JP3006099B2 - Epoxy resin composition and prepreg - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an epoxy resin composition and a prepreg.

[0002]

2. Description of the Related Art A composition containing an epoxy resin and a bismaleimide or a prepolymer thereof is excellent in electrical properties, mechanical properties, chemical resistance and adhesiveness as well as heat resistance. It is used in many fields such as fields, civil engineering, adhesives, and paints. Above all, they are often used as electric insulating materials because of their excellent electrical properties. In recent years, in these fields, materials having various high performances and high functions have been required. For example, in the fields of electrical insulation and electronic materials, reductions in water absorption and dielectric constant are required. However, a material that can sufficiently meet these demands for high performance has not been obtained so far. In order to obtain a resin that meets these requirements,
In the molecular structure, as a substituent that expresses these properties,
It is considered effective to introduce a substituent containing a large number of fluorine atoms.

[0003] Epoxy resins containing fluorine include:
Compounds such as Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 are known.

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Further, Japanese Patent Publication No. 63-37786 discloses a compound represented by Chemical Formula 5 as a fluorine-containing imide compound, and describes that a composition containing the compound and an epoxy resin is an excellent heat-resistant material.

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[0005]

Both the fluorine-containing epoxy resin described above and the imide compound described in JP-B-63-37786 have low fluorine contents, and it is difficult to achieve the required performance described above. Therefore, in order to solve such problems, the present inventors have developed a novel fluorine-containing imide compound or a prepolymer thereof, in which a perfluoroalkenyloxy group has been introduced into the molecular structure as a substituent having many fluorine atoms. An epoxy resin composition containing the same and a prepreg obtained by using the same.

[0006]

The epoxy resin composition of the present invention comprises an epoxy resin,

Embedded image [However, during reduction 6 Rf is, -C _n F _2n-1 (where n is 6 to
12 indicating an integer of 12), which contains one double bond; The hydrogen on the benzene ring may be branched.
(I.e., 1 to 5 carbon atoms) alkyl group, a lower (sand
That is, it may be substituted with an alkoxy group having 1 to 5 carbon atoms) , fluorine, chlorine or bromine , and each of the two imide groups has an aromatic ring in an ortho, meta or para position with respect to an ether bond. And D is a dicarboxylic acid residue having an ethylenically unsaturated double bond , wherein -CH = CH
-, - CH = C (CH 3) -, - C (= CH 2) -CH-
as well as

Embedded image And a thermosetting prepolymer obtained by reacting a polyamine compound with a fluorine-containing imide compound represented by the following formula:

[0007] As the epoxy resin, those having at least two epoxy groups in one molecule are used.
As the epoxy resin used in the present invention, any epoxy resin containing at least two epoxy groups in one molecule may be used, and bisphenol A type epoxy resins [for example, Epicoat 828, Epicoat 827, Epicoat 834, Epicoat 1001, Epicoat 100
4. Epicoat 1009 (all of these are trade names of Yuka Shell Co., Ltd.)], bisphenol F type epoxy resin [for example, Epicoat 807 (trade name of Yuka Shell Co., Ltd.)], bisphenol S type epoxy resin, phenol Novolak type epoxy resin [for example, Epicoat 15
2. Epicoat 154 (all of these are trade names of Yuka Shell Co., Ltd.), EOCN-201 (trade name of Nippon Kayaku Co., Ltd.), cresol novolak type epoxy resin [for example, EOCN102S, EOCN103S, EOCN1]
04S (all of these are trade names of Nippon Kayaku Co., Ltd.)] and bisphenol A novolak type epoxy resins [for example, N-880 and N-865 (all of these are trade names of Dainippon Ink and Chemicals, Inc.)] ], Bisphenol F novolak type epoxy resin, alicyclic epoxy resin [for example, CY175, CY177 (all of these are trade names of Ciba-Geigy)], glycidyl ester type epoxy resin [for example, CY182, CY192 (these are All are Ciba-Geigy brands), Epikote 8
71, Epicoat 872 (all of these are trade names of Yuka Shell Co., Ltd.)], glycidylamine type epoxy resin [for example, MY720 (trade name of Ciba-Geigy)],
Hydantoin type epoxy resin [for example, CY350 (trade name of Ciba-Geigy)], isocyanurate type epoxy resin [for example, PT810 (trade name of Ciba-Geigy)], aliphatic chain epoxy resin [for example, Adeka Resin ED506 (Asahi) Denki Kogyo Co., Ltd.), Epicron 707 (Dainippon Ink Kogyo Co., Ltd.), etc., and these may be halogenated or hydrogenated, and may be used in combination of two or more. You can also.

The epoxy resin composition of the present invention preferably contains a curing agent for epoxy resin. As the curing agent, any one may be used as long as it is generally used as a curing agent for an epoxy resin.
Kakiuchi Unbiased, "New Epoxy Resin" (Shokodo, 1960) 1
Polyamine compounds, acid anhydrides, polyamide resins, imidazoles, polyhydric phenol compounds, phenolic resins, polyvinylphenols, amino resins, boron trifluoride amine complexes, dicyandiamide or as described on page 64 Its derivatives, organic acid dihydrazide, diaminomaleonitrile and its derivatives, melamine and its derivatives, polymercaptans, polysulfide resins and the like, and aromatic diazonium salts, diallyliodonium salts, triallylsulfonium salts, triallylselenium salts and the like Ultraviolet curing agents can also be used.

