numbers of 1 or more. ) Compounds having an aliphatic ether group having a structure represented by: Very typical examples of such aliphatic maleimides include N-2,2'-hydroxyethoxyethylmaleimide, N-1-methoxymethylpropylmaleimide, N-1-ethoxymethylpropylmaleimide, and N-1-methoxy Methylbutylmaleimide, 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 number 3.5, and b is approximately 13.5 to 45.5.) (In the formula, the sum of x, y and z is approximately 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. Further, aliphatic maleimides can be used alone or in combination of two or more types. In the composition of the present invention, N-
There is no particular limitation on the proportion of both (alkenyl phenyl) maleimide and aliphatic maleimide used, but generally the former is 2 to 99% of the total amount of both components.
% by weight, preferably from 5 to 95% by 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 as necessary for the purpose of imparting a homogeneous and dense structure, toughness and mechanical strength to the cured product according to the present invention has the following formula: Z-(NH ₂ )l (wherein Z is Consists of 1 to 150 carbon atoms, hydrogen,
is an l-valent organic group that can contain atoms of oxygen, sulfur, halogen, nitrogen, phosphorus, and silicon;
is an integer greater than or equal to 1. ), typical examples of which are ethylamine, 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, trimethylenediamine, hexamethylenediamine, decamethylenediamine, octamethylenediamine, 2,2,4-trimethylhexamethylenediamine, p-(or m-)phenylenediamine, 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'-diaminodiphenylsulfone, 3,3'-
Diaminodiphenyl sulfone, 4,4'-diaminodicyclohexylmethane, p-(or m-)xylylenediamine, 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-trimethylindane, vinylanilines, or isopropenylanilines trimer or higher polymers, aromatic amines (e.g. aniline, toluidine) and aldehydes (e.g. formaldehyde, paraform , acetaldehyde), particularly poly(phenylene methylene) polyamines obtained by the reaction of aniline with formaldehyde (e.g. MDA-150, trade name manufactured by Mitsui Toatsu Chemical Co., Ltd.), and the polyamines obtained by hydrogenation. Examples include alicyclic polyamines. 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 not particularly limited, but is based on the total number of maleimide groups in the maleimide component of N-(alkenylphenyl)maleimide derivatives and aliphatic maleimide. It is preferable that the ratio of the total number of amino groups (general formula ()) is 1 or less,
The range of 0.01 to 1 is more preferable. (ma・na/Ma)/(mi・ni/Mi) () (In the formula, 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
indicate the amount of amino compound used, the average number of amino groups in the molecule, and the average molecular weight, respectively. ) When the amount of the amino compound used exceeds the above range, the heat resistance of the cured product decreases, while when it falls below the above range, the adhesive strength tends to decrease and the mechanical strength of the cured product tends to decrease. The thermosetting resin composition of the present invention may be a simple mixture of components A, B, and optionally component C,
Further, the composition may contain at least a part of these prepolymers. What is prepolymer? A:
N-(alkenylphenyl)maleimides, B:
Aliphatic maleimide and C: It is a preliminary reaction product obtained by reacting two components selected from amino compounds or three components A, B, and C, and there are no restrictions on the specific reaction method, Reaction temperature is 0~
At 200℃ and reaction time from 5 minutes to 10 hours, each component can be directly mixed and reacted uniformly without a solvent, or a homogeneous solution or suspension of each component can be reacted using a solvent. . Further, in the present invention, the epoxy resin D used for the purpose of improving adhesive strength, adjusting viscosity, etc. may be any known solid or liquid product, and a representative example thereof is bisphenol A type epoxy resin. , bisphenol F type epoxy resin,
Heterocyclic epoxy resins such as halogenated bisphenol A epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, cycloaliphatic epoxy resins, triglycidyl cyanurate, triglycidyl isocyanurate or hydantoin epoxy, water Added 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 resin is a glycidyl ether type epoxy resin which is a reaction product of an orthoarylphenol novolak compound and epichlorohydrin, and is represented by the following molecular formula. p, p'-
N,N,N',N'-tetraglycidylaminodiphenylmethane Or triglycidyl-p-aminophenol represented by the following molecular formula Epoxy resins obtained by the reaction of aliphatic or aromatic amines with epichlorohydrin, such as
and epoxy resins in which part of the above epoxy resins is ring-opening polymerized, as well as epoxidized or epoxy-modified resins (for example, acrylic resins with 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 monofunctional so-called reactive diluent may be partially included. The amount of epoxy resin used is not particularly limited, but in order not to impair the heat resistance of the cured product obtained from the composition of the present invention, 50% of the total weight of the composition should be used.
