JP2677911B2 - Method for producing fluorine-containing polyimide, fluorine-containing polyamic acid and polyimide resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a fluorine-containing polyimide,
The present invention relates to a method for producing a fluorine-containing polyamic acid and a polyimide resin.

[0002]

2. Description of the Related Art Generally, a polyimide resin is produced by reacting a tetracarboxylic dianhydride and a diamine. Due to its excellent heat resistance, polyimide resins are used in a wide range of fields from electronic materials to aerospace materials. In recent years, in particular, polyimide-based resins as electronic materials are strongly required to have not only heat resistance but also improved moisture resistance and low dielectric properties as electronic devices have higher density and higher performance.

Examples of polyimide include, for example, Japanese Patent Publication No. Sho 43.
In Japanese Patent Application Laid-Open No. 1876 and Japanese Patent Publication No. 60-500109,

Embedded image Are obtained using acid dianhydrides such as However, such a polyimide has not been able to sufficiently satisfy the above requirements.

As an example of the aromatic diamine containing more fluorine atoms, Japanese Patent Application Laid-Open No. 190562/1989 discloses chemical formula 9:

Embedded image The aromatic diamine represented by But,
This aromatic diamine has a low fluorine content because it only contains fluorine in the form of trifluoromethyl groups. Therefore,
Even if the aromatic diamine is reacted with tetracarboxylic dianhydride to produce a polyimide, it is difficult to achieve the required performance.

In Japanese Patent Application Laid-Open No. 1-180860,

Embedded image And the polyimide obtained by reacting the aromatic diamine with the tetracarboxylic dianhydride. However, since the aromatic diamine has a methylene group of a hydrocarbon having a weak intermolecular bonding force between the benzene ring and the perfluoroalkyl group, the bond is easily broken when heated, and therefore, the aromatic diamine is The polyimide obtained by using was poor in heat resistance.

[0006]

DISCLOSURE OF THE INVENTION In order to meet such demands, the present inventors have devised that it is necessary to introduce a large number of fluorine atoms into the molecular structure of polyimide and its introduction. It is found that it is necessary to create a novel fluorine-containing aromatic diamine and a novel fluorine-containing polyimide and fluorine-containing polyamic acid.

[0007]

The fluorine-containing polyimide of the present invention is represented by the chemical formula 11 [general formula (I)]

Embedded image [However, in the general formula (I), tetravalent residue of R tetracarboxylic dianhydride, Rf is selected from the group consisting is -C _n F _{2n-1 (n,} where 6
Which represents an integer of ~ 12), which contains one double bond and may be appropriately branched, and the hydrogen of the benzene ring is
Which may be optionally substituted with a substituent]. Examples of the substituent which may be bonded to the above benzene ring include a lower alkyl group, a lower alkoxy group, fluorine, chlorine, bromine and the like.

This fluorine-containing polyimide is further
[General Formula (I ′)]

Embedded image [However, in the general formula (I ′), R ′ is a tetravalent residue of tetracarboxylic dianhydride, and X is a compound represented by the formula 1 in the general formula (I).
3 (general formula (A))

Embedded image (Here, the hydrogen of the benzene ring may be appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, bromine, etc.), and the divalent residue of the diamine is excluded. The group may be included].

The fluorine-containing polyamic acid in the present invention is
Chemical formula 14 [general formula (II)]

Embedded image [Wherein, in the general formula (II), R and Rf are the same as those in the general formula (I), and hydrogen of the benzene ring may be appropriately substituted with a substituent] It will be. Examples of the substituent that may be bonded to the above benzene ring include a lower alkyl group, a lower alkoxy group,
There are fluorine, chlorine, bromine, etc.

This fluorine-containing polyamic acid is further
5 [general formula (II ')]

Embedded image However, R'and X in the general formula (II ') are the same as those in the general formula (I').

The fluorine-containing polyimide has the general formula
The structural unit represented by (I) and the structural unit represented by the general formula (I ′) are molar ratio of the latter / the former is 0/100 to 95/5.
It is preferable to include such that
It is preferably contained so that it becomes / 10. Similarly, in the fluorine-containing polyamic acid, the constituent unit represented by the general formula (II) and the constituent unit represented by the general formula (II ′) are 0/100 to a molar ratio of the latter / the former. It is preferably contained so as to be 95/5, and particularly preferably contained so as to be 0/100 to 90/10. A polyimide obtained from a fluorine-containing polyimide having less structural units represented by the general formula (I) and a fluorine-containing polyamic acid having less structural units represented by the general formula (II) has reduced moisture resistance, The dielectric constant tends to be high.

As the precursor of the fluorine-containing polyimide, there are the fluorine-containing polyamic acid and the fluorine-containing polyamic acid partially imidized. In the present invention, the polyimide-based resin is a generic term for the fluorine-containing polyimide and its precursor. The polyimide resin includes (a) tetracarboxylic dianhydride and (b) chemical formula 16 [general formula (III)].

Embedded image [Wherein Rf in the general formula (III) is the same as in the general formula (I), and hydrogen of the benzene ring is appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, bromine and the like. Optionally, the two amino groups are each bonded to the aromatic ring at the ortho position, the meta position or the para position with respect to the ether bond]. The fluorine-containing polyimide can be also produced by subjecting the fluorine-containing polyamic acid to a dehydration ring-closing reaction.

As the tetracarboxylic dianhydride,
Pyromellitic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-
Diphenyl tetracarboxylic dianhydride, 2,2-bis
(3,4, -dicarboxyphenyl) propane dianhydride,
2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4- Dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-
Dicarboxyphenyl) sulfone dianhydride, 3,4
9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride,
Benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ', 4'-benzophenone tetracarboxylic dianhydride, 2,3,2', 3-benzophenone tetra Carboxylic dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6,-
Naphthalene tetracarboxylic dianhydride, 2, 3, 6,
7, -naphthalenetetracarboxylic dianhydride, 1,2,
4,5-naphthalene-tetracarboxylic dianhydride, 1,
4,5,8-naphthalene-tetracarboxylic dianhydride,
2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-
1,4,5,8, tetracarboxylic dianhydride, 2,3
6,7-Tetrachlornaphthalene-1,4,5,8-tetracarboxylic dianhydride, Phenanthrene-1,8,
9,10-tetracarboxylic dianhydride, pyrazine-2,
3,5,6-tetracarboxylic dianhydride, thiophene-
2,3,4,5-tetracarboxylic dianhydride, 2,3
3 ', 4'-biphenyltetracarboxylic dianhydride,
3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,3,2', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethyl Silane dianhydride, bis (3,4-dicarboxyphenyl) methylphenyl silane dianhydride, bis (3,4
-Dicarboxyphenyl) diphenylsilane dianhydride,
1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane Dianhydride, p-phenylbis (trimellitic acid monoester acid anhydride) ethylene glycol bis (trimethylitrate anhydride), propanediol bis (trimethylitrate anhydride), butanediol bis (trimethylitrate anhydride), pentanediol bis ( Trimellitic anhydride), hexanediol bis (trimellitic anhydride), octanediol bis (trimellitic anhydride), decanediol bis (trimellitic anhydride),
Ethylene tetracarboxylic dianhydride, 1,2,3,4-
Butanetetracarboxylic 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 Anhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2
2,1] heptane-2,3-dicarboxylic anhydride) sulfone bicyclo- (2,2,2) -oct (7) -ene-2,
3,5,6-Tetracarboxylic acid dianhydride, 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 (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) ) -3-Methyl-3-cyclohexene-
1,2-dicarboxylic anhydride, tetrahydrofuran-
There are 2,3,4,5-tetracarboxylic dianhydride, etc., and two or more kinds may be mixed and used.