Examples of the polyamine compound include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine (dipropylenetriamine), bis (hexamethylene) triamine,
1,3,6 trisaminomethylhexane, trimethylhexamethylenediamine, diethyleneglycolbispropyldiamine, diethylaminopropylamine, mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine, Meta-xylylenediamine, tetrachloro-p-xylylenediamine, 2,4 (p-β-amino-t-butylphenyl) ether, p-bis-2- (2
-Methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene,
Hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,11-diaminododecane, 1,1
2-diaminooctadecane, 2,2-dimethylpropylenediamine, 2,5-dimethylhexamethylenediamine, 3-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methyl Nonamethylenediamine,
Aliphatic amines such as 1,4-diaminocyclohexane, bis (p-aminocyclohexyl) methane, 3-methoxyhexamethylenediamine, 1,2-bis- (3-aminopropoxy) ethane, and bis (3-aminopropyl) sulfide , 4-aminophenyl-3-aminobenzoic acid, 2,2-bis (4-aminophenyl) propane,
2,6-diaminopyridine, bis (4-amiphenyl)
Diethylsilane, bi- (4-aminophenyl) diphenylsilane, bis- (4-aminophenyl) ethylphosphoxide, bis- (4-aminophenyl) -N-
Butylamine, bis- (4-aminophenyl) -N-methylamine, N- (3-aminophenyl) -4-aminobenzamide, 4-aminophenyl-3-aminobenzoic acid, 3,3'-diaminodiphenylmethane, 3, 3'-
Diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenylsulfide, p-phenylenediamine, m-phenylenediamine, 4 , 4 '
-Diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,3'-diaminobenzophenone,
4,4'-diaminodiphenyl sulfide, 4,4'-
Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,4-bis (β-
Amino-t-butyl) toluene, bis (p-β-amino-t-butyl-phenyl) ether, bis (p-β-methyl-γ-amino-pentyl) benzene, bis-p-
(1,1-dimethyl-5-aminopentyl) benzene,
2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy)
Phenyl) hexafluoropropane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-
Diethyl-4,4'-diaminodiphenylmethane, 3,
3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'diethoxy-4,4'-diaminodiphenylmethane, 3,3'-difluoro-4,4'-diaminodiphenylmethane, 3, 3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dibromo-4,
4'-diaminodiphenylmethane, 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylether, 3,3 '-Diisopropyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-
4,4'-diaminodiphenyl ether, 3,3'-diethoxy-4,4'-diaminodiphenyl ether,
3,3'-difluoro-4,4'-diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenyl ether, 3,3'-dibromo-4,4'-diaminodiphenyl ether 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenyl ether,
3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-dimethoxy-4,4'-diaminodiphenylsulfone, 3,3'-diethoxy-4,4'-
Diaminodiphenylsulfone, 3,3'-difluoro-
4,4'-diaminodiphenylsulfone, 3,3'-dichloro-4,4'-diaminodiphenylsulfone, 3,
3'-dibromo-4,4'-diaminodiphenylsulfone, 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,
4'-diaminodiphenylpropane, 3,3'-dimethoxy-4,4'-diaminodiphenylpropane, 3,
3'-diethoxy-4,4'-diaminodiphenylpropane, 3,3'-difluoro-4,4'-diaminodiphenylpropane, 3,3'-dichloro-4,4'-diaminodiphenylpropane, , 3'-dibromo-4,
4'-diaminodiphenylpropane, 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenylpropane, 3,3'-dimethyl-4,4'-diaminodiphenylsulfide, 3 , 3'-Dimethoxy-4,4'-
Diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide, 3,3 '
-Difluoro-4,4'-diaminodiphenylsulfide 3,3'-dichloro-4,4'-diaminodiphenylsulfide, 3,3'-dibromo-4,4'-diaminodiphenylsulfide 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenyl sulfide, 3,
3'-dimethyl-4,4'-diaminodiphenylhexafluoropropane, 3,3'-dimethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3'-
Diethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3'-difluoro-4,4'-diaminodiphenylhexafluoropropane, 3,3'-dichloro-4,4'-diaminodiphenylhexafluoro Propane, 3,3'-dibromo-4,4'-diaminodiphenylhexafluoropropane, 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenylhexafluoropropane, 3,3'- Dimethyl-4,4'-diaminobenzophenone, 3,3'-dimethoxy-4,4 '
-Diaminobenzophenone, 3,3'-diethoxy-
4,4'-diaminobenzophenone, 3,3'-difluoro-4,4'-diaminobenzophenone, 3,3'-
Dichloro-4,4'-diaminobenzophenone, 3,
3'-dibromo-4,4'-diaminobenzophenone,
3,3'-di (trifluoromethyl) -4,4'-diaminobenzophenone, benzidine, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine,
3'-dimethylbenzidine, 3,3'-dimethyl-4,
4-diaminobiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,
3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetramethoxy-4,4'-diaminodiphenylmethane, 3,
3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetrafluoro-4,4'-diaminodiphenylmethane, 3,3 ',
5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetrabromo-4,
4'-diaminodiphenylmethane, 3,3 ', 5,5'
-Tetra (trifluoromethyl) -4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylether, 3,3',
5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetramethoxy-
4,4'-diaminodiphenyl ether, 3,3 ',
5,5'-tetraethoxy-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetrafluoro-
4,4'-diaminodiphenyl ether, 3,3 ',
5,5'-tetrachloro-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetrabromo-4,
4'-diaminodiphenyl ether, 3,3 ', 5
5'-tetra (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylsulfone, 3,
3 ', 5,5'-tetramethoxy-4,4'-diaminodiphenylsulfone, 3,3', 5,5'-tetraethoxy-4,4'-diaminodiphenylsulfone, 3,3 ',
5,5'-tetrafluoro-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetrachloro-4,
4'-diaminodiphenylsulfone, 3,3 ', 5
5'-tetrabromo-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'-diaminodiphenylsulfone, 3,
3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylpropane, 3,3', 5,5'-tetramethoxy-4,4'-diaminodiphenylpropane, 3,3 ',
5,5'-tetraethoxy-4,4'-diaminodiphenylpropane, 3,3 ', 5,5'-tetrafluoro-
4,4'-diaminodiphenylpropane, 3,3 ',
5,5'-tetrachloro-4,4'-diaminodiphenylpropane, 3,3 ', 5,5'-tetrabromo-4,
4'-diaminodiphenylpropane, 3,3 ', 5
5'-tetra (trifluoromethyl) -4,4'-diaminodiphenylpropane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylsulfide, 3,
3 ', 5,5'-tetramethoxy-4,4'-diaminodiphenyl sulfide, 3,3', 5,5'-tetraethoxy-4,4'-diaminodiphenyl sulfide, 3,
3 ', 5,5'-tetrafluoro-4,4'-diaminodiphenyl sulfide, 3,3', 5,5'-tetrachloro
-4,4'-diaminodiphenyl sulfide, 3,3 ',
5,5'-tetrabromo-4,4'-diaminodiphenylsulfide, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'-diaminodiphenylsulfide, 3, 3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylhexafluoropropane, 3,3',
5,5'-tetramethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5,5'-tetrafluoro-4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetrachloro-4,4'-diaminodiphenylhexafluoropropane, 3,3',
5,5'-tetrabromo-4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'-diaminodiphenylhexafluoropropane, 3 ', 5,5'-tetramethyl-4,4'-diaminobenzophenone, 3,
3 ', 5,5'-tetramethoxy-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethoxy-4,4'-diaminobenzophenone, 3,3 ', 5 ,
5'-tetrafluoro-4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetrachloro-4,4'-
Diaminobenzophenone, 3,3 ', 5,5'-tetrabromo-4,4'-diaminobenzophenone, 3,
3 ', 5,5'-tetra (trifluoromethyl) -4,
4'-diaminobenzophenone, 3,3 ', 5,5'-
Tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-
4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5
5'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-diisopropyl-5,5'-diethyl-
4,4'-diaminodiphenyl ether, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diisopropyl-
5,5'-diethyl-4,4'-diaminodiphenylpropane, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3 '
-Diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylsulfone, 1,3-diamino-5-
(Perfluorononenyloxy) benzene, 1,3-diamino-4-methyl-5- (perfluorononenyloxy) benzene, 1,3-diamino-4-methoxy-5- (perfluorononenyloxy) benzene 1,3-diamino-2,4,6-trifluoro-5- (perfluorononenyloxy) benzene, 1,3-diamino-4-chloro-5- (perfluorononenyloxy) benzene,
3-diamino-4-bromo-5- (perfluorononenyloxy) benzene, 1,2-diamino-4- (perfluorononenyloxy) benzene, 1,2-diamino-
4-methyl-5- (perfluorononenyloxy) benzene, 1,2-diamino-4-methoxy-5- (perfluorononenyloxy) benzene, 1,2-diamino-3,
4,6-trifluoro-5- (perfluorononenyloxy) benzene, 1,2-diamino-4-chloro-5-
(Perfluorononenyloxy) benzene, 1,2-diamino-4-bromo-5- (perfluorononenyloxy)
Benzene, 1,4-diamino-3- (perfluorononenyloxy) benzene, 1,4-diamino-2-methyl-5- (perfluorononenyloxy) benzene, 1,4
-Diamino-2-methoxy-5- (perfluorononenyloxy) benzene, 1,4-diamino-2,3,6-trifluoro-5- (perfluorononenyloxy) benzene, 1,4-diamino- 2-chloro-5- (perfluorononenyloxy) benzene, 1,4-diamino-2
-Bromo-5- (perfluorononenyloxy) benzene, 1,3-diamino-5- (perfluorohexenyloxy) benzene, 1,3-diamino-4-methyl-5-
(Perfluorohexenyloxy) benzene, 1,3-diamino-4-methoxy-5- (perfluorohexenyloxy) benzene, 1,3-diamino-2,4,6-trifluoro-5- (perfluorohexenyloxy ) Benzene, 1,3-diamino-4-chloro-5- (perfluorohexenyloxy) benzene, 1,3-diamino-4-
Bromo-5- (perfluorohexenyloxy) benzene,
1,2-diamino-4- (perfluorohexenyloxy) benzene, 1,2-diamino-4-methyl-5- (perfluorohexenyloxy) benzene, 1,2-diamino-4-methoxy-5- (per (Fluorohexenyloxy)
Benzene, 1,2-diamino-3,4,6-trifluoro-5- (perfluorohexenyloxy) benzene,
1,2-diamino-4-chloro-5- (perfluorohexenyloxy) benzene, 1,2-diamino-4-bromo-5- (perfluorohexenyloxy) benzene, 1,
4-diamino-3- (perfluorohexenyloxy)
Benzene, 1,4-diamino-2-methyl-5- (perfluorohexenyloxy) benzene, 1,4-diamino-
2-methoxy-5- (perfluorohexenyloxy) benzene, 1,4-diamino-2,3,6-trifluoro-
5- (perfluorohexenyloxy) benzene, 1,
4-diamino-2-chloro-5- (perfluorohexenyloxy) benzene, 1,4-diamino-2-bromo-5
-(Perfluorohexenyloxy) benzene N, N-bis (4-aminophenyl) aniline, N, N-bis (4
-Aminophenyl) methylamine, N, N-bis (4-
(Aminophenyl) -n-butylamine, N, N-bis (4-aminophenyl) amine, m-aminobenzoyl-p-aminoanilide, 4-aminophenyl-3-aminobenzoate, 4,4′-diaminoazobenzene,
3,3'-diaminoazobenzene, bis (4-aminophenyl) phenylphosphine oxide, 2,5-diamino-1,3,4-oxadiazole, N, N-bis (3
-Aminopropyl) methylamine, 2,2'-bis [4
-(4-aminophenoxy) phenyl] propane, 2,
2'-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4
-Aminophenoxy) phenyl] propane, 2,2-bis [3-ethyl-4- (4-aminophenoxy) phenyl] propane, 2,4-diaminodiphenylamine,
2,4-diamino-5-methyl-diphenylamine,
2,4-diamino-4'-methyl-diphenylamine,
1-anilino-2,4-diaminonaphthalene, 3,3 '
Aromatic amines such as -diamino-4-anilinobenzophenone, 3,9-bis (3-aminopropyl) -2,
Diamine having a spiro ring such as 4,8,10-tetraspiro (5,5) undecane;

Embedded image [Wherein R ₀ is an alkylidene group containing a methylene group, and n is an average number of 0.1 or more]. These may be used in combination of two or more. The above-mentioned polyamine compounds include salts such as nylon salts with aliphatic dicarboxylic acids having 3 to 8 carbon atoms such as adipic acid, salts with polyhydroxyphenol, salts with phenylphosphonic acid, and salts with phenylphosphoric acid. You may use as.

The acid anhydrides include phthalic anhydride,
Pyromellitic anhydride trimellitic anhydride, 2,2 bis (2,3-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 1 2,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7, -naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride Product, 2,2-bis (3,4, -dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic acid Acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid Acid dianhydride, , 6-dichlorobenzene naphthalene -
1,4,5,8-tetracarboxylic dianhydride, 2,7-
Dichloronaphthalene-1,4,5,8, tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1, 8,9,10-tetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride Anhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-
Dicarboxyphenyl) methane dianhydride, bis (3,4
-Dicarboxyphenyl) methane dianhydride, bis (3,
4-dicarboxyphenyl) sulfone dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,
4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone Tetracarboxylic dianhydride, pyrazine-2,3,5,6-
Tetracarboxylic dianhydride, thiophene-2,3,4
5-tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8
-Tetracarboxylic dianhydride, 4,8-dimethyl-1,
2,3,5,6,7-hexahydronaphthalene-1,
2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride,
1,2,3,4-butanetetracarboxylic dianhydride, bicyclo- (2,2,2) -oct (7) -ene-2,
3,5,6-tetracarboxylic dianhydride, 2,3
3 ', 4'-biphenyltetracarboxylic dianhydride,
3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,3,2', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethyl Silane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4
-Dicarboxyphenyl) diphenylsilane dianhydride,
Bis (2,3-dicarboxyphenyl) dimethylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-di Carboxyphenyl) -1,1,3,3-
Tetramethyldicycloxane dianhydride, p-phenylbis (trimellitic acid monoester anhydride), ethylene glycol bis (trimellitic anhydride), propanediol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride) ), Pentanediol bis (trimellitic anhydride), hexanediol bis (trimellitic anhydride), octanediol bis (trimellitic anhydride), decanediol bis (trimellitic anhydride), 2,2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl]
Hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (tri Melitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride)
Such as aromatic acid anhydrides, maleic anhydride, succinic anhydride,
Aliphatic anhydrides or cycloaliphatics such as tetrahydrophthalic anhydride, methylnadic anhydride, alkenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenecarboxylic acid, chlorendic acid, and tetrabromophthalic anhydride There are acid anhydrides and the like, and two or more kinds may be used as a mixture.

