JPH093044A - Fluorine-containing bismaleimide compound and thermosetting resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject new compound having especially excellent low dielectric constant and resistance to hydrolysis as well as physical properties such as processability, moisture resistance, heat resistance and adhesive property and useful as insulating part materials for various electronic devices. CONSTITUTION: This fluorine-containing bismaleimide compound is expressed by formula I (R<1> and R<2> are each a halogen, a non-substituted or a fluorine- substituted aliphatic hydrocarbon or H), e.g. 2,2-bis(3-maleimidephenyl)-1,1,1,3,3,3- hexafluoropropane. The compound of formula I is obtained by e.g. obtaining a bismaleimide acid compound by reacting 1mol equivalent of an aromatic diamine compound of formula II with >=2mol equivalents of a maleic acid anhydride of formula III or a maleic acid derivative anhydride in an organic solvent and subjecting the resultant product to dehydrating cyclization. For instance, a thermosetting resin composition is obtained from 1mol equivalent of a fluorine- containing bismaleimide compound of formula I and 0.01-1mol equivalent of a diamine compound of the formula: H2 N-ϕ-NH2 (ϕ is a bifunctional organic group).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel fluorine-containing bismaleimide compound and a thermosetting resin composition containing the fluorine-containing bismaleimide compound.

[0002]

2. Description of the Related Art In recent years, with the pursuit of large capacity, high speed, small size and light weight, high density and high reliability of electronic equipment,
There is a demand for an insulating material having excellent moldability, moisture resistance, hydrolysis resistance, and other environmental stability, heat resistance, and adhesiveness, and having a low dielectric constant. As such an insulating material, for example, the use of a bismaleimide-based cured resin has been conventionally studied,
In particular, the generation of decomposed gas due to hydrolysis and the high dielectric constant of 3.5 or more have been problems.

In order to lower the dielectric constant of the bismaleimide-based cured resin, the amount of the bismaleimide compound used as the raw material is 2,
2-bis (3-maleimido-4-methylphenyl)-
It has been proposed to introduce fluorine using 1,1,1,3,3,3-hexafluoropropane (for example, JP-A-3-255067). However, even with such a bismaleimide-based cured resin, there remains a problem that generation of decomposition gas due to hydrolysis cannot be suppressed.

[0004]

As described above, the conventional bismaleimide-based cured resin does not satisfy all the physical properties required as an insulating material for electronic devices. The object of the present invention is not only physical properties such as moldability, moisture resistance, heat resistance, and adhesiveness, but also a raw material of a bismaleimide-based cured resin that can particularly satisfy low dielectric constant and hydrolysis resistance. It is intended to provide a fluorine bismaleimide compound and a thermosetting resin composition containing the fluorine-containing bismaleimide compound.

[0005]

The fluorine-containing bismaleimide compound of the present invention has the following general formula (1):

[0006]

Embedded image (In the formula, R ¹ and R ² may be the same or different and each is a halogen atom, an unsubstituted or substituted aliphatic hydrocarbon group or a hydrogen atom.)
It is represented by.

The first thermosetting resin composition of the present invention comprises 1 molar equivalent of the above-mentioned fluorine-containing bismaleimide compound and the following general formula (2) H ₂ N-φ-NH ₂ (2) (wherein φ Represents a divalent organic group) and the diamine compound represented by 0.01 to 1 molar equivalent.

A second thermosetting resin composition of the present invention comprises 1 molar equivalent of the above-mentioned fluorine-containing bismaleimide compound and the following general formula (3) HO-Ar- (ψ-Ar) _n -OH (3) ( ψ is a single bond, an oxy group (—O—), a sulfenyl group (—S—), a sulfinyl group (—SO—), a sulfonyl group (—SO ₂ —), a carbonyl group (—CO—), an imino group ( -NH-) or a substituted or unsubstituted hydrocarbon group, Ar represents a divalent aromatic hydrocarbon group or aromatic heterocyclic group, and n is 0 or 1.) 2
It is characterized by containing 0.5 to 1.5 molar equivalents of a hydric phenol compound. Hereinafter, the present invention will be described in more detail. The fluorine-containing bismaleimide compound of the present invention has the following general formula (1):

[0009]

Embedded image (In the formula, R ¹ and R ² may be the same or different and each is a halogen atom, an unsubstituted or substituted aliphatic hydrocarbon group or a hydrogen atom.)
It is represented by.