The fluorine-containing aromatic diamine compound represented by the general formula (III) is a novel compound and has a long-chain or bulky perfluoroalkenyl group in the molecule. The fluorine-containing aromatic diamine compound is contained in an amount of 5 to 100 mol%, particularly 10% by mole based on the total amount of the diamine compound used.
It is preferable to use ˜100 mol%. If the amount of the fluorine-containing aromatic diamine compound is too small, the effect of improving the moisture resistance and the effect of decreasing the dielectric constant tend to be small.

The fluorine-containing aromatic diamine compound represented by the general formula (III) is 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- (per) Fluorohexenyloxy) 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-
Examples include diamino-2-bromo-5- (perfluorohexenyloxy) benzene.

In these compounds, the perfluorononenyl group is one in which Rf in the general formula (III) is -C ₉ F ₁₇ , and the perfluorohexenyl group is the general formula (II
It is intended Rf is -C ₆ F ₁₁ in I), and the same applies hereinafter. In the compounds exemplified above, instead of a perfluorononenyl group or a perfluorohexenyl group,
Group -C ₁₀ F _19, compounds having a group -C ₁₂ F ₂₃ or the like can be exemplified similarly.

The fluorine-containing aromatic diamine compound represented by the general formula (III) is represented by the chemical formula 17 [general formula (IV)]

Embedded image (However, in the general formula (IV), Rf is the same as in the general formula (I), and R ¹ and R ² each independently represent an optionally substituted alkyl group or an optionally substituted aryl group. , The hydrogen of the aromatic ring may be appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and the two urethane groups are each attached to the aromatic ring by an ortho group to an ether bond. Position-, meta-position or para-position) -containing fluorine-containing aromatic diurethane compound is subjected to a deprotection reaction of a urethane-type protecting group.

As the compound represented by the general formula (IV),
1,3-bis (N- (methyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene,
1,3-bis (N- (ethyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene,
1,3-bis (N- (n-propyloxycarbonyl)
Amino) -5- (perfluorononenyloxy) benzene, 1,3-bis (N- (i-propyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene, 1,3-bis (N -(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- (methyl (Oxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2-bis (N- (ethyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2-bis ( N- (n-propyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2-bis (N- (i-propyloxycarbonyl) amino) -4- (perfluorononenyloxy) Benzene, 1,2-bis (N- (n-butyloxycarbonyl) amino) -4- (perfluorononenyloxy) benzene, 1,2-bis ( - (i-butyloxycarbonyl) amino) -4- (perfluoro root) 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- (perfluoro Nonenyloxy) benzene, 1,4-bis (N- (n-propyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N- (i
-Propyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N-
(N-Butyloxycarbonyl) amino) -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, 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- (methyloxycarbonyl) amino) -5
(Perfluorohexenyloxy) benzene, 1,3-
Bis (N- (ethyloxycarbonyl) amino) -5-
(Perfluorohexenyloxy) benzene, 1,3-
Bis (N- (n-propyloxycarbonyl) amino)
-5- (perfluorohexenyloxy) benzene,
1,3-bis (N- (i-propyloxycarbonyl)
Amino) -5- (perfluorohexenyloxy) benzene, 1,3-bis (N- (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- (n
-Propyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N
-(I-Propyloxycarbonyl) amino) -4-
(Perfluorohexenyloxy) benzene, 1,2-
Bis (N- (n-butyloxycarbonyl) amino)-
4- (perfluorohexenyloxy) benzene, 1,
2-bis (N- (i-butyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (t-butyloxycarbonyl) amino) -4- (perfluorohexenyl) Oxy)
Benzene, 1,2-bis (N- (pentyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (hexyloxycarbonyl) amino) -4- (perfluorohexenyl) Oxy) benzene, 1,2-bis (N- (heptyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (octyloxycarbonyl) amino) -4- (per) Fluorohexenyloxy) benzene, 1,2-bis (N- (benzyloxycarbonyl) amino) -4- (perfluorohexenyloxy) benzene, 1,2-bis (N- (phenyloxycarbonyl) amino) -4 -(Perfluorohexenyloxy) benzene, 1,4-bis (N- (methyloxycarbonyl)) Mino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N- (ethyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N- (n- Propyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N-
(I-Propyloxycarbonyl) amino) -3- (perfluorohexenyloxy) benzene, 1,4-bis (N- (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- (perfluorohexenyl) (Oxy) benzene, 1,4-bis (N- (benzyloxycarbonyl) amino) -3- (perfluorononenyloxy) benzene, 1,4-bis (N- (phenyloxycarbonyl) amino) -3- (Perfluorohexenyloxy) benzene and the like. In the compounds exemplified in this way, instead of a perfluorononenyl group or a perfluorohexenyl group, a group —C ₁₀ F ₁₉ , a group —C ₁₂ F ₂₃
Compounds having, etc. can be similarly exemplified.

The urethane type protecting group specifically means -COOR ¹ and -COOR ² in the general formula (IV).

The deprotection reaction can be carried out, for example, by the following method. 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 is added with hydrogen gas at 0 to 100 ° C. in the presence of a catalyst such as palladium carbon. (Particularly preferably around room temperature) (a hydrogen gas passing time may be appropriately determined, but 1 to 10 hours is usually sufficient),
A method in which the fluorine-containing aromatic diurethane compound is dissolved in the organic solvent as described above, and hydrogen acids such as HF, HBr, HCl, and H ₂ SO ₄ are added and reacted (hydrogen acid is fluorine-containing aromatic diurethane). It is preferable to react at an equivalent amount or more with respect to the compound. When HF is used, it is preferable to react at room temperature or lower, particularly 0 ° C. or lower, and for other hydrogen acids, it is reacted at 0 to 100 ° C., particularly near room temperature. Furthermore, although the reaction time is appropriately determined, it is usually HF.
Is used for 0.1 to 1 hour, and other hydrogen acids are used for 1 to 10 hours), the fluorine-containing aromatic diurethane compound is treated with sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide. , A method of reacting in the presence of a basic compound such as potassium hydroxide and water (water is preferably used in an amount equal to or more than the amount of the fluorine-containing aromatic diurethane compound, and the reaction is performed in addition to the organic solvent as described above). In addition, water, alcohol such as methanol or ethanol, cresol or the like may be used as a solvent). The aromatic diamine compound represented by the general formula (III) thus obtained can be purified by recrystallization from alcohol or the like.

The aromatic diurethane compound represented by the general formula (IV) is represented by the following chemical formula 18 [general formula (V)]

Embedded image [However, in the general formula (V), Rf is the same as in the general formula (I), 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, bromine or the like. Optionally, the two carboxyl groups are respectively bonded to the aromatic ring at the ortho position, the meta position or the para position with respect to the ether bond, and a fluorine-containing aromatic dicarboxylic acid compound represented by the formula: 19 [General formula (VI)]

Embedded image (However, in the general formula (VI), R ³ represents a lower alkyl group or an aryl group.)

Embedded image R ⁴ OH (VII) (In the general formula (VII), R ⁴ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. The alcohol represented by) can be produced by reacting with or without a solvent in the presence of a base.

Examples of the dicarboxylic acid compound represented by the general formula (V) include 5- (perfluorononenyloxy) isophthalic acid, 4- (perfluorononenyloxy) phthalic acid and 2- (perfluorononenyloxy). Terephthalic acid, 4-methyl-5- (perfluorononenyloxy)
Isophthalic acid, 4-methoxy-5- (perfluorononenyloxy) isophthalic acid, 2,4,6-trifluoro-5- (perfluorononenyloxy) 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- (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, 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.

