JPH04202509A - Thermosetting resin composition and insulating material for electronic device - Google Patents

Abstract

PURPOSE:To obtain the title composition suitable as an insulating material, having excellent moldability, providing a cured material with excellent heat resistance, containing a specific bismaleimide compound. CONSTITUTION:The objective composition comprising a bismaleimide compound shown by the formula (Rf is F or 1-10C perfluoroalkyl) and preferably an ethylenic unsaturated double bond-containing compound, an epoxy compound, a phenol formaldehyde condensate, a melamine compound, an N-substituted unsaturated imide group-containing compound, a cyanato compound or a cyanamide compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermosetting resin composition, and more particularly to a resin composition suitable for moldability, heat resistance, and low dielectric constant insulating material for electronic ViW. .

[Prior art] Fluorine resins such as polytetrafluoroethylene (PTFE) and hydrocarbon resins such as polyethylene and polybutadiene have been known as low dielectric constant insulating materials in the field of electronic materials, and are widely used. has been applied. These materials have a dielectric constant of 3 or less.

However, although the former fluororesin is excellent in terms of heat resistance and electrical properties, it generally has a softening temperature because it is a thermoplastic resin. At temperatures higher than the softening temperature, a rapid decrease in mechanical strength and an increase in the coefficient of thermal expansion are observed, resulting in a significant decrease in material properties. However, it cannot be used at temperatures above the softening temperature, which limits its field of use. Furthermore, since there is no suitable solvent for making varnish with PTFE, it is generally heated and melt-molded. The molding temperature is high at 300°C or higher (and the melt viscosity is extremely high at IQll, l011 voids), resulting in poor moldability and workability.On the other hand, hydrocarbon-based resins are used for many types of resins such as butadiene resin and allyl resin. Thermosetting resins have been developed.These have a three-dimensional crosslinked structure and are expected to be materials that require mechanical strength and dimensional stability at high temperatures.However, hydrocarbon resins have As can be inferred, it is easily oxidized,
Poor thermal decomposition resistance. Therefore, it is hardly used as a highly heat-resistant material. In fields where such heat resistance is required, many resins having heteroaromatic rings such as imide rings are used. Typical examples include polyimide, polybenzimidazole, polybenzothiazole, and bismaleimide.
These include triazine, biscyanamide, etc. Among these, bismaleimide compounds are used in various structural materials and FR as addition type heat-resistant materials that do not generate side reaction products such as bound water during curing reactions.
It is expected to be applied in a wide range of fields such as P, molding materials, wiring boards, and interlayer insulating films for LSI. In particular, wiring boards, LS
As materials for electronic devices such as glabellar insulating films and molding materials, it is strongly desired to have a low dielectric constant from the viewpoint of high-speed calculation processing in computers.

[Problems to be Solved by the Invention] However, the conventional heat-resistant material made of a thermosetting resin using a bismaleimide compound has a problem in that it has a larger dielectric constant than the above-mentioned low dielectric constant material. 55-463
No. 6), many heat-resistant materials using bismaleimide compounds developed to date have a dielectric constant of 3 or more.

Therefore, it is necessary to reduce the aX ratio while utilizing the maleimide ring structure without impairing heat resistance.

An object of the present invention is to provide a thermosetting resin composition containing a bismaleimide compound having excellent moldability and heat resistance and a low dielectric constant, and an insulating material for electronic devices.

[Means to solve the problem] The gist of the present invention for achieving the above object is as follows.

In a thermosetting resin composition containing a bismaleimide compound represented by the general formula (1) (wherein R and f represent fluorine or a perfluoroalkyl group having 1 to 1 carbon atoms), the unsaturated This can be achieved by providing a three-dimensionally crosslinked cured product through a polymerization reaction of bonds.

Furthermore, depending on the desired heat resistance and electrical properties, the composition can be combined with various compounds copolymerizable with the double bond of bismaleimide to obtain a resin composition with excellent moldability. can.

As such compounds, cyanamide compounds, cyanato compounds, incyanato compounds, vinyl compounds, and other various maleimide compounds are useful. Other similar products include epoxy compounds, various -grade to quaternary amine compounds, carboxylic acid compounds, polyamides, phenol resins, melamine resins, urea resins, urethane resins,
Examples include polyamino bismaleimide resin.

