JPH04239519A - Epoxy resin composition and prepreg - Google Patents

Abstract

PURPOSE:To obtain the subject resin composition, containing a thermosetting prepolymer prepared by reacting an epoxy resin with a fluorine-containing imide compound or further with a polyamine compound, having heat resistance and low water absorptivity and useful as prepregs for electrical insulating materials, etc. CONSTITUTION:The objective epoxy resin composition is obtained by blending a thermosetting prepolymer prepared by reacting an epoxy resin with a fluorine- containing imide compound [e.g. 1,3-bismaleimido-5-(perfluorononenyloxy)benzene] expressed by the formula [Rf represents CnF2n-1 ((n) is an integer of 6-12) which contains one double bond and may suitably be branched; hydrogens in the aromatic ring may suitably be substituted with substituent groups; two imide groups are respectively bonded to the o-, m- or p-position with respect to the ether bond of the aromatic ring; (D) represents dicarboxylic acid residue having ethylenically unsaturated double bond] or further reacting the resultant product with a polyamine compound (e.g. diethylenetriamine) with other components.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to epoxy resin compositions and prepregs.

0002

[Prior Art] Compositions containing epoxy resins and bismaleimide or their prepolymers have excellent heat resistance, electrical properties, mechanical properties, chemical resistance, and adhesive properties, and are therefore used in the field of electrical insulation and electronic materials. It is used in many fields such as civil engineering, adhesives, and paints. Among them, it is widely used as an electrical insulating material because of its excellent electrical properties. In recent years, in these fields, there has been a need for materials that have a variety of high performance and high functionality. 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 higher performance has not been obtained so far. In order to obtain a resin that satisfies these requirements,
As substituents in the molecular structure that exhibit these performances,
It is considered effective to introduce substituents containing many fluorine atoms.

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

[Case 2]

[Chemical formula 3]

[C4]

[0004] Furthermore, Japanese Patent Publication No. 37786/1986 discloses a compound of formula 5 as a fluorine-containing imide compound, and describes that a composition containing this and an epoxy resin is an excellent heat-resistant material.

[C5]

[0005]

Problems to be Solved by the Invention Both the fluorine-containing epoxy resin described above and the imide compound described in Japanese Patent Publication No. 63-37786 have a low fluorine content, making it difficult to achieve the required performance described above. Therefore, in order to solve these problems, the present inventors developed a new fluorine-containing imide compound or a prepolymer thereof, in which a perfluoroalkenyloxy group is introduced into the molecular structure as a substituent having many fluorine atoms. The present invention provides an epoxy resin composition containing the same, and a prepreg obtained using the same.

[0006]

[Means for Solving the Problems] The epoxy resin resin composition of the present invention comprises an epoxy resin and chemical compound 6

[Chemical formula 6] [However, Rf in Chemical formula 6 is -CnF2n-1 (here n
represents an integer of 6 to 12), which contains one double bond and may be branched as appropriate, and the hydrogen of the aromatic ring is
It may be appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, bromine, etc., and the two imide groups are attached to the aromatic ring at an ortho position, a meta position, or a meta position relative to the ether bond. bonded to the para position, and D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond] or a thermosetting preform obtained by reacting this with a polyamine compound. It contains a polymer.

[0007] As the above-mentioned epoxy resin, one having at least two epoxy groups in one molecule is used. The epoxy resin used in the present invention may be any resin as long as it contains at least two epoxy groups in one molecule, and bisphenol A type epoxy resin [
For example, Epicote 828, Epicote 827, Epicote 834, Epicote 1001, Epicote 1004
, Epicoat 1009 (all these are trade names of Yuka Shell Co., Ltd.)], bisphenol F type epoxy resin [
For example, Epicote 807 (product name of Yuka Shell Co., Ltd.)
], bisphenol S type epoxy resin, phenol novolac type epoxy resin [e.g., Epicoat 152, Epicoat 154 (all manufactured by Yuka Shell Co., Ltd.)
(product name), EOCN-201 (Nippon Kayaku Co., Ltd. product name)
], cresol novolac type epoxy resin [for example, E
OCN102S, EOCN103S, EOCN104S
(These are all trade names of Nippon Kayaku Co., Ltd.)], bisphenol A novolak type epoxy resin [for example, N-
880, N-865 (these are all trade names of Dainippon Ink Industries, Ltd.)], bisphenol F novolac type epoxy resin, alicyclic epoxy resin [for example, CY17
5. CY177 (these are all Ciba Geigy brand names)], glycidyl ester type epoxy resins [for example, CY182, CY192 (all these are Ciba Geigy brand names), Epicote 871, Epicote 872 (these are are all product names of Yuka Shell Co., Ltd.)
], glycidylamine type epoxy resin [for example, MY7
20 (trade name of Ciba Geigy)], hydantoin type epoxy resins [e.g. CY350 (trade name of Ciba Geigy)], isocyanurate type epoxy resins [e.g.
PT810 (trade name of Ciba Geigy Co., Ltd.)], aliphatic chain epoxy resins [for example, Adekal Resin ED506 (trade name of Asahi Denka Kogyo Co., Ltd.), Epicron 707 (trade name of Dainippon Ink Industries Co., Ltd.)], etc. These may be halogenated or hydrogenated, or two or more types may be used in combination.

[0008] The epoxy resin composition of the present invention preferably contains an epoxy resin curing agent. As the curing agent, any curing agent that is generally used as a curing agent for epoxy resins may be used, for example,
“New Epoxy Resin” written by Hiroki Kakiuchi (Shokodo, 1985) 1
Polyamine compounds, acid anhydrides, polyamide resins, imidazoles, polyphenol compounds, phenolic resins, polyvinylphenols, amino resins, boron trifluoride amine complexes, dicyandiamide or Its derivatives, organic acid dihydrazide, diaminomaleonitrile and its derivatives, melamine and its derivatives, polymercaptans, polysulfide resins, aromatic diazonium salts, diallyliodonium salts, triallylsulfonium salts, triallylselenium salts, etc. Ultraviolet curing agents can also be used.