The perfluorononenyloxyisophthalic acid and the perfluorohexenyloxyisophthalic acid are hexafluoropropene trimer or dimer, for example, according to the method disclosed in JP-A-60-51146. It can be produced by reacting hydroxyisophthalic acid in an aprotic polar solvent at room temperature or lower in the presence of a base catalyst such as triethylamine.

In the above method, other dicarboxylic acids can be prepared by using oligomers other than hexafluoropropene trimers and dimers and other fluoroalkene oligomers.

The above-mentioned dicarboxylic acid represented by the general formula (IV) is, for example, a diphenyl ester or dibenzyl ester of hydroxy-dicarboxybenzene according to the method described in JP-A-50-121243. Etc. and an oligomer of fluoroalkene such as fluoropropene trimer and tetrafluoroethylene pentamer in an aprotic organic solvent at or near room temperature in the presence of a base catalyst such as triethylamine. It can be produced by isolating the reaction product, hydrolyzing the reaction product in the presence of a basic compound such as sodium hydroxide and potassium hydroxide, and further appropriately treating with an acid such as hydrochloric acid. The reaction product and the final product are appropriately purified by means such as washing and recrystallization.

As the compound represented by the general formula (VI),
Examples include diphenylphosphoryl azide, diethylphosphoryl azide, di-p-nitrophenylphosphoryl azide, and dimorpholylphosphoryl azide.

Examples of the alcohol represented by the general formula (V) include methanol, ethanol, propanol, i-propanol, butanol, i-butanol, t-butanol, pentanol, hexanol, heptanol, octanol, phenol and benzyl alcohol. There is.

The synthetic reaction for obtaining the fluorine-containing aromatic diurethane compound represented by the general formula (IV) is described by Takayuki Shioiri, Shunichi Yamada, Journal of Organic Synthetic Chemistry, Vol. 31, No. 8, 666-67.
The new Curtius reaction, as shown on page 4 (1973), can be applied. That is, a dicarboxylic acid compound represented by the general formula (V), an azide compound represented by the general formula (VI), and an alcohol represented by the general formula (VII) are reacted in the presence of a base to give a target fluorinated compound. An 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 can be carried out in an organic solvent or can be carried out by the general formula (VI
It is carried out using the alcohol represented by I) also as a solvent. As the organic solvent, it is preferable to use benzene, toluene, tetrahydrofuran, dioxane, diethyl ether or the like. These solvents may be used as a mixture of two or more if they are compatible with each other.

In the above reaction, the dicarboxylic acid compound represented by the general formula (V) and the general formula (VI) are added in the middle.
The carboxylic acid azide and the carboxylic acid azide are subjected to a thermal rearrangement reaction to form an isocyanate compound, but the intermediate compound may be isolated once or the reaction may proceed without isolation. You can
The conditions of the above reaction vary depending on the reagents used and are not particularly limited, but the following conditions are preferable.

First, the dicarboxylic acid compound represented by the general formula (V), the azide compound represented by the general formula (VI), the tertiary amine and the alcohol represented by the general formula (VII) are reacted at once. When the intended fluorine-containing aromatic diurethane compound is obtained in one step in appearance, the reaction temperature is preferably −80 to 250 ° C., and particularly room temperature to 1
50 ° C. is preferred. The azide compound, the tertiary amine and the alcohol are used in amounts of 0.5 to 5.0 molar equivalents, 0.5 to 3.0 molar equivalents and 0.5 molar equivalents to the dicarboxylic acid compound. Is preferred.

Secondly, 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 to isolate the resulting carboxylic acid azide. To 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 mol equivalents and 0.5 to 3.0 mols, respectively, with respect to the dicarboxylic acid compound. It is preferable to use an equivalent amount. Then, the isolated carboxylic acid azide is reacted in an alcohol in an amount of 0.5 molar equivalent to a large excess thereof, whereby the desired fluorine-containing aromatic diurethane compound can be obtained. The reaction temperature at this time is -8.
0-250 ° C is preferred.

Thirdly, when the isocyanate compound is isolated once, first, the dicarboxylic acid compound and the azide compound represented by the general formula (V) are reacted in the presence of a tertiary amine to give the resulting isocyanate as a simple compound. Let go. At this time, 0.5 to 5.0 molar equivalents of the azide compound and 0.5 to 3.5 of the tertiary amine with respect to the dicarboxylic acid compound.
It is preferable to use 0 molar equivalent, and the reaction temperature is -80 to 2
50 ° C. is preferred. Then, the obtained isocyanate is reacted in an alcohol of 0.5 molar equivalent to a large excess relative to it to obtain a fluorine-containing aromatic diurethane compound. At this time, the reaction temperature is -8.
0-250 ° C is preferred.

The first to third methods 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.

In the above general formulas (I) to (IV), Rf is
It may be linear or branched, but is preferably branched. The branched structure has a more compact three-dimensional structure than the linear structure, so that the glass transition temperature of the polyimide resin tends to increase.

In the above general formulas (I) to (IV), a specific example of Rf is a perfluorononenyl group
[Formula (A)]

Embedded image The group of the formula 22 [Formula (B)]

Embedded image Of the formula 23 [Formula (C)]

Embedded image The group of formula 24 [Formula (D)]

Embedded image Of the formula 25 [Formula (E)]

Embedded image And the like. As a perfluorohexenyl group,

Embedded image The group of formula 27 [Formula (G)]

Embedded image A group of formula 28 [Formula (H)]

Embedded image And the like. As a perfluorodecenyl group,
9 [Formula (J)]

Embedded image There are groups such as.

In the method for producing a polyimide resin of the present invention, the diamine compound which can be used in combination with the aromatic diamine compound represented by the general formula (III) includes 4-aminophenyl-3-aminobenzoic acid and 2,2-bisbenzoic acid. (4-aminophenyl) propane, 2,6-diaminopyridine, bis (4-aminophenyl) diethylsilane, bis- (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'-diaminodiphenylether 3,3'-diaminodiphenylsulfone, 3,3 '
-Diaminodiphenylpropane, 3,3'-diaminodiphenylsulfide, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,3 '
-Diaminobenzophenone, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 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, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylene Diamine, decamethylenediamine, tetramethylenediamine, propylenediamine, 3-methylheptamethylenediamine, 4.4'-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,2-bis (3-aminopropoxy) ethane, 2,2-dimethylpropylenediamine, 3-methoxy-hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,
5-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 2,17-diaminoeicosadecane, 1,4-diaminocyclohexane, 1,10-diamino-1,10-dimethyldecane, 1,12-diaminooctadecane, 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'-diaminodiphenyl ether, 3,3'-difluoro-4,4'-diaminodiphenyl ether, 3 , 3'-dichloro-4,
4'-diaminodiphenyl ether, 3,3'-dibromo-4,4'-diaminodiphenyl ether, 3,3 '
-Di (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 3,3'-dimethoxy-4,
4'-diaminodiphenyl sulfone, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfone, 3,
3'-difluoro-4,4'-diaminodiphenyl sulfone, 3,3'-dichloro-4,4'-diaminodiphenyl sulfone, 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'-
Diaminodiphenyl hexafluoropropane, 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, 3,3'-dimethylbenzidine, 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'-tetofluoro-4,4'-diaminodiphenyl ether, 3,3 '
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'-diaminodiphenyl sulfone,
3,3 ', 5,5'-tetramethoxy-4,4'-diaminodiphenyl sulfone, 3,3', 5,5'-tetraethoxy-4,4'-diaminodiphenyl sulfone,
3,3 ', 5,5'-tetrafluoro-4,4'-diaminodiphenyl sulfone, 3,3', 5,5'-tetrachloro-4,4'-diaminodiphenyl sulfone, 3,3 '
3 ', 5,5'-tetrabromo-4,4'-diaminodiphenyl sulfone, 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'
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'-diamino Diphenyl 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,
There are 4'-diaminodiphenyl sulfone, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenyl sulfone, and the like, and two or more kinds may be used in combination.

