JPH0314836A - Imide prepolymer, its preparation, its cured product and preparation of sealing material and laminate board using same prepolymer - Google Patents

Abstract

PURPOSE:To prepare an imide prepolymer giving a cured product excellent in the heat resistance, electrical properties, and adhesive strength by compounding a specific bismaleimide and a specific diamine in a specified molar ratio. CONSTITUTION:A bismaleimide of formula I (wherein D is a divalent group contg. a carbon-carbon double bond; and R<1> to R<6> are each H, 1-5C alkyl, or halogen) and a diamine of formula II (wherein R<7> to R<12> are each R<1>) are compounded in a molar ratio of the bismaleimide to the diamine of 1.0-50.0.

Description

[Detailed Description of the Invention] Industrial Application Fields The present invention relates to a hardened Brevolimer that has good heat resistance and electrical properties as well as adhesive strength when cured, and is particularly suitable for use in multilayer printed circuit boards and other applications. This article relates to imide-based brevolimers that pass through sealing materials such as ICs, their manufacturing methods, and their uses.

Conventional technology> Conventionally, N. An imide prepolymer (trade name: Kelimide) consisting of N'-4,4'-diphenylmethane bismaleimide and diayonodiphenylmethane is well known. This resin has good moldability and heat resistance, so
Applications such as multilayer printed wiring boards have been developed.

However, glass cloth laminates using this resin have low glabellar peeling or copper foil peeling strength, which limits their uses.

In addition, in recent years, resins with excellent electrical properties such as low dielectric constants have been required in order to cope with the increasing speed of computer calculations and the increasing density of wiring.

be.

Formula [1] Problems to be Solved by the Invention The present invention solves the problems in the prior art and provides an imide prepolymer which has good electrical properties as a cured product and is suitable for multilayer printed circuit boards and sealants. The purpose is to provide methods for producing the same and their uses.

(Here, D represents a divalent group containing a carbon-carbon double bond, and R1 to R6 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom) Formula [I! ] Means for Solving the Problems> A first aspect of the present invention provides at least a bismaleimide compound represented by the following formula [1] and the following formula [! ■] and the diamine component represented by [Il formula bismaleimide component/[1
An imide-based brevolimer containing the diamine component of formula 11 at a molar ratio of 1.0 to 50.0 and its cured product (where R7 to R+2 are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or halogen atoms). A second aspect of the present invention is a method for producing an imide-based brevolimer, in which at least a bismaleimide component represented by the following formula [I] and a diamine component represented by the following formula [II] are heated and reacted.

Formula [I] (Here, D represents a divalent group containing a carbon-carbon double bond, and R1 to R6 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom) [I1] A varnish is prepared by dissolving a mid-type Brevolimer in an inert solvent, the reinforcing fibers are impregnated with the varnish, dried to form a prepreg, and the prepregs are laminated and compression molded by heating and pressing. This is the manufacturing method of the board.

A fourth aspect of the present invention is a sealing material containing an imide Brevolimer as a main component.

Here, the bismaleimide component has the following formula [II1]
A bismaleimide represented by is preferred.

(Here, R7 to R+2 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom)
D represents a divalent group containing a carbon-carbon double bond,
R1, .

The novel imide-based brevolimer of the present invention contains at least units of a bismaleimide component represented by the following formula [I] and units of a diamine component represented by the following formula [I1].

The unit of the bismaleimide component used in the present invention has the formula [■] (where D represents a divalent group containing a carbon-carbon double bond, and R1 to R6 are a hydrogen atom and a carbon number 1 ~5 alkyl group or halogen atom).

In formula [I], D represents a divalent group containing a carbon-carbon double bond. Specific examples of D include the following.

Further, R1 to R6 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and may be the same or different from each other. 1 to 5 carbon atoms
Examples of the alkyl group include methyl group, ethyl group,
Examples of the halogen atom include isobrobyl group and the like, and examples of the halogen atom include bromine, chlorine, and fluorine.

Specific examples of the bismaleimide component represented by formula [I] include the following.