Examples of polyamine compounds include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine (dipropylenetriamine), bis(hexamethylene)triamine,
1, 3, 6 trisaminomethylhexane, trimethylhexamethylenediamine, diethylene glycol bispropyldiamine, diethylaminopropylamine, menthenediamine, isophoronediamine, bis(4-amino-3-methylcyclohexyl)methane, N-aminoethylpiperazine, meta-xylylene diamine, tetrachloro p-xylylene diamine, 2,4 (p-β-amino-t-butylphenyl) ether, p-bis-2-(2
-methyl-4-aminopentyl)benzene, p-bis(
1,1-dimethyl-5-aminopentyl)benzene, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 2,11-diaminododecane, 1,12
-diaminoctadecane, 2,2-dimethylpropylenediamine, 2,5-dimethylhexamethylenediamine,
3-Methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methynonamethylenediamine, 1,4
- Aliphatic amines such as diaminocyclohexane, bis(p-aminocyclohexyl)methane, 3-methoxyhexamethylenediamine, 1,2-bis-(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide, 4- Aminophenyl-3-aminobenzoic acid, 2,
2-bis(4-aminophenyl)propane, 2,6-diaminopyridine, bis(4-aminophenyl)diethylsilane, bi(4-aminophenyl)diphenylsilane,
Bis-(4-aminophenyl)ethylphosphine oxide, 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'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylpropane, 3,3
'-Diaminodiphenyl sulfide, 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'-diaminodiphenyl ether, 3
, 3'-diisopropyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-4,4'-diaminodiphenyl ether, 3,3'-diethoxy-4,4
'-Diamino diphenyl 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'-diaminodiphenyl sulfone, 3,3'-
dimethoxy-4,4'-diaminodiphenyl sulfone,
3,3'-diethoxy-4,4'-diaminodiphenylsulfone, 3,3'-difluoro-4,4'-diaminodiphenylsulfone, 3,3'-dichloro-4,4'-
Diaminodiphenylsulfone, 3,3'-dibromo-4
, 4'-diaminodiphenyl sulfone, 3,3'-di(
trifluoromethyl)-4,4'-diaminodiphenyl sulfone, 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, 3,3'-dibromo-4,4'-diaminodiphenylpropane, 3,3'-di(trifluoromethyl)-
4,4'-diaminodiphenylpropane, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 3
, 3'-dimethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-difluoro-4,4
'-Diaminodiphenyl sulfide 3,3'-dichloro-4,4'-diaminodiphenyl sulfide, 3,3'
-dibromo-4,4'-diaminodiphenyl sulfide, 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'
-diaminodiphenylhexafluoropropane, 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, 3,3'-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'-diaminodiphenyl ether, 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'-diaminodiphenyl sulfone, 3,3',5
, 5'-tetraethoxy-4,4'-diaminodiphenylsulfone, 3,3',5,5'-tetrafluoro-4
, 4'-diaminodiphenyl sulfone, 3,3',5,
5'-tetrachloro-4,4'-diaminodiphenylsulfone, 3,3',5,5'-tetrabromo-4,4'
-diaminodiphenylsulfone, 3,3',5,5'-
Tetra(trifluoromethyl)-4,4'-diaminodiphenyl sulfone, 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'-diaminodiphenyl sulfide, 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'-diaminodiphenyl sulfide, 3,3
',5,5'-tetra(trifluoromethyl)-4,4
'-Diaminodiphenyl sulfide, 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,3,3',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, 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-(perfluorohexenyloxy)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-(perfluorohexenyl) oxy)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- 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
- Aromatic amines such as diaminonaphthalene, 3,3'-diamino-4-anilinobenzophenone, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro(5,5) Diamine having a spiro ring such as undecane, chemical formula 7

[Chemical formula 7] [However, in Chemical formula 7, R0 is an alkylidene group containing a methylene group, and n represents a number of 0.1 or more on average]. Two or more of these may be used in combination. The above polyamine compound has 3 to 8 carbon atoms such as adipic acid.
It may be used as a salt such as a nylon salt with an aliphatic dicarboxylic acid, a salt with polyhydroxyphenol, a salt with phenylphosphonic acid, a salt with phenylphosphoric acid, etc.

[0010] The acid anhydrides include phthalic anhydride,
Trimellitic anhydride pyromellitic anhydride, 2,2bis(2,3-dicarboxyphenyl)hexafluoropropane dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 1 , 2,5,6,-naphthalenetetracarboxylic dianhydride, 2,3,6,7,-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride substance, 2,2-bis(3
,4,-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis(3, 4-dicarboxyphenyl)ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,6- Dichlornaphthalene-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, 1,1-bis(3,4-dicarboxyphenyl) carboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride enyl) 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'-benzophenonetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetra Carboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, ethylenetetracarboxylic 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)-en-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)dimethylsilane 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-dicarboxyphenyl)-1,1,3,3-tetramethyldicycloxane dianhydride p-phenyl bis (trimellitic acid monoester anhydride), ethylene glycol bis (trimellitic anhydride), propanediol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), pentanediol bis (trimellitic anhydride) acid 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(trimellitic anhydride), 1,3-bis(
Aromatic acid anhydrides such as 2-hydroxyhexafluoroisopropyl)benzenebis(trimellitic anhydride), maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, alkenyl succinic anhydride,
There are aliphatic acid anhydrides or cyclic aliphatic acid anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenecarboxylic acid, chlorendic acid, and tetrabromophthalic anhydride, and two or more types are used in combination. It's okay.

[0011] As the polyamide, there is one obtained by a condensation reaction of the dimer acid shown in Chemical formula 8 and a polyamine such as diethylenetriamine or triethylenetetramine.

[Chemical formula 8]

Examples of the imidazoles include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2- Heptadecylimidazole, 4,5-diphenylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-
Methylimidazole, 2-methylimidazoline, 2-ethylimidazoline, 2-isopropylimidazoline, 2
-Heptadecylimidazoline, 2-phenylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4
-Methyl imidazoline, etc. Furthermore, imidazole imino groups masked with acrylonitrile, phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, methylene bisphenyl isocyanate, and melamine acrylate can also be used.

[0013] Examples of the polyhydric phenol compounds include bisphenol A, bisphenol F, and resorcinol.

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

Examples of the amino resin include aniline or aniline derivatives, and addition condensates of formaldehyde and amino compounds such as melamine, benzoguanamine, and acetoguanamine.

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

The dicyandiamide and its derivatives include dicyandiamide, o-tolyl biguanide, 2
, 5-dimethylbiguanide, diphenylbiguanide, 5
-Hydroxynaphthyl-1-biguanide, α,α'-bisguanylguanidinodiphenyl ether, phenylbiguanide, p-chlorophenylbiguanide, α-benzylbiguanide, α,ω-dimethylbiguanide, α,α'
-Hexamethylenebis(ω-(p-chlorophenyl))
Examples include biguanides and their zinc salts, iron salts, copper salts, hydrochlorides, nickel salts, and the like.

The organic acid dihydrazide can be easily synthesized from a carboxylic acid ester and hydrazine, and includes, for example, succinic acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide, salicylic acid dihydrazide, and phenylaminopropionic acid dihydrazide.

As the diaminomaleonitrile or its derivative, there is one represented by the following formula.

[Chemical 9] However, in Chemical 9, R is -NH2, -N=CHCH2C
H3, -N=CHCH2(CH3)2, -N=CHCH
2(CH3)2, -NHCHCH2(CH3)2, -
It represents N=C(CH3)COOCH3, -N=CH-Ph or -N=CHCH2-Ph (here, Ph represents a phenyl group).