As the polyamide, there is a polyamide obtained by a condensation reaction of the dimer acid of Chemical formula 8 with a polyamine such as diethylenetriamine and triethylenetetramine.

Embedded image

Examples of the imidazoles include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, Heptadecylimidazole, 4,5-diphenylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4
-Methylimidazole, 2-methylimidazoline, 2-
Ethyl imidazoline, 2-isopropylimidazoline,
2-heptadecylimidazoline, 2-phenylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-
Examples thereof include 4-methylimidazoline and the like, and those obtained by masking the imino group of imidazole with acrylonitrile, phenylene diisocyanate, toluene diisocyanate, naphthalenediisoisonate, hexamethylene diisocyanate, methylene bisphenyl isocyanate, and melamine acrylate can also be used.

The polyhydric phenol compound includes bisphenol A, bisphenol F, resorcin and the like.

The phenol resin may be any resin having at least two phenolic hydroxyl groups in the molecule. Examples thereof include phenol compounds such as phenol, cresol, alkylphenol, catechol, bisphenol A and bisphenol F. There are phenol novolak resins obtained from formaldehyde, and halides of such phenol novolak resins.

Examples of the amino resin include addition condensation products of formaldehyde with an amino compound such as aniline or an aniline derivative, melamine, benzoguanamine or acetoguanamine.

Examples of the boron trifluoride amine complexes include boron trifluoride-n-hexylamine, boron trifluoride-monoethylamine, boron trifluoride-benzylamine, boron trifluoride-diethylamine, and boron trifluoride-diethylamine. Examples include boron fluoride-piperidine, boron trifluoride-triethylamine, and boron trifluoride-aniline.

The dicyandiamide and derivatives thereof include dicyandiamide, o-tolylbiguanide,
2,5-dimethylbiguanide, diphenyl biguanide,
5-hydroxynaphthyl-1-biguanide, α, α′-bisguanylguanidinodiphenyl ether, phenylbiguanide, p-chlorophenylbiguanide, α-benzylbiguanide, α, ω-dimethylbiguanide, α,
α'-hexamethylenebis (ω- (p-chlorophenyl)) biguanide and the like, and their zinc salts, iron salts, copper salts,
Hydrochloride, nickel salt and the like.

The organic acid dihydrazide can be easily synthesized from a carboxylic acid ester and hydrazine, and examples thereof include succinic dihydrazide, adipic dihydrazide, isophthalic dihydrazide, salicylic dihydrazide, and phenylaminopropionic dihydrazide.

As the above-mentioned diaminomaleonitrile or a derivative thereof, there is one represented by the following formula (9).

Embedded image However, in reduction 9, R is -NH _2, -N = CHCH ₂ C
_{H 3, -N = CHCH 2 (} CH 3) 2, -N = CHCH 2 (CH
_{3) 2, -NHCHCH 2 (CH} 3) 2, -N = C (CH 3) CO
OCH _3, -N = CH-Ph, or -N = CHCH ₂ -Ph
(Where Ph represents a phenyl group).

As the melamine and its derivatives, diallyl melamine can be used in addition to melamine.

Examples of the polymercaptans include a reaction product of an epoxy resin with hydrogen sulfide, a polyhydric alcohol ester of mercaptopropionic acid and mercaptogluconic acid. Examples of a reaction product of the epoxy resin with hydrogen sulfide include: There is one shown in Chemical formula 10.

Embedded image However, in Chemical formula 10, n shows the integer of 1-7. Examples of the polyhydric alcohol ester of mercaptopropionic acid and mercaptogluconic acid include, for example, trimethylolpropane trimercaptopropionate, trimethylolpropanetrithiogluconate, pentaerythritol tetramercaptopropionate, and pentaerythritol tetrathiogluconate And trimethylolethane trimercaptopropionate.

As the polysulfide resin,
Some are represented by

Embedded image HS- (C ₂ H ₄ OCH ₂ O—C ₂ H ₄ —S—
_{S) n -C 2 H 4 O} -C 2 H 4 -SH However, in reduction 11, n
Represents an integer of 1 to 10.

The aromatic diazonium salt includes
There is one represented by 2.

Embedded image Wherein R and R ′ are each independently chlorine,
Represents fluorine, iodine, bromine, an alkyl group, an alkoxy group or a nitro group, and M represents boron, phosphorus, arsenic, tin, iron,
X represents a metal atom such as antimony, X represents chlorine, fluorine, iodine or bromine, and n represents an integer of 2 to 8. In Chemical Formula 12, M
Xn includes BF ₄ , PF ₆ , AsF ₆ , SbF _{6 and the} like. Examples of the aromatic diazonium salt include:
Chemical formula 14, chemical formula 15, chemical formula 16, chemical formula 17, etc.

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The diaryliodonium salts include:
There is one represented by Chemical formula 18.

Embedded image Wherein R, R ′, M, X and n and MX
n is the same as in Chemical formula 12. Examples of the diaryliodonium salts include Chemical Formulas 19, 20, and 21.

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The triallylsulfonium salt includes:
There is one represented by Chemical formula 22.

Embedded image However, in Chemical formula 22, R, M, X and n and MXn are the same as Chemical formula 12. Examples of the triallylsulfonium salt include Chemical formulas 23, 24 and 25.

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Examples of the triallyl selenium salt include those represented by Chemical Formula 26.

Embedded image Wherein R, R ′, M, X and n and MX
n is the same as in Chemical formula 12. Examples of the triallyl selenium salt include Chemical formulas 27, 28 and 29.

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As the compound represented by the above formula 6,
1,3-bismaleimide-5- (perfluorononenyloxy) benzene, 1,3-bismaleimide-4-methyl-5- (perfluorononenyloxy) benzene,
1,3-Bismaleimide-4-methoxy-5- (perfluorononenyloxy) benzene, 1,3-Bismaleimide-2,4,6-trifluoro-5- (perfluorononenyloxy) benzene, 1 , 3-Bismaleimide-
4-chloro-5- (perfluorononenyloxy) benzene, 1,3-bismaleimide-4-bromo-5- (perfluorononenyloxy) benzene, 1,2-bismaleimide-4- (perfluorononene Nyloxy) benzene, 1,2-bismaleimide-4-methyl-5- (perfluorononenyloxy) benzene, 1,2-bismaleimide-4-methoxy-5- (perfluorononenyloxy) benzene, , 2-Bismaleimide-3,4,6
-Trifluoro-5- (perfluorononenyloxy)
Benzene, 1,2-bismaleimide-4-chloro-5-
(Perfluorononenyloxy) benzene, 1,2-bismaleimide-4-bromo-5- (perfluorononenyloxy) benzene, 1,4-bismaleimide-3-
(Perfluorononenyloxy) benzene, 1,4-bismaleimide-2-methyl-5- (perfluorononenyloxy) benzene, 1,4-bismaleimide-2-methoxy-5- (perfluorononenyloxy) ) Benzene, 1,4-bismaleimide-2,3,6-trifluoro-5- (perfluorononenyloxy) benzene,
1,4-Bismaleimide-2-chloro-5- (perfluorononenyloxy) benzene, 1,4-Bismaleimide-2-bromo-5- (perfluorononenyloxy)
Benzene, 1,3-bismaleimide-5- (perfluorohexenyloxy) benzene, 1,3-bismaleimide-4-methyl-5- (perfluorohexenyloxy) benzene, 1,3-bismaleimide-4-methoxy -5- (perfluorohexenyloxy) benzene,
1,3-bismaleimide-2,4,6-trifluoro-
5- (perfluorohexenyloxy) benzene, 1,
3-Bismaleimide-4-chloro-5- (perfluorohexenyloxy) benzene, 1,3-Bismaleimide-4-bromo-5- (perfluorohexenyloxy)
Benzene, 1,2-bismaleimide-4- (perfluorohexenyloxy) benzene, 1,2-bismaleimide-4-methyl-5- (perfluorohexenyloxy) benzene, 1,2-bismaleimide-4-methoxy -5- (perfluorohexenyloxy) benzene,
1,2-bismaleimide-3,4,6-trifluoro-
5- (perfluorohexenyloxy) benzene, 1,
2-Bismaleimide-4-chloro-5- (perfluorohexenyloxy) benzene, 1,2-Bismaleimide-4-bromo-5- (perfluorohexenyloxy)
Benzene, 1,4-bismaleimide-3- (perfluorohexenyloxy) benzene, 1,4-bismaleimido-2-methyl-5- (perfluorohexenyloxy) benzene, 1,4-bismaleimide-2-methoxy -5- (perfluorohexenyloxy) benzene,
1,4-bismaleimide-2,3,6-irifluoro-
5- (perfluorohexenyloxy) benzene, 1,
4-bismaleimido-2-chloro-5- (perfluorohexenyloxy) benzene, 1,4-bismaleimido-2-bromo-5- (perfluorohexenyloxy)
Benzene, 1,3-bis (dichloromaleimide) -5-
(Perfluorononenyloxy) benzene, 1,2-bis (dichloromaleimide) -4- (perfluorononenyloxy) benzene, 1,4-bis (dichloromaleimide) -3- (perfluorononenyloxy) )benzene,
1,3-bis (citraconimide) -5- (perfluorononenyloxy) benzene, 1,2-bis (citraconimide) -4- (perfluorononenyloxy) benzene, 1,4-bis (citraconimide) ) -3- (Perfluorononenyloxy) benzene, 1,3-bis (itaconimido) -5- (perfluorononenyloxy)
Benzene, 1,2-bis (itaconimido) -4- (perfluorononenyloxy) benzene, 1,4-bis (itaconimido) -3- (perfluorononenyloxy) benzene, 1,3-bis (endomethylene) Tetrahydrophthalimide) -5- (perfluorononenyloxy) benzene, 1,2-bis (endomethylenetetrahydrophthalimide) -4- (perfluorononenyloxy) benzene, 1,4-bis (endomethylenetetrahydrophthalimide)- 3- (perfluorononenyloxy) benzene and the like.