α,α-bis(N-4-maleimidophenyl)-m-
Diisoprobylbenzene, α,α-bis(N-4-maleikudophenyl)-p-diisoprobylbenzene, α,
α'-bis(N-4-maleimido-3-methylphenyl)-p-diisobrobylbenzene, α. α′-bis(N
-4-maleimido-3-methylphenyl)-m-diisobrobylbenzene, α,α-bis(N-4-maleimido-3,5-dibromophenyl)-m-diisopropylbenzene, α,α-bis( N-4-maleimide-3.5-
dibromophenyl)-p-diisopropylbenzene, α
．． α′-bis(N-4-maleimidophenyl)-1.3
-diisopropyl-5-methylbenzene, α,α'-bis(N-4-maleimido-3,5-dibromophenyl)
-1,3-diisobrobyl-5-methylbenzene, α,
α-bis(N-4-citrakoimidophenyl)-m-
Diisoprobylbenzene, α,α-bis(N-4-citrakoimidophenyl)-p-diisobrobylbenzene, and the like.

Moreover, a mixture of two or more of these can also be used.

Preferably α. α'-bis(N-4-maleimidophenyl)-m-diisobrobylbenzene, α. α-bis(
N-4'-maleimidophenyl)-p-diisopropylbenzene, α. α-bis(N-4-maleimido 3
(1methylphenyl)1p-diisobrobylbenzene, α
．． α-bis(N-4-maleimito-3-methylphenyl)-m-diisopropylbenzene, α,α′-bis(
N-4-maleimido-3,5-dibromophenyl)-m
-diisopropylbenzene, α,α′-bis(N-4-
maleimide (3,5-dibromophenyl)-p-diisobrobylbenzene.

The diamine component used in the present invention is It is shown by the formula [■].

Further, R7 to R'2 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and may be the same or different. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, ethyl group, and isobrobyl group, and examples of the halogen atom include bromine, chlorine, and fluorine.

Specific examples of the diamine component represented by the formula [TI] include the following.

α. α'-bis(4-aminophenyl)-m-diisobrobylbenzene, α. α-bis(4-aminophenyl)-p-diisobrobylbenzene, α1 α′-bis(4-amino-3,5-dibromophenyl)-m-diisopropylbenzene, α. α′-bis(4-amino-3
．． 5-dibromophenyl)-1p-diisoprobylbenzene, α,α'-bis(4-amino-3-methylphenyl)1p-diisoprobylbenzene, α,α'-bis(4
-amino-3-methylphenyl)-m-diisopropylbenzene, α. α'-bis(4-aminophenyl)1.
3-diisobroblue 5-methylbenzene, α, α-
Bis(4-amino-3,5-dibromophenyl)-1.
3-diisobrobylbenzene, etc. Of course, mixtures of the above may also be used.

Preferably α,α′-bis(4-aminophenyl)-
m-diisopropylbenzene and α,α-bis(4-aminophenyl)-p-diisobrobylbenzene are good.

The bismaleimide component represented by formula [I] and the formula [I1
] The ratio of the diamine component represented by formula [I] to the diamine component of formula [II] is a molar ratio of 1.0 to 50.0 depending on the purpose of use of the imide-based brevolimer. and select.

Usually, the molar ratio is 1 to 10, and the cured product obtained by heating and curing has high heat resistance such as Tg and thermal decomposition start temperature, and when used as a sealant, and when made into a copper-clad laminate, adhesive strength and copper foil 1 to 5 in terms of high peel strength, high interlayer peel strength, and low dielectric constant.
It is preferably 1.5 to 3.5, more preferably 2.5 to 3.5.

The prepolymer of the present invention has a number average molecular weight (Mn) of 550 to 1500, preferably 600 to tooo, and a weight average molecular weight (Mw) of 70
0 to 3500, preferably 800 to 3000.

In addition, the imide-based prepolymer in which the bismaleimide component represented by formula [11] is m-diisopropylbenzene-bismaleimide represented by the following i[LH] has a dielectric constant of a cured resin obtained using the imide prepolymer. is low.

Formula [II1] (Here, D represents a divalent group containing a carbon-carbon double bond, and R1 to R6 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom) In [II+], D and R1 to R6 are represented by the formula [
This is the same as what was already mentioned in [I].