[0020] As the melamine and its derivatives, diallylmelamine can be used in addition to melamine.

Examples of the polymercaptans include reaction products of epoxy resin and hydrogen sulfide, polyhydric alcohol esters of mercaptopropionic acid and mercaptogluconic acid, and examples of reaction products of epoxy resin and hydrogen sulfide include:
For example, there is one shown in chemical formula 10.

embedded image In Chemical Formula 10, n represents an integer of 1 to 7. Examples of polyhydric alcohol esters of mercaptopropionic acid and mercaptogluconic acid include trimethylolpropane trimercaptopropionic acid ester, trimethylolpropane trithiogluconate, pentaerythritol tetramercaptopropionic acid ester, and pentaerythritol tetrathiogluconate ester. , trimethylolethane trimercaptopropionic acid ester, etc.

[0022] As the polysulfide resin, chemical formula 11
There is something expressed as

[Chemical formula 11] HS-(C2H4OCH2O-C2H4-S
-S) n-C2H4O-C2H4-SH However, chemical formula 11
In the formula, n represents an integer of 1 to 10.

[0023] As the aromatic diazonium salt, chemical formula 1
There is something represented by 2.

[Chemical Formula 12] However, in Chemical Formula 12, R and R' are each independently chlorine,
It represents fluorine, iodine, bromine, an alkyl group, an alkoxy group, or a nitro group, and M is boron, phosphorus, arsenic, tin, iron,
It represents a metal atom such as antimony, X represents chlorine, fluorine, iodine or bromine, and n represents an integer of 2 to 8. 12, M
Examples of Xn include BF4, PF6, AsF6, and SbF6. Examples of the aromatic diazonium salts include chemical formula 1
3, Chemical No. 14, Chemical No. 15, Chemical No. 16, Chemical No. 17, etc.

[Chemical formula 13]

[Chemical formula 14]

[Chemical formula 15]

[Chemical formula 16]

[Chemical formula 17]

[0024] As the diaryliodonium salt,
There is one represented by chemical formula 18.

[Chemical Formula 18] However, in Chemical Formula 18, R, R', M, X and n, and MX
n is the same as chemical formula 12. Examples of the above-mentioned diaryliodonium salts include Compound 19, Compound 20, Compound 21, and the like.

[Chemical formula 19]

[C20]

[C21]

[0025] As the triallylsulfonium salt,
There is something expressed by chemical formula 22.

embedded image In Chemical Formula 22, R, M, X, n, and MXn are the same as in Chemical Formula 12. Examples of the above triallylsulfonium salts include Chemical Formula 23, Chemical Formula 24, Chemical Formula 25, and the like.

[C23]

[C24]

[C25]

[0026] As the above-mentioned triallylselenium salt, there is one represented by the following formula.

[Chemical Formula 26] However, in Chemical Formula 26, R, R', M, X and n, and MX
n is the same as chemical formula 12. Examples of the above-mentioned triallylselenium salts include Compound 27, Compound 28, Compound 29, and the like.

[C27]

[C28]

[C29]

As the compound represented by the above formula 6, 1
, 3-bismaleimido-5-(perfluorononenyloxy)benzene, 1,3-bismaleimido-4-methyl-5-(perfluorononenyloxy)benzene, 1,
3-bismaleimido-4-methoxy-5-(perfluorononenyloxy)benzene, 1,3-bismaleimido-2,4,6-trifluoro-5-(perfluorononenyloxy)benzene, 1,3 -Bismaleimide-4-
Chloro-5-(perfluorononenyloxy)benzene, 1,3-bismaleimido-4-bromo-5-(perfluorononenyloxy)benzene, 1,2-bismaleimido-4-(perfluorononenyloxy) )benzene,
1,2-bismaleimido-4-methyl-5-(perfluorononenyloxy)benzene, 1,2-bismaleimido-4-methoxy-5-(perfluorononenyloxy)benzene, 1,2-bismaleimide -3,4,6-trifluoro-5-(perfluorononenyloxy)benzene, 1,2-bismaleimido-4-chloro-5-(perfluorononenyloxy)benzene, 1,2-bismaleimide- 4-bromo-5-(perfluorononenyloxy)benzene, 1,4-bismaleimido-3-(perfluorononenyloxy)benzene, 1,4-bismaleimido-2-methyl-5-(perfluoronone 1,4-bismaleimido-2-methoxy-5-(perfluorononenyloxy)benzene, 1,
4-bismaleimide-2,3,6-trifluoro-5-
(perfluorononenyloxy)benzene, 1,4-bismaleimido-2-chloro-5-(perfluorononenyloxy)benzene, 1,4-bismaleimido-2-bromo-5-(perfluorononenyloxy) )benzene,
1,3-bismaleimido-5-(perfluorohexenyloxy)benzene, 1,3-bismaleimido-4-methyl-5-(perfluorohexenyloxy)benzene, 1,3-bismaleimido-4-methoxy-5 -(perfluorohexenyloxy)benzene, 1,3-bismaleimido-2,4,6-trifluoro-5-(perfluorohexenyloxy)benzene, 1,3-bismaleimido-4-chloro-5-(perfluorohexenyloxy)benzene fluorohexenyloxy)benzene, 1,3-bismaleimido-4-bromo-
5-(perfluorohexenyloxy)benzene, 1,
2-bismaleimido-4-(perfluorohexenyloxy)benzene, 1,2-bismaleimido-4-methyl-5-(perfluorohexenyloxy)benzene, 1
, 2-bismaleimido-4-methoxy-5-(perfluorohexenyloxy)benzene, 1,2-bismaleimido-3,4,6-trifluoro-5-(perfluorohexenyloxy)benzene, 1,2- Bismaleimide-4-chloro-5-(perfluorohexenyloxy)
Benzene, 1,2-bismaleimido-4-bromo-5-
(perfluorohexenyloxy)benzene, 1,4-
Bismaleimido-3-(perfluorohexenyloxy)benzene, 1,4-bismaleimide-2-methyl-5
-(perfluorohexenyloxy)benzene, 1,4
-Bismaleimide-2-methoxy-5-(perfluorohexenyloxy)benzene, 1,4-bismaleimide-2,3,6-ylifluoro-5-(perfluorohexenyloxy)benzene, 1,4-bismaleimide- 2
-Chloro-5-(perfluorohexenyloxy)benzene, 1,4-bismaleimido-2-bromo-5-(perfluorohexenyloxy)benzene, 1,3-bis(dichloromaleimide)-5-(perfluoro nonenyloxy)benzene, 1,2-bis(dichloromaleimido)-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(citraconimido)-3-(perfluorononenyloxy)benzene, 1,3-bis(itaconimide)-5-(
Perfluorononenyloxy)benzene, 1,2-bis(itaconimido)-4-(perfluorononenyloxy)benzene, 1,4-bis(itaconimide)-3-
(Perfluorononenyloxy)benzene, 1,3-bis(endomethylenetetrahydrophthalimide)-5-
(Perfluorononenyloxy)benzene, 1,2-bis(endomethylenetetrahydrophthalimide)-4-
(Perfluorononenyloxy)benzene, 1,4-bis(endomethylenetetrahydrophthalimide)-3-
(Perfluorononenyloxy)benzene, etc.