The perfluorononenyl group is -C ₉
A F ₁₇ group, the perfluoro hexenyl -C ₆ F
_{There are 11} units, and so on. In the compounds illustrated above, instead of perfluoro root sulfonyl group or a perfluoroalkyl hexenyl group, -C ₁₀ F ₁₉ group, can be exemplified similarly compounds having -C ₁₂ F ₂₃ group and the like.

The fluorine-containing imide compound represented by the above formula (6) can be produced by a method characterized by subjecting a fluorinated bisamic acid compound represented by the following formula (30) to a cyclization dehydration reaction.

Embedded image However, in Chemical formula 30, Rf is the same as Chemical formula 6, and hydrogen of the aromatic ring is a lower alkyl group, a lower alkoxy group, fluorine,
Chlorine, may be appropriately substituted with a substituent such as bromine,
The two amic acid groups are each bonded to the aromatic ring at the ortho, meta or para position with respect to the ether bond,
Represents a dicarboxylic acid residue having the same ethylenically unsaturated double bond as in Chemical formula 6 . Examples of the fluorinated bisamic acid compound represented by Chemical formula 30 include those exemplified as the compound represented by Chemical formula 6, wherein "imide" is replaced with "amic acid".

As a method for subjecting the fluorinated bisamic acid compound represented by the above formula to a cyclization dehydration reaction, a method using an acid anhydride such as acetic anhydride or a condensing agent such as dicyclohexylcarbodiimide, a method using p-toluenesulfonic acid or acetic acid or the like. There is a method of heating and dehydrating in the presence. For example, US Pat. No. 3,018,290, US Pat.
A known method described in Japanese Patent No. 2,127,414 or the like may be used. That is, a method is used in which acetic anhydride is used as a dehydrating agent and the reaction is carried out in an organic solvent in the presence of a base and a catalyst. At this time, the amount of acetic anhydride to be used is usually 1 to 2 mol based on the amide acid group. The catalyst used is an oxide of an alkaline earth metal,
Iron (II, III), copper (I, II), nickel (I
I), manganese (II, III), cobalt (II, I
Carbonates, sulfates, acetates, phosphates and the like such as II). Specifically, there are nickel (II) acetate, cobalt (II) acetate, magnesium oxide and the like, which are usually used in an amount of 0.01 to 0.5 mol per amic acid group. The base used is an alkali metal acetate or a tertiary amine. Specifically, there are sodium acetate, triethylamine and the like.
~ 2.0 moles are used. Reaction conditions vary depending on the reagent, and are not particularly limited. The intermediate amic acid generated in the first step does not necessarily need to be isolated, and the cyclization dehydration reaction in the second step can be performed as it is.

The fluorinated bisamic acid compound represented by the above formula can be produced by reacting a fluorinated aromatic diamine represented by the following formula with an unsaturated dicarboxylic acid represented by the following formula.

Embedded image However, in Chemical Formula 31, Rf is the same as Chemical Formula 6, and the hydrogen of the aromatic ring may be appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, or bromine. Each amino group is bonded to the aromatic ring at the ortho, meta or para position relative to the ether bond.

Embedded image However, in Chemical formula 32, D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond.

The compound represented by Chemical formula 31 includes 1,
3-diamino-5- (perfluorononenyloxy) benzene, 1,3-diamino-4-methyl-5- (perfluorononenyloxy) benzene, 1,3-diamino-
4-methoxy-5- (perfluorononenyloxy) benzene, 1,3-diamino-2,4,6-trifluoro-5- (perfluorononenyloxy) benzene, 1,
3-diamino-4-chloro-5- (perfluorononenyloxy) benzene, 1,3-diamino-4-bromo-
5- (perfluorononenyloxy) benzene, 1,2
-Diamino-4- (perfluorononenyloxy) benzene, 1,2-diamino-4-methyl-5- (perfluorononenyloxy) benzene, 1,2-diamino-4
-Methoxy-5- (perfluorononenyloxy) benzene, 1,2-diamino-3,4,6-trifluoro-
5- (perfluorononenyloxy) benzene, 1,2
-Diamino-4-chloro-5- (perfluorononenyloxy) benzene, 1,2-diamino-4-bromo-5
-(Perfluorononenyloxy) benzene, 1,4-
Diamino-3- (perfluorononenyloxy) benzene, 1,4-diamino-2-methyl-5- (perfluorononenyloxy) benzene, 1,4-diamino-2-
Methoxy-5- (perfluorononenyloxy) benzene, 1,4-diamino-2,3,6-trifluoro-5
-(Perfluorononenyloxy) benzene, 1,4-
Diamino-2-chloro-5- (perfluorononenyloxy) benzene, 1,4-diamino-2-bromo-5-
(Perfluorononenyloxy) benzene, 1,3-diamino-5- (perfluorohexenyloxy) benzene, 1,3-diamino-4-methyl-5- (perfluorohexenyloxy) benzene, 1,3-diamino -4
-Methoxy-5- (perfluorohexenyloxy) benzene, 1,3-diamino-2,4,6-trifluoro-5- (perfluorohexenyloxy) benzene,
1,3-diamino-4-chloro-5- (perfluorohexenyloxy) benzene, 1,3-diamino-4-bromo-5- (perfluorohexenyloxy) benzene, 1,2-diamino-4- (per Fluorohexenyloxy) benzene, 1,2-diamino-4-methyl-5
-(Perfluorohexenyloxy) benzene, 1,2
-Diamino-4-methoxy-5- (perfluorohexenyloxy) benzene, 1,2-diamino-3,4,6
-Trifluoro-5- (perfluorohexenyloxy) benzene, 1,2-diamino-4-chloro-5-
(Perfluorohexenyloxy) benzene, 1,2-
Diamino-4-bromo-5- (perfluorohexenyloxy) benzene, 1,4-diamino-3- (perfluorohexenyloxy) benzene, 1,4-diamino-
2-methyl-5- (perfluorohexenyloxy) benzene, 1,4-diamino-2-methoxy-5- (perfluorohexenyloxy) benzene, 1,4-diamino-2,3,6-trifluoro-5 -(Perfluorohexenyloxy) benzene, 1,4-diamino-2-chloro-5- (perfluorohexenyloxy) benzene, 1,4-diamino-2-bromo-5- (perfluorohexenyloxy) benzene, etc. is there.

In the compounds exemplified above, compounds having a group -C ₁₀ F ₁₉ , a group -C ₁₂ F ₂₃ or the like in place of the perfluorononenyl group or the perfluorohexenyl group can also be exemplified.

Examples of the unsaturated dicarboxylic acid anhydride represented by Chemical Formula 32 include maleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, and pyrosiconic anhydride, or the Diels of these compounds with cyclodiene.・ Alder (Diels-Alde)
r) At least one of the adducts is used.

As a method of reacting the fluorinated aromatic diamine represented by the above formula with the unsaturated dicarboxylic anhydride represented by the above formula, a known method is applied. There is a method in which the fluorinated aromatic diamine represented by the formula (31) and the unsaturated dicarboxylic anhydride represented by the formula (32) are brought into contact in an organic solvent which is a solvent for both. Usually, solvents generally used include halogenated hydrocarbons such as chloroform, methylene chloride and trichloroethylene, ketones such as acetone, methyl ethyl ketone, cyclohexanone and diisopropyl ketone, ethers such as ether, tetrahydrofuran and dioxane, benzene, toluene and chlorobenzene. Aromatic compounds such as acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N
Aprotic polar solvents such as -methylpyrrolidone.

The fluorine-containing aromatic diamine represented by the above formula (31) can be produced by subjecting a fluorine-containing aromatic diurethane compound represented by the following formula (33) to a deprotection reaction of a urethane type protecting group.

Embedded image However, in Formula 33, Rf is the same as in Formula 6, R ¹ and R ² each independently represent an alkyl group which may be substituted or an aryl group which may be substituted, and hydrogen of the aromatic ring is , A lower alkyl group, a lower alkoxy group, a substituent such as fluorine, chlorine, bromine, etc., which may be appropriately substituted, and two urethane groups are each ortho-, meta- or para-position to the ether bond to the aromatic ring. Bound to the position.

Here, the urethane-type protecting group specifically means —COOR ¹ and —COOR ² in Chemical formula 33.

