JP2900617B2 - Thermosetting resin composition and thermosetting imide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to relates to a thermosetting resin composition and a thermosetting imide resin composition.

[0002]

2. Description of the Related Art Thermosetting imide resins have excellent heat resistance,
It is used in a wide range of fields, from electronic materials to aerospace materials. In recent years, in these fields, in addition to excellent heat resistance, materials having various high performances and high functions have been required. For example, in the field of 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 satisfying such requirements, it is effective to introduce a substituent containing a large number of fluorine atoms into the molecular structure as a substituent exhibiting these properties. Conceivable.

Japanese Patent Publication No. 63-37786 discloses a compound represented by the following formula 3 as a fluorine-containing imide compound. When this compound is reacted with a polyamine, particularly a diamine, a heat-resistant material having excellent flexibility can be obtained. Is described.

Embedded image

[0005]

[Problems to be Solved by the Invention] JP-B-63-3778
No. 6, the imide compound has a hexafluoroisopropylidene group in the molecular structure,
In this case, the fluorine content is low, and it is difficult to achieve the required performance described above. Therefore, in order to solve such problems, the present inventors have developed a thermosetting resin containing a novel fluorine-containing imide compound in which a perfluoroalkenyloxy group is introduced into the molecular structure as a substituent having many fluorine atoms. Provided are a resin composition and a fluorinated thermosetting imide resin composition obtained by heating and reacting the composition. .

[0006]

Means for Solving the Problems The thermosetting resin composition of the present invention is represented by the following formula:

Embedded image [However, in Chemical Formula 4, Rf is -CnF _2n-1 (where n is 6
Represents an integer of from 1 to 12, which contains one double bond and may be branched, and the hydrogen of the aromatic ring is a lower alkyl group (i.e., having 1 to 5 carbon atoms), That is, it may be substituted by an alkoxy group having 1 to 5 carbon atoms), fluorine, chlorine or bromine, and the two imide groups are respectively attached to the aromatic ring at the ortho, meta or para position with respect to the ether bond. D is a dicarboxylic acid residue having an ethylenically unsaturated double bond, -CH = CH-,-
_{CH = C (CH 3) -} , - C (= CH 2) -C H 2 -, -
CCl = CCl−, and

Embedded image And a divalent organic group selected from the group consisting of:

Embedded image Q (NH ₂₎ y [However, in Formula 5, y is 2 or 3 of an integer, Q is a divalent or
Which represents a trivalent organic group].

[0007] By subjecting this thermosetting resin composition to a heat reaction, a fluorine-containing thermosetting imide resin composition can be produced.

The compounds represented by Chemical Formula 4 include 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- (perfluorononenyloxy) benzene,
1,2-Bismaleimide-4-methyl-5- (perfluorononenyloxy) benzene, 1,2-Bismaleimide-4-methoxy-5- (perfluorononenyloxy) benzene, 1,2-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 ( 4 ) can be produced by a method characterized by subjecting a fluorinated bisamic acid compound represented by the following formula (6) to a cyclization dehydration reaction.

Embedded image However, in Chemical formula 6, Rf and D are the same as Chemical formula 4, and 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; The two amic acid groups are respectively bonded to the aromatic ring at the ortho, meta or para position with respect to the ether bond. Examples of the fluorinated bisamic acid compound represented by Chemical Formula 6 include those exemplified as the compound represented by Chemical Formula 4, wherein "imide" is replaced with "amic acid".

As a method for subjecting the fluorinated bisamic acid compound represented by the above formula (6) to a cyclodehydration 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.
And the known methods described in US Pat. No. 3,127,414. 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 catalysts used are alkaline earth metal oxides, 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 formed 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 (6) can be produced by reacting a fluorinated aromatic diamine represented by the following formula (7) with an unsaturated dicarboxylic acid represented by the following formula (8).

Embedded image However, in Chemical formula 7, Rf is the same as Chemical formula 4, 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 amino groups are respectively bonded to the aromatic ring at the ortho, meta or para position with respect to the ether bond.

Embedded image However, in Chemical formula 8, D is the same as Chemical formula 4.

As the compound represented by the formula 7, 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 -C ₁₀ F ₁₉ group, a -C ₁₂ F ₂₃ group 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 8 include maleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, and pyrosiconic anhydride, or the Diels of these compounds with cyclodiene.・ Alder (Diels-Alder)
At least one of the adducts is used.

As a method of reacting the fluorinated aromatic diamine represented by the above formula (7) with the unsaturated dicarboxylic acid anhydride represented by the above formula (8), a known method is applied. There is a method in which the fluorinated aromatic diamine represented by the formula (7) and the unsaturated dicarboxylic anhydride represented by the formula (8) 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. And aprotic polar solvents such as acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.