[0028] The perfluorononenyl group is -C9
It is F17 group, and perfluorohexenyl group is -C6
It is an F11 group, and the same applies to the following. In the compounds exemplified above, -C10F19 group, -C1 instead of perfluorononenyl group or perfluorohexenyl group
Compounds having 2F23 groups and the like can be similarly exemplified.

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

[Chemical Formula 30] However, in Chemical Formula 30, Rf is the same as in Chemical Formula 6, and the hydrogen of the aromatic ring is a lower alkyl group, a lower alkoxy group, a fluorine,
May be appropriately substituted with substituents such as chlorine and bromine,
The two amic acid groups are each bonded to the aromatic ring at the ortho position, meta position, or para position relative to the ether bond, and D
represents a dicarboxylic acid residue having an ethylenically unsaturated double bond. Examples of the fluorine-containing bisamidic acid compound represented by Chemical Formula 30 include those exemplified as the compound represented by Chemical Formula 6 above, with "imide" replaced with "amic acid".

Methods for cyclization and dehydration of the fluorine-containing bisamidic acid compound represented by the above formula 30 include a method using an acid anhydride such as acetic anhydride, a condensing agent such as dicyclohexylcarbodiimide, and a method using a condensing agent such as p-toluenesulfonic acid or acetic acid. There is a method of heating and dehydrating in the presence of For example, US Patent No. 3018290, US Patent No. 301829
Known methods described in Specification No. 2, US Pat. No. 3,127,414, etc. 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 used is usually 1 to 2 moles based on the amic acid group. The catalysts used are alkaline earth metal oxides,
Iron (II, III), Copper (I, II), Nickel (II
), manganese (II, III), cobalt (II, II)
I) carbonates, sulfates, acetates, phosphates, etc. Specifically, there are nickel (II) acetate, cobalt (II) acetate, magnesium oxide, etc., and they are usually used in an amount of 0.01 to 0.5 mol based on the amic acid group. The base used is an alkali metal acetate or a tertiary amine. Specifically, there are sodium acetate, triethylamine, etc., and it is usually 0.01% based on the amic acid group.
~2.0 mol is used. Reaction conditions vary depending on the reagent and are not particularly limited. The intermediate amic acid produced in the first step does not necessarily need to be isolated, and can be directly subjected to the second step cyclization and dehydration reaction.

The fluorine-containing bisamidic acid compound represented by the above formula 30 can be produced by reacting the fluorine-containing aromatic diamine represented by the following formula 31 with the unsaturated dicarboxylic acid represented by the following formula 32.

[Chemical Formula 31] However, in Chemical Formula 31, Rf is the same as in Chemical Formula 6, and the hydrogen of the aromatic ring is appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, or bromine. Preferably, the two amino groups are each bonded to the aromatic ring at the ortho, meta, or para position relative to the ether bond.

embedded image In Chemical Formula 32, D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond.

Compounds represented by formula 31 include 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-(perfluorohexenyloxy)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 and the like.

Among the compounds exemplified above, compounds having a group -C10F19, a group -C12F23, etc. instead of a perfluorononenyl group or a perfluorohexenyl group can also be exemplified.

Examples of the unsaturated dicarboxylic anhydride represented by the formula 32 include maleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, pyrosiconic anhydride, etc., or a Diels compound of these compounds and cyclodiene.・Alder (Diels-Alder)
) at least one adduct is used.

As for the method of reacting the fluorine-containing aromatic diamine represented by the above chemical formula 31 with the unsaturated dicarboxylic acid anhydride represented by the above chemical formula 32, any known method can be applied, but an advantageous method is There is a method in which a fluorine-containing aromatic diamine represented by 31 and an unsaturated dicarboxylic acid anhydride represented by Chemical Formula 32 are brought into contact with each other in an organic solvent that is a solvent for both. Usually, commonly used solvents 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,
Examples include aprotic polar solvents such as dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.

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

[Chemical Formula 33] However, in Chemical Formula 33, Rf is the same as in Chemical Formula 6, R1 and R2 each independently represent an optionally substituted alkyl group or an optionally substituted aryl group, and Hydrogen may be appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, bromine, etc., and the two urethane groups are attached to the aromatic ring at ortho and meta positions relative to the ether bond, respectively. or attached to the para position.

Here, the urethane type protecting group specifically means -COOR1 and -COOR2 in Chemical Formula 33.

The above deprotection reaction can be carried out, for example, by the following method. Hydrogen gas is added to a solution of the fluorine-containing aromatic diurethane compound dissolved in an organic solvent such as ethyl acetate, dimethylformamide, dimethylacetamide, benzene, xylene, acetone, or tetrahydrofuran at 0 to 100°C in the presence of a catalyst such as palladium on carbon. Particularly preferably near room temperature) (the time for passing hydrogen gas may be determined as appropriate, but usually 1 to 10 hours is sufficient)
, the fluorine-containing aromatic diurethane compound is dissolved in the above-mentioned organic solvent, and HF, HBr, HCl, H2SO
A method of adding and reacting a hydrogen acid such as No.
In particular, it is preferable to carry out the reaction at 0°C or lower, and for other hydrogen acids, it is preferable to carry out the reaction at 0 to 100°C, particularly around room temperature. Furthermore, the reaction time is determined appropriately, but usually
When using HF, 0.1 to 1 hour is sufficient; when using other hydrogen acids, 1 to 10 hours is sufficient). , a method of reacting in the presence of a basic compound such as potassium hydroxide and water (it is preferable to use at least an equivalent amount of water to the fluorine-containing aromatic diurethane compound, and the reaction is carried out using an organic solvent such as the one described above). , water, alcohol such as methanol or ethanol, or cresol as a solvent). The aromatic diamine compound represented by Chemical Formula 8 thus obtained can be purified by recrystallization from alcohol or the like.