The above deprotection reaction can be carried out, for example, by the following method. In a solution of the above fluorinated aromatic diurethane compound in an organic solvent such as ethyl acetate, dimethylformamide, dimethylacetamide, benzene, xylene, acetone, tetrahydrofuran or the like, hydrogen gas is added at 0 to 100 ° C in the presence of a catalyst such as palladium carbon. A method of passing hydrogen gas (particularly preferably around room temperature) (the time for passing hydrogen gas may be determined as appropriate, but usually 1 to 10 hours is sufficient), dissolving the fluorine-containing aromatic diurethane compound in the organic solvent as described above. HF, HBr, HCl, H ₂
A method of adding and reacting a hydrogen acid such as SO ₄ (hydrogen acid is
The reaction is preferably performed in an equivalent amount or more with respect to the fluorinated aromatic diurethane compound. When HF is used, the reaction is preferably performed at room temperature or lower, particularly at 0 ° C or lower. The reaction is preferably performed at around room temperature. Further, the reaction time is appropriately determined, but usually, 0.1 to 1 hour when HF is used, and 1 to 10 hours when other hydrogen acid is used), the above-mentioned fluorinated aromatic diurethane A method of reacting a compound in the presence of a basic compound such as sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide, potassium hydroxide and water (water is preferably used in an equivalent amount or more to the fluorine-containing aromatic diurethane compound) The reaction may be carried out using water, an alcohol such as methanol or ethanol, cresol or the like as a solvent in addition to the organic solvent as described above.)
and so on. The thus obtained aromatic diamine compound represented by Chemical formula 8 can be purified by recrystallization from alcohol or the like.

Examples of the fluorine-containing aromatic diurethane compound represented by Chemical Formula 33 include 1,3-bis (N- (methyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene and 1,3-bis (N -(Ethyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene, 1,3-bis (N- (propyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene, 1,3 -Bis (N- (i-propyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene, 1,3-bis (N- (butyloxycarbonyl) amino) -5- (perfluorononenyloxy) ) Benzene, 1,3-bis (N- (i-butyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene 1,3-bis (N- (t-butyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene, 1,3-bis (N- (pentyloxycarbonyl) amino) -5- (perfluoro Nonenyloxy) benzene, 1,3-bis (N- (hexyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene, 1,3-bis (N- (heptyloxycarbonyl) amino) -5 -(Perfluorononenyloxy) benzene, 1,3-bis (N- (octyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene, 1,3-bis (N- (benzyloxycarbonyl) Amino) -5- (perfluorononenyloxy) benzene, 1,3-bis (N- (phenyloxycarbonyl) amino) -5- ( -Fluorononenyloxy) benzene, 1,2-bis (N- (methyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2-bis (N- (ethyloxycarbonyl) amino) 4- (perfluorononenyloxy) benzene, 1,2-bis (N- (propyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2-bis (N- (i- Propyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2-bis (N- (butyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2-bis (N- (i-butyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2-bis (N- (t-butyl) (Oxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2-bis (N- (pentyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2-bis ( N- (hexyloxycarbonyl) amino) -4-perfluorononenyloxy) benzene, 1,2-bis (N- (heptyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2 -Bis (N- (octyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2-bis (N- (benzyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene , 1,2-Bis (N- (phenyloxycarbonyl) amino) -4- (perfluorononenyloxy) benze 1,4-bis (N- (methyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N- (ethyloxycarbonyl) amino) -3- (perfluoronone Nyloxy) benzene, 1,4-bis (N- (propyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N- (i-propyloxycarbonyl) amino)- 3- (perfluorononenyloxy) benzene, 1,4-bis (N- (butyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N- (i-butyl) Oxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N- (t-butyloxycarbonyl) amino) -3- Perfluorononenyloxy) benzene, 1,4-bis (N- (pentyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N- (hexyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N- (heptyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N- (octyloxy) Carbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N- (benzyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N -(Phenyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,3-bis (N- (methyl (Xycarbonyl) amino) -5- (perfluorohexenyloxy) benzene, 1,3-bis (N- (ethyloxycarbonyl) amino) -5- (perfluorohexenyloxy) benzene, 1,3-bis (N- (Propyloxycarbonyl) amino) -5- (perfluorohexenyloxy) benzene, 1,3-bis (N- (i-propyloxycarbonyl) amino) -5- (perfluorohexenyloxy) benzene, 1,3- Screw (N-
(Butyloxycarbonyl) amino) -5- (perfluorohexenyloxy) benzene, 1,3-bis (N-
(I-butyloxycarbonyl) amino) -5- (perfluorohexenyloxy) benzene, 1,3-bis (N- (t-butyloxycarbonyl) amino) -5
(Perfluorohexenyloxy) benzene, 1,3-
Bis (N- (pentyloxycarbonyl) amino) -5
-(Perfluorohexenyloxy) benzene, 1,3
-Bis (N- (hexyloxycarbonyl) amino)-
5- (perfluorohexenyloxy) benzene, 1,
3-bis (N- (heptyloxycarbonyl) amino)
-5- (perfluorohexenyloxy) benzene,
1,3-bis (N- (octyloxycarbonyl) amino) -5- (perfluorohexenyloxy) benzene, 1,3-bis (N- (benzyloxycarbonyl)
Amino) -5- (perfluorononenyloxy) benzene, 1,3-bis (N- (phenyloxycarbonyl)
Amino) -5- (perfluorohexenyloxy) benzene, 1,2-bis (N- (methyloxycarbonyl)
Amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (ethyloxycarbonyl)
Amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (propyloxycarbonyl) amino) -4- (perfluorohexenyloxy)
Benzene, 1,2-bis (N- (i-propyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (butyloxycarbonyl) amino) -4- (per Fluorohexenyloxy) benzene, 1,2-bis (N- (i-butyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (t-butyloxycarbonyl) amino ) -4- (Perfluorohexenyloxy) benzene, 1,2-bis (N- (pentyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (hexyloxycarbonyl) ) Amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (heptyloxycal Yl) amino) -4- (perfluoro-hexenyl) benzene, 1,2-bis (N-
(Octyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N
-(Benzyloxycarbonyl) amino) -4- (perfluorohexenyloxy) henzen, 1,2-bis (N- (phenyloxycarbonyl) amino) -4-
(Perfluorohexenyloxy) benzene, 1,4-
Bis (N- (methyloxycarbonyl) amino) -3-
(Perfluorohexenyloxy) benzene, 1,4-
Bis (N- (ethyloxycarbonyl) amino) -3-
(Perfluorohexenyloxy) benzene, 1,4-
Bis (N- (propyloxycarbonyl) amino) -3
-(Perfluorohexenyloxy) benzene, 1,4
-Bis (N- (i-propyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N- (butyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene , 1,4-bis (N- (i-butyloxycarbonyl) amino) -3- (perfluorohexenyloxy)
Benzene, 1,4-bis (N- (t-butyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N- (pentyloxycarbonyl) amino) -3- (per Fluorohexenyloxy) benzene, 1,4-bis (N- (hexyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N- (heptyloxycarbonyl) amino) -3- (Perfluorohexenyloxy) benzene, 1,4-bis (N- (octyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N- (benzyloxycarbonyl) amino)- 3- (perfluorononenyloxy) benzene, 1,4-bis (N- (phenyloxycarbonyl) Is amino) -3- (perfluoro-hexenyl) benzene and the like. In the compounds exemplified as above, instead of the perfluorononenyl group or the perfluorohexenyl group, a —C ₁₀ F ₁₉ group, a —C ₁₂
Compounds with F ₂₃ group or the like can be exemplified similarly.

The aromatic diurethane compound represented by the above formula (33) can be obtained by mixing a fluorine-containing aromatic dicarboxylic acid compound represented by the following formula (34), an azide compound represented by the following formula (35) and an alcohol represented by the following formula (36) in a solvent or without solvent. And by reacting in the presence of a base.

Embedded image However, in Chemical formula 34, Rf is the same as Chemical formula 6, and the hydrogen of the aromatic ring may be appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, bromine or the like. Each carboxyl group is bonded to the aromatic ring at the ortho, meta or para position with respect to the ether bond.

Embedded image However, in Chemical formula 35, R ³ represents a lower alkyl group or an aryl group.

Embedded image in R ⁴ OH where reduction 36, R ⁴ represents an optionally substituted alkyl group, or an aryl group which may have a substituent.

Examples of the dicarboxylic acid compound represented by Chemical Formula 34 include 5- (perfluorononenyloxy) isophthalic acid, 4- (perfluorononenyloxy) phthalic acid,
2- (perfluorononenyloxy) terephthalic acid, 4
-Methyl-5- (perfluorononenyloxy) isophthalic acid, 4-methoxy-5- (perfluorononenyloxy) isophthalic acid, 2,4,6-trifluoro-5-
(Perfluoronenyloxy) isophthalic acid, 4-chloro-5- (perfluorononenyloxy) isophthalic acid, 4-bromo-5- (perfluorononenyloxy)
Isophthalic acid, 4-methyl-5- (perfluorononenyloxy) phthalic acid, 4-methoxy-5- (perfluorononenyloxy) phthalic acid, 3,4,6-trifluoro-5- (perfluorononene Nyloxy) phthalic acid, 4
-Chloro-5- (perfluorononenyloxy) phthalic acid, 4-bromo-5- (perfluorononenyloxy)
Phthalic acid, 2-methyl-5- (perfluorononenyloxy) terephthalic acid, 4-methoxy-5- (perfluorononenyloxy) terephthalic acid, 2,3,6-trifluoro-5- (perfluorononene Nyloxy) terephthalic acid, 2-chloro-5- (perfluorononenyloxy) terephthalic acid, 2-bromo-5- (perfluorononenyloxy) terephthalic acid, 5- (perfluorohexenyloxy) isophthalic acid, -(Perfluorohexenyloxy) phthalic acid, 2- (perfluorohexenyloxy) terephthalic acid, 4-methyl-5- (perfluorohexenyloxy) isophthalic acid, 4-methoxy-
5- (perfluorohexenyloxy) isophthalic acid,
2,4,6-trifluoro-5- (perfluorohexenyloxy) isophthalic acid, 4-chloro-5- (perfluorohexenyloxy) isophthalic acid, 4-bromo-
5- (perfluorohexenyloxy) isophthalic acid,
4-methyl-5- (perfluorohexenyloxy) phthalic acid, 4-methoxy-5- (perfluorohexenyloxy) phthalic acid, 3,4,6-trifluoro-5-
(Perfluorohexenyloxy) phthalic acid, 4-chloro-5- (perfluorohexenyloxy) phthalic acid,
4-bromo-5- (perfluorohexenyloxy) phthalic acid, 2-methyl-5- (perfluorohexenyloxy) terephthalic acid, 4-methoxy-5- (perfluorohexenyloxy) terephthalic acid, 2,3,6 -Trifluoro-5- (perfluorohexenyloxy) terephthalic acid, 2-chloro-5- (perfluorohexenyloxy) terephthalic acid, 2-bromo-5- (perfluorohexenyloxy) terephthalic acid and the like. In the compound thus exemplified, instead of the perfluorononenyl group or the perfluorohexenyl group, -C ₁₀ F ₁₉
Compounds having a group, —C ₁₂ F ₂₃ group, and the like can also be exemplified.