Specific examples of the bismaleimide component represented by formula [III] include α α′-bis(N-4-maleimidophenyl)-m-
Diisopropylbenzene, α. α-bis(N-4-maleimido-3-methylphenyl) 1m-diisobrobylbenzene, α. α′-bis(N-4-maleimido 3.
5-dibromophenyl)-m-diisobrobylbenzene, α. α′-bis(N-4-maleimidophenyl)-1
．． 3-diisopropyl-5-methylbenzene, α. α′
-bis(N-4-maleimido-3,5-dibromophenyl)-1,3-diisobrobyl-5-methylbenzene,
α. α′-bis(N-4-citrakoimidophenyl)-
Examples include m-diisobrobylbenzene and the like. Moreover, a mixture of two or more of these can also be used.

Preferably α,α'-bis(N-4-maleimidophenyl)-m-diisobrobylbenzene, α,α'-bis(
N-4-maleimido-3-methylphenyl)-m-diisobrobylbenzene.

In addition to the above-mentioned bisimide component and diamine component, the prepolymer of the present invention may contain a vinyl monomer such as triallyl isocyanurate, triallyl trimellitate,
Reactive monomers such as m- or p-arynoisobropenylbenzene, styrene, allyl glycidyl ether, methacrylic acid glycidyl ester, or epoxy compounds such as ethylene glycol diglycidyl ether can also be included. Furthermore, it may contain reactive rubber components such as epoxy resin, ayon-terminated butadiene acrylonitrile rubber (ATBN), carboxy-terminated butadiene acrylonitrile rubber, and eboxidized polybutadiene rubber, silicone resin, fluororesin, aniline resin, phenolic resin, etc. .

The content of these third components is usually 5 to 50% based on the total weight of the unsaturated bis-yide compound and the aromatic diamine compound.
It is about 100% by weight, preferably about 10 to 50% by weight.

The novel imide-based prepolymer of the present invention is produced by mixing the bismaleimide component of formula [1] and the diamine component of formula [■]] and other necessary components, and then mixing the mixture at an appropriate temperature of 100°C to 250°C. It can be produced by reacting for minutes to several hours.

On the other hand, it can also be produced using a polar solvent such as dimethylformide or N-methylpyrrolidone.

It can also be produced by heating and reacting in solution in an inert polar solvent such as dimethylformamide or N-methylpyrrolidone. At this time, in order to control the reaction rate, a radical scavenger, an anionic polymerization catalyst, a radical generator, a Michael addition reaction promoter, etc. may be used as a catalyst, if necessary.

Examples of the radical scavenger include 1,1-diphenyl-2-picrylhydrazyl, 1,3.5-triphenylferdazyl, 2,6-di-t-butyl-α-(3,5
Stable radicals such as τ-di-t-butyl-4-oxo-2,5-cyclohexadiene-1-ylidene-p-tolyloxy): hydroquinone, 2.5-di-t-butylhydroquinone, t-butylcatechol, t-butylhydroquinone, 2 , 5-phenol derivatives such as di-t-butyl-4-methylphenol; benzoquinone derivatives such as benzoquinone, 2-methylbenzoquinone, and 2-chlorobenzoquinone; nitrosobenzene and its derivatives; nitrobenzene derivatives such as nitrobenzene and m-dinitrobenzene; sulfur : High-valent metal salts such as iron chloride (II1), etc., especially hydroquinone, 2, 5
-di-1-butylhydroquinone and 1,1-diphenyl-2-vicrylhydrazyl are preferred.

When using these radical scavengers, the amount is usually 0.0% based on the total weight of the bisimide compound and diamine compound.
It is used in an amount of 0.001 to 5% by weight.

Examples of anionic polymerization catalysts include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-
Imidazoles such as benzyl-2-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; tertiary amines such as triethylamine and penzyldimethylamine; and the like.

Among these, Idazoles are preferred, and 2-phenyl-4-methylimidazole and 1-benzyl-2-methylimidazole are particularly preferred.

Examples of radical generators include peroxides such as cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, and di-t-butyl peroxide; α, α azobisisobutyronitrile, azobiscyclohexanecarbohydrate; Examples include azo compounds such as nitrile.