The inventors of the present invention have studied the physical properties of bismaleimide-based cured resins produced by using various bismaleimide compounds, particularly, hydrolysis resistance, and as a result, the substituent introduced into the bismaleimide compound is an important factor. I found out that

For example, the conventionally used 2,2-bis (3-maleimido-4-methylphenyl) -1,1,
In 1,3,3,3-hexafluoropropane, a methyl group is present in the para position with respect to the hexafluoropropylidene group in the two benzene rings in the atomic group connecting the two maleimide groups. It has been found that the bismaleimide-based cured resin produced using such a bismaleimide compound is apt to generate a hydrolysis product such as aniline and an aniline derivative such as toluidine.

On the other hand, in the fluorine-containing bismaleimide compound of the present invention, a substituent is present at the para position with respect to the hexafluoropropylidene group in the two benzene rings in the atomic group connecting the two maleimide groups. It was found that the bismaleimide-based cured resin produced using such a fluorine-containing bismaleimide compound was not easily hydrolyzed.

The method for producing the fluorine-containing bismaleimide compound of the present invention is not particularly limited, but the following method is usually used. (A) First, an aromatic diamine compound represented by the following general formula (4), that is, 2,2-bis (3-
Aminophenyl) -1,1,1,3,3,3-hexafluoropropane 1 molar equivalent and maleic anhydride or maleic acid derivative anhydride 2 represented by the following general formula (5)
A molar equivalent or more is reacted in an organic solvent to synthesize a bismaleamic acid compound represented by the following general formula (6).
(B) Next, the bismaleamic acid compound represented by the general formula (6) is dehydrated and cyclized to produce the fluorine-containing bismaleimide compound represented by the general formula (1).

[0014]

Embedded image (In the formula, R ¹ and R ² have the same meanings as in the general formula (1).) As the maleic anhydride or the maleic acid derivative anhydride represented by the general formula (5) used in the step (A), , And the following. For example, maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, ethyl maleic anhydride, diethyl maleic anhydride, fluoromaleic anhydride, difluoromaleic anhydride, chloromaleic anhydride, dichloro. Maleic anhydride and the like. These maleic anhydrides or maleic acid derivative anhydrides may be used alone or in combination of two or more.

As the method for synthesizing the bismaleamic acid compound represented by the above general formula (6) in the step (A), all known methods can be applied, but it is preferable to carry out the reaction in an organic solvent. Examples of the organic solvent used in this reaction include the following. For example,
Acetone, methyl ethyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclohexanone, chloroform, methylene chloride, dichloroethane, trichloroethylene, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide,
N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,
N-methylcaprolactam, diethyl ether, dipropyl ether, 1,2-dimethoxyethane, bis (2-
Methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-
Examples include dioxane, 1,4-dioxane, pyrroline, picoline, dimethyl sulfoxide, sulfolane and the like. These organic solvents may be used alone or in combination of two or more. The reaction temperature is usually set to 100 ° C. or lower. The reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure. The reaction time varies depending on the type of solvent, but is 0.5
~ 24 hours is sufficient.

The dehydration cyclization reaction of the bismaleamic acid compound in the step (B) can be applied to all known methods, but usually it is dehydrated in an organic solvent using acetic anhydride as a dehydrating agent in the presence of a base and a catalyst. The method of cyclization is used (for example, Japanese Patent Publication No. 46-23250 and Japanese Patent Publication No.
9-40231, Japanese Patent Publication No. 59-52660). The upper limit of the amount of acetic anhydride used in this reaction is not particularly limited, but it is usually set in the range of 2 to 4 molar equivalents per 1 molar equivalent of the bismaleamic acid compound. Examples of the organic solvent used in this reaction include the following. For example, acetone, methyl ethyl ketone, N,
N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,
3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2 -Methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-
Examples include dioxane, 1,4-dioxane, phenol, cresol, anisole, pyrroline, picoline, dimethyl sulfoxide, sulfolane and the like. These organic solvents may be used alone or in combination of two or more.

Examples of the base used in the step (B) include alkali metal acetates and tertiary amines. For example, sodium acetate, potassium acetate, trimethylamine, triethylamine, tributylamine, pyridine and the like. The amount of the base used is usually set in the range of 0.05 to 2 molar equivalents with respect to 1 molar equivalent of the bismaleamic acid compound.