Examples of the fluorine-containing aromatic diurethane compound represented by formula 33 include 1,3-bis(N-(methyloxycarbonyl)amino)-5-(perfluorononenyloxy)benzene, 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-(perfluorononenyloxy)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-(perfluorononenyloxy)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-(perfluoronone Nyloxy)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 -butyloxycarbonyl)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)benzene, 1,4-bis(N-(methyloxycarbonyl)amino)-3-( Perfluorononenyloxy)benzene, 1,4-bis(N-(ethyloxycarbonyl)amino)-3-(perfluorononenyloxy)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)-3-(perfluorononenyloxy)benzene, 1,4-bis(N-(i-butyloxycarbonyl)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, Fluorononenyloxy)benzene, 1,4-bis(N-(octyloxycarbonyl)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-(methyloxy) carbonyl)amino)-5-(perfluorohexenyloxy)benzene, 1,3-bis(N-(ethyloxycarbonyl)amino)-5-(perfluorohexenyloxy)benzene, 1,3-bis(N-( propyloxycarbonyl)-5-(perfluorohexenyloxy)benzene, 1,3-bis(N-(i-propyloxycarbonyl)amino)-5-(perfluorohexenyloxy)benzene, 1,3-bis (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-(perfluorohexenyloxy)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 Fluorohexenyloxy)benzene, 1,2-bis(N-(hexyloxycarbonyl)amino)-4-(perfluorohexenyloxy)benzene, 1,2-bis(N-(heptyloxycarbonyl)amino)-4- (Perfluorohexenyloxy)benzene, 1,2-bis(N-(octyloxycarbonyl)amino)-4-(perfluorohexenyloxy)benzene, 1,2-bis(N-(benzyloxycarbonyl)amino)- 4-(perfluorohexenyloxy)henzene, 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-(propyloxy) carbonyl)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
-(perfluorohexenyloxy)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,
Examples include 1,4-bis(N-(phenyloxycarbonyl)amino)-3-(perfluorohexenyloxy)benzene. Among the compounds exemplified above, compounds having -C10F19 groups, -C12F23 groups, etc. instead of perfluorononenyl groups or perfluorohexenyl groups can also be exemplified.

The aromatic diurethane compound represented by the above formula 33 can be prepared by adding 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 a solvent. It can be produced by reacting in the presence of a base.

[Chemical Formula 34] However, in Chemical Formula 34, Rf is the same as in Chemical Formula 6, and the hydrogen of the aromatic ring is appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, or bromine. The two carboxyl groups may each be bonded to the aromatic ring at the ortho, meta or para position relative to the ether bond.

embedded image In Chemical Formula 35, R3 represents a lower alkyl group or an aryl group.

embedded image R4OH However, in Chemical Formula 36, R4 represents an alkyl group which may have a substituent or an aryl group which may have a substituent.

Examples of the dicarboxylic acid compound represented by 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)isophthalic acid, fluorononenyloxy)phthalic acid, 4-methoxy-5-(perfluorononenyloxy)phthalic acid, 3,4,6-trifluoro-5-(perfluorononenyloxy)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-(perfluorononenyloxy)terephthalic acid, 2-chloro-5-(perfluorononenyloxy)
Terephthalic acid, 2-bromo-5-(perfluorononenyloxy)terephthalic acid, 5-(perfluorohexenyloxy)isophthalic acid, 4-(perfluorohexenyloxy)phthalic acid, 2-(perfluorohexenyloxy)terephthalic acid 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) Examples include terephthalic acid, 2-bromo-5-(perfluorohexenyloxy)terephthalic acid, and the like. Among the compounds exemplified above, compounds having -C10F19 groups, -C12F23 groups, etc. instead of perfluorononenyl groups or perfluorohexenyl groups can also be exemplified.

The above-mentioned perfluorononenyloxyisophthalic acid and perfluorohexenyloxyisophthalic acid can be prepared as hexafluoropropene trimer or 2
It can be produced by reacting the polymer with hydroxyisophthalic acid in an aprotic polar solvent at room temperature or lower in the presence of a base catalyst.

Examples of the perfluorononenyl group include the group shown below.

[C37]

Examples of the perfluorohexenyl group include the following group.

[C38]

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

Further, the dicarboxylic acid represented by the above-mentioned formula 34 can be converted into esters such as diphenyl ester and dibenzyl ester of hydroxy-dicarboxybenzene according to the method described in JP-A-50-121243. After reacting with oligomers of fluoroalkenes such as fluoropropene trimer and tetrafluoroethylene pentamer in the presence of a base catalyst in the presence of a proton acceptor in an aprotic organic solvent at or below room temperature. It 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 further appropriately treating with an acid such as hydrochloric acid. The above reaction product and final product are purified by washing, recrystallization, etc., as appropriate.

The azide compound represented by formula 35 includes diphenylphosphoryl azide, diethylphosphoryl azide, di-p-nitrophenylphosphoryl azide, dimorpholylphosphoryl azide, and the like.

The alcohol represented by formula 36 is as follows:
Methanol, ethanol, propanol, i-propanol, butanol, i-butanol, t-butanol,
Examples include pentanol, hexanol, heptanol, octanol, phenol, and benzyl alcohol.

The synthesis reaction for obtaining the fluorine-containing aromatic diurethane compound represented by Chemical Formula 33 was carried out by Takayuki Shioiri, Shunichi Yamada,
The new Curtius reaction as shown in Journal of the Society of Organic Synthetic Chemistry, Vol. 31, No. 8, pp. 666-674 (1973) can be applied. That is, by reacting a dicarboxylic acid compound represented by Chemical Formula 34, an azide compound represented by Chemical Formula 35, and an alcohol represented by Chemical Formula 36 in the presence of a base, the desired fluorine-containing aromatic diurethane compound can be obtained. As the base, it is preferable to use a tertiary amine such as trimethylamine, triethylamine, or pyridine. The above reaction is carried out in an organic solvent or by using an alcohol represented by the formula 36 as a solvent. As the organic solvent, benzene, toluene, tetrahydrofuran, dioxane, diethyl ether, etc. are preferably used. These solvents are
Two or more types may be used in combination as long as they are compatible with each other.

In the above reaction, in the middle, the dicarboxylic acid compound represented by Chemical Formula 34 and the azide compound represented by Chemical Formula 35 react to form a carboxylic acid azide and the carboxylic acid azide undergo a thermal rearrangement reaction to produce an isocyanate compound. However, the reaction can proceed with or without isolation of these intermediates. The conditions for the above reaction vary depending on the reagent used and are not particularly limited, but the following conditions are preferred.

First, the dicarboxylic acid compound represented by the formula 34, the azide compound represented by the formula 35, the tertiary amine, and the alcohol represented by the formula 36 are reacted at once to obtain the desired compound in what appears to be one step. When obtaining a fluoroaromatic diurethane compound, the reaction temperature is -80 to 250°C.
is preferable, and particularly preferably room temperature to 150°C. The azide compound, the tertiary amine, and the alcohol each have a ratio of 0.5 to 5% relative to the dicarboxylic acid compound.
It is preferable to use 0 molar equivalent, 0.5 to 3.0 molar equivalent, and 0.5 molar equivalent to a large excess.