Michael addition reaction promoters include benzoic acid, o-toluic acid and its isomers, O-tart-butylbenzoic acid and its isomers, O-chlorobenzoic acid and its isomers, 0-dichlorobenzoic acid and its isomers. O-bromobenzoic acid and its isomers, O-nitrobenzoic acid and its isomers, O-hydroxybenzoic acid and its isomers, 0-methoxybenzoic acid and its isomers, 0-nitrobenzoic acid and its isomers aromatic monocarboxylic acids such as O-aminobenzoic acid and its isomers. Aromatic dicarboxylic acids such as phthalic acid and its isomers. Tricarboxylic acids such as trimellitic acid, aromatic tetracarboxylic acids such as pyromellitic acid, and penzophenone tetracarboxylic acid. Aliphatic monocarboxylic acids such as formic acid, acetic acid, brobionic acid, phenylacetic acid, silicic acid, glycolic acid, lactic acid, tartaric acid. Also, aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, maleic acid, and fumaric acid.

Or acid anhydrides such as: maleic anhydride, telorahydroxyphthalic anhydride, telorahydroxymethylphthalic anhydride, nadic anhydride, trimellitic anhydride,
Examples thereof include biromellitic dianhydride, 3.3',4.4'-benzophenonetetracarboxylic dianhydride, and the like.

The amount of these carboxylic acids or acid anhydrides is 0.01 to 5.0% based on the total weight of the bismaleimide component represented by the formula [1] and the diamine component represented by the formula [II].
It is used in a range of 0% by weight.

When the Brevolimer of the present invention obtained as described above is reacted in a heated molten state, the resulting reaction product is used as it is, or dissolved or suspended in an appropriate solvent to form a varnish, and then pulverized. It can be applied in powder form for various purposes. In addition, when the reaction is carried out in a solution state, the resulting reaction product may be used as a varnish in the form of a solution or suspension without removing the solvent, or the product obtained by removing the solvent may be pulverized. It can be dissolved as a powder in a solvent to make a varnish, or it can be used directly as a powder for various purposes. Examples of the solvent used include inert polar solvents such as N-dimethylformamide and N-methylpyrrolidone.

Curing of the Brevolimer of the present invention can be carried out by heating at about 180 to 250° C. for about 10 to 180 minutes, and applying pressure if necessary. The obtained cured product is
Infusible and insoluble. It also has high resistance to thermal strain, good electrical properties, low water absorption, and is stable against chemicals. In addition, the blepolymer of the present invention may optionally contain a lubricant,
It is also possible to add mold release agents, coupling agents, inorganic or organic fillers.

Examples of lubricants and mold release agents include carnauba wax, beeswax, stearic acid, fatty acid esters such as butyl ester; fatty acid amides such as ethylene and bis-stearamide; fatty acids such as montanic acid and stearic acid, and their metals. Salts; petroleum wax, polyethylene wax, polypropylene wax and their oxidation products; silicone oils such as polymethylsiloxane and polymethylphenylsiloxane; coupling agents include, for example, γ-glycidoxybro bilmethoxysilane,
Examples include N-β(aminoethyl)-γ-aminopropyltrimethoxysilane. When adding this lubricant, mold release agent or coupling agent, the amount added is usually about 0.1 to 5% by weight based on the weight of the imide Brevolimer.

Inorganic or organic fillers include, for example, silica powder, alumina powder, glass powder, mica, talc, barium sulfate, titanium oxide, molybdenum disulfide, alkali powder, iron powder, copper powder, aluminum hydroxide, hydroxide, etc. Metal hydroxides such as magnesium; hollow bodies of silica, alumina, glass or phenolic resin; glass fibers, carbonized fibers, alumina fibers, silicon carbide IA fibers,
Examples include reinforcing fibers such as aluminum fibers and copper fibers.

When adding this inorganic or organic filler, the amount added is usually 50% by weight based on the weight of the imide Brevolimer.
~500% by weight.