The catalyst used in the step (B) is an oxide of an alkaline earth metal, or iron (II), iron (III), nickel (II), manganese (II), manganese (III), copper ( I), copper (II), cobalt (II) or cobalt (III) carbonate, sulfate, phosphate or acetate and the like. Particularly preferred catalysts are nickel (II) acetate, cobalt acetate (I
II) or magnesium oxide. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is usually set in the range of 0.0005 to 0.2 molar equivalent relative to 1 molar equivalent of the bismaleamic acid compound.

The method of carrying out these reactions is not particularly limited, and for example, the dehydration cyclization reaction of the step (B) may be carried out as it is without isolating the bismaleamic acid compound which is the reaction product of the step (A). . The reaction temperature in the step (B) is usually 200 ° C. or lower, preferably 20 to 120 ° C. The reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure. The reaction time varies depending on the type of bismaleamic acid compound and the solvent, but 0.5 to 10 hours is sufficient.
After completion of the reaction, the precipitated crystals are filtered or put into water or methanol to obtain the target bismaleimide compound.

The first thermosetting resin composition of the present invention comprises 1 molar equivalent of the above fluorine-containing bismaleimide compound and the following general formula (2) H ₂ N-φ-NH ₂ (2) (wherein φ Represents a divalent organic group) and the diamine compound represented by 0.01 to 1 molar equivalent.

Examples of the diamine compound represented by the general formula (2) include the following. For example, m-
Phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,
4'-diaminodiphenyl ether, bis (3-aminophenyl) sulfide, (3-aminophenyl) (4-
Aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl)
Sulfoxide, bis (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,3′-diaminobenzophenone , 3,4'-diaminobenzophenone,
4,4'-diaminobenzophenone, 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,
4'-diaminobiphenyl, 1,3-phenylene-4,
4'-dianiline, 1,4-phenylene-4,4'-dianiline, 3,3'-diaminodiphenylmethane, 3,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylethane, 3,4'-diaminodiphenylethane, 4,4'-
Diaminodiphenylethane, 3,3'-diaminodiphenylpropane, 3,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylpropane, 1,3-
Bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4
-Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2 -Bis (4-aminophenyl) -1,
1,1,3,3,3-hexafluoropropane, 1,3
-Bis [2- (4-aminophenyl) -2-propyl]
Benzene, 1,4-bis [2- (4-aminophenyl)
-2-propyl] benzene, 2,2-bis [4- (4-
Aminophenoxy) phenyl] -1,1,1,3,3,3
3-hexafluoropropane, 2,2-bis [4- (3
-Aminophenoxy) phenyl] -1,1,1,3
3,3-hexafluoropropane, bis [3-amino-
5- (trifluoromethyl) phenyl] ether, bis [4-amino-2- (trifluoromethyl) phenyl]
Ether, bis [3-amino-5- (trifluoromethyl) phenyl] sulfone, bis [4-amino-2- (trifluoromethyl) phenyl] sulfone, 4,4′-diamino-2,2′-bis ( Trifluoromethyl) biphenyl, 3,3′-diamino-5,5′-bis (trifluoromethyl) biphenyl, 2,2-bis [3-amino-
5- (trifluoromethyl) phenyl] -1,1,1,
3,3,3-hexafluoropropane, 1,8-diaminonaphthalene, 2,7-diaminonaphthalene, 2,6-
Diaminonaphthalene, 2,5-diaminopyridine, 2,
6-diaminopyridine, 2,6-diamino-4- (trifluoromethyl) pyridine, 2,5-diaminopyrazine, 2,4-diamino-s-triazine, methanediamine, 1,2-ethanediamine, 1,3 -Propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decane Diamine, 1,2-bis (3-
Aminopropoxy) ethane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (3-
Aminocyclohexyl) methane, bis (4-aminocyclohexyl) methane, 1,2-bis (3-aminocyclohexyl) ethane, 1,2-bis (4-aminocyclohexyl) ethane, 2,2-bis (3-aminocyclohexyl) ) Propane, 2,2-bis (4-aminocyclohexyl) propane, bis (3-aminocyclohexyl) ether, bis (4-aminocyclohexyl) ether,
Bis (3-aminocyclohexyl) sulfone, bis (4
-Aminocyclohexyl) sulfone, 2,2-bis (3
-Aminocyclohexyl) -1,1,1,3,3,3-
Hexafluoropropane, 2,2-bis (4-aminocyclohexyl) -1,1,1,3,3,3-hexafluoropropane, 1,3-xylylenediamine, 1,4-
Examples include xylylenediamine. These diamine compounds may be used alone or in combination of two or more.