Silicon diamine may be used as a part of the diamine. As silicon diamine, 1,3-bis (3-aminopropyl) -1,1,1
-Tetraphenyldisiloxane, 1,3-bis (3-aminopropyl) -1,1,1-tetramethyldisiloxane, 1,3-bis (4-aminobutyl) -1,1,1-
Tetramethyldisiloxane and the like. When using silicon diamines, these are preferably used in an amount of 0.1 to 10 mol% based on the total amount of the diamines. The use of silicon diamine improves the adhesiveness of the obtained polyimide resin.

In producing the polyimide resin,
The tetracarboxylic dianhydride and the diamine are reacted at a suitable temperature. In this reaction, the degree of imidization can be appropriately adjusted by selecting appropriate conditions. For example, by reacting at 100 ° C. or higher, particularly 120 ° C. or higher, if necessary, in the presence of a catalyst such as tributylamine, triethylamine, triphenyl phosphite, etc., to produce a completely or almost completely imidized polyimide. (The catalyst is preferably used in an amount of 0 to 15% by weight, based on the total amount of the reaction components.
01 to 15% by weight is preferable), and when it is reacted at 80 ° C. or lower, particularly 50 ° C. or lower, it is a precursor of the polyimide and is not or hardly imidized.
Polyamic acids can be produced. Further, a polyimide precursor in which imidization is partially advanced can also be produced.

The polyamic acid or the polyimide precursor partially imidized is further added to 100 ° C.
Above, in particular, a method of imidization by heating to 120 ° C. or more, or an acid anhydride such as acetic anhydride, propionic anhydride, or benzoic anhydride, a ring-closing agent such as carbodiimide such as dicyclohexylcarbodiimide, and further pyridine, isoquinoline, if necessary. Chemical ring closure (imidization) in the presence of a ring closure catalyst such as trimethylamine, aminopyridine, imidazole
(The ring-closing agent and the ring-closing catalyst are preferably used in the range of 1 to 8 mol per 1 mol of the acid anhydride), thereby producing a polyimide in which imidization is almost or completely completed. it can. These reactions are preferably performed in the presence of an organic solvent.

As the organic polar solvent which can be used in the above reaction, N, N-dimethylformamide, N, N-
Dimethylacetamide, N-methyl-2-pyrrolidone,
Dimethyl sulfoxide, hexamethylphosphoramide,
There are phenol, m-cresol, chlorobenzene and the like, and two or more kinds may be mixed and used as long as they are compatible with each other. Also, with these organic polar solvents, toluene,
A general-purpose solvent such as xylene, cellosolve acetate, or methyl cellosolve can be used in combination as long as the solubility of the polyimide resin or its precursor is not deteriorated. The order of adding the reaction raw materials is not particularly limited.

The polyimide-based resin such as polyimide or polyamic acid in the present invention can be used in the form of varnish dissolved in an organic solvent or in the form of powder. In particular, a polyamic acid and a polyimide precursor having a low degree of imidization are soluble in an organic solvent and can be used in the form of a varnish. Some are soluble and some are insoluble.
The latter is preferably used in powder form.

Further, in order to prevent voids due to the generation of condensed water accompanying the imidization reaction, it is preferable to use a polyimide in which imidization is almost completed. The polyimide resin varnish can be formed into a polyimide film by applying it to a substrate surface such as glass or a silicon wafer by a commonly used method such as spin coating, spraying or brush coating, and then heating. In this case, when a polyimide precursor is used, it is imidized during the heat treatment.

Further, a polyimide resin varnish is cast and coated on a glass plate, a stainless plate or the like, dried to remove the solvent, and then the film obtained from the glass plate or the stainless plate is peeled off to produce a film. can do. This film can be used as an adhesive or the like.

The above polyimide film is composed of hydrazine,
Through holes and the like can be easily processed by using an etching liquid such as tetramethylammonium hydroxide which is usually used for polyimide resins.

The polyamic acid is preferably dissolved in N, N-dimethylformamide at a concentration of 0.1 g / dl and has a reduced viscosity of 0.1 dl / g or more when measured at 30 ° C.

The glass transition temperature of the polyimide can be easily adjusted to 150 ° C. to 300 ° C., and the thermal decomposition temperature can be adjusted to 350 ° C. or higher. Further, the polyimide can have a water absorption of 1% or less, particularly 0.5% or less.

[0047]

Next, examples of the present invention will be described. The 5- (perfluorononenyloxy) isophthalic acid used below is

Embedded image Is a compound of

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

The physical properties and elemental analysis values of this compound are shown below. (1) Melting point 69-71 ° C. (2) ¹ H-NMR spectrum (solvent acetone-d ₆ , TM
S standard); 8.72ppm (2H, NH, s), 7.61ppm
(1H, Aromatic, t), 7.09ppm (2H, Aromati
c, s), 1.49 ppm (9H, t-Bu, t) [() indicates the integrated intensity ratio of hydrogen, the base group for absorption and the type of peak, and s is a singlet, t indicates a triple line. The same applies to the following. ] (3) ¹⁹ F-NMR spectrum (solvent acetone-d ₆ , trifluorotoluene standard); 11.32 ppm (3 F, C
_{F 3, d), - 3.54ppm} (6F, CF 3, s), - 4.
_{82ppm (6F, CF 3, d} ), - 99.70ppm (1F,
CF, quart.), -101.49ppm (1F, CF, quin
t.) [() shows the integrated intensity ratio of fluorine, the base group for absorption and the types of peaks in order, s is a singlet, d is a doublet, quart. is a quartet, quint Indicates a quintuplet. The same applies to the following. ] (4) IR absorption spectrum; 3336 cm ^-1 (N-H, urethane), 1710 cm ^-1 (C = O, urethane), 1548
cm ^-1 (N-H, ^{urethane), 1244cm -1 (C-F} ) (5) minutes containing analysis (%): as shown in Table 1.

[Table 1]

From the above, the production of the desired product was confirmed. The structural formula of this is shown below.

Embedded image

Synthesis Example 2 To 0.200 g (0.265 mmol) of 1,3-bis (N- (t-butyloxycarbonyl) amino) -5- (perfluorononenyloxy) benzene obtained in Synthesis Example 1 was obtained. Four
Add 4.0 mL of sodium hydrogen carbonate / methanol,
Stir at room temperature for 4 hours. Next, methanol was distilled off, and the mixture was extracted with ether. After washing the ether solution with water, the ether was distilled off, and column separation was performed with ether / hexane to obtain the target product, 1,3-diamino-5- (perfluorononenyloxy) benzene, in a yield of 65%. Obtained.