The fluorine-containing aromatic diamine represented by the above formula (7) can be produced by subjecting a fluorine-containing aromatic diurethane compound represented by the following formula (9) to a deprotection reaction of a urethane type protecting group.

Embedded image However, in Chemical formula 9, Rf is the same as Chemical formula 4, 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 , Lower alkyl group, lower alkoxy group, fluorine,
Chlorine, may be appropriately substituted with a substituent such as bromine,
The two urethane groups are respectively bonded to the aromatic ring at the ortho, meta or para position relative to the ether bond.

[0018] Here, the urethane-type protecting groups, specifically refers to -COOR ¹ and -COOR ² in the formula 9.

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 carried out in an equivalent amount or more with respect to the fluorine-containing aromatic diurethane compound. When HF is used, the reaction is preferably carried out 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 is sufficient), and the above-mentioned fluorinated aromatic diurethane is sufficient. A method in which a compound is reacted in the presence of water and a basic compound such as sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide, and potassium hydroxide (water is preferably used in an equivalent amount or more with respect to the fluorinated 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 described above.)
and so on. The thus obtained aromatic diamine compound represented by Chemical Formula 7 can be purified by recrystallization from alcohol or the like.

Examples of the fluorinated aromatic diurethane compound represented by the chemical formula 9 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, , 3-Bis (N- (t-butyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene, 1,3-bis (N- (pentyloxycarbonyl) amino) -5- (perfluorononene Nyloxy) 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-propyl) (Oxycarbonyl) 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 (Xycarbonyl) 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- (perfluorononenyl) Oxy) 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-butyloxy) Carbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N- (t-butyloxycarbonyl) amino) -3- ( -Fluorononenyloxy) 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- (methyloxy (Carbonyl) 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 (9) can be prepared by mixing a fluorine-containing aromatic dicarboxylic acid compound represented by the following formula (10), an azide compound represented by the following formula (11) and an alcohol represented by the following formula (12) in a solvent or without solvent. And reacting in the presence of a base.

Embedded image However, in Chemical formula 10, Rf is the same as Chemical formula 4, and 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, etc. Each of the carboxyl groups 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 11, R ³ represents a lower alkyl group or an aryl group.

R ⁴ OH wherein R ⁴ 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 the chemical formula 10 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 compounds 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 trimerizing hexafluoropropene or dimerizing hexafluoropropene according to the method described 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.

The perfluorononenyl group includes, for example, a group represented by the following formula (13).

Embedded image

As the perfluorohexenyl group, for example, there is 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-mentioned chemical formula (10) can be prepared, for example, according to the method described in Japanese Patent Application Laid-Open No. 50-123243, such as an ester such as diphenyl ester or dibenzyl ester of hydroxy-dicarboxybenzene. 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, potassium hydroxide or the like, and further 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.

The compounds represented by the formula (11) include diphenyl phosphoryl azide, diethyl phosphoryl azide,
Di-p-nitrophenyl phosphoryl azide, dimorpholyl phosphoryl azide and the like.

The alcohol represented by Chemical formula 12 includes
Methanol, ethanol, propanol, i-propanol, butanol, i-butanol, t-butanol,
Pentanol, hexanol, heptanol, octanol, phenol, benzyl alcohol and the like.

The synthesis reaction for obtaining the fluorine-containing aromatic diurethane compound represented by Chemical formula 9 is described in Takayuki Shioiri and Shunichi Yamada, Journal of the Society of Synthetic Organic Chemistry, Vol. 31, No. 8, pp. 666-674 (1973). The new Curtius reaction can be applied. That is, by reacting the dicarboxylic acid compound represented by the chemical formula 10, the azide compound represented by the chemical formula 11, and the alcohol represented by the chemical formula 12 in the presence of a base, an intended fluorine-containing aromatic diurethane compound can be obtained. 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 12 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, the dicarboxylic acid compound represented by the chemical formula (10) and the azide compound represented by the chemical formula (11) react in the middle, and the carboxylic acid azide and the 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 (10), the azide compound represented by the chemical formula (11), the tertiary amine and the alcohol represented by the chemical formula (12) are reacted at once, 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. Then, 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 is reacted with the azide compound represented by the formula (II) in the presence of a tertiary amine, and the resulting isocyanate is isolated. At this time, the azide compound is added to the dicarboxylic acid compound in an amount of 0.5 to 0.5.
It is preferable to use 0 molar equivalents and 0.5 to 3.0 molar equivalents of the above tertiary amine, and the reaction temperature is preferably -80 to 250 ° C. 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 -80 to 250
C is preferred.

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 (4).