These are used in polymeric, oligomeric, and monomeric units. Such resin compositions have functional groups such as polymerizable double bonds or triple bonds in their molecular structures,
A crosslinking reaction occurs under heat, light irradiation, or in the presence of a radical polymerization initiator, resulting in a cured product with a three-dimensional structure with excellent heat resistance. By creating a three-dimensional structure, a heat-resistant insulating material that maintains mechanical properties, dimensional stability, etc. at high temperatures can be obtained.

In addition, in the cross-linking and curing reaction, reaction by-products such as condensed water are not produced, so it can be used as a material for many electronic devices such as laminated materials, various structural materials, and molding. 2 Typical fluorine-containing bismaleimide compounds represented by the general formula (1) of the present invention are, for example, 1 .4-Bis[
2-(4-maleimido-2-trifluoromethylphenoxy)-1,1,1,3,3,3-hexafluoroisopropyl]benzene, 1,4-bis[2-(3-maleimido-5-trifluoro Methylphenoxy L-1,1,
1,3,3,3-hexafluoroisopropylcobenzene, 1,4-bis[2-(4-maleimido-2-pentafluoroethylphenoxy)-1,1,1,3,3,3
-hexafluoroisopropyl]benzene, 1,3-bis[2-(4-maleimido-2-trifluoromethylphenoxy)-1,1,1,3,3,3-hexafluoroisopropyl]benzene, 1,4 -bis[2-(4-maleimido-2-nonafluorobutylphenoxy)-1゜1.1,3,3.3-hexafluoroisoprobylcobenzene, 1-[2-(4-maleimido-2-tri- Fluoromethylphenoxy)-1,1,1,3,3,3-hexafluoroisobyl]-4-[2-(3-maleimido-5-trifluoromethylphenoxy)-1,1,1
, 3,3,3-hexafluoroisopropyl]benzene and the like.

Examples of compounds having ethylenically unsaturated double bonds include ethylene, propylene, butadiene, tetrafluoroethylene, hexafluoroethylene, hexafluorobutadiene, styrene, pentafluorostyrene, divinylbenzene, tetrafluorodivinylbenzene, α-
Trifluoromethylstyrene, p-trifluoromethylstyrene, m-trifluoromethylstyrene, 0-trifluoromethylstyrene, trifluoromethyl methacrylate, trifluoromethyl acrylate, trifluoromethyl α-trifluoromethyl methacrylate, 1,
1,1,3,3.3-hexafluoro-2,2-bis(
Examples include 4-methacryloxyphenyl)propane, diallyl phthalate, and tetrafluorodiallyl phthalate.

As an epoxy compound, 2.2-bis[4-(2゜3-
Epoxypropoxy) phenylcopropane, 1°1.1
,3,3.3-hexafluoro-2,2-bis[4-(
2,3-epoxypropoxy) phenylcobroban, bis(2,3-epoxypropyl) tylphthalate, bis(2,3-epoxypropyl) inphthalate, bis(
2,3-Epoxypropyl) phthalate, 1,3.5-
Tris(2,3-epoxyprobyl)phloroglucinol, 4,4-bis(2,3-epoxypropylphenyl)ether, 2-(2゜3-epoxyprobyl)phenyl, 2,3-epoxypropylphenyl Biyl ether, 2,2-bis[4-(2,3-epoxypropoxy)-3,5-dibromophenyl]propane, 1,1,2,2-tetrakis[4-(2,3-epoxypropoxy)phenyl ] Ethane, polyphenol formaldehyde poly(2,3-epoxypropyl) ether, poly-cresol formaldehyde poly(2,3-epoxypropyl)-ethyl, -1,4-bis(2,3-epoxypropoxy) Butane, 1,2-bis(2,3-epoxy-2=methylpropoxy)ethane, 1,3-bis[3-(2゜3-epoxypropoxy)propylcotetramethyldisiloxane, epoxidized polybutadiene, polypropylene glycol Rouge (2,3-epoxyprobyl) ether, 1,2
．． 3-tris(2,3-epoxypropoxy)propane, 2,3-epoxypropyl allyl ether telomer,
2.6-bis(2゜3-epoxypropoxy)norbornene, 2.2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane, 4-(1,2-epoxyethyl)-1, Examples of phenol-formaldehyde condensates such as 2-epoxycyclohexane include resol resins such as phenol, cresol, dimethylphenol, trimethylphenol, and trifluoromethylphenol, and novolak resins.