The analytical data of the obtained 1,3-diamino-5- (perfluorononenyloxy) benzene are shown below. (1) Melting point 105.5-106.9 ° C. (2) ¹ H-NMR spectrum (solvent acetone-d ₆ , T
MS standard); 5.87 (1H, Aromatic, t) 5.63 (2H, Aromatic, t) 4.75 (4H, NH2, s) (3) ¹⁹ F-NMR spectrum (solvent acetone-d ₆ , tri). fluorotoluene _{standard); 11.03 (3F, CF 3} , d) -3.68 (6F, CF 3, s) -4.98 (6F, CF 3, d) -99.71 (1F, CF, quart .) -101.67 (1F, CF, quint.) (4) IR absorption spectrum; 3452 cm ^-1 , 3380c
m ^-1 , 1628 cm ^-1 (N-H, amine), 1298 cm ^-1 ,
1238 cm ^-1 , 1190 cm ^-1 (CF) (5) Elemental analysis value (%): As shown in Table 2.

[Table 2]

From the above, it was confirmed to be the target compound. The structural formula of this compound is represented by the following chemical formula 32 [Structural formula (a)]
It is as follows.

Embedded image

Example 1 4 equipped with a thermometer, a stirring device, a drying tube, and a nitrogen introducing tube
Into a one-necked flask, 8 g of dried N, N-dimethylacetamide and 1.1 g (2 mmol) of 1,3-diamino-5- (perfluorononenyloxy) benzene [structural formula (a)] were charged and stirred. After the diamine was dissolved, while cooling with an ice bath, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 0.89
g (2 mmol) was added in small portions. After the addition was completed, the reaction was carried out for 5 hours while cooling in an ice bath to obtain a polyamic acid solution.

The polyamic acid solution was poured into water or methanol, and the precipitated polyamic acid was filtered off and dried. The infrared absorption spectrum (IR spectrum) of this polyamic acid is shown in FIG. In addition, the polyamic acid is
It was dissolved in N-dimethylacetamide at a concentration of 0.1 g / dl, and the reduced viscosity was measured at 30 ° C. Table 3 shows the results.

Further, the above-mentioned polyamic acid solution was applied onto a glass substrate by spin coating, and the solution was heated at 150 ° C. for 200 hours.
A polyimide film was obtained by sequentially heating each at 30 ° C., 250 ° C. and 300 ° C. for 30 minutes. The results obtained by measuring the IR spectrum of the polyimide using the obtained polyimide film are shown in FIG. 2, and the results obtained by measuring the glass transition temperature, thermal decomposition temperature, water absorption rate and dielectric constant are shown in Table 3.

Example 2 4 equipped with a thermometer, a stirring device, a drying tube and a nitrogen introducing tube
Dried N-methyl-2-pyrrolidone 8 in a one-necked flask
g, and then 1,3-diamino-5- (perfluorononenyloxy) benzene [structure (a)] 1.1
g (2 mmol) was added and the mixture was stirred. After the diamine was dissolved, 0.64 g (2 mmol) of 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride was added little by little. After the addition was completed, the reaction was carried out at room temperature for 5 hours to obtain a polyamic acid solution. Thereafter, the polyamic acid was isolated according to Example 1, and the IR spectrum and reduced viscosity were measured. Further, a polyimide film was prepared according to Example 1, and the IR spectrum, glass transition temperature, thermal decomposition temperature and water absorption were measured. The IR spectrum of polyamic acid is shown in FIG. 3, and the IR spectrum of polyimide is shown in FIG. Other measurement results are shown in Table 3.

Example 3 4 equipped with a thermometer, a stirring device, a drying tube, and a nitrogen introducing tube
8 g of N, N-dimethylacetamide was placed in a one-necked flask, and then 0.55 g of 1,3-diamino-5- (perfluorononenyloxy) benzene [structure (a)]
(4 mmol) and 0.2 g (1 mmol) of 4,4'-diaminodiphenyl ether were added and stirred until a homogeneous solution was obtained. Next, at room temperature, 0.58 g (2 mmol) of 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride was added little by little. After the addition was completed, the reaction was carried out at room temperature for 5 hours to obtain a polyamic acid. Thereafter, the polyamic acid was isolated according to Example 1, and the IR spectrum and reduced viscosity were measured. Further, a polyimide film was prepared according to Example 1, and the IR spectrum, glass transition temperature, thermal decomposition temperature and water absorption were measured. The IR spectrum of the polyamic acid is shown in FIG. 5, and the IR spectrum of the polyimide is shown in FIG.
Other measurement results are shown in Table 3.

Example 4 4 equipped with a thermometer, a stirring device, a drying tube and a nitrogen introducing tube
8 g of N, N-dimethylformamide was placed in a one-necked flask, and then 1,3-diamino-5- (perfluorononenyloxy) benzene [structure (a)] 0.06 g
(0.1 mmol) and 0.34 g (1.9 mmol) of 4,4'-diaminodiphenylmethane were added and stirred until a homogeneous solution was obtained. Next, while cooling in an ice bath, ethylene glycol bis (trimellitic anhydride) 0.82
g (2 mmol) was added in small portions. After the addition was completed, the reaction was carried out for 3 hours while cooling with an ice bath and then for 2 hours at room temperature to obtain a polyamic acid. Thereafter, the polyamic acid was isolated according to Example 1, and the IR spectrum and reduced viscosity were measured. Further, a polyimide film was prepared according to Example 1, and the IR spectrum, glass transition temperature, thermal decomposition temperature and water absorption were measured. The IR spectrum of polyamic acid is shown in FIG. 7, and the IR spectrum of polyimide is shown in FIG.
Other measurement results are shown in Table 3.

Example 5 4 equipped with a thermometer, a stirring device, a drying tube, and a nitrogen introducing tube
Into a one-necked flask, 8 g of dried N, N-dimethylacetamide and 1.1 g (2 mmol) of 1,3-diamino-5- (perfluorononenyloxy) benzene [structural formula (a)] were charged and stirred. After the diamine was dissolved, 0.392 g (2 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added little by little while cooling with an ice bath. After the addition was completed, the reaction was carried out for 5 hours while cooling in an ice bath to obtain a polyamic acid solution. Thereafter, the polyamic acid was isolated according to Example 1, and the IR spectrum and reduced viscosity were measured. Further, a polyimide film was prepared according to Example 1, and the IR spectrum, glass transition temperature, thermal decomposition temperature and water absorption were measured. The IR spectrum of the polyamic acid is shown in FIG. 9, and the IR spectrum of the polyimide is shown in FIG. Other measurement results are shown in Table 3.

Example 6 4 equipped with a thermometer, a stirring device, a drying tube and a nitrogen introducing tube
Into a one-necked flask, 8 g of dried N, N-dimethylacetamide and 1.1 g (2 mmol) of 1,3-diamino-5- (perfluorononenyloxy) benzene [structural formula (a)] were charged and stirred. After the diamine was dissolved, 0.396 g (2 mmol) of butanetetracarboxylic dianhydride was added little by little while cooling with an ice bath. After the addition was completed, the reaction was carried out for 5 hours while cooling in an ice bath to obtain a polyamic acid solution. Thereafter, the polyamic acid was isolated according to Example 1, and the IR spectrum and reduced viscosity were measured.
Further, a polyimide film was prepared according to Example 1,
The IR spectrum, glass transition temperature, thermal decomposition temperature and water absorption were measured. FIG. 11 shows the IR spectrum of the polyamic acid.
Fig. 12 shows the IR spectrum of polyimide. Other measurement results are shown in Table 3.