% or less. 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 to improve workability and adjust curing speed depending on the form of use of the composition include boron trifluoride amine complexes such as boron trifluoride monoethylamine complexes and boron trifluoride piperidine complexes; Tertiary amines such as triethylamine, N,N-dimethylpenzylamine, hexamethylenetetramine, N,N-dimethylaniline, quaternary ammonium salts such as tetramethylammonium bromide, borates such as triphenylborate, tricresylborate, etc. compounds, imidazole compounds such as N-methylimidazole and N-phenylimidazole, zinc acetate, sodium acetate, titanium acetylacetonate, sodium methylate, aluminum chloride, zinc chloride, tin chloride, manganese naphthenate, cobalt naphthenate, etc. Metal compounds, 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, etc., 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 curable resin composition of the present invention can be used for impregnation, prepreg, coating and lamination varnishes, molding powders,
It has a wide range of uses including paints, adhesives, sealants, and rubber chemicals. 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 impregnated into 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 is generally 30 seconds or more.
A sufficient time for the resin component to be completely cured may be selected within the range of 20 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 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 and an aliphatic maleimide or a homogeneous solution containing an organic solvent is prepared. When using a solvent, the concentration of the composition of the invention in solution is 10
It is desirable that the content be in the range of ~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. A glass cloth is impregnated with the varnish, air-dried for a certain period of time, and then precured in an oven at 50 to 200°C to obtain a prepreg. 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 10 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 using Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, parts and percentages in the examples are based on weight unless otherwise specified. Further, various measurement methods in Examples are as follows. Thermogravimetric analysis: Measured using DTG-30M manufactured by Shimadzu Corporation at a heating rate of 10° C./min in a nitrogen stream. Gel time: Approximately 1.5 g of the sample was placed on a stainless steel hot plate heated to 180°C, kneaded with a spatula at a rotation speed of once per minute, and the time required for the sample to start stringing was measured. 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: According to JIS C-6481. Impact resistance: 50g of spherical bronze was dropped onto a circular cured product with a thickness of 1mm from a height of 60cm, and the degree of cracking was observed according to the following criteria. 〇: Not cracked, △: Cracks, ×: Broken into pieces. Example 1 60 parts of 4-methyl-2,4-bis(p-N-maleimidophenyl)-1-pentene (the manufacturing method is as shown in Manufacturing Example 1 below) and N,N'-4,
7-Dioxadecane-1,10-bismaleimide 40
A portion was thoroughly mixed and the gel time of the portion was measured. Next, 100 parts of the mixture was dissolved in 100 parts of 1,4-dioxane at 30°C to prepare a varnish.
A predetermined amount (equivalent to about 5 g of resin) of this varnish was applied to an aluminum container with a smooth bottom, an inner diameter of 60 mm, and a depth of 14 mm, after applying a mold release agent, and heated to 80°C on a hot plate under a nitrogen stream for 2 hours. After holding, the temperature was gradually raised to 130℃ over 30 minutes, held at this temperature for 3 hours, and then
The temperature was gradually raised to 200°C over 1 hour, and this temperature was maintained for 2 hours to cure. Thereafter, after-curing was carried out at 250° C. for 2 hours to prepare a brown cured product (test piece), and the impact resistance of this cured product was examined and thermogravimetric analysis was performed. 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, and the temperature of this reaction solution was raised 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 1,500 parts of thoroughly stirred water to obtain a precipitate. This precipitate was separated and poured into water, and an aqueous sodium carbonate solution was added to adjust the pH to 8.5.