Second, when the carboxylic azide is to be isolated once, the dicarboxylic acid compound and the azide compound are first reacted in the presence of the tertiary amine, and the resulting carboxylic azide is isolated. do. At this time, the reaction temperature is preferably -80 to 100°C, and the azide compound and the tertiary amine are used in an amount of 0.5 to 5.0 molar equivalent and 0.5 to 3.0 mol, respectively, relative to the dicarboxylic acid compound. Preferably, equivalent amounts are used. Next, the isolated carboxylic acid azide is reacted in 0.5 molar equivalent to a large excess of alcohol to obtain the desired fluorine-containing aromatic diurethane compound. The reaction temperature at this time is preferably -80 to 250°C.

Thirdly, when isocyanate compounds are to be isolated 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, and the resulting isocyanate is isolated. isolate. 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 to the dicarboxylic acid compound, and the reaction temperature is -80 to 250°C. preferable. Next, a fluorine-containing aromatic diurethane compound can be obtained by reacting the obtained isocyanate in 0.5 molar equivalent to a large excess of alcohol. At this time,
The reaction temperature is preferably -80 to 250°C.

[0054] The first to third methods described above are appropriately selected in consideration of yield and the like. The fluorine-containing 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 a fluorine-containing imide compound represented by the above formula 6.

[0056] The above fluorine-containing thermosetting imide resin material is
In addition to the fluorine-containing imide compound represented by the above formula 6, 1
It may contain a compound having at least two thermosetting imide groups in its molecule (hereinafter referred to as "other reactive imide compound"). Other reactive imide compounds include
parabismaleimidobenzene, metabismaleimidobenzene, parabismaleimidotoluene, 1,4-bis(p
-maleimidocumyl)benzene, 1,4-bis(m-maleimidocumyl)benzene, and compounds represented by the following chemical formulas 39, 40, or 41.

[Chemical 39] However, in Chemical 39, X is O, CH2, CF2, SO2,
S, CO or C(CF3)2, R1, R2, R3
and R4 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.

[Chemical 40] However, in Chemical 40, Y is O, CH2, CF2, SO2,
S, CO, C(CH3)2 or C(CF3)2,
R5, R6, R7 and R8 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.

[C41] However, in chemical formula 41, n is a number from 0 to 4.

Examples of the thermosetting imide compound represented by formula 39 include 4,4'-bismaleimido diphenyl ether, 4,4'-bismaleimide diphenyl methane,
4,4'-bismaleimido-3,3'-dimethyl-diphenylmethane, 4,4'-bismaleimidodiphenyl sulfone, 4,4'-bismaleimidodiphenyl sulfide, 4,4'-bismaleimidodiphenyl Ketone, 2,
2-bis(4-maleimidophenyl)propane, 4,4
'-bismaleimidodiphenylfluoromethane, 1,1
,1,3,3,3-hexafluoro-2,2-bis(4
-maleimidophenyl)propane, etc.

Examples of the thermosetting imide compound represented by 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 preferred.

The thermosetting prepolymer can be obtained by reacting a fluorine-containing imide compound represented by Chemical Formula 6 with a polyamine compound. Through this heating reaction, the amino group of the polyamine compound undergoes an addition reaction with the double bond of the fluorine-containing imide compound. The heating conditions in this case are conditions for partial curing, preferably a temperature within the range of 50 to 350°C, particularly preferably a temperature within the range of 80 to 200°C. The heating time is determined as appropriate, taking into account the reaction to a state more suitable for molding.
Preferably it is in the range of 5 to 10 hours. The fluorine-containing imide compound and the polyamine compound are preferably used in a molar ratio of 50:1 to 1:1.5. If the proportion of the polyamine compound used is small, the cured product will not exhibit a reduction in moisture absorption rate or dielectric constant, or an improvement in transparency. On the other hand, if the proportion of the polyamine compound used is too large, it will adversely affect the heat resistance of the cured product. The reaction is carried out by dissolving the fluorine-containing imide compound and the polyamine compound in an organic solvent. After that, the reaction solution is poured into a poor solvent, the precipitated resin is filter-dried, and if necessary, it is further made into pellets or powder. It may be used after being processed into a shape. Examples of organic solvents include halogenated hydrocarbons such as methylene chloride, dichloroethane, and trichloroethylene, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diisopropyl ketone, ethers such as tetrahydrofuran, dioxane, and methyl cellosolve, and aromatic solvents such as benzene, toluene, and chlorobenzene. compounds, aprotic polar solvents such as acetonitrile, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. It is. Examples of poor solvents include water, hexane, and petroleum ether. Alternatively, the fluorine-containing imide compound and the polyamine compound may be mixed in powder form and reacted.

In the synthesis of the above thermosetting prepolymer, other polyimide compounds may be used in addition to the fluorine-containing imide compound as long as the object of the present invention is not impaired. Other polyimide compounds will be described later.

[0062] In the epoxy resin composition of the present invention, the fluorine-containing imide compound or the thermosetting prepolymer
It is desirable to mix 5 to 100 parts by weight of the epoxy resin with respect to 100 parts by weight of the epoxy resin. Moisture resistance when less than 5 parts by weight;
The improvement in heat resistance is small, and if the amount exceeds 100 parts by weight, moldability will deteriorate.

[0063] The epoxy resin composition of the present invention may contain the curing agent as appropriate. When using a curing agent, it is preferably blended in an amount of 0.1 to 100 parts by weight per 100 parts by weight of the epoxy resin. The blending amount is determined depending on the purpose of use and does not necessarily have to be equivalent to the epoxy resin.

Further, a curing accelerator may be used to accelerate the curing reaction, and examples include imidazoles, benzyldimethylaminepyridine, picoline, piperidine, triethanolamine, dimethylaniline, and tetramethylguanidine. The imidazoles mentioned above apply. The amount of this curing accelerator to be blended is also determined appropriately, and may be blended in consideration of storage stability and curability. The blending amount is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the epoxy resin. If it is less than 0.01 part by weight, the accelerated curing of the curing reaction will be small, and if it is more than 5 parts by weight, storage stability will be poor.

[0065] In order to accelerate the curing of the fluorine-containing imide compound or the thermosetting prepolymer, a conventional radical polymerization initiator may be used. As radical polymerization initiators, acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, benzoyl peroxide, octanoyl peroxide, acetyl peroxide, dicumyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, etc. are used. be done. The amount of the radical initiator to be blended is not particularly limited, but it is preferably 0.01 to 1 part by weight per 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 by mixing the constituent substances in powder form, or may be used in the form of a varnish by dissolving it 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, and N-methyl-2-pyrrolidone, and two or more of these may be used in combination.