The above-mentioned perfluorononenyloxyisophthalic acid and perfluorohexenyloxyisophthalic acid can be prepared, for example, by using hexafluoropropene trimer or dimer according to the method disclosed in JP-A-60-511146.
And hydroxyisophthalic acid in an aprotic polar solvent at room temperature or lower in the presence of a base catalyst.

As the perfluorononenyl group, for example, there is a group represented by the following formula.

Embedded image

The perfluorohexenyl group includes, for example, a group represented by the following formula:

Embedded image

In the above method, it is also possible to prepare other dicarboxylic acids by using oligomers other than trimers and dimers of hexafluoropropene and oligomers of other fluoroalkenes.

The dicarboxylic acid represented by the above formula can be prepared, for example, according to the method described in Japanese Patent Application Laid-Open No. Sho. And oligomers of fluoroalkenes such as fluoropropene trimer and tetrafluoroethylene pentamer in the presence of a proton acceptor in an aprotic organic solvent at or below room temperature in the presence of a base catalyst The reaction product can be produced by isolating the reaction product, hydrolyzing the reaction product in the presence of a basic compound such as sodium hydroxide or potassium hydroxide, and appropriately treating the reaction product with an acid such as hydrochloric acid. The reaction product and the final product are appropriately purified by means such as washing and recrystallization.

Examples of the azide compound represented by Chemical formula 35 include diphenyl phosphoryl azide, diethyl phosphoryl azide, di-p-nitrophenyl phosphoryl azide, and dimorpholyl phosphoryl azide.

As the alcohol represented by Chemical formula 36,
Methanol, ethanol, propanol, i-propanol, butanol, i-butanol, t-butanol,
Pentanol, hexanol, heptanol, octanol, phenol, benzyl alcohol and the like.

In the synthesis reaction for obtaining the fluorine-containing aromatic diurethane compound represented by Chemical formula 33, Takayuki Shioiri, Shunichi Yamada,
A new Curtius reaction can be applied as shown in Journal of Synthetic Organic Chemistry, Vol. 31, No. 8, pages 666-674 (1973). That is, the desired fluorinated aromatic diurethane compound can be obtained by reacting the dicarboxylic acid compound represented by the chemical formula with the azide compound represented by the chemical formula and the alcohol represented by the chemical formula in the presence of a base. As the base, it is preferable to use a tertiary amine such as trimethylamine, triethylamine and pyridine. The above reaction is carried out in an organic solvent or by using an alcohol represented by Chemical formula 36 as a solvent. As the organic solvent, it is preferable to use benzene, toluene, tetrahydrofuran, dioxane, diethyl ether and the like. These solvents are
Two or more kinds may be used as a mixture as long as they are mutually compatible.

In the above reaction, a dicarboxylic acid compound represented by the chemical formula (C) and an azide compound represented by the chemical formula (C) are reacted in the middle, and a carboxylic acid azide and this carboxylic acid azide undergo a thermal rearrangement reaction to form an isocyanate compound. However, the reaction can proceed with or without isolation of these intermediates. The conditions for the above reaction differ depending on the reagent used and are not particularly limited, but the following conditions are preferred.

First, the dicarboxylic acid compound represented by the chemical formula (C), the azide compound represented by the chemical formula (C), the tertiary amine and the alcohol represented by the chemical formula (36) are reacted at a time, and apparently the desired compound is reacted in one step. When obtaining a fluorine aromatic diurethane compound, the reaction temperature is -80 to 250 ° C.
And more preferably room temperature to 150 ° C. The azide compound, the tertiary amine and the alcohol are each added to the dicarboxylic acid compound in an amount of 0.5 to 5.0.
It is preferable to use molar equivalents, 0.5 to 3.0 molar equivalents, and 0.5 molar equivalents to a large excess.

Second, when the carboxylic acid azide is isolated once, first, the dicarboxylic acid compound and the azide compound are reacted in the presence of the tertiary amine, and the resulting carboxylic acid azide is isolated. I do. At this time, the reaction temperature is preferably −80 to 100 ° C., and the azide compound and the tertiary amine are 0.5 to 5.0 mole equivalents and 0.5 to 3.0 moles, respectively, based on the dicarboxylic acid compound. It is preferable to use an equivalent amount. Next, the isolated carboxylate azide is reacted in a 0.5 molar equivalent to a large excess of alcohol with respect to the isolated carboxylate azide to obtain a desired fluorinated aromatic diurethane compound. The reaction temperature at this time was -8
0-250 ° C is preferred.

Third, when isolating the isocyanate compound once, first, the dicarboxylic acid compound represented by the formula (34) and the azide compound represented by the formula (35) are reacted in the presence of a tertiary amine to obtain the isocyanate compound. Is isolated. At this time, it is preferable to use 0.5 to 5.0 molar equivalents of the azide compound and 0.5 to 3.0 molar equivalents of the tertiary amine with respect to the dicarboxylic acid compound. preferable. Then, the obtained isocyanate is reacted in an alcohol in a molar excess of 0.5 to a large excess thereof, whereby a fluorinated aromatic diurethane compound can be obtained. At this time, the reaction temperature is preferably from -80 to 250C.

The first to third methods are appropriately selected in consideration of the yield and the like. The fluorinated aromatic diurethane compound thus obtained can be purified by recrystallization from hexane or the like.

The present invention further provides a fluorine-containing thermosetting imide resin material containing the fluorine-containing imide compound represented by the above formula (6).

The fluorine-containing thermosetting imide resin material is as follows:
In addition to the fluorinated imide compound represented by the above formula 6,
A compound having at least two thermosetting imide groups in a molecule (hereinafter, referred to as “another reactive imide compound”) may be contained. As other reactive imide compounds,
Parabismaleimidebenzene, metabismaleimidebenzene, parabismaleimidetoluene, 1,4-bis (p
-Maleimidocumyl) benzene, 1,4-bis (m-maleimidocumyl) benzene and the like, and those represented by the following formulas (39), (40) or (41).

Embedded image Where X is O, CH ₂ , CF ₂ , SO ₂ ,
S, CO or C (CF ₃ ) ₂ , R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine; It is a dicarboxylic acid residue having an unsaturated double bond.

Embedded image Where Y is O, CH ₂ , CF ₂ , SO ₂ ,
S, CO, C (CH ₃ ) ₂ or C (CF ₃ ) ₂ ;
R ₅ , R ₆ , R ₇ and R ₈ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and D is a dicarboxylic acid residue having an ethylenically unsaturated double bond. is there.

Embedded image However, in Chemical formula 41, n is the number of 0-4.

Examples of the thermosetting imide compound represented by Chemical formula 39 include 4,4'-bismaleimide diphenyl ether, 4,4'-bismaleimide diphenylmethane,
4,4′-bismaleimide-3,3′-dimethyl-diphenylmethane, 4,4′-bismaleimidediphenylsulfone, 4,4′-bismaleimidediphenylsulfide, 4,4′-bismaleimidediphenyl Ketone, 2,
2-bis (4-maleimidophenyl) propane, 4,
4'-bismaleimidodiphenylfluoromethane, 1,
1,1,3,3,3-hexafluoro-2,2-bis (4-maleimidophenyl) propane and the like.

Examples of the thermosetting imide compound represented by Chemical formula 40 include bis [4- (4-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] methane, Bis [4- (4-maleimidophenoxy) phenyl] fluoromethane, bis [4- (4-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2-bis [4-
(4-maleimidophenoxy) phenyl] propane,
1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-maleimidophenoxy) phenyl] propane and the like.

As the polyamine compound for producing the thermosetting prepolymer, the above-mentioned polyamine compounds can be used, and the above-mentioned aromatic amines are particularly preferable.

The thermosetting prepolymer can be obtained by reacting a fluorine-containing imide compound represented by the formula (6) with a polyamine compound. By this heating reaction, the amino group of the polyamine compound undergoes an addition reaction to the double bond of the fluorinated imide compound. The heating condition in this case is a condition for partially curing, and preferably a temperature in the range of 50 to 350C, particularly preferably a temperature in the range of 80 to 200C. The heating time is appropriately determined in consideration of the reaction to such an extent that it becomes more suitable for molding, but is preferably in the range of 5 to 10 hours. It is preferable to use the fluorine-containing imide compound and the polyamine compound so that the former: the latter is in a molar ratio of 50: 1 to 1: 1.5. If the proportion of the polyamine compound used is small, the cured product does not exhibit a reduction in moisture absorption and dielectric constant or an improvement in transparency. Conversely, if the proportion of the polyamine compound is too large, the heat resistance of the cured product is adversely affected. The reaction is carried out by dissolving the fluorine-containing imide compound and the polyamine compound in an organic solvent. It may be used after processed into a shape. Organic solvents include methylene chloride, dichloroethane,
Halogenated hydrocarbons such as trichloroethylene, ketones such as acetone, methyl ethyl ketone, cyclohexanone and diisopropyl ketone; ethers such as tetrahydrofuran, dioxane and methyl cellosolve; aromatic compounds such as benzene, toluene and chlorobenzene; acetonitrile, N, N'- Dimethylformamide, N,
N'-dimethylacetamide, dimethylsulfoxide,
N-methyl-2-pyrrolidone, 1,3-dimethyl-2-
Aprotic polar solvents such as imidazolidinone; Examples of the poor solvent include water, hexane and petroleum ether. Alternatively, the fluorinated imide compound and the polyamine compound may be mixed and reacted in powder form.