The fluorinated thermosetting imide resin material comprises:
A compound containing a fluorine-containing bisimide compound represented by the above formula (4) and a compound having at least two thermosetting imide groups in one molecule (hereinafter, referred to as “another reactive imide compound”). They may be contained in a range that does not impair the object of the invention. Other reactive imide compounds include parabismaleimidebenzene, metabismaleimidebenzene, parabismaleimidetoluene, 1,4
-Bis (p-maleimidocumyl) benzene, 1,4-bis (m-maleimidocumyl) benzene, etc.
There are those represented by Chemical Formula 5, Chemical Formula 16 or Chemical Formula 17.

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 17, n is the number of 0-4.

Examples of the thermosetting imide compound represented by Chemical Formula 15 include 4,4'-bismaleimidediphenyl ether, 4,4'-bismaleimidediphenylmethane,
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 16 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.

In the present invention, as the polyamine compound represented by the formula 5, 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, , 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, , 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, etc., m-phenylenediamine, p-phenylenediamine, benzidine, 3,3'-dimethyl-4,4-
Diaminobiphenyl, 3,3'-dichlorobenzidine,
3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylmethane, 1,1-bis (4-aminophenyl) ethane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- Aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl)-
1,3-dichloro-1,1,3,3-tetrafluoropropane, 4,4′-diaminodiphenyl ether, 4,
4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodisulfide Enyl sulfone,
3,3'-diaminodibenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 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 (3-aminophenyl) diethylsilane, bis (4-aminophenyl) phenyl Enylphosphine oxide, bis (4
-Aminophenyl) ethylphosphine oxide, 1,5
-Diaminonaphthalene, 2,6-diaminopyridine,
2,5-diamino-1,3,4-oxadiazole, m
-Xylylenediamine, 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, 1,12-diaminooctadecane, 2,2-
Dimethylpropylenediamine, 2,5-dimethylhexamethylenediamine, 3-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4
-Dimethylheptamethylenediamine, 5-methinonamethylenediamine, 1,4-diaminocyclohexane, bis (p-aminocyclohexyl) methane, 3-methoxyhexamethylenediamine, 1,2-bis- (3-aminopropoxy) ethane, Bis (3-aminopropyl) sulfide, N, N-bis (3-aminopropyl) methylamine, 2,2'-bis [4- (4-aminophenoxy)
Phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane,
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 and the like. Also, 2,
4-diaminodiphenylamine, 2,4-diamino-5
-Methyl-diphenylamine, 2,4-diamino-4 '
-Methyl-diphenylamine, 1-anilino-2,4-
N-aryl-substituted aromatic triamines such as diaminonaphthalene and 3,3'-diamino-4-anilinobenzophenone. Further, there is a polyamine represented by Chemical Formula 18. These may be used in combination of two or more.

Embedded image [In the formula, R ₀ is an alkylidene group containing a methylene group, and n is an average number of 0.1 or more.]

In the thermosetting resin composition, the fluorine-containing compound represented by the chemical formula (4) and the polyamine compound represented by the chemical formula (5) are in a molar ratio of 50: 1 to 1:
It is preferable to use it in the range of 1.5. If the use ratio of the polyamine compound is too 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.

Examples of the form of the thermosetting resin composition include the following. (1) A fluorinated imide compound and a polyamine compound which are ground and mixed in a solid state. (2) A fluorinated imide compound and a polyamine compound dissolved in an organic solvent. In this case, usable effective solvents are limited in that they do not substantially react with both components, but in addition, it is desirable that they be good solvents for both components. 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 aromatics 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. (3) A solution obtained by pouring the solution of the above (2) into a poor solvent and filtering and drying the deposited precipitate into a pellet or powder. In this case, the poor solvent includes water, hexane, petroleum ether and the like.

The thermosetting resin composition of the present invention includes:
Other thermosetting resins (phenolic resin, epoxy resin, etc.), 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) 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 thermosetting 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 colorant are added within a range not to impair the object of the present invention. Can be.

The thermosetting resin composition is heated and reacted to obtain the above-mentioned thermosetting imide resin which is a prepolymer. 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 up to the prepolymer stage, preferably 50 to 35.
Temperatures in the range 0 ° C., particularly preferably in the range 80-200 ° C., are selected. 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 50 hours. When using a thermosetting resin composition dissolved in an organic solvent, pour the reaction solution into a poor solvent, filter the precipitated resin, and if necessary, further process into pellets or powder. You may use it. Examples of the poor solvent include water, hexane and petroleum ether.

[0046] <br/> thermosetting imide resin of the thermosetting resin composition and the invention of the present invention, compression molding, molded by trans Sulfur molding, extrusion molding, injection molding or the like known molding method And put to practical use.