Among the diamine compounds represented by the general formula (2), it is preferable to use the following diamine compounds having an aromatic ring from the viewpoint of heat resistance and environmental stability of the bismaleimide-based cured resin. . For example, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis (3-aminophenyl) sulfone, (3-aminophenyl ) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone,
4,4'-diaminobenzophenone, 3,3'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,
4'-diaminobiphenyl, 1,3-phenylene-4,
4'-dianiline, 1,4-phenylene-4,4'-dianiline, 3,3'-diaminodiphenylmethane, 3,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylethane, 3,4'-diaminodiphenylethane, 4,4'-
Diaminodiphenylethane, 3,3'-diaminodiphenylpropane, 3,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylpropane, 1,3-
Bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4
-Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2 -Bis (4-aminophenyl) -1,
1,1,3,3,3-hexafluoropropane, 1,3
-Bis [2- (4-aminophenyl) -2-propyl]
Benzene, 1,4-bis [2- (4-aminophenyl)
-2-propyl] benzene, 2,2-bis [4- (4-
Aminophenoxy) phenyl] -1,1,1,3,3,3
3-hexafluoropropane, 2,2-bis [4- (3
-Aminophenoxy) phenyl] -1,1,1,3
3,3-hexafluoropropane, bis [3-amino-
5- (trifluoromethyl) phenyl] ether, bis [4-amino-2- (trifluoromethyl) phenyl]
Ether, bis [3-amino-5- (trifluoromethyl) phenyl] sulfone, bis [4-amino-2- (trifluoromethyl) phenyl] sulfone, 4,4′-diamino-2,2′-bis ( Trifluoromethyl) biphenyl, 3,3′-diamino-5,5′-bis (trifluoromethyl) biphenyl, 2,2-bis [3-amino-
5- (trifluoromethyl) phenyl] -1,1,1,
3,3,3-hexafluoropropane, 1,8-diaminonaphthalene, 2,7-diaminonaphthalene, 2,6-
Diaminonaphthalene, 2,5-diaminopyridine, 2,
6-diaminopyridine, 2,6-diamino-4- (trifluoromethyl) pyridine, 2,5-diaminopyrazine, 2,4-diamino-s-triazine and the like.

In the first thermosetting resin composition of the present invention, the compounding amount of the diamine compound represented by the general formula (2) is 1 molar equivalent of the fluorine-containing bismaleimide compound represented by the general formula (1). The reason why 0.01 to 1 molar equivalent is defined is as follows. That is, when the blending amount of the diamine compound is too small, the progress of the curing reaction becomes insufficient, and the bismaleimide molecules react with each other, so that the resulting cured product has heat resistance, environmental stability, and flexibility. It may decrease. On the contrary, when the amount of the diamine compound is too large, unreacted diamine compound may remain in the cured product, and the heat resistance and the environment resistance may be deteriorated.

In the first thermosetting resin composition of the present invention, in addition to the diamine compound represented by the general formula (2), the diamine compound represented by the following general formula (7), that is, bis (aminoalkyl) peroxide is used. You may use together an alkyl polysiloxane compound.

[0025]

Embedded image (R ³ may be the same or different and each represents an alkyl group having 1 to 5 carbon atoms, m and n are integers of 1 to 10, and p is a positive integer.) General formula (7) Examples of the bis (aminoalkyl) peralkylpolysiloxane compound represented by are as follows. For example, 1,3-bis (aminomethyl) -1,1,3,3-tetramethyldisiloxane,
1,3-bis (2-aminoethyl) -1,1,3,3-
Tetramethyldisiloxane, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (4-aminobutyl) -1,1,3
3-tetramethyldisiloxane, 1,3-bis (5-aminopentyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (6-aminohexyl) -1,
1,3,3-Tetramethyldisiloxane, 1,3-bis (7-aminoheptyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (8-aminooctyl)
-1,1,3,3-tetramethyldisiloxane, 1,3
-Bis (10-aminodecyl) -1,1,3,3-tetramethyldisiloxane, 1,5-bis (3-aminopropyl) -1,1,3,3,5,5-hexamethyltrisiloxane, 1,7-bis (3-aminopropyl) -1,
1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,11-bis (3-aminopropyl) -1,
1,3,3,5,5,7,7,9,9,11,11-dodecamethylhexasiloxane, 1,15-bis (3-aminopropyl) -1,1,3,3,5,5 , 7, 7,
9,9,11,11,13,13,15,15-hexadecamethyloctasiloxane, 1,19-bis (3-aminopropyl) -1,1,3,3,5,5,7,7,
9, 9, 11, 11, 13, 13, 15, 15, 17,
17,19,19-eicosamethyldecasiloxane and the like.

The bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (7) improves the adhesion and adhesiveness of the bismaleimide-based cured resin onto a semiconductor substrate such as a glass substrate or a silicon substrate. Has the effect of causing. It is preferable to use these compounds in an amount of 0.02 to 0.2 molar equivalent based on all diamine components. This is, although the adhesion and adhesion to the substrate of the bismaleimide-based cured resin obtained by blending such a compound is improved, excessive blending may lead to a decrease in heat resistance of the bismaleimide-based cured resin. Because there is.

The second thermosetting resin composition of the present invention comprises 1 molar equivalent of the above-mentioned fluorine-containing bismaleimide compound and the following general formula (3) HO-Ar- (ψ-Ar) _n -OH (3) ( ψ is a single bond, an oxy group (—O—), a sulfenyl group (—S—), a sulfinyl group (—SO—), a sulfonyl group (—SO ₂ —), a carbonyl group (—CO—), an imino group ( -NH-) or a substituted or unsubstituted hydrocarbon group, Ar represents a divalent aromatic hydrocarbon group or aromatic heterocyclic group, and n is 0 or 1.) 2
It is characterized by containing 0.5 to 1.5 molar equivalents of a hydric phenol compound.

Examples of the dihydric phenol compound represented by the general formula (3) include the following. For example,
Resorcinol, pyrocatechol, hydroquinone,
4,4'-dihydroxydiphenyl ether, 3,3 '
-Dihydroxydiphenyl ether, 3,4'-dihydroxydiphenyl ether, bis (3-hydroxyphenyl) sulfide, (3-hydroxyphenyl) (4-
Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfide, bis (3-hydroxyphenyl) sulfoxide, (3-hydroxyphenyl) (4-
Hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfoxide, bis (3-hydroxyphenyl) sulfone, (3-hydroxyphenyl) (4-
Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, 3,3′-dihydroxybenzophenone, 3,4′-dihydroxybenzophenone, 4,
4'-dihydroxybenzophenone, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,3-phenylene-4,4'-diphenol, 1,4-phenylene- 4,4'-diphenol, 3,3'-dihydroxydiphenylmethane, 3,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethane, 3,
3'-dihydroxydiphenylethane, 3,4'-dihydroxydiphenylethane, 4,4'-dihydroxydiphenylethane, 3,3'-dihydroxydiphenylpropane, 3,4'-dihydroxydiphenylpropane,
4,4'-dihydroxydiphenylpropane, 1,3-
Bis (3-hydroxyphenoxy) benzene, 1,4-
Bis (3-hydroxyphenoxy) benzene, 1,3-
Bis (4-hydroxyphenoxy) benzene, 1,4-
Bis (4-hydroxyphenoxy) benzene, 2,2-
Bis (3-hydroxyphenyl) -1,1,1,3
3,3-hexafluoropropane, 2,2-bis (4-
Hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 1,4-bis [2- ( 4-hydroxyphenyl) -2-propyl]
Benzene, 2,2-bis [4- (4-hydroxyphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-hydroxyphenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane, bis [3-hydroxy-5-
(Trifluoromethyl) phenyl] ether, bis [4
-Hydroxy-2- (trifluoromethyl) phenyl]
Ether, bis [3-hydroxy-5- (trifluoromethyl) phenyl] sulfone, bis [4-hydroxy-
2- (trifluoromethyl) phenyl] sulfone, 4,
4'-dihydroxy-2,2'-bis (trifluoromethyl) biphenyl, 3,3'-dihydroxy-5,5 '
-Bis (trifluoromethyl) biphenyl, 2,2-bis [3-hydroxy-5- (trifluoromethyl) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,8-dihydroxy Naphthalene, 2,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,5-dihydroxypyridine, 2,6-dihydroxypyridine, 2,6-dihydroxy-4- (trifluoromethyl) pyridine, 2,5-dihydroxy Pyrazine, 2,4-dihydroxy-s-triazine, 1,3-
Bis [3- (4-hydroxyphenyl) propyl]-
1,1,3,3-tetramethyldisiloxane, 1,3-
Bis [4- (4-hydroxyphenyl) butyl] -1,
1,3,3-tetramethyldisiloxane, 1,3-bis [3- (4-hydroxyphenyl) propyl] -1,
1,3,3-tetraphenyl, 1,5-bis [3- (4
-Hydroxyphenyl) propyl] -1,1,3,3,3
5,5-hexamethyltrisiloxane, 1,7-bis [3- (4-hydroxyphenyl) propyl] -1,
1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,9-bis [3- (4-hydroxyphenyl) propyl] -1,1,3,3,5,5,7, 7,
For example, 9,9-decamethylpentasiloxane. These dihydric phenol compounds may be used alone or 2
You may mix and use more than one kind.