The cured product of the Brevolimer of the present invention has excellent electrical properties, heat resistance, and low water absorption, and can be used in laminated materials such as printed wiring boards, IC sealing materials, adhesives, insulating varnishes, etc. It is applicable to various uses.

In order to produce a laminate using the Burepolymer of the present invention, a fibrous or cloth-like reinforcing material or a porous sheet is impregnated with a solution of the prepolymer and then dried to produce a Buregu. For example, a glass cloth is impregnated with a varnish containing the Brevolimer of the present invention and dried to produce a Breebreg.

Next, stack the required number of pre-regs obtained, 180 ~ 2
50℃, 10~40 Kgf/cm2, 20~
Pressurized for 180 minutes, with excellent electrical properties and heat resistance,
Laminates with low water absorption can be obtained. The obtained laminate can be used as it is, but preferably 2
It is preferable to cure after several hours to 48 hours at a temperature of 00°C to 250°C.

In addition, using this imide-based Brevolimer, IC elements,
A suitable method for use as a sealing material for LSI devices, etc. is to add a filler such as fused silica, a binder such as a silane coupling agent, a mold release agent such as wax, and curing of imidazole, peroxide, etc. to the imide-based Brevolimer. Mix the agent.

Preferably, 150 to 400 parts by weight of the filler and 0.5 to 2 parts by weight of the mold release agent are added to loo parts by weight of the imide-based Brevolimer.
parts by weight, 0.5 to 2 parts by weight of the binder, and 0.5 to 2 parts by weight of the curing agent.
2 parts by weight are mixed to form a sealing material.

The above raw materials are roll-kneaded for 1 to 10 minutes at 100 to 140°C to obtain a molding material. This shaped material is preferably molded at 180 to 200°C for 2 to 10 minutes using a transfer molding machine or the like, and then post-cured at iao to 200°C for 5 to 24 hours.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

Brevolimers of the present invention and comparative examples were prepared under the following conditions, made into a varnish using a solvent, impregnated into fibers with this varnish, dried to form a Bribbreg, and this Bribbreg and copper foil were stacked to form a laminate with physical properties. was evaluated. In addition, cured raw resin products and test pieces were prepared under the following conditions, and their physical properties were evaluated.

Evaluation Test (1) Copper Foil Peel Strength The copper foil was peeled off under the conditions of JIS C6481, and the strength was determined.

(2) Interlayer peel strength Under conditions similar to those used for measuring copper foil peel strength, pre-reg layers were separated by 'i. um, and the strength was determined.

(3) Glass transition point (Tg) Tg is measured using a measuring device manufactured by Seiko Electronics (TMA-100)
The measurement was performed using a heating rate of 10'e/min.

(4) Dielectric constant, tan δ Measurement was performed at IMHz using a flat plate (cured raw resin as described in Example 1) according to JIS K-6911.

(5) Bending strength Evaluation was made according to JIS K-6911.

(6) Flexural modulus Evaluation was made according to JIS K-6911.

(7) Volume resistance Measured at 21°C and 150°C based on JIS K-6911.

(8) Absorption rate The water absorption rate was measured by immersing the sample in distilled water at 125°C for 20 hours.

(Example 1) 314.3 g of α. α-bis(N-4-maleimidophenyl)-m-diisobrobylbenzene, 85.7 g α. αbis(4-aminophenyl)-p-diisobrobylbenzene and 400 g of N-methylpyrrolidone were added and reacted at 120°C for 5 hours (bismaleimide/diamine, molar ratio = 2.5).
. Apply this varnish to glass cloth (manufactured by Nittobo Co., Ltd.)
was impregnated with water and dried at 160° C. for 9 minutes to produce a blibreg (resin content: 38%). 200 pieces of copper foil (manufactured by Mitsui Kinzoku Mining Co., Ltd.) are stacked on top and bottom of these 9 pieces of blibregs.
It was placed on a press at 10°C and compression-molded for 60 minutes under a pressure of 10 kgf/cm'' to produce a copper foil laminate.

Subsequently, it was post-cured at 200° C. for 24 hours.