Separately, washing with water was repeated several times to thoroughly wash with water, and finally, the product was purified by washing with 100 parts of methanol. Dry at a temperature of 50°C under reduced pressure to obtain 4-methyl-2,4-bis(p-N
-maleimidophenyl)-1-pentene (melting point 148
~150°C) 194 parts 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, 76.9% dimer,
It was produced in the same manner as above using 8.2% of trimers and 11.7% of tetramers or more. Examples 2 to 13 N,N′-4,7-dioxadecane-1,10-bismaleimide, N,
N'-4,9-dioxadodecane-1,12-bismaleimide, N,N'-7-methyl-4,10-dioxatridecane-1,13-bismaleimide, diefamine D-230 and D- 400 (diefamine is polyoxypropylene amine, a product of Mitsui Texaco Chemical Co., Ltd.) bismaleimide, N
-(alkenyl phenyl)maleimide N-p
-isopropenyl phenyl maleimide, 4-methyl-2,4-bis(p-N-maleimidophenyl)-2-pentene, m-phenylene diamine as an amino compound, 4,4'-diaminodiphenyl ether, 4 -4′-diaminodiphenylmethane,
Using 1,4-dioxane and methyl ethyl ketone as solvents, they were sufficiently mixed at the compounding ratio shown in Table 1, and the gel time value and cured product were obtained in the same manner as in Example 1. Comparative example 1,2 4-methyl-2,4-bis(p-N-maleimidophenyl)-1-pentene and N,N'-4,
The gel time of each individual 7-dioxadecane-1,10-bismaleimide was measured, and a cured product was obtained in the same manner as in Example 1. However, 4-methyl-2,4-bis(p-N-maleimidophenyl)
The cured product of -1-pentene did not have a circular shape and was broken into pieces, and the impact resistance was measured by selecting sufficiently large pieces. For the compositions of Examples 1 to 13 and Comparative Examples 1 and 2, the formulations as well as the measurement results of gel time, impact resistance of cured products, and thermal gravimetric analysis are shown in Table 1. Example 14 N-(p-isopropenylphenyl)maleimide oligomer (composition: 3.1% monomer, 76.5% dimer)
%, trimer 8.3%, tetramer or more 12.1%) and 50 parts of N,N'-7-methyl-4,10-dioxatridecane-1,13-bismaleimide to
An impregnating varnish was prepared dissolved in 100 parts of dioxane. Next, a glass cloth (thickness: 0.18 mm) treated with aminosilane was impregnated, air-dried, and then dried at 150° C. for 9 minutes to obtain a prepreg. Stack 9 sheets of this prepreg, place one sheet of copper foil on top of it, and apply a hot press pressure of 75kg/
cm ² at 180°C for 30 minutes to obtain a copper-clad laminate. After that, this laminate was placed in an oven at 200℃ for 8 hours.
Time after cure. Example 15 N,N'-4,7-dioxadecane-1,10-
After thoroughly mixing 82 parts of bismaleimide and 24 parts of 4,4'-diaminodiphenylmethane, the reaction temperature was
A melt reaction was performed at 120°C for 20 minutes to produce a prepolymer. 30 parts of this prepolymer and N-(p-
An impregnated varnish was prepared by dissolving 70 parts of isopropenyl phenyl maleimide oligomer (composition: same as in Example 14) in a mixed solvent of 50 parts of 1,4-dioxane and 50 parts of methyl ethyl ketone. Examples below
A copper-clad laminate subjected to after-curing was obtained in the same manner as in No. 14. Examples 16-24 N-(p-isopropenylphenyl)maleimide as N-(alkenylphenyl)maleimide,
N-(p-vinylphenyl)maleimide, N-(p
-isopropenylphenyl) dichloromaleimide, 4-methyl-2,4-bis(p-N-maleimidophenyl)-1-pentene, 4-methyl-2,
4-bis(p-N-maleimidophenyl)-2-
pentene, the aforementioned N-(p-isopropenylphenyl)maleimide oligomer, N,N'-4,7-dioxadecane-1 as aliphatic maleimide,
10-bismaleimide, diefamine D-
230, D-400 and D-2000 bismaleimides,
As amino compounds, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether,
The above-mentioned MDA-150, epoxy resins such as Epicote 828 (trade name of bisphenol epoxy resin manufactured by Ciel Chemical Co., Ltd.) and DEN431 (trade name of novolac type epoxy resin manufactured by Dow Chemical Company), 2-ethylimidazole and anhydrous trimeriz as catalysts. An impregnated varnish was prepared by melting or dissolving an acid and 1,4-dioxane and methyl ethyl ketone as a solvent in the formulation shown in Table 2. Other examples are examples