Melamine compounds include melamine, benzoguanamine,
Examples include dicyandiamide, vinyltriazine, hydroxyliazine, o-tolylguanidi-3-di-0-tolylguanidine, 1,3-diphenylguanidine, propyltriazine, and the like.

Examples of compounds having an N-substituted unsaturated maleimide group include bis(4-maleimidophenyl)methane, bis(
4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) sulfoxide, bis(4-maleimidophenyl)
Sulfoxide, bis(4-maleimidophenyl) sulfone, bis(4-maleimidophenyl) ketone, 2.2
-bis(4-maleimidophenyl)propane, 1,1,
1,3,3゜3-trifluoromethyl-2,2-bis(
4-maleimidophenyl)propane, bis(3-methyl-4-maleimidophenyl)methane, bis(3-trifluoromethyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, 2,2-bis[4-(4-maleimidophenoxy)phenylcopropane, 1,1,1,3,3.3-hexafluoro-2,2-bis[4-(4-maleimidophenoxy)phenylcopropane, Lucopropane, 1,1,1°3.3.3-
hexafluoro-2,2-bis[4-(2-trifluoromethyl-4-maleimidophenoxy)phenyl]propane, 1,1,1,3,3.3-hexafluoro-2,
2-bis[4-(3-trifluoromethyl-4-maleimidophenoxy)phenyl]propane, 1,1,1,3
,3.3-hexafluoro-2,2-bis[4-(2-
Examples include pentafluoroethyl-4-maleimidophenoxy)phenylcopropane.

Examples of cyanato compounds include bis(4-cyanatophenyl)methane, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)sulfide, bis(4-cyanatophenyl)sulfoxide, bis(4-cyanatophenyl)sulfoxide, and bis(4-cyanatophenyl)sulfoxide. -cyanatophenyl) sulfone, bis(4-cyanatophenyl)ketone, 2,2-bis(4-cyanatophenyl)propane, 1,1,1°3.3.3-trifluoromethyl-2,2 -Bis(4-cyanatophenyl)propane, bis(3-methyl-4-cyanatophenyl)methane, bis(3-trifluoroconvex methyl-4-cyanatophenyl)methane, bis(3,5-dimethyl-4 -cyanatophenyl)methane, 2,2-bis[4-(4-cyanatophenoxy)phenyl]propane, 1,1,1,3,3,3-hexafluoro-2,2-bis[4-( 4-cyanatophenoxy) phenylcopropane, 1,1,1,3°3.3
-hexafluoro-2,2-bis[4-(2-trifluoromethyl-4-cyanatophenoxy)phenylcopropane, 1,1,1,3,3.3-hexafluoro-2,
2-bis[4-(3-trifluoro-amethyl-4-cyanatophenoxy)phenyl]propane, 1,1,1,3,
Examples include 3.3-hexafluoro-2°2-bis[4-(2-pen'j fluoro-amethyl-4-cyanatophenoxy)phenylcopropane.

Examples of the isocyanato compound include bis(4-inocyanatophenyl)methane, bis(4-isocyanatophenyl)ether, bis(4-isocyanatophenyl)
Sulfide, bis(4-isocyanatophenyl) sulfoxide, bis(4-isocyanatophenyl) sulfone,
Bis(4-isocyanatophenyl)ketone, 2,2-
Bis(4-isocyanatophenyl)propane, 1,1,
1,3,3.3-trifluoromethyl-2,2-bis(
4-incyanatophenyl)propane, bis(3-methyl-4-isocyanatophenyl)methane, bis(3-trifluoromethyl-4-incyanatophenyl)methane, bis(3,5-dimethyl-4-incyanato) phenyl)methane, 2,2-bis[4-(4-incyanatophenoxy)phenyl]propane, 1,1,1,3,3゜3
-hexafluoro-2,2-bisC4(4-isocyanatophenoxy)phenyl]propane, 1°1.1,3,
3.3-hexafluoro-2,2-bis[4-(2-1
Lifluoromethyl-4-isocyanatophenoxy)phenyl]propane, 1,1,1,3゜3.3-hexafluoro-2,2-bis[4-(3-trifluoromethyl-
4-isocyanatophenoxy)phenylcopropane, 1
, 1,1,3,3.3-hexafluoro-2,2-bis[4-(2-pentafluoromethyl-4-incyanatophenoxy)phenyl]propane, and the like.