[0067] The epoxy resin composition of the present invention includes:
Other polyimide compounds may be contained within the range that does not impair the purpose of the present invention. Other polyimide compounds include parabismaleimidobenzene, metabismaleimidobenzene, parabismaleimidotoluene, 1,4-bis(p-maleimidocumyl)benzene, 1,4-bis(
m-maleimidocumyl)benzene, 4,4'-bismaleimido diphenyl ether, 4,4'-bismaleimido diphenylmethane, 4,4'-bismaleimide-3,3
'-dimethyl-diphenylmethane, 4,4'-bismaleimido diphenyl sulfone, 4,4'-bismaleimido diphenyl sulfide, 4,4'-bismaleimido diphenyl ketone, 2,2-bis(4-maleimide) phenyl)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-maleimidophenoxy)phenyl]ketone, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 1,1,1,3,3,3-
Examples include hexafluoro-2,2-bis[4-(4-maleimidophenoxy)phenyl]propane. These other polyimide compounds may be used together with the fluorine-containing imide compound during the synthesis of the thermosetting prepolymer.

The above-mentioned other polyimide compound can be a thermosetting prepolymer similar to the above-mentioned thermosetting prepolymer, and this thermosetting prepolymer can be used in the present invention to the extent that the object of the present invention is not impaired. It can be included in the epoxy resin composition in the invention.

[0069] The epoxy resin composition of the present invention also includes thermoplastic resins (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) fibers, etc.),
It is also possible to blend fillers (clay, mica, silica, graphite, glass beads, alumina, calcium carbonate, etc.) in appropriate amounts depending on the purpose.

The epoxy resin composition of the present invention includes:
Furthermore, one or more conventional additives such as antioxidants, heat stabilizers, ultraviolet absorbers, flame retardant aids, antistatic agents, lubricants, and colorants may be added to the extent that the purpose of the present invention is not impaired. I can do it.

Further, the epoxy resin composition can be impregnated into a base material such as glass cloth, glass fiber cloth such as glass nonwoven cloth, other cloth, paper, etc. and dried to form a prepreg. At this time, the epoxy resin composition used is a varnish-like composition dissolved in an organic solvent, and methods for impregnating the base material with the epoxy resin composition include brushing, spraying, dipping, etc. I can do it. Drying is 8
It is preferable to carry out the process at a temperature of 0 to 200°C, and there are cases in which the solvent is only removed and those which are partially cured. The degree of drying is determined as appropriate, and is adjusted so that the melt viscosity is suitable for final molding. This prepreg can be laminated as appropriate and heated and cured under pressure to form a laminate, with the degree of pressure being 50 to 100 kg/cm2.
degree is preferred. The heating temperature is as follows. This laminate is useful as a substrate for wiring boards.

Generally, the epoxy resin composition may be partially cured without being completely cured to adjust the melt viscosity, and may be used in a so-called B-stage state.

[0073] The epoxy resin composition, its B-stage state, and prepreg are heated from approximately 100°C to 2°C.
It is cured by heating to a temperature in the range of 50°C.

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, etc., and put into practical use.

[0075]

[Examples] Examples of the present invention will be shown below, but the present invention is not particularly limited by the following examples.

Synthesis Example 1 5-(perfluorononenyloxy)isophthalic acid 0.
61g (1.0mmol), diphenylphosphoryl azide 0.66g (2.4mmol), triethylamine 0
．． 24g (2.4mmol) in t-butanol 10mL
The mixture was reacted for 20 hours at reflux temperature. After the reaction is complete, t-
Butanol was distilled off, ether was added thereto, and the mixture was washed with dilute hydrochloric acid and aqueous sodium hydrogen carbonate solution. The ether was distilled off and recrystallized from hexane to obtain the target product, 1,3-bis-N-(t-butyloxycarbonyl)amino)-5.
-Perfluorononenyloxybenzene was obtained in a yield of 86%.

The physical properties and elemental analysis values of this compound are shown below. (1) Melting point 69-71°C (2) 1H-NMR spectrum (solvent acetone-d
6, TMS standard); 8.72 ppm (2H, NH, s)
, 7.61ppm (1H, Aromatic, t), 7
．． 09ppm (2H, Aromatic, s), 1.4
9ppm (9H, t-Bu, t) (3) 19F-N
MR spectrum (solvent acetone-d6, benzotrifluoride standard); 11.32 ppm (3F, CF3, d
), -3.54ppm (6F, CF3,s), -4.8
2ppm (6F, CF3, d), -99.70ppm (
1F, CF, quart. ), -101.49ppm(
1F, CF, quint. ), (4) IR absorption spectrum; 3336 cm-1 (N
-H, urethane), 1710 cm-1 (C=O, urethane), 1548 cm-1 (N-H, urethane), 124
4cm-1 (C-F) (5) Elemental analysis value (%); as shown in Table 1.

[Table 1]

From the above, it was confirmed that the target product was produced. The structural formula of this is shown in Chemical formula 42.

[C42]

Synthesis Example 2 1,3-bis(N-(t-butyloxycarbonyl)amino)-5-(perfluorononenyloxy) of Chemical formula 42
5.3 mL of 3N hydrochloric acid/ethyl acetate was added to 0.200 g (0.265 mmol) of benzene, and the mixture was stirred at room temperature for 4 hours. After adding an aqueous sodium hydroxide solution thereto until it became basic, the oil layer was extracted with ether. The ether was distilled off and column separation was performed using ether/hexane to obtain the target product, 1,3-diamino-5-(perfluorononenyloxy)benzene, 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℃ (2)
1H-NMR spectrum (solvent acetone-d6, TM
S standard); 5.87ppm (1H, Aromatic, t) 5.6
3ppm (2H, Aromatic, t) 4.75pp
m(4H,NH2,s) (3) 19F-NMR spectrum (solvent acetone-d6, benzotrifluoride standard); 11.03p
pm(3F,CF3,d)-3.68ppm(6F,C
F3,s)-4.98ppm(6F,CF4,d)-9
9.71ppm (1F, CF, quart.) -101
．． 67ppm (1F, CF, quint.) (4)
IR absorption spectrum; 3452cm-1, 3380cm
-1,1628 cm-1 (NH, amine), 1298
cm-1, 1238 cm-1, 1190 cm-1 (C-
F) (5) Elemental analysis value (%); as shown in Table 2.

[Table 2]

From the above, it was confirmed that the target compound was produced. The structural formula of this compound is shown below.

[C43]

Synthesis Example 3 0.431 g (4.40 mmol) of maleic anhydride was dissolved in 5 mL of acetone, and while stirring on an ice water bath, 1,3-diamino-5-(perfluoro nonenyloxy)benzene 1.11g (2.0
0 mmol) of acetone solution (5 mL) was added dropwise, and the mixture was stirred for 6 hours. After the reaction is completed, the precipitate formed is filtered,
After washing with acetone, it was dried under reduced pressure to obtain 1,3-bismaleamic acid-5-(perfluorononenyloxy)benzene in a yield of 99%.