In the second thermosetting resin composition of the present invention, the amount of the dihydric phenol compound represented by the general formula (3) is changed to the fluorine-containing bismaleimide compound 1 represented by the general formula (1). The reason for defining 0.5 to 1.5 molar equivalents relative to the molar equivalents is as follows. That is, if the amount of the dihydric phenol compound is too small, the degree of progress of the curing reaction will be insufficient, and the bismaleimide molecules will react with each other.
Environmental stability and flexibility may decrease. vice versa,
If the blending amount of the dihydric phenol compound is too large, unreacted dihydric phenol compound may remain in the cured product, and the heat resistance and the environment resistance may decrease.

In the thermosetting resin composition of the present invention,
A curing catalyst may be added, if necessary, for the purpose of promoting the curing reaction. Examples of the curing catalyst include boron tetrafluoride complex, aluminum complex / phenol catalyst, aluminum complex / silicon catalyst and the like. By appropriately selecting and using these curing catalysts, it is possible to control the curing reaction to produce high molecular weight cured resins having various two-dimensional structures or three-dimensional structures. Further, in the thermosetting resin composition of the present invention, in addition to the above-mentioned components, various additives such as polyamic acid, an epoxy resin, an isocyanate compound, a triazine resin, a phenol resin, and an acrylic compound are blended. Good.

A method for forming, for example, an interlayer insulating film or other insulating member of a semiconductor device by using the first and second thermosetting resin compositions of the present invention will be described below. First, the bismaleimide compound represented by the general formula (1), the diamine compound represented by the general formula (2) or the dihydric phenol compound represented by the general formula (3), and optionally other components The component (1) is dissolved in an organic solvent to prepare the resin composition of the present invention in the form of varnish. As the organic solvent used here, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-
Methyl-2-pyrrolidone, methyl isobutyl ketone,
1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2
-Methoxyethyl) ether, bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, phenol, cresol,
Examples include anisole, pyrroline, picoline, dimethyl sulfoxide, sulfolane and the like. These organic solvents may be used alone or in combination of two or more.

Next, the varnish of the obtained composition is applied on a predetermined substrate using a spinner to form a film. Prior to this step, the varnish was heated at 50-150 ° C for 5
By heating for 5 minutes to 5 hours, the addition reaction of the diamine compound or the dihydric phenol compound to the bismaleimide compound is allowed to proceed to some extent to form a prepolymer (A-stage).
It is desirable to increase the viscosity of the varnish so that it is convenient to apply the varnish. Subsequently, the film is heated to 50 to 150 ° C. for 5 to 10 using a hot plate or the like.
Heat for minutes to evaporate the solvent. Further, the film is heated at a predetermined temperature in a vacuum oven or an oven that is replaced with nitrogen to cure the composition. This heating temperature is usually set in the range of 100 to 450 ° C. Thus, the interlayer insulating film made of the bismaleimide-based cured resin is formed.

After cooling the prepolymerized varnish to room temperature, the solvent is removed by vacuum drying to form a powder, which is then press-molded using a spacer having a thickness of about 2 mm to cure the bismaleimide system. A resin may be obtained.

The bismaleimide-based curable resin obtained by the above-mentioned method not only has excellent physical properties such as heat resistance, but is left in the atmosphere for a long time as compared with conventional bismaleimide-based curable resins. However, the amount of hydrolyzable gas such as aniline and aniline derivatives generated is very small, the environmental stability is excellent, and the dielectric constant is low.