Examples of cyanamide compounds include 1,1,1°3.3
．． 3-hexafluoro-2,2-bis[4-(2-trifluoromethyl-4-cyanamidophenoxy)phenyl]propane, 1,1,1,2,2,4°4.5,5.5
-decafluoro-3,3-bis[4-(2-trifluoromethyl-4-cyanamidophenoxy)phenylcopentane, 1,1,1,3.3.3-hexafluoro-2,
2-bis[4-(2-pentafluoroethyl-4-cyanamidophenoxy)phenyl]propane, 1,1,1,
3.3.3-hexafluoro2.2-bis[4-(2
-hebutafluoropropyl-4-cyanamidophenoxy)phenyl]propane, 1,1,1,3,3.3-hexafluoro-2,2-bis[4-(3-trifluoromethyl-4-cyanamidophenoxy) phenyl]propane, 1.1,1,3,3.3-hexafluoro-2,2-
Bis[4-(3-trifluorometal-5-cyanamidophenoxy)phenylcopropane, 1,1,1,3゜3
．． 3-hexafluoro-2,2-bis[4-(2-trifluoromethyl-5-cyanamidophenoxy)phenyl]propane, 1,1,1,3,3.3-hexafluoro-2,2-bis[ 4-(2-trifluoromethyl-3-
Cyanamidophenoxy)phenyl]propane, 4.4'
-bis(2-trifluoromethyl-4-cyanamidophenoxy)biphenyl, bis[4-(2-trifluoromethyl-4-cyanamidophenoxy)phenyl]ether, bis[4-(2-trifluoromethyl-4-cyanamid) phenoxy)phenyl] sulfide, bis[4-(
2-trifluoromethyl-4-cyanamidophenoxy)
phenyl] sulfoxide, bis[4-(2-1-lifluoromethyl-4-cyanamidophenoxy)phenyl]sulfone, bis[4-(2-trifluoromethyl-4-cyanamidophenoxy)phenylkoketone, bis[4- (
2-1-lifluoromethyl-4-cyanamidophenoxy)phenylcomethane, 2,2-bis[4-(2-trifluoromethyl-4-cyanamidophenoxy)phenyl]
Propane, bis(4-cyanamidophenyl)methane, bis(4-cyanamidophenyl)ether, bis(4-cyanamidophenyl)sulfide, bis(4-cyanamidophenyl)sulfoxide, bis(4-cyanamidophenyl)sulfone, bis(4-cyanamidophenyl)sulfoxide -cyanamidophenyl)ketone, 2,2-bis(4-cyanamidophenyl)propane,
1. l.

1,3,3,3-trifluoromethyl-2,2
-bis(4-cyanamidophenyl)propane, bis(3
-Methyl-4-cyanamidophenyl)methane, bis(3
-trifluoromethyl-4-cyanamidophenyl)methane, bis(3,5-dimethyl-4-cyanamidophenyl)methane, 2.2-bis[4-(4-cyanamidophenoxy)phenyl]propane, l.

1.1,3,3.3-hexafluoro-2,2-bis[
Examples include 4-(4-cyanamidophenoxy)phenyl]propane.

The cured product is obtained by filling a mold or the like in the temperature range of the molten state and then raising the temperature to a predetermined polymerization temperature or higher to proceed with the crosslinking reaction. If a radical polymerization initiator such as peroxide is added at this time, it becomes possible to shift the polymerization temperature to a lower temperature side, and at the same time, the reaction time can be shortened.