The melting point and spectral data of this compound are as follows. (1) Melting point 196-201°C (2) 1H-NMR spectrum (solvent DMSO-d
6, TMS standard); 12.90ppm (2H, COOH, s) 10.61p
pm(2H,CONH,s)7.90ppm(1H,A
romatic, s) 7.22 ppm (2H, Arom
atic, s) 6.38 ppm (4H, olefini
c, q) [The numbers in parentheses indicate the integrated intensity ratio of hydrogen, the group forming the basis of absorption, and the type of peak, s is a singlet,
t indicates triplet, q indicates quartet, and m indicates multiplet. The same applies below. ] (3) 19F-NMR spectrum (solvent DMSO-
d6, benzotrifluoride standard); 12.00 ppm (3F, CF3, d) - 3.04 ppm
m(6F,CF3,s)-4.14ppm(6F,CF
3, d) -99.60 ppm (1F, CF, quart
．． )-101.57ppm (1F, CF, quint.
) [The numbers in parentheses indicate the integrated intensity ratio of fluorine, the group forming the basis of absorption, and the type of peak, where s is a singlet, d is a doublet, quart. is a quartet, quint. indicates a quintet. The same applies below. ] (4) IR spectrum 3304cm-1 (NH, amide)
3124cm-1(OH) 1716cm-1(C=
O, carboxylic acid) 1604 cm-1 (C=O, amide) 1558 cm-1 (NH-R, amide)
1240cm-1 (C-F)

From the above, production of the target product was confirmed. The structural formula of this compound is
It is as follows.

[C44]

Synthesis Example 4 1.35 g (1.80 mm
ol), acetic anhydride 0.816g (8.00mmol),
Triethylamine 0.202g (2.00mmol),
Nickel (II) acetate tetrahydrate 0.050g (0.20
mmol) was stirred in 15 mL of acetone under a nitrogen stream at reflux temperature for 8 hours. After the reaction was completed, 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, it was recrystallized from chloroform/methanol to obtain the target product, 1,3-bismaleimido-5-(perfluorononenyloxy)benzene, in a yield of 89%.

The melting point, spectral data, and elemental analysis values of this compound are as follows. (1) Melting point 173-176°C (2) 1H-NMR spectrum (solvent acetone-d
6, TMS standard); 7.57 ppm (1H, Aromatic, t) 7.3
0ppm (2H, Aromatic, d) 7.08pp
m(4H, olefinic, s) (3) 19F-
NMR spectrum (solvent acetone-d6, trifluorotoluene standard); 11.03 ppm (3F, CF3, d) - 3.68 pp
m(6F,CF3,s)-4.98ppm(6F,CF
3, d) -99.71 ppm (1F, CF, quart
．． )-101.67ppm (1F, CF, quint.
) (4) IR spectrum; 3112 cm-1 (C=CH), 1726 cm-1 (C
=O), 1242 cm-1 (C-F) (5) Elemental analysis value (%); as shown in Table 3.

[Table 3]

From the above, it was confirmed that the target product was produced. The structural formula of this compound is as shown in Chemical Formula 45.

[C45]

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

Example 1 Bisphenol A epoxy resin (Epicote 10
01,
Epoxy equivalent 450)
100 parts by weight 4,4'-diaminodiphenylmethane
25 parts by weight benzyldimethylamine

0.3 parts by weight and bismaleimide compound A

20 parts by weight of 90% by weight of methyl ethyl ketone and N,N
The mixture was dissolved in a mixed solvent containing 10% by weight of -dimethylformamide to obtain a varnish with a non-volatile content of 60%, impregnated into glass cloth, and dried at 150° C. for 5 minutes to obtain a prepreg. Five sheets of this prepreg were stacked at a temperature of 180℃, 50kg/
A glass cloth-containing laminate was produced by pressing at a pressure of cm2 for 60 minutes.

Example 2 Bisphenol A epoxy resin (Epicote 50
45
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 bismaleimide compound A

50 parts by weight of 90% by weight of methyl ethyl ketone and N,N
The mixture was dissolved in a mixed solvent containing 10% by weight of -dimethylformamide to obtain a varnish with a non-volatile content of 60%, impregnated into glass cloth, and dried at 150°C for 5 minutes to obtain a prepreg. Five sheets of this prepreg were stacked at a temperature of 180℃, 50kg/
A glass cloth-containing laminate was produced by pressing at a pressure of cm2 for 60 minutes.

Example 3 Cresol novolac type epoxy resin (EOCN1
02S,
Epoxy equivalent 20
0) 100 parts by weight phenol novolac resin [
H-100, Meiwa Kasei Co., Ltd. product name
Hydroxyl value 10
8] 30 parts by weight 2-undecyl imidazole
0.4
Part by weight and bismaleimide compound A

After kneading 10 parts by weight in powder form, it was molded using a transfer molding machine at a temperature of 170°C and a pressure of 30 kg/cm2, and then post-cured at 200°C for 1 hour.

Example 4 Bisphenol A epoxy resin (Epicote 10
01
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 were mixed without using a solvent, and 1 part by weight was mixed in a casting mold.
It was heated at 20° C. for 24 hours and molded.

Example 5 Brominated bisphenol A type epoxy resin (epoxy equivalent: 530,
Bromine content 18% by weight) 100 parts by weight Phenol novolac resin [H-100, Meiwa Kasei Co., Ltd. trade name,
Hydroxyl value 108] 80 parts by weight 1-cyanoethyl-2-undecyl imidazole 0.3 parts by weight and the thermosetting prepolymer synthesized above
70 parts by weight was dissolved in a mixed solvent of methyl ethyl ketone and ethylene glycol monomethyl ether to obtain a varnish with a non-volatile content of 65%. A glass cloth was impregnated with this and dried at 150°C for 10 minutes to obtain a prepreg. Five prepregs obtained in this way were stacked at a temperature of 180°C and 30kg/c.
A glass cloth-containing laminate was produced by pressing at a pressure of m2 for 90 minutes.

Comparative Example 1 The procedure of Example 1 was followed except that bismaleimide compound A was not blended.

Comparative Example 2 The procedure of Example 3 was followed except that bismaleimide compound A was not blended.

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

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

[0097]

EFFECTS OF THE INVENTION The epoxy resin composition according to claim 1 and the cured prepreg according to claim 2 have excellent heat resistance and low water absorption.

Claims (2)

[Claims] Claim 1: Epoxy resin, and chemical formula 1 [chemical formula 1] [However, Rf in chemical formula 1 is -CnF2n-1 (here n
represents an integer of 6 to 12), which contains one double bond and may be branched as appropriate, and the hydrogen of the aromatic ring is
The two imide groups may be appropriately substituted with a substituent, and the two imide groups are located at the ortho position to the ether bond on the aromatic ring, respectively.
The heat obtained by reacting a fluorine-containing imide compound or a polyamine compound with a fluorine-containing imide compound, which is bonded to the meta or para position, and D represents a dicarboxylic acid residue having an ethylenically unsaturated double bond. An epoxy resin composition containing a curable prepolymer. 2. A prepreg obtained by impregnating and drying a base material with the epoxy resin composition according to claim 1.