Example 7 4 equipped with a thermometer, a stirring device, a drying tube and a nitrogen introducing tube
Into a one-necked flask, 8 g of dried N, N-dimethylacetamide and 1.1 g (2 mmol) of 1,3-diamino-5- (perfluorononenyloxy) benzene [structural formula (a)] were charged and stirred. After the diamine was dissolved, while cooling with an ice bath, bis (exo-bicyclo [2,2,2
1] 0.788 g (2 mmol) of hepta-2,3-dicarboxylic acid anhydride) sulfone was added little by little. After the addition was completed, the reaction was carried out for 5 hours while cooling in an ice bath to obtain a polyamic acid solution. Thereafter, the polyamic acid was isolated according to Example 1, and the IR spectrum and reduced viscosity were measured.
Further, a polyimide film was prepared according to Example 1,
The IR spectrum, glass transition temperature, thermal decomposition temperature and water absorption were measured. FIG. 13 shows the IR spectrum of the polyamic acid.
Fig. 14 shows the IR spectrum of polyimide. Other measurement results are shown in Table 3.

Comparative Example 1 4 equipped with a thermometer, a stirring device, a drying tube, and a nitrogen introducing tube
8 g of N, N-dimethylacetamide in a two-necked flask,
0.44 (4 mmol) of 4,4'-diaminodiphenyl ether was added and stirred until a uniform solution was obtained. After the diamine was dissolved, 0.89 g (2 mmol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added little by little while cooling with an ice bath. After the addition was completed, the reaction was continued for 5 hours while cooling with an ice bath.
Polyamic acid was obtained. Thereafter, the polyamic acid was isolated according to Example 1 and the reduced viscosity was measured. Further, a polyimide film was prepared according to Example 1, and the glass transition temperature, thermal decomposition temperature and water absorption were measured. Table 3 shows the measurement results.

Comparative Example 2 0.89 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride in Comparative Example 1
A polyamic acid was obtained according to Comparative Example 1, except that 0.64 g (2 mmol) of benzophenonetetracarboxylic dianhydride was used instead of (2 mmol). After this,
Polyamic acid was isolated according to Example 1 and the reduced viscosity was measured. Further, a polyimide film was prepared according to Example 1, and the glass transition temperature, thermal decomposition temperature and water absorption were measured. Table 3 shows the measurement results.

In the above, the conditions for measuring the glass transition temperature, the thermal decomposition temperature, the water absorption rate and the dielectric constant are as follows. 1) Glass transition temperature Using a Perkin Elma DSC-7 model, the temperature rising rate is 10 ° C.
/ Min Measured with a sample amount of about 10 mg. 2) Thermal decomposition temperature It was measured at a temperature rising rate of 10 ° C./min using a differential thermal balance (TG-7000 type manufactured by Vacuum Riko Co., Ltd.). 3) Water absorption rate The polyimide film was immersed in water at room temperature for 24 hours, and the weight change before and after the immersion was calculated. 4) Dielectric constant The dielectric constant was measured using a dielectric constant measuring device under the conditions of a frequency of 10 kHz and room temperature.

[0066]

[Table 3]

The fluorine-containing polyimide and the fluorine-containing polyamic acid obtained in Examples 1 to 7 contain the following constitutional units. In the following, Rf 'represents a group of the above formula (A). (1) Structural unit of polyimide obtained in Example 1: Chemical formula 33

Embedded image (2) Structural unit of the polyamic acid obtained in Example 1: Chemical formula 3
4

Embedded image (3) Structural unit of polyimide obtained in Example 2:

Embedded image (4) Structural unit of the polyamic acid obtained in Example 2: Chemical formula 3
6

Embedded image (5) Constitutional unit of polyimide obtained in Example 3:

Embedded image 50 mol% and:

Embedded image 50 mol%. (6) Structural unit of the polyamic acid obtained in Example 3: Chemical formula 3
9

Embedded image 50 mol% and 40

Embedded image 50 mol%. (7) Structural unit of polyimide obtained in Example 4:

Embedded image 5 mol% and

Embedded image 95 mol%. (8) Structural unit of the polyamic acid obtained in Example 4: Chemical formula 4
3

Embedded image 5 mol% and 44

Embedded image 95 mol%. (9) Constitutional unit of polyimide obtained in Example 5:

Embedded image (10) Constitutional unit of the polyamic acid obtained in Example 5:

Embedded image (11) Structural unit of polyimide obtained in Example 6:

Embedded image (12) Structural unit of the polyamic acid obtained in Example 6:
8

Embedded image (13) Structural unit of polyimide obtained in Example 7:

Embedded image (14) Structural unit of the polyamic acid obtained in Example 7:
0

Embedded image

[0068]

The polyimide according to claim 1 or 2 and the polyamic acid according to claim 3 or 4 are novel, and these polyimides and the polyimides obtained from these polyamic acids have a low dielectric constant, It has a low water absorption rate, excellent moisture resistance, and good heat resistance. Claim 5
By the method described in (1), the polyimide-based resin containing the polyimide and the polyamic acid can be easily produced.

[Brief description of the drawings]

1 is an IR spectrum of the polyamic acid obtained in Example 1. FIG.

2 is an IR spectrum of the polyimide obtained in Example 1. FIG.

3 is an IR spectrum of the polyamic acid obtained in Example 2. FIG.

FIG. 4 is an IR spectrum of the polyimide obtained in Example 2.

5 is an IR spectrum of the polyamic acid obtained in Example 3. FIG.

6 is an IR spectrum of the polyimide obtained in Example 3. FIG.

7 is an IR spectrum of the polyamic acid obtained in Example 4. FIG.

8 is an IR spectrum of the polyimide obtained in Example 4. FIG.

9 is an IR spectrum of the polyamic acid obtained in Example 5. FIG.

10 is an IR spectrum of the polyimide obtained in Example 5. FIG.

11 is an IR spectrum of the polyamic acid obtained in Example 6. FIG.

FIG. 12 is an IR spectrum of the polyimide obtained in Example 6.

13 is an IR spectrum of the polyamic acid obtained in Example 7. FIG.

FIG. 14 is an IR spectrum of the polyimide obtained in Example 7.

Front page continuation (72) Inventor Yasuo Miyadera 48, Wadai, Tsukuba, Ibaraki Hitachi Chemical Co., Ltd. Tsukuba R & D Laboratory (56) References JP-A-1-118527 (JP, A) Proc. Volume 7, pages 2089-2091 (October 1990) J. POLYM. SCI. POLY M .; CHEM. ED. VOL. 28 (2) 1990. P. 323-331

Claims (6)