Examples of such radical polymerization initiators include benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, dichromyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, and cyclohexanone peroxide. , bis(1-hydroxycyclohexyl peroxide, 2,5-dimethylhexane-2
, 5-dihydroperoxide, t-butylperbenzoate, 2,5-dimethyl-2,5-(t-butylperoxy)hexane, 2,5-dimethyl-2,5-(1-butylperoxy)hexane -3,2,5-dimethylhexyl-2,5-di(peroxybenzoate), cumene hydroperoxide, t-butyl hydroperoxide,
t-butyl peroxybenzoate, t-butyl peroxy acetate, t-butyl peroxy octate, t
-butylperoxyisobutyrate, dibenzylperoxide, di-t-butylperoxyphthalate, and the like. One or more types of these can be used.

The amount of the polymerization initiator blended is 0.01 to 5 parts by weight based on 100 parts by weight of the resin composition, and particularly preferably 0.01 to 5 parts by weight.
．． 1 to 3 parts by weight. Further, polymerization accelerators, retarders, various pigments, fillers, etc. may be added as necessary.

Examples of materials for electronic devices containing the thermosetting resin composition of the present invention include mounting materials for computers. For example, there are various laminated materials for printed boards, encapsulating materials for semiconductors, interlayer insulation films for semiconductors, coating materials for cables, structural materials for connectors, etc.

Examples of laminated materials for various prints 1 include laminates, copper-clad laminates, prepregs, adhesive sheets, resist materials, and plating adhesives. For all of these, low dielectric constant materials are desired in order to increase heat resistance and signal transmission speed of computers, and the insulating material containing the resin composition of the present invention is suitable for these uses. be.

Next, a general method for manufacturing a typical laminated material as the electronic material of the present invention will be described.

First, a varnish is prepared by dissolving the resin composition in a solvent at a predetermined concentration. At this time, heating may be performed to promote dissolution or to advance the reaction to some extent. Examples of solvents include water, toluene, xylene, acetone, methanol, ethanol, methyl ethyl ketone, methyl isobutyl ketone, 3-methoxypropanol, 2-methoxyethanol, N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, trichloroethylene, Examples include 1,1,2-trichloroethane, tetrahydrofuran, dichloromethane, diisobutyl ether, trichlorotrifluoroethane, and mixtures thereof, and there are no particular limitations on the solvent as long as it can dissolve or mix the resin composition components. can.

Next, the obtained impregnating varnish is impregnated and coated on a sheet-like base material, and the solvent is removed to obtain a coated fabric (prepreg).At this time, the setting of the drying temperature is determined by the solvent used, the starting material, etc.

Layer the required number of coated cloths (one sheet is fine), 10
Adhesion is performed at 0 to 250° C. and under pressure of 1 to 100 kg/cm'' to obtain a laminate. At this time, by using W4 foil on both or one side of the upper and lower sides of the coated fabric, a copper-clad laminate is obtained. Almost all woven fabrics, non-woven fabrics, films, etc. that are generally used for laminated materials can be used as the sheet material as the base material.For example, inorganic materials such as E glass, C glass, A glass, and T glass containing silica, alumina, etc. glass,
There are woven fabrics and non-woven fabrics made of various glass fibers such as D glass and Q glass. Examples of materials include woven fabrics, nonwoven fabrics, and films made of aramid, fluoropolymers including polytetrafluoroethylene, polyamide, polyimide, polyether, polyester, and the like.

[Function] The reason why the resin composition of the present invention is excellent as a heat-resistant material is that a fluorine group is introduced into the bismaleimide structure in the form of a trifluoromethyl group.

By incorporating a large number of fluorine groups into the structure, the molar specific solubility of the resulting cured product was increased, and by lowering the polarization density, it was possible to lower the dielectric constant.

Furthermore, since the fluorine group has a large bond dissociation energy with carbon, it is possible to improve the thermal decomposition initiation temperature, which is a measure of heat resistance.

[Example] The present invention will be specifically explained with reference to Examples.

First, 1,4-bis[2-
A method for synthesizing (4-maleimido-2-trifluoromethylpheenoxy)-1,1,1,3,3,3-hexafluoroisopropyl]benzene (p-BMTHB) will be explained as a representative example.