In the synthesis of the above thermosetting prepolymer, other polyimide compounds may be used together with the above-mentioned fluorine-containing imide compound within a range not to impair the object of the present invention. Other polyimide compounds will be described later.

In the epoxy resin composition of the present invention, the fluorine-containing imide compound or the thermosetting prepolymer
Is preferably blended in an amount of 5 to 100 parts by weight based on 100 parts by weight of the epoxy resin. If less than 5 parts by weight, moisture resistance,
The improvement in heat resistance is small, and if it is more than 100 parts by weight, the moldability deteriorates.

The epoxy resin composition of the present invention is appropriately blended with the above-mentioned curing agent. When a curing agent is used, it is desirable to blend 0.1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin. The compounding amount is determined according to the purpose of use and does not necessarily have to be equivalent to the epoxy resin.

Further, a curing accelerator may be used for accelerating the curing reaction, and examples thereof include imidazoles, benzyldimethylamine pyridine, picoline, piperidine, triethanolamine, dimethylaniline, and tetramethylguanidine. The imidazoles correspond to those described above. The amount of the curing accelerator is also appropriately determined, and may be blended in consideration of storage stability and curability. The amount is preferably about 0.01 to 5 parts by weight based on 100 parts by weight of the epoxy resin. When the amount is less than 0.01 part by weight, the accelerated curing of the curing reaction is small, and when it is more than 5 parts by weight, the storage stability is deteriorated.

In order to accelerate the curing of the fluorinated imide compound or the thermosetting prepolymer, a usual radical polymerization initiator may be used. As the radical polymerization initiator, acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, benzoyl peroxide, octanoyl peroxide, acetyl peroxide, dicumyl peroxide, cumene hydroperoxide, azobisisobutyronitrile and the like are used. Is done. The amount of the radical initiator is not particularly limited, but is preferably 0.01 to 1 part by weight based on 100 parts by weight of the fluorine-containing imide compound or the thermosetting prepolymer.

The epoxy resin composition of the present invention may be used in the form of a powdery mixture of the substances to be used as components, or in the form of a varnish dissolved in a solvent. Any solvent may be used as long as it dissolves the above compound, such as acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, N , N-dimethylacetamide, N-methyl-2-pyrrolidone, etc., and these may be used as a mixture of two or more.

The epoxy resin composition of the present invention includes:
Other polyimide compounds can be contained as long as the object of the present invention is not impaired. Other polyimide compounds include parabismaleimidebenzene, metabismaleimidebenzene, parabismaleimidetoluene, 1,4-bis (p-maleimidocumyl) benzene, 1,4-bis (m-maleimidocumyl) benzene, 4,4'-bismaleimide diphenyl ether, 4,4'-bismaleimide diphenylmethane, 4,4'-bismaleimide-3,
3'-dimethyl-diphenylmethane, 4,4'-bismaleimide diphenyl sulfone, 4,4'-bismaleimide diphenyl sulfide, 4,4'-bismaleimide diphenyl ketone, 2,2-bis (4- Maleimidophenyl) propane, 4,4'-bismaleimidodiphenylfluoromethane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-maleimidophenyl) propane, bis [4 -(4-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] fluoromethane, bis [4- (4
-Maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimide) Phenoxy) phenyl] ketone, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 1,1,1,1
3,3,3-hexafluoro-2,2-bis [4- (4
-Maleimidophenoxy) phenyl] propane. These other polyimide compounds may be used together with the fluorine-containing imide compound at the time of synthesizing the thermosetting prepolymer.

The other polyimide compound can be a thermosetting prepolymer as in the case of the thermosetting prepolymer, and this thermosetting prepolymer can be used as long as the object of the present invention is not impaired. It can be contained in the epoxy resin composition of the present invention.

The epoxy resin composition of the present invention contains a thermoplastic resin (polyethylene, polypropylene,
Polyamide, polycarbonate, polysulfone, polyethersulfone, polyetheretherketone, modified polyphenylene oxide, polyphenylene sulfide, etc., reinforcing materials (glass fiber, carbon fiber, aromatic polyamide fiber, alumina fiber, potassium titanate) Fiber, etc.),
Fillers (clay, mica, silica, graphite, glass beads, alumina, calcium carbonate, etc.) and the like can be added in appropriate amounts according to the purpose.

The epoxy resin composition of the present invention includes:
Furthermore, one or more ordinary additives such as an antioxidant and a heat stabilizer, an ultraviolet absorber, a flame retardant aid, an antistatic agent, a lubricant and a coloring agent are added within a range not to impair the object of the present invention. Can be.

The epoxy resin composition can be impregnated into a glass fiber cloth such as a glass cloth and a glass non-woven cloth, other cloths, a base material such as paper, and dried to obtain a prepreg. At this time, a varnish-like solution dissolved in an organic solvent is used as the epoxy resin composition, and as a method of impregnating the epoxy resin composition into the base material, brushing, spraying, dipping, or the like is used. Can be. Drying is 8
It is preferably carried out at a temperature of 0 to 200 ° C., for example, one obtained by simply removing the solvent, or one obtained by partially curing the solvent. The degree of drying is appropriately determined, but is adjusted so as to have a melt viscosity suitable for final molding. The prepreg can be appropriately laminated and cured by heating under pressure to form a laminate. The degree of pressure at this time is preferably about 50 to 100 kg / cm ² . The heating temperature is as follows. This laminated board is useful as a wiring board substrate.

The epoxy resin composition may be used in a so-called B-stage state in which the epoxy resin composition is generally partially cured without being completely cured in order to adjust the melt viscosity.

The epoxy resin composition, its B-stage state, and prepreg are generally kept at 100 ° C. to 2 ° C.
Heat to 50 ° C. range to cure.

The epoxy resin composition or its B-stage state is molded by a known molding method such as a compression molding method, a transfer molding method, an extrusion molding method, an injection molding method, and put into practical use.

[0075]

The present invention will now be described by way of examples, which should not be construed as limiting the present invention.

Synthesis Example 1 5- (Perfluorononenyloxy) isophthalic acid
61 g (1.0 mmol), diphenylphosphoryl azide 0.66 g (2.4 mmol), triethylamine 0.24 g
(2.4 mmol) was reacted in 10 mL of t-butanol at a reflux temperature for 20 hours. After completion of the reaction, t-butanol was distilled off, ether was added thereto, and the mixture was washed with dilute hydrochloric acid and an aqueous solution of sodium hydrogen carbonate. The ether was distilled off, and the residue was recrystallized from hexane to give 1,3-bis-N- (t
-Butyloxycarbonyl) amino) -5-perfluorononenyloxybenzene was obtained at a yield of 86%.

The physical properties and elemental analysis values of this compound are shown below. (1) Melting point 69-71 ° C. (2) ¹ H-NMR spectrum (solvent acetone-d ₆ , T
8.72 ppm (2H, NH, s), 7.61 p.
pm (1H, Aromatic, t), 7.09 ppm (2H, Aromat
ic, s), 1.49 ppm (9H, t-Bu, t) (3) ¹⁹ F-NMR spectrum (solvent acetone-d ₆ ,
Benzotrifluoride standard); 11.32 ppm (3F,
_{CF 3, d), - 3.54ppm} (6F, CF 3, s), -
_{4.82ppm (6F, CF 3, d} ), - 99.70ppm (1
F, CF, quarter.), -101.49 ppm (1F, CF,
quint.), (4) IR absorption spectrum; 3336 cm ^-1 (NH, urethane), 1710 cm ^-1 (C = O, urethane), 154
8cm ^-1 (N-H, ^{urethane), 1244cm -1 (C-F} ) (5) minutes containing analysis (%); as shown in Table 1.

[Table 1]

From the above, formation of the desired product was confirmed. Its structural formula is as shown in Chemical formula 42.

Embedded image

Synthesis Example 2 1,3-Bis (N- (t-butyloxycarbonyl) amino) -5- (perfluorononenyloxy)
0.20 g (0.265 mmol) of benzene was added to 3N hydrochloric acid /
5.3 mL of ethyl acetate was added, and the mixture was stirred at room temperature for 4 hours. After an aqueous sodium hydroxide solution was added thereto until the solution became basic, the oil layer was extracted with ether. The ether was distilled off, and column separation was performed with ether / hexane to obtain 1,3-diamino-5- (perfluorononenyloxy) benzene as a target substance in a yield of 73%.

The analytical data of the obtained 1,3-diamino-5- (perfluorononenyloxy) benzene are shown below. (1) Melting point 105.5-106.9 ° C. (2) ¹ H-NMR spectrum (solvent acetone-d ₆ , T
5.87 ppm (1H, Aromatic, t) 5.63 ppm (2H, Aromatic, t) 4.75 ppm (4H, NH ₂ , s) (3) ¹⁹ F-NMR spectrometer (solvent acetone-)
d _6, benzotrifluoride _{standard); 11.03ppm (3F, CF 3} , d) -3.68ppm (6F, CF 3, s) -4.98ppm (6F, CF 4, d) -99.71ppm (1F , CF, quart.) -101.67 ppm (1F, CF, quint.) (4) IR absorption spectrum; 3452 cm ^-1 , 3380 cm
^{-1, 1628cm -1 (N-H} , an amine), 1298cm ^-1,
1238 cm ^-1 , 1190 cm ^-1 (CF) (5) Elemental analysis value (%);

[Table 2]

From the above, formation of the target compound was confirmed.
The structural formula of this compound is as shown in Chemical formula 43.