[0035]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. Examples 1 to 4 and Comparative Examples 1 to 4 (1) 2,2-bis (3-maleimidophenyl) -1,
Synthesis of 1,1,3,3,3-hexafluoropropane 10.79 g of maleic anhydride (110 m
(mol) was collected and dissolved in 100 mL of N-methylpyrrolidinone with stirring. A solution prepared by dissolving 16.71 g (50.0 mmol) of 2,2-bis (3-aminophenyl) -2-hexafluoropropane in 50 mL of dimethylformamide was slowly added dropwise to this solution at room temperature using a dropping funnel, and the temperature was 60 ° C. And reacted for 2 hours. afterwards,
10 mg of cobalt (II) tetrahydrate was added, and 13 g of acetic anhydride was added dropwise at room temperature through a dropping funnel over 30 minutes. The mixture was further stirred at 60 ° C. for 1 hour, 1 L of water was added little by little to the reaction solution, and the precipitated crude crystals were collected by filtration. The crude crystals were purified by recrystallization, and the obtained crystals were vacuum dried to obtain the target compound. The infrared absorption spectrum of this compound is shown in FIG.

Molecular formula: C ₂₃ H ₁₂ N ₂ F ₆ O ₄ , molecular weight:
494.35 Yield: 23.73 g (48.0 mmol), Yield: 96
% Infrared absorption spectrum: 1780, 1710 cm ^-1 C = O stretching vibration (cyclic imide) 1250, 1210, 1160, 1140 cm ^-1 CF
₃ Symmetrical bending vibration (2) Preparation of bismaleimide-based cured resin and measurement of physical properties As shown in Table 1, a bismaleimide compound and a diamine compound or a dihydric phenol compound were used at a predetermined mixing ratio (expressed in molar equivalents). , N, N-dimethylacetamide to prepare a 50 wt% solution of the resin composition. This solution was heated at 80 ° C. for about 1 hour to react the bismaleimide compound with the diamine compound or the dihydric phenol compound to some extent to form a prepolymer. Then, N, N-dimethylacetamide was added until the viscosity of the solution became about 1 poise, to prepare a varnish of the bismaleimide thermosetting resin composition.

The abbreviations used in Table 1 are explained below. (Bismaleimide compound) m6FDM: 2,2-bis (3-maleimidophenyl)
-1,1,1,3,3,3-hexafluoropropane p6FDM: 2,2-bis (4-maleimidophenyl)
-1,1,1,3,3,3-hexafluoropropane pMDM: bis (4-maleimidophenyl) methane m6FDTM: 2,2-bis (3-maleimido-4-methylphenyl) -1,1,1, 3,3,3-hexafluoropropane (diamine compound) m6FDA: 1,1,1,3,3,3-hexafluoro-2,2-propylidene-3,3'-dianiline pODA: oxy-4,4 ' -Dianiline 6FpBPDA: 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl pMDA: methylene-4,4'-dianiline p6FDA: 1,1,1,3,3,3-hexafluoro- 2,2-Propylidene-4,4′-dianiline m6FDT: 2,2-bis (3-amino-4-methylphenyl) -1,1,1,3,3,3-hexafluoro Propane (dihydric phenol compound) p6FDP: 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-diphenol Next, various physical properties were measured as follows. The results are also shown in Table 1.

(A) Decomposition start temperature 1 mm × 130 mm × a varnish of the thermosetting resin composition
A glass plate having a size of 150 mm was applied with a bar coater to a thickness of 75 μm, and then prebaked at 110 ° C. for 1 hour. In a dryer introduced with nitrogen gas,
Elevate from room temperature to 150 ° C, 250 ° C, and 350
Heat at each temperature of ℃ for 1 hour, and finally at 400 ℃ 30
A bismaleimide-based cured resin film was formed by heating for a minute. The temperature rising time between the respective temperatures was 1 hour. About the obtained bismaleimide-based cured resin film, thermogravimetric analysis / differential thermal analysis (TG
/ DTA) was performed and the temperature at which a weight loss of 0.5 wt% occurred was measured to determine the decomposition start temperature of the bismaleimide-based cured resin film. As a result, it was confirmed that the bismaleimide-based cured resin films of Examples 1 to 4 had heat resistance equivalent to or higher than those of Comparative Examples 1 to 4.