(57) [Claims] 1. Chemical formula 1 [general formula (I)] [In the formula (I), hydrogen benzene ring, rather it may also be substituted by a substituent, R represents Piromeritsuto dianhydride, 3,3 ', 4,4'-diphenyl tetracarboxylic acid-free
Water product, 2,2 ', 3,3'-diphenyltetracarboxylic acid dinone
Water, 2,2-bis (3,4, -dicarboxyphenyl) propa
Dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propa
Dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane
Dianhydride , 1,1-bis (3,4-dicarboxyphenyl) ethane
Dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride
Substance, bis (3,4-dicarboxyphenyl) methane dianhydride
Things, bis (3,4-dicarboxylate Schiff enyl) sulfone dianhydride
, 3,4,9,10-perylenetetracarboxylic dianhydride
Things, bis (3,4-dicarboxylate Schiff enyl) ether dianhydride
Substance, benzene-1,2,3,4-tetracarboxylic dianhydride
, 3,4,3 ', 4'-benzophenone tetracarboxylic acid
Dianhydride , 2,3,2 ', 3-benzophenone tetracarboxylic acid dianhydride
Anhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic acid
Dianhydride , 1,2,5,6-naphthalenetetracarboxylic dianhydride
, 2,3,6,7 , -naphthalenetetracarboxylic dianhydride
, 1,2,4,5-naphthalene-tetracarboxylic dianhydride
, 1,4,5,8-naphthalene-tetracarboxylic dianhydride
Objects, 2,6-chloronaphthalene-1,4,5,8-tetra
Carboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8, tetra
Carboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4
5,8-Tetracarboxylic acid dianhydride, Phenanthrene-1,8,9,10-tetracarboxylic acid
Dianhydride , pyrazine-2,3,5,6-tetracarboxylic acid dianhydride
, Thiophene-2,3,4,5-tetracarboxylic dianhydride
, 2,3,3 ', 4'-biphenyltetracarboxylic acid dinone
Water product, 3,4,3 ', 4'-biphenyltetracarboxylic acid dinone
Water product, 2,3,2 ', 3'-biphenyltetracarboxylic acid
Water, bis (3,4-dicarboxyphenyl) dimethylsilane
Dianhydride , bis (3,4-dicarboxyphenyl) methylphenyl
Silane dianhydride, bis (3,4-dicarboxyphenyl) diphenyl sila
Dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethyl)
Silyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,
1,3,3-Tetramethyldicyclohexane dianhydride, p-phenylbis (trimellitic acid monoester acid anhydride
Products) ethylene glycol bis (trimellitic anhydride), propanediol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), pentanediol bis (trimellitic anhydride), hexanediol bis (trimellitic anhydride) ), Octanediol bis (trimellitic anhydride), decanediol bis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4- butanetetracarboxylic dianhydride, decahydronaphthalene- 1,4,5,8-tetracarb
Acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahi
Dronaphthalene-1,2,5,6-tetracarboxylic acid di
Anhydrous, cyclopentane-1,2,3,4-tetracarboxylic acid diacid
Anhydrous, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride
, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride
Things, bis (exo - bicyclo [2,2,1] heptane -2,
3-dicarboxylic anhydride) sulfonbicyclo- (2,2,2) -oct (7) -ene-2,
3,5,6-Tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexaful
Oropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy)
Si) phenyl] hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) di
Phenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopro
Pill) benzene bis (trimellitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopro )
Pill) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-me
Cyl-3-cyclohexene-1,2-dicarboxylic acid anhydride
And tetrahydrofuran-2,3,4,5-tetracarboxylic
A tetracarboxylic acid dianhydride selected from the group of acid dianhydrides
Shows a tetravalent residue of an anhydride, Rf is, -C _n F _2n-1 indicates the (where n is an integer of 6-12), which includes one double bond, branched even if the good. ] A fluorine-containing polyimide containing a structural unit represented by the following. 2. Chemical formula 2 [general formula (II)] [In the general formula (II), the hydrogen of the benzene ring is, rather it may also be substituted by a substituent, R and Rf is a means in the Chemical Formula 1 [Formula (I)]
Is the same. ] A fluorine-containing polyamic acid containing the structural unit represented. 3. (a) Pyromellitic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic acid dianhydride
Water product, 2,2 ', 3,3'-diphenyltetracarboxylic acid dinone
Water, 2,2-bis (3,4, -dicarboxyphenyl) propa
Dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propa
Dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane
Dianhydride , 1,1-bis (3,4-dicarboxyphenyl) ethane
Dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride
Substance, bis (3,4-dicarboxyphenyl) methane dianhydride
Things, bis (3,4-dicarboxylate Schiff enyl) sulfone dianhydride
, 3,4,9,10-perylenetetracarboxylic dianhydride
Things, bis (3,4-dicarboxylate Schiff enyl) ether dianhydride
Substance, benzene-1,2,3,4-tetracarboxylic dianhydride
, 3,4,3 ', 4'-benzophenone tetracarboxylic acid
Dianhydride , 2,3,2 ', 3-benzophenone tetracarboxylic acid dianhydride
Anhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic acid
Dianhydride , 1,2,5,6-naphthalenetetracarboxylic dianhydride
, 2,3,6,7 , -naphthalenetetracarboxylic dianhydride
, 1,2,4,5-naphthalene-tetracarboxylic dianhydride
, 1,4,5,8-naphthalene-tetracarboxylic dianhydride
Objects, 2,6-chloronaphthalene-1,4,5,8-tetra
Carboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8, tetra
Carboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4
5,8-Tetracarboxylic acid dianhydride, Phenanthrene-1,8,9,10-tetracarboxylic acid
Dianhydride , pyrazine-2,3,5,6-tetracarboxylic acid dianhydride
, Thiophene-2,3,4,5-tetracarboxylic dianhydride
, 2,3,3 ', 4'-biphenyltetracarboxylic acid dinone
Water product, 3,4,3 ', 4'-biphenyltetracarboxylic acid dinone
Water product, 2,3,2 ', 3'-biphenyltetracarboxylic acid
Water, bis (3,4-dicarboxyphenyl) dimethylsilane
Dianhydride , bis (3,4-dicarboxyphenyl) methylphenyl
Silane dianhydride, bis (3,4-dicarboxyphenyl) diphenyl sila
Dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethyl)
Silyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,
1,3,3-Tetramethyldicyclohexane dianhydride, p-phenylbis (trimellitic acid monoester acid anhydride
Products) ethylene glycol bis (trimellitic anhydride), propanediol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), pentanediol bis (trimellitic anhydride), hexanediol bis (trimellitic anhydride) ), Octanediol bis (trimellitic anhydride), decanediol bis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4- butanetetracarboxylic dianhydride, decahydronaphthalene- 1,4,5,8-tetracarb
Acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahi
Dronaphthalene- 1,2,5,6-tetracarboxylic acid di
Anhydrous, cyclopentane-1,2,3,4-tetracarboxylic acid diacid
Anhydrous, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride
, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride
Things, bis (exo - bicyclo [2,2,1] heptane -2,
3-dicarboxylic anhydride) sulfonbicyclo- (2,2,2) -oct (7) -ene-2,
3,5,6-Tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexaful
Oropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy)
Si) phenyl] hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) di
Phenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopro
Pill) benzene bis (trimellitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopro )
Pill) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-me
Cyl-3-cyclohexene-1,2-dicarboxylic acid anhydride
And tetrahydrofuran-2,3,4,5-tetracarboxylic
An acid anhydride containing one or more tetracarboxylic acid dianhydrides selected from the group of acid dianhydrides ; and (b) the general formula (III): [However, in the general formula (III), hydrogen benzene ring, rather it may also be substituted by a substituent, two amino groups are each ortho to the ether bond to the aromatic ring, meta or para bonded to position, Rf is, -C _n F _2n-1 indicates the (where n is an integer of 6-12), which includes one double bond, but it may also be branched . ] A diamine containing a fluorine-containing aromatic diamine compound represented by: is reacted, and a method for producing a fluorine-containing polyimide resin. 4. Chemical formula 4 (formula (I) ) [In the chemical formula 4 (formula (I)), hydrogen on the benzene ring is a substituent.