Embedded image

Synthesis Example 3 0.431 g (4.40 mmol) of maleic anhydride was dissolved in 5 mL of acetone, and the mixture was stirred on an ice-water bath under a nitrogen stream under a stream of nitrogen to give 1,3-diamino-5- (perfluoro Nonenyloxy) benzene 1.11 g (2.00 mmo
An acetone solution (5 mL) of 1) was added dropwise, and the mixture was stirred for 6 hours. After completion of the reaction, the resulting precipitate was filtered, washed with acetone, and dried under reduced pressure to give 1,3-bismaleamic acid-
5- (perfluorononenyloxy) benzene yield 99
%.

The melting point and spectrum data of this compound are as follows. (1) Melting point 196-201 ° C. (2) ¹ H-NMR spectrum (solvent DMSO-d ₆ , T
12.90 ppm (2H, COOH, s) 10.61 ppm (2H, CONH, s) 7.90 ppm (1H, Aromatic, s) 7.22 ppm (2H, Aromatic, s) 6.38 ppm (4H, MS standard); olefinic, q) [In the parentheses, the integrated intensity ratio of hydrogen, the basic group of the absorption and the type of peak are sequentially shown, s is a singlet, t is a triplet, q is a quadruple, and m is multiple. Indicates a line. The same applies to the following. (3) ¹⁹ F-NMR spectrum (solvent DMSO-d ₆ ,
Benzotrifluoride _{standard); 12.00ppm (3F, CF 3} , d) -3.04ppm (6F, CF 3, s) -4.14ppm (6F, CF 3, d) -99.60ppm (1F, CF, quart.) -10.57 ppm (1F, CF, quint.) [Figures in parentheses indicate the integrated intensity ratio of fluorine, the group and peak as the basis of absorption, s is a singlet, and d is a doublet. Line, quart. Is a quadruple line, quint. Indicates a quintet. The same applies to the following. (4) IR spectrum 3304 cm ^-1 (NH, amide) 3124 cm ^-1 (OH) 1716 cm ^-1 (C = O, carboxylic acid) 1604 cm ^-1 (C = O, amide) 1558 cm ^-1 (NH-R , Amide) 1240 cm ^-1 (CF)

From the above, the formation of the desired product was confirmed. The structural formula of this compound is as shown in Chemical formula 44.

Embedded image

Synthesis Example 4 1.35 g (1.80 mmol) of 1,3-bismaleamic acid-5- (perfluorononenyloxy) benzene of the formula
l), 0.816 g (8.00 mmol) of acetic anhydride, 0.202 g (2.00 mmol) of triethylamine, 0.050 g (0.20 mmol) of nickel (II) acetate tetrahydrate in 15 mL of acetone under a nitrogen stream, Stirred at reflux temperature for 8 hours. After completion of the reaction, the reaction solution was poured into 500 mL of water, and the resulting precipitate was filtered and washed with water. After drying under reduced pressure,
Recrystallization from chloroform / methanol yielded 1,3-bismaleimido-5- (perfluorononenyloxy) benzene, which was the desired product, at a yield of 89%.

The melting point, spectrum data and elemental analysis value of this compound are as follows. (1) Melting point 173-176 ° C (2) ¹ H-NMR spectrum (solvent acetone-d ₆ , T
MS Standard); 7.57ppm (1H, Aromatic, t) 7.30ppm (2H, Aromatic, d) 7.08ppm (4H, olefinic, s) (3) 19 F-NMR spectrum (solvent acetone -d _6,
Trifluorotoluene _{standard); 11.03ppm (3F, CF 3} , d) -3.68ppm (6F, CF 3, s) -4.98ppm (6F, CF 3, d) -99.71ppm (1F, CF, quart.) -101.67 ppm (1F, CF, quint.) (4) IR spectrum; 3112 cm ^-1 (C = CH), 1726 cm ^-1 (C = O),
1242 cm ^-1 (CF) (5) Elemental analysis value (%);

[Table 3]

From the above, the production of the desired product was confirmed. The structural formula of this compound is as shown in Chemical formula 45.

Embedded image

Synthesis Example 5 (Synthesis of thermosetting prepolymer) In a flask equipped with a stirrer and a reflux condenser, 1,3-bismaleimide-5- (perfluorononenyloxy) benzene of the formula (45) was prepared. , A bismaleimide compound A) and 1 mol of 4,4'-diaminodiphenylmethane, and dimethylformamide in an amount such that the resin concentration becomes 30% by weight was added and dissolved to obtain a thermosetting resin composition. I got This composition was heated and reacted at 130 ° C. for 1 hour, poured into water, and the resulting precipitate was filtered, washed with water, and dried under reduced pressure to obtain a thermosetting prepolymer (glass transition temperature: 310 ° C.).

Example 1 100 parts by weight of bisphenol A type epoxy resin (Epicoat 1001, epoxy equivalent 450) 25 parts by weight of 4,4'-diaminodiphenylmethane 0.3 parts by weight of benzyldimethylamine and 20 parts by weight of bismaleimide compound A were methyl ethyl ketone 90% by weight and 10% by weight of N, N-dimethylformamide in a mixed solvent.
0% varnish, impregnated with glass cloth, 150
It dried at ℃ for 5 minutes to obtain a prepreg. Five prepregs were stacked and pressed at a temperature of 180 ° C. and a pressure of 50 kg / cm ² for 60 minutes to produce a laminated board containing a glass cloth.

Example 2 Bisphenol A type epoxy resin (Epicoat 5045 epoxy equivalent 530) 80 parts by weight Cresol novolac type epoxy resin (EOCN102S, epoxy equivalent 200) 20 parts by weight Dicyandiamide 3 parts by weight 2-ethyl-4-methylimidazole 0.2 parts by weight And 50 parts by weight of the bismaleimide compound A are dissolved in a mixed solvent of 90% by weight of methyl ethyl ketone and 10% by weight of N, N-dimethylformamide, and
0% varnish, impregnated with glass cloth, 150
It dried at ℃ for 5 minutes to obtain a prepreg. Five prepregs were stacked and pressed at a temperature of 180 ° C. and a pressure of 50 kg / cm ² for 60 minutes to produce a laminated board containing a glass cloth.

Example 3 100 parts by weight of cresol novolak type epoxy resin (EOCN102S, epoxy equivalent: 200) 30 parts by weight of phenol novolak resin [H-100, trade name of Meiwa Kasei Co., Ltd., hydroxyl value 108] 2-undecylimidazole 4 parts by weight and 10 parts by weight of the bismaleimide compound A are kneaded in powder form, and then molded using a transfer molding machine at a temperature of 170 ° C. and a pressure of 30 kg / cm ² , and then post-cured at 200 ° C. for 1 hour. Was done.

Example 4 Bisphenol A type epoxy resin (Epicoat 1001, epoxy equivalent 450) 100 parts by weight Methyltetrahydrophthalic anhydride 80 parts by weight 1-cyanoethyl-2-phenylimidazole 0.5 parts by weight and bismaleimide compound A 5 parts by weight as a solvent And heated at 120 ° C. for 24 hours in a casting mold to mold.

Example 5 100 parts by weight of a brominated bisphenol A type epoxy resin (epoxy equivalent: 530, bromine content: 18% by weight) 80 parts by weight of phenol novolak resin [H-100, trade name of Meiwa Kasei Co., Ltd., hydroxyl value 108] 0.3 parts by weight of 1-cyanoethyl-2-undecylimidazole and 70 parts by weight of the thermosetting prepolymer synthesized above were dissolved in a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether to prepare a varnish having a nonvolatile content of 65%. This was impregnated in a glass cloth and dried at 150 ° C. for 10 minutes to obtain a prepreg. Five prepregs obtained in this manner are stacked at a temperature of 180 ° C. and 30 kg / c.
The laminate was pressed at a pressure of m ² for 90 minutes to produce a laminated board containing a glass cloth.

Comparative Example 1 The procedure was as in Example 1, except that the bismaleimide compound A was not used.

Comparative Example 2 The same procedure as in Example 3 was carried out except that bismaleimide compound A was not used.

The molded articles of the epoxy resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were measured for water absorption and glass transition temperature. Table 4 shows the results.

[Table 4] Characteristics evaluation method Water absorption: 121 ° C. by pressure cooker, 2.
The treatment was performed at 2 atm for 3 hours, and the weight was calculated from the change in weight before and after the treatment. Glass transition temperature: Measured at a heating rate of 10 ° C./min using a DSC-7 model manufactured by PerkinElmer.

[0097]

The epoxy resin composition according to the first aspect and the cured prepreg according to the second aspect have excellent heat resistance and low water absorption.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-290847 (JP, A) JP-A-1-304105 (JP, A) JP-B-63-37786 (JP, B2) (58) Field (Int.Cl. ⁷ , DB name) C08L 63/00-63/10 C08L 79/08 C08G 59/40 C08J 5/24

Claims (2)

(57) [Claims] 1. An epoxy resin, and [However, during reduction 1 Rf is, -C _n F _2n-1 (where n is 6 to
12 indicating an integer of 12), which contains one double bond; May be branched, hydrogen of the benzene ring, the carbon
An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms,
Fluorine may be substituted by chlorine or bromine, the two imide groups, respectively ortho to the ether links in the aromatic ring, is bonded to the meta or para position, D is -
CH = CH -, - CH = C (CH 3) -, - C (= C
H ₂ ) —CH—, —CCl ＝ CCl— and And an epoxy resin composition containing a thermosetting prepolymer obtained by reacting a fluorine-containing imide compound represented by the formula (1) with a polyamine compound. 2. A prepreg obtained by impregnating and drying a substrate with the epoxy resin composition according to claim 1.