1,4-bis(2-hydroxy-1,1,
1,3,3,3-hexafluoro-2-propyl)benzene 8.20 g (0.02 mol), 3-trifluoromethyl-4-bromonitrobenzene 21.6 g (
0.08 mol), 13.8 g (0.10 mol) of 2C0° and 50 mε of dimethylacetamide as a solvent,
0.38 g (10 mol%) of Cur was added as a catalyst, and the temperature was maintained at 100°C with stirring for 48 hours to react.
-nitrophenoxy)-1,1,1,3,3,3-hexafluoro-2-propyl)benzene was obtained (yield.

88%).

Next, after filtering this reaction solution, 200 mff of water was added, extracted with 200 mff of ether, dried over magnesium sulfate, filtered, and evaporated to obtain a crude 1°4-bis[2-
(2-trifluoromethyl-°4-nitrophenoxy L
-1,1,1,3,3,3-hexafluoroD-2-p0
22.24 g of solid benzene was obtained. This solid substance was mixed with methanol (400mj!) H20
(Purified product 11 with a purity of 99.4% after recrystallization with 40 mj
．． 11 g was obtained (yield: 71%).

1 obtained above was placed in a 100 mg glass pressure-resistant reaction tube.
4-bis[2-(2-trifluoromethyl-4-nitrophenoxy)-1,l,1,3,3.3-hexafluoro-2-propyl]benzene 7.88 g (0.01 mo/l, ), 5%Pd/C (50% by weight) 0.08g (
0.5% by weight) and 50 m ethyl acetate as solvent
The resulting reaction solution was filtered and evaporated to produce 1.4-bis[2-(2-
trifluoromethyl-4-aminophenoxy)-1,1
, 6.67 g of 1,3,3,3-hexafluoro-2-probylcobenzene was obtained (yield, 90%).

1,4-bis[2-(2-trifluoromethyl-4-aminophenoxy)-1°1.1,3,3.
3-hexafluoro-2-propyl]benzene 7.26
g (0.01 mol), maleic anhydride 2.16 g (
0,022 mol) and 50 m2 of ethyl acetate as solvent
was added, reacted at room temperature (25°C) for 2 hours, filtered and dried to obtain 8.30 g (0.09 mol) of 1.4-bismaleamic acid crystals with a purity of 99.9% (yield: 90%)
.

1,4-bismaleamic acid obtained in a 100me three-turoh flask equipped with a Dimroth condenser and a thermometer 4.
62g (0,005 mol), potassium acetate 1.96
g (0.02 mol) and 49 g of acetic anhydride as solvent
(0.05 mol) was added and reacted at room temperature for 48 hours with stirring. After filtering the reaction solution, 200 mJ of water! When the crystals precipitated were filtered and dried, 3.91 g (yield near 7%) of the target crude maleimide was obtained.

Furthermore, 8 mJ of ethyl acetate - 16 mJ of methanol! By recrystallizing with
g (yield, 70%). The IR spectrum of the obtained maleimide is shown in FIG.

[Example 1] 1.4-bis[2-(4-maleimido-2-trifluoromethylphenoxy)-1,1,1,3,3゜3-hexafluoroisopropyl]benzene (p-B M T
HB) (1100 g of Central Nitrogen was dissolved in 200 g of methyl isobutyl ketone, and 1.0 g of 2,5-dimethyl-2,5-(t-butylperoxy)hexyne-3 (NOF) was added as a radical polymerization initiator. A varnish for impregnation was obtained.The obtained varnish was coated with the D glass cloth (
Thickness 50μm) (B bundled) - impregnated coating, 110
A coated cloth was obtained by drying in the air at .degree. C. for 10 minutes.

Copper foils were layered on top and bottom of the obtained coated fabric and laminated and bonded in a press. The bonding conditions were 130° C. for an IFR reaction, and then the temperature was raised to 250° C. and heat and pressure was applied for 250° C. to obtain a copper-clad laminate.

The pressure was 30 kg/cm2.

The dielectric constant, thermal expansion coefficient, thermal decomposition temperature, copper foil peel strength, and flame retardance of the obtained copper-clad laminate were investigated. Results first
Shown in the table.