R may be substituted, R is pyromellitic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic acid dianhydride
Water product, 2,2 ', 3,3'-diphenyltetracarboxylic acid dinone
Water, 2,2-bis (3,4, -dicarboxyphenyl) propa
Dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propa
Dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane
Dianhydride , 1,1-bis (3,4-dicarboxyphenyl) ethane
Dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride
Substance, bis (3,4-dicarboxyphenyl) methane dianhydride
Things, bis (3,4-dicarboxylate Schiff enyl) sulfone dianhydride
, 3,4,9,10-perylenetetracarboxylic dianhydride
Things, bis (3,4-dicarboxylate Schiff enyl) ether dianhydride
Substance, benzene-1,2,3,4-tetracarboxylic dianhydride
, 3,4,3 ', 4'-benzophenone tetracarboxylic acid
Dianhydride , 2,3,2 ', 3-benzophenone tetracarboxylic acid dianhydride
Anhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic acid
Dianhydride , 1,2,5,6-naphthalenetetracarboxylic dianhydride
, 2,3,6,7 , -naphthalenetetracarboxylic dianhydride
, 1,2,4,5-naphthalene-tetracarboxylic dianhydride
, 1,4,5,8-naphthalene-tetracarboxylic dianhydride
Objects, 2,6-chloronaphthalene-1,4,5,8-tetra
Carboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8, tetra
Carboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4
5,8-Tetracarboxylic acid dianhydride, Phenanthrene-1,8,9,10-tetracarboxylic acid
Dianhydride , pyrazine-2,3,5,6-tetracarboxylic acid dianhydride
, Thiophene-2,3,4,5-tetracarboxylic dianhydride
, 2,3,3 ', 4'-biphenyltetracarboxylic acid dinone
Water product, 3,4,3 ', 4'-biphenyltetracarboxylic acid dinone
Water product, 2,3,2 ', 3'-biphenyltetracarboxylic acid
Water, bis (3,4-dicarboxyphenyl) dimethylsilane
Dianhydride , bis (3,4-dicarboxyphenyl) methylphenyl
Silane dianhydride, bis (3,4-dicarboxyphenyl) diphenyl sila
Dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethyl)
Silyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,
1,3,3-Tetramethyldicyclohexane dianhydride, p-phenylbis (trimellitic acid monoester acid anhydride
Products) ethylene glycol bis (trimellitic anhydride), propanediol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), pentanediol bis (trimellitic anhydride), hexanediol bis (trimellitic anhydride) ), Octanediol bis (trimellitic anhydride), decanediol bis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4- butanetetracarboxylic dianhydride, decahydronaphthalene- 1,4,5,8-tetracarb
Acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahi
Dronaphthalene-1,2,5,6-tetracarboxylic acid di
Anhydrous, cyclopentane-1,2,3,4-tetracarboxylic acid diacid
Anhydrous, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride
, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride
Things, bis (exo - bicyclo [2,2,1] heptane -2,
3-dicarboxylic anhydride) sulfonbicyclo- (2,2,2) -oct (7) -ene-2,
3,5,6-Tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexaful
Oropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy)
Si) phenyl] hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) di
Phenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopro
Pill) benzene bis (trimellitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopro )
Pill) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-me
Cyl-3-cyclohexene-1,2-dicarboxylic acid anhydride
And tetrahydrofuran-2,3,4,5-tetracarboxylic
A tetracarboxylic acid dianhydride selected from the group of acid dianhydrides
Shows a tetravalent residue of an anhydride, Rf _{is, CF (CF 3) 2 \} / C = C
(A) / \ F ₃ C
CF (CF ₃ ) ₂ and CF ₃ \ / C = C
(F) / \ F ₃ CF ₂ C
It is any group selected from CF ₃ . ]
A fluorine-containing polyimide containing a structural unit. 5. Chemical formula 5 [Formula (II)] [ Chemical Formula 5 (Formula (II)], hydrogen on the benzene ring is a substituent
R may be substituted, R has the same meaning as in Chemical formula 4 (Formula (I)), and Rf is CF (CF ₃ ) ₂ \ / C = C
(A) / \ F ₃ C
CF (CF ₃ ) ₂ and CF ₃ \ / C = C
(F) / \ F ₃ CF ₂ C
It is any group selected from CF ₃ . Represented by]
Fluorine-containing polyamic acid containing a structural unit. 6. (a) Pyromellitic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic acid dianhydride
Water product, 2,2 ', 3,3'-diphenyltetracarboxylic acid dinone
Water, 2,2-bis (3,4, -dicarboxyphenyl) propa
Dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propa
Dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane
Dianhydride , 1,1-bis (3,4-dicarboxyphenyl) ethane
Dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride
Substance, bis (3,4-dicarboxyphenyl) methane dianhydride
Things, bis (3,4-dicarboxylate Schiff enyl) sulfone dianhydride
, 3,4,9,10-perylenetetracarboxylic dianhydride
Things, bis (3,4-dicarboxylate Schiff enyl) ether dianhydride
Substance, benzene-1,2,3,4-tetracarboxylic dianhydride
, 3,4,3 ', 4'-benzophenone tetracarboxylic acid
Dianhydride , 2,3,2 ', 3-benzophenone tetracarboxylic acid dianhydride
Anhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic acid
Dianhydride , 1,2,5,6-naphthalenetetracarboxylic dianhydride
, 2,3,6,7 , -naphthalenetetracarboxylic dianhydride
, 1,2,4,5-naphthalene-tetracarboxylic dianhydride
, 1,4,5,8-naphthalene-tetracarboxylic dianhydride
Objects, 2,6-chloronaphthalene-1,4,5,8-tetra
Carboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8, tetra
Carboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4
5,8-Tetracarboxylic acid dianhydride, Phenanthrene-1,8,9,10-tetracarboxylic acid
Dianhydride , pyrazine-2,3,5,6-tetracarboxylic acid dianhydride
, Thiophene-2,3,4,5-tetracarboxylic dianhydride
, 2,3,3 ', 4'-biphenyltetracarboxylic acid dinone
Water product, 3,4,3 ', 4'-biphenyltetracarboxylic acid dinone
Water product, 2,3,2 ', 3'-biphenyltetracarboxylic acid
Water, bis (3,4-dicarboxyphenyl) dimethylsilane
Dianhydride , bis (3,4-dicarboxyphenyl) methylphenyl
Silane dianhydride, bis (3,4-dicarboxyphenyl) diphenyl sila
Dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethyl)
Silyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,
1,3,3-Tetramethyldicyclohexane dianhydride, p-phenylbis (trimellitic acid monoester acid anhydride
Products) ethylene glycol bis (trimellitic anhydride), propanediol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), pentanediol bis (trimellitic anhydride), hexanediol bis (trimellitic anhydride) ), Octanediol bis (trimellitic anhydride), decanediol bis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4- butanetetracarboxylic dianhydride, decahydronaphthalene- 1,4,5,8-tetracarb
Acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahi
Dronaphthalene-1,2,5,6-tetracarboxylic acid di
Anhydrous, cyclopentane-1,2,3,4-tetracarboxylic acid diacid
Anhydrous, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride
, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride
Things, bis (exo - bicyclo [2,2,1] heptane -2,
3-dicarboxylic anhydride) sulfonbicyclo- (2,2,2) -oct (7) -ene-2,
3,5,6-Tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexaful
Oropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy)
Si) phenyl] hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) di
Phenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopro
Pill) benzene bis (trimellitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopro )
Pill) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-me
Cyl-3-cyclohexene-1,2-dicarboxylic acid anhydride
And tetrahydrofuran-2,3,4,5-tetracarboxylic
One or more tetra selected from the group of acid dianhydrides
An acid anhydride containing a carboxylic acid dianhydride; and (b) Chemical formula 6 [Formula (III)] [In the chemical formula 6 (formula (III)], hydrogen of the benzene ring is a substituent
May be substituted with two amino groups,
Ortho position, meta position or ether position to the aromatic ring
Rf is bonded to the para position and is represented by: CF (CF ₃ ) ₂ \ / C = C
(A) / \ F ₃ C
CF (CF ₃ ) ₂ and CF ₃ \ / C = C
(F) / \ F ₃ CF ₂ C
It is any group selected from CF ₃ . Represented by]
A fluorine- containing polyimide system characterized by reacting a diamine containing a fluorine-containing aromatic diamine compound;
Resin manufacturing method.