Separately, the above varnish was poured into a large amount of water with stirring, and the precipitated resin was filtered and collected. This was placed in a vacuum dryer and dried under reduced pressure at 60° C. for 8 hours and at 80 tons for 8 hours. This resin was compression molded for 60 minutes using a 200 t press to produce a flat plate with a thickness of 2 mm. Continue to heat at 200℃ for 24 hours.
The raw resin cured product was cured after a period of time.

(Example 2) α,α-bis(N-4-maleimidophenyl)-m-
α. instead of diisobutylbenzene. α-bis(N
The procedure was the same as in Example 1 except that -4-maleimidophenyl)-p-diisobrobylbenzene was used.

(Example 3) α,α-bis(4-aminophenyl)-p-diisobrobylbenzene was replaced with α. Except that after reacting α-bis(4-aminophenyl)-m-diisopropylbenzene in an N-methylpyrrolidone solution at 120°C for 5 hours, 1.2g of 1-benzyl-2-methylimidazole was added. The procedure was the same as in Example 1.

(Comparative Example 1) In a Tfl flask, 327.6 g of N, N'4.4
'-diphenylmethane bismaleimide, 72.4 g of 4
．． 4'-diaxonodiphenylmethane and 400 g N
-Methylpyrrolidone was added and reacted at 120°C for 3 hours (bismaleimide/diamine, molar ratio = 2.5).
Glass cloth laminates and flat plates were produced under the same conditions as in Example 1.

(Example 4) 314.3 g of α. α-bis(
N-4-maleimidophenyl)-m-diisobrobylbenzene was added and melted by immersion in an oil bath at 160°C. To this was added 85.7 g of α,α'-bis(4-aminophenyl)p-diisopropylbenzene over about 1 minute while stirring (molar ratio=2.5). Furthermore,
Continue stirring and add α,α′-bis(4-aminophenyl) 1p
- One hour after the start of addition of diisobrobylbenzene, the prepolymer was taken out into a vat. Immediately before the prepolymer was taken out into the vat (30 seconds), a curing accelerator was mixed into the Brevolimer by adding 1.2 g of 1-benzyl-2-methylimidazole dissolved in 5 g of toluene.

The extracted prepolymer was cooled and then pulverized.

This Brepolymer was dissolved in N-methylpyrrolidone to prepare a varnish with a resin concentration of 50%.

A glass cloth was impregnated with this varnish and dried at 160° C. for 9 minutes to produce a brev leg. 9 pieces of these pre-regs and copper foil are placed on top and bottom of them and placed in a press at 200℃, 1
Compression molded for 60 minutes under a pressure of 0 kgf/am2,
A copper foil laminate was produced. Subsequently, it was post-cured at 200° C. for 24 hours.

Separately, the Brevolimer was placed in an air oven at 170° C. and heated for 30 minutes to advance the reaction, then taken out, cooled, and pulverized. This prepolymer was compressed in a press at 200° C. for 1 hour to produce a flat plate with a thickness of 2 mm.
This precept is then placed in an air oven at 200℃.
It was cured after 4 hours. This was used as a raw resin cured product, and the dielectric constant was measured using this.

(Example 5) α. Preparation was performed in the same manner as in Example 4, except that α,α-bis(4-aminophenyl) 1m-diisoprobylbenzene was used instead of α′-bis(4-aminophenyl)1p-diisoprobylbenzene. The polymer was synthesized. A molded article was obtained from this Brevolimer in the same manner as in Example 4.

(Example 6) 325.9g of α. α-bis(N-4-maleimidophenyl)-m-diisopropylbenzene was melted by immersing it in an oil bath at 160°C. 74.1g for this
The copper A foil laminate and cured raw resin were produced.

(Example 7) α. Prepolymer was prepared in the same manner as in Example 6 except that α,α-bis(4-aminophenyl)-m-diisoprobylbenzene was used instead of α-bis(4-aminophenyl)-p-diisoprobylbenzene. was synthesized.

A molded article was obtained from this Brevolimer in the same manner as in Example 6.

The evaluation results of Examples 1 to 7 and Comparative Example 1 are shown in Table 1.

(Example 8) In a flask at 1°C, 325.9gα,α-bis(N-4
-maleimidophenyl) 1m-diisobrobylbenzene was added and melted by immersing it in an oil bath at 160°C.