[0047]

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

Synthesis Example 1 0.61 g (1.0 mmol) of 5- (perfluorononenyloxy) isophthalic acid having a group of the above formula as a perfluorononenyl group, 0.66 g (2.4 mmol) of diphenylphosphoryl azide ) And 0.24 g (2.4 mmol) of triethylamine were 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 obtain 1,3-bis-N- (t-butyloxycarbonyl) amino) -5-perfluorononenyloxybenzene, which was the target substance, at a yield of 86%. .

The physical properties and elemental analysis 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), 1548 cm ^-1 (NH, urethane), 1244
cm ^-1 (CF) (5) Analytical value of the element (%);

[Table 1]

From the above, formation of the desired product was confirmed. Its structural formula is as shown in Chemical formula 19.

Embedded image

Synthesis Example 2 1,3-bis (N- (t-butyloxycarbonyl) amino) -5- (perfluorononenyloxy)
0.20 g (0.265 mmol) of benzene in 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 analysis data of the obtained 1,3-diamino-5- (perfluorononenyloxy) benzene is 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 3, 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, it was confirmed that the compound was the target compound. The structural formula of this compound is as shown in Chemical formula 20.

Embedded image

Synthesis Example 3 0.431 g of maleic anhydride (4.
40 mmol) was dissolved in 5 mL of acetone, and while stirring on an ice-water bath, 1.11 g (2.00 mmol) of 1,3-diamino-5- (perfluorononenyloxy) benzene of Chemical Formula 20 was stirred under a nitrogen stream. Solution (5 mL)
Was added dropwise and 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 was obtained at a yield of 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 21.

Embedded image

Synthesis Example 4 1.35 g (1.80 mmol) of 1,3-bismaleamic acid-5- (perfluorononenyloxy) benzene of Chemical Formula 21
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,
Benzotrifluoride _{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, formation of the desired product was confirmed. The structural formula of this compound is as shown in Chemical formula 22.

Embedded image

Examples 1 to 6 In a flask equipped with a stirrer and a reflux condenser, 1,3-bismaleimide-5- (perfluorononenyloxy) benzene represented by Chemical Formula 22 and various diamines shown in Table 4 were added. Each was charged at the molar ratio shown in Table 5, and the resin concentration was 30
Dimethylformamide (DMF) was added and dissolved in an amount of weight% to obtain a thermosetting resin composition. The 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 fluorine-containing thermosetting imide resin. The fluorine-containing thermosetting imide resin is pressed at a pressure of 20 kg / cm ² at 200 ° C.
Heating was performed for 2 hours and post-curing was further performed at 250 ° C. for 5 hours to obtain a cured product. Table 5 shows the glass transition temperature, 5% weight loss temperature, water absorption and dielectric constant of this cured product.

Comparative Example 1 4,4'-Bismaleimidodiphenylmethane and 4,4 '
The same operation as in Examples 1 to 6 was carried out using -diaminodiphenylmethane and the charged molar ratios shown in Table 5, and the results in Table 5 were obtained.

As is clear from the results shown in Table 5, the cured products obtained in Examples 1 to 6 have low water absorption and low dielectric constant, high glass transition temperature and high 5% weight loss temperature, and have excellent properties. have.

[Table 4]

[Table 5] * 1 A and B are imide compounds (A) in Table 4, respectively.
And polyamine (B). * 2 The ratio of the weight change from the weight after drying under reduced pressure (dry weight) at 100 ° C. for 3 hours (dry weight) to the weight after treatment with pressurized car (condition: 121 ° C., 2.2 atm, 3 hours) to the dry weight * 3. Permittivity at 10 KHz

[0063]

The cured product of the thermosetting resin composition according to the first aspect and the thermosetting imide resin obtained according to the second aspect has a low water absorption and a low dielectric constant.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 73/00-73/12 C08L 79/00-79/08 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (1) Chemical formula (1) [However, Rf in Chemical Formula 1 is -CnF _2n-1 (where n is 6
Represents an integer of from 1 to 12, which contains one double bond and may be branched, and the hydrogen of the aromatic ring has 1 carbon atom.
Alkyl group, an alkoxy group having 1 to 5 carbon atoms, which may be substituted with fluorine, chlorine or bromine, two imide groups each having an ortho position, a meta position or And D is -CH =
CH -, - CH = C ( CH 3) -, - C (= CH 2) -C
H _2- , -CCl = CCl- and Divalent fluorine-containing imide compound represented by an organic group showing a] and of 2 ## STR2 ## Q (NH ₂₎ y [However selected from the group consisting of, among of 2, y is 2 or 3 of an integer, Q Is divalent or
Which shows a trivalent organic group]. 2. A thermosetting imide resin composition obtained by heating and reacting the thermosetting resin composition according to claim 1.