A copper-clad laminate subjected to after-curing was obtained in the same manner as in No. 14. Comparative Example 3 70 parts of N,N'-(methylenedi-p-phenylene)bismaleimide and 30 parts of N,N'-4,7-dioxadecane-1,10-bismaleimide were mixed with N,N
- An impregnated varnish was prepared by dissolving it in 100 parts of dimethylformamide, and a copper-clad laminate was obtained in the same manner as in Example 14. The surface of the resin-containing glass cloth after air drying is N,
N'-(methylenedi-p-phenylene) bismaleimide was precipitated and a good prepreg could not be obtained. The solder heat resistance, peel strength and bending strength of the copper foil of the copper-clad laminates obtained in Examples 14 to 24 and Comparative Example 3 were measured, and the results are shown in Table 2. Example 25 N-(p-isopropenylphenyl) described above
50 parts of maleimide oligomer, N,N'-4,7-
120℃ after thoroughly mixing 25 parts of dioxadecane-1,10-bismaleimide and 15 parts of MDA-150.
A melt reaction was performed for 20 minutes to produce a prepolymer. Next, 90 parts of this prepolymer, Epicoat 828,
10 parts, 3.3 parts of trimellitic anhydride, 120 parts of natural graphite and 2.5 parts of calcium stearate.
The mixture was kneaded for 30 minutes using a pressure kneader at a temperature of 100°C.
Next, this composition was molded at a mold temperature of 200℃ and a pressure of 120Kg/
Pressure molding was carried out for 1 hour under the condition of cm ² . This molded product
Bending strength measured according to JIS K-6911 at 25℃
18.7Kg/mm ² , after heating for 500 hours at 250℃
16.0Kg/mm ² , indicating satisfactory heat deterioration resistance.

【table】

[Table] 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-B N,N'-4,9-dioxadodecane-1,12-bismaleimide ABM- C N,N'-7-methyl-4,10-dioxatridecane-1.13-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-A m-phenylenediamine AM-B 4,4'-diaminodiphenyl ether AM-C 4,4'-diaminodiphenylmethane AM-D MDA-150 (represented by the following formula) Note *) In Examples 15, 20, 22, 23 and 24, the N-(alkenylphenyl)maleimide and/or aliphatic maleimide and the amino compound are not a mere mixture but a prepolymer of the two or three components. . However, all the production was in accordance with Example 15. Example 20: Prepolymer of ABM-A and AM-D Example 22: Prepolymer of ABM-D and AM-C Examples 23, 24: Three-component prepolymer

Claims (1)

[Claims] 1 A: General formula () (In the formula, R ₁ to R ₆ are the same or different,
Each is a hydrogen atom, a halogen atom, an optionally branched alkyl group having 1 to 10 carbon atoms, or a phenyl group, or an optionally branched alkyl group having 1 to 10 carbon atoms, or a halogen atom , R ₇ O- group, [Formula] [Formula] is a phenyl group substituted with a hydroxyl group or a cyano group, and each of R ₄ , R ₅ and R ₆ may be the same when a plurality of them exist. may be different, and X is a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, R ₇ O-
group, [Formula] [Formula] or cyano group, and when multiple Xs exist, they may be the same or different, m ₁ ,
m ₂ and m ₃ are each 0 to 4, and m ₁ +
m ₂ + m ₃ = 5, and R ₇ is an optionally branched alkyl group having 1 to 10 carbon atoms or a phenyl group, or an optionally branched alkyl group having 1 to 5 carbon atoms. N-(alkenylphenyl)maleimide derivatives (which are phenyl groups substituted with an alkyl group or a halogen atom, and when multiple R _7s are present, they may be the same or different) , at least one maleimide compound selected from the group consisting of dimers and multimers thereof, and B: a thermosetting resin composition comprising at least one aliphatic maleimide having an ether bond. .