In addition to this, 74.1g of α. α'-bis(4-aminophenyl)-p-diisopropylbenzene was added with stirring over about 1 minute (mole ratio=3.0).

Further, stirring was continued and α,α′-bis(4-aminophenyl)
One hour after the start of addition of p-diisopropylbenzene, the reaction mixture was taken out into a vat.
After allowing this to cool to room temperature, it was pulverized to obtain a prepolymer.

Using this prepolymer, the following formulation was prepared, and a sealing material was prepared by kneading with two rolls at 120° C. for 5 minutes.

Prepolymer blend of sealing material: 100 parts by weight γ-aminopropyltriethoxysilane 1 part by weight Fused silica 233 parts by weight Carnauba wax 1 part by weight 2-methylimidazole
From the encapsulating material obtained in 2 parts by weight, one transfer shape (1
A test piece for physical property evaluation was molded at 90°C, 20 Kg/cIl1' for 5 minutes, and then post-cured at 190°C for 10 hours. Table 2 shows the evaluation results of the physical properties of the test pieces.

(Comparative Example 2) Example 8 except that N,N'-4.4'-bismaleimidophenylmethane and diaminodiphenylmethane were used.
A prepolymer was synthesized in the same manner as in Example 8, and a sealing material was prepared in the same manner as in Example 8, except that 1 part by weight of 2-methylimidazole was used. A test piece was formed using this sealing material under the same conditions as in Example 8, and was post-cured to evaluate the physical properties, which are shown in Table 2.

: Coefficient of thermal expansion and effect of the invention> The imide-based Brevolimer of the present invention has good heat resistance and electrical properties of the cured product, and is excellent in adhesive strength.

A sealing agent using this has a low dielectric constant and is useful as a sealing material for ICs, LSIs, etc.

Further, the laminate has high copper foil peel strength and glabella peel strength, and is suitable for multilayer printed circuit boards.

Claims (7)

[Claims] (1) At least the bismaleimide component represented by the following formula [I] and the diamine component represented by the following formula [II] at a molar ratio of bismaleimide component of the formula [I]/diamine component of the formula [II] of 1. An imide-based prepolymer characterized by containing an amount of 0 to 50.0. Formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, D represents a divalent group containing a carbon-carbon double bond, and R^1 to R^6 are a hydrogen atom, a carbon , number 1~
5 represents an alkyl group or a halogen atom) Formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R^7 to R^1^2 are hydrogen atoms, carbon atoms 1
~5 represents an alkyl group or a halogen atom) (2) The imide prepolymer according to claim 1, wherein the bismaleimide component is a bismaleimide represented by the following formula (III). Formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, D represents a divalent group containing a carbon-carbon double bond, and R^1 to R^6 are hydrogen atoms, carbon Numbers 1-5
(represents an alkyl group or halogen atom) (3) A cured product obtained by heating and curing the imide prepolymer according to claim 1 or 2. (4) A method for producing an imide prepolymer, which comprises heating and reacting at least a bismaleimide component represented by the following formula [I] and a diamine component represented by the following formula [II]. Formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, D represents a divalent group containing a carbon-carbon double bond, and R^1 to R^6 are hydrogen atoms, carbon Numbers 1-5
(Represents an alkyl group or halogen atom) Formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R^7 to R^1^2 are hydrogen atoms, carbon atoms 1
~5 alkyl group or halogen atom) (5) The imide prepolymer according to claim 1, wherein the bismaleimide component is a bismaleimide represented by the following formula (III). Formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, D represents a divalent group containing a carbon-carbon double bond, and R^1 to R^6 are hydrogen atoms, carbon Numbers 1-5
The method for producing an imide-based prepolymer according to claim 4 (representing an alkyl group or a halogen atom) (6) A varnish is prepared by dissolving the imide prepolymer according to claim 1 or 2 in an inert solvent, the varnish is impregnated into reinforcing fibers and then dried to form a prepreg, and the prepreg is laminated. A method for manufacturing a laminate, which is characterized by compression molding by heating and pressing. (7) A sealing material containing the imide prepolymer according to claim 1 or 2 as a main component.