[Example 2] 100 g of p-BMTHB and 100 g of pentafluorostyrene (P, C, R,) used in Example 1 were mixed with N-
It was dissolved in 200 g of methylpyrrolidone and reacted by heating at 100° C. for 1 hour to obtain an impregnating varnish. The obtained varnish was coated on an aramid cloth (thickness: 50 μm) (Asahi Shavel) and dried in air at a constant temperature of 180° C. for 10 minutes to obtain a coated cloth. Copper foils were layered on top and bottom of the obtained coated fabric and laminated and bonded in a press. The bonding conditions were as follows: After reacting at 200° C. for 1 hour, the temperature was raised to 250° C. for 2 hours, followed by heating and pressing to obtain a copper-clad laminate.

The pressure was 40 kg/cm'. The properties of the obtained copper-clad laminate were measured in the same manner as in Example 1.

The measurement results are shown in Table 1.

[Example 3] 100 g of p-BMTHB used in Example 1 and 1°1
．． 1,3,3.3-hexafluoro-2,2-bis[4
100 g of -(4-maleimido-2-tofluoromethylphenoxy)phenyl]propane (p-HFBP) (Central Glass) was dissolved in >300 g of acetate, and dicumyl peroxide (NOF) was added as a radical polymerization initiator.
A varnish for impregnation was obtained by adding 0.4 g. The obtained varnish was impregnated and coated on Q glass cloth (thickness: 50 μm) (Nichishutsu), and dried in air at 110° C. for 10 minutes to obtain a coated cloth.

Copper foils were layered on top and bottom of the obtained coated fabric and laminated and bonded in a press. The bonding conditions were as follows: After reacting at 130° C. for 1 hour, the temperature was raised to 220° C. and heating and pressing was carried out for 2 hours to obtain a copper-clad laminate. The pressure was 30 kg/cm2.

Table 1 shows the properties of the copper-clad laminate obtained.

[Example 4] 100 g of p-BMTHB used in Example 1 1.1,3,3.3-hexafluoro-2,2-bis(
4-cyanatophenyl)propane (Manac) 100g
was dissolved in 200 g of N,N-dimethylformamide and 12
After heating at 0° C. for 1 hour, the mixture was cooled to room temperature, and 0.4 g of dicumyl peroxide (NOF) was added as a radical polymerization initiator to obtain a varnish for impregnation. The obtained varnish was impregnated and coated on E glass cloth (thickness 50 μm) (8 Tobo) and heated at 110°C.
, and dried for 1° in constant temperature air to obtain a coated cloth. Copper foils were layered on top and bottom of the obtained coated fabric and laminated and bonded in a press. The bonding conditions were to react at 130°C for 1 hour, then raise the temperature to 220°C.
C. for 2 hours to obtain a copper-clad laminate. pressure is 30k
g/cm".

Table 1 shows the properties of the copper-clad laminate obtained.

C Example 5] 1.3-bis[2-(4-maleimido-2-trifluoromethylphenoxy)-1,1,1,3,3°3-hexafluoroisopropyl]benzene (m-BMTHB
) (-1=antral glass) 100g and 1°1.1.3,
3.3-hexafluoro-2,2-bis[4-(4-cyanamidophenoxy)phenylcopropane (HFCP)
(Manac) 50g to 200g of methyl isobutyl ketone
A varnish for impregnation was obtained. The obtained varnish was impregnated and coated on T glass cloth (thickness 50 μm) (Nichishutsui).
The coated cloth was dried at 20° C. for 10 minutes in constant temperature air. Copper foils were layered on top and bottom of the obtained coated fabric and laminated and bonded in a press. The bonding conditions were as follows: After reacting at 150° C. for 1 hour, the temperature was raised to 250°C for 1 hour and 280°C for 1 hour to obtain a copper-clad laminate.The pressure was 20 kg/cm.

Table 1 shows the properties of the copper-clad laminate obtained.

[Example 6] p-BMTHB used in Example 1, loog, and 2.2-
100 g of bis[4-(4-maleimidophenoxy)phenyl]butane (BMPP) (Hitachi Chemical) was dissolved in 200 g of methyl isobutyl ketone and reacted by heating at 100° C. for 1 hour to obtain a varnish for impregnation. The obtained varnish was impregnated and coated on aramid cloth (thickness: 50 μm) (Asahi Siepel) and dried at 110°C for 20 minutes in the air to obtain a coated cloth. Copper foils were laminated and bonded in a stack press. The bonding conditions were 130°C. After reacting for 1 hour, the temperature was raised to 250°C and heat and pressure was applied for 2 hours to obtain a copper-clad laminate. The pressure was 40 kg/cm. .