(B) Dielectric constant A varnish of the thermosetting resin composition was used to measure 1 mm × 100 mm ×
An aluminum plate having a size of 100 mm was spin-coated 2 to 4 times so that the film thickness after curing would be 40 to 60 μm. By heating this from room temperature in a drier in which nitrogen gas is introduced, heating at each temperature of 150 ° C, 250 ° C, and 350 ° C for 1 hour, and finally heating at 400 ° C for 30 minutes. A bismaleimide-based cured resin film was formed. The temperature rising time between each temperature was 30 minutes. With respect to the obtained bismaleimide-based cured resin film, the dielectric constant at 100 kHz was measured. As a result, it was confirmed that the bismaleimide-based cured resin films of Examples 1 to 4 had a low dielectric constant of 2.80 or less and were superior in dielectric properties to those of Comparative Example 1 which was generally used. Was done.

(C) Moisture absorption rate and generation amount of decomposed gas A varnish of the thermosetting resin composition was spin-coated on a 4-inch diameter silicon substrate so that the film thickness after curing was 5 to 10 μm. . This is heated from room temperature to 150 ° C., 250 ° C., and 3 ° C. in a dryer in which nitrogen gas is introduced.
The bismaleimide-based cured resin film was formed by heating each temperature of 50 ° C. for 1 hour and finally heating at 400 ° C. for 30 minutes. The temperature rising time between each temperature was 30 minutes. Next, the silicon substrate on which the bismaleimide-based cured resin film was formed was allowed to stand for 1 week at 20 ° C. under saturated steam. Then, the bismaleimide-based cured resin film was introduced into a pyrofoil, heated at 358 ° C. for 3 seconds with a Curie pyrolyzer, and the generated gas component was analyzed by GC-MASS. The amount of aniline, which is a hydrolyzable gas generated at this time, was defined as the amount of decomposed gas generated. In Table 1, the amount of decomposed gas generated from each sample is shown as a relative value with the amount of aniline gas generated from Comparative Example 1 (pMDM + pMDA) being 1000. As a result, in the bismaleimide-based cured resin films of Examples 1 to 4, the generation amount of aniline gas was 1/10 or less as compared with that of Comparative Example 1, and the environmental stability such as hydrolysis resistance was low. It was confirmed to be excellent.

[0041]

[Table 1]

[0042]

As described above in detail, when the fluorine-containing bismaleimide compound of the present invention and the thermosetting resin composition containing the fluorine-containing bismaleimide compound are used, moldability, moisture resistance, heat resistance and adhesion are improved. Not only physical properties such as sex,
In particular, it is possible to provide a bismaleimide-based cured resin that satisfies low dielectric constant and hydrolysis resistance and is useful as an insulating member for various electronic devices.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of a fluorine-containing bismaleimide compound synthesized in an example of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshihiro Kawamon 1 Komukai Toshiba Town, Komukai, Kawasaki City, Kanagawa Prefecture R & D Center, Toshiba Corporation (72) Shuji Hayase Komukai, Kawasaki City, Kanagawa Prefecture Toshiba Town No. 1 Inside Toshiba Research and Development Center

Claims (3)

[Claims] 1. The following general formula (1): (In the formula, R ¹ and R ² may be the same or different and each is a halogen atom, an unsubstituted or substituted aliphatic hydrocarbon group or a hydrogen atom.)
Fluorine-containing bismaleimide compound represented by. 2. One mole equivalent of the fluorine-containing bismaleimide compound according to claim 1 and the following general formula (2) H ₂ N-φ-NH ₂ (2) (wherein φ represents a divalent organic group). .) 0.01 to 1 molar equivalent of a diamine compound represented by the formula (1). 3. One molar equivalent of the fluorine-containing bismaleimide compound according to claim 1 and the following general formula (3) HO—Ar— (ψ-Ar) _n —OH (3) (ψ is a single bond or an oxy group ( -O-), sulfenyl group (-S-), sulfinyl group (-SO-), a sulfonyl group (-SO ₂ -), carbonyl group (-CO-), an imino group (-NH-) or substituted or unsubstituted Represents a substituted hydrocarbon group, Ar represents a divalent aromatic hydrocarbon group or an aromatic heterocyclic group, and n is 0 or 1.) 2
A thermosetting resin composition containing 0.5 to 1.5 molar equivalents of a hydric phenol compound.