Table 1 shows the properties of the copper-clad laminate obtained.

[Example 7] 100 g of 1.4-bis[2-(4-maleimido-2-pentaethylpheenoxy)-1,1,1,3,3,3-hexafluoroisopropylcobenzene was added to 200 g of methyl ethyl ketone. It was dissolved to obtain a varnish for impregnation. The obtained varnish is impregnated and coated on D glass cloth (thickness 50 μm) (B bundle) and dried in air at 110° C. for 10 minutes to obtain a coated cloth. Copper foils are layered on top and bottom of the obtained coated fabric and laminated and bonded in a press. The bonding conditions were as follows: After reacting at 130° C. for 1 hour, the temperature was raised to 250° C. for 1 hour under heating and pressure to obtain a copper-clad laminate. The pressure was 30 kg/cm''.

Table 1 shows the properties of the copper-clad laminate obtained.

The resin composition can be used as a laminated material for various multilayer boards, a sealing material for semiconductors, a semiconductor interlayer insulating film, a covering material for cables, a structural material for connectors, a laminate, a copper-clad laminate, a prepreg,
It can be used for adhesive sheets, resist materials, plating adhesives, etc.

[Comparative Example 1] 2.2-bis[4-(4-maleimidophenoquine)phenylcopropane (BMPP) (Hitachi Chemical) was dissolved in 200 g of N,N-dimethylformamide to obtain an impregnating varnish. The obtained varnish was coated with Q glass cloth (thickness: 50 μm)
) (8 bundles) was impregnated and coated, and dried in the air at 150°C for 10 minutes to obtain earthwork fabric.

L14 foil was layered on top and bottom of the obtained coated fabric and laminated and bonded in a press. The bonding conditions were 170° C., after reacting for 1 hour, the temperature was raised to 250° C., and heating and pressing was carried out for 1 hour to obtain a copper-clad laminate. The pressure was 20 kg/am''.

The properties of the obtained copper-clad laminate were measured in the same manner as in Example 1. The measurement results are shown in Table 1.

[Effects of the Invention] The fluorine-containing biscyanamide resin composition of the present invention has excellent moldability, and the resulting cured product has excellent heat resistance. Further, the dielectric constant, which is important as an electrical property of an insulating material, is 3 or less, and a resin composition suitable as an insulating material for various electronic devices can be provided.

[Brief explanation of the drawing]

FIG. 1 is an IR spectrum of the maleimide compound of the present invention. Agent: Patent attorney Akio Takahashi, 2 (and 1 other person)
′Say

Claims (1)

[Claims] 1. General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, Rf represents fluorine or a perfluoroalkyl group having 1 to 10 carbon atoms.) A thermosetting resin composition comprising a bismaleimide compound. 2. A thermosetting resin composition comprising a bismaleimide compound represented by the general formula (1) and a compound having an ethylenically unsaturated double bond. 3. A thermosetting resin composition comprising a bismaleimide compound represented by the general formula (1) and an epoxy compound. 4. A thermosetting resin composition comprising a bismaleimide compound represented by the general formula (1) and a phenol-formaldehyde condensate. 5. A thermosetting resin composition comprising a bismaleimide compound represented by the general formula (1) and a melamine compound. 6. A thermosetting resin composition comprising a bismaleimide compound represented by the general formula (1) and a compound having an N-substituted unsaturated imide group or a derivative thereof. 7. A thermosetting resin composition comprising a bismaleimide compound represented by the general formula (1) and a cyanato compound or a derivative thereof. 8. A thermosetting resin composition comprising a bismaleimide compound represented by the general formula (1) and an isocyanate compound or a derivative thereof. 9. A thermosetting resin composition comprising a bismaleimide compound represented by the general formula (1) and a cyanamide compound or a derivative thereof. 10. Heat curing of a bisether cyanamide compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, Rf represents fluorine or a perfluoroalkyl group having 1 to 10 carbon atoms.) 1. An insulating material for electronic devices, characterized in that it contains a synthetic resin composition.