JP3052617B2 - Fluorinated polyimide, fluorinated polyamic acid and polyimide resin, and methods for producing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluorine-containing polyimide,
Fluorinated polyamic acid and fluorinated polyimide resin,
And their production methods.

[0002]

2. Description of the Related Art Generally, a polyimide resin is produced by reacting a tetracarboxylic dianhydride with a diamine. Polyimide resins are used in a wide range of fields from electronic materials to aerospace materials due to their excellent heat resistance. In recent years, polyimide resins used especially for electronic materials have been required not only to have improved heat resistance but also to have improved moisture resistance and low dielectric properties with the increase in density and performance of electronic devices.

[0003] Conventionally, for example, polyimide is disclosed in
No. 3-1876 and Japanese Patent Publication No. Sho 60-500109,

Embedded image Those obtained using an acid dianhydride such as are shown. However, such a polyimide could not sufficiently satisfy the above requirements.

An example of an aromatic diamine containing more fluorine atoms is disclosed in JP-A-1-190652.

Embedded image Is shown. However, this aromatic diamine contains only fluorine in the form of a trifluoromethyl group, and therefore has a low fluorine content. Therefore, the aromatic diamine of the formula 8 is reacted with tetracarboxylic dianhydride to produce a polyimide. However, it is difficult to satisfy the required performance described above.

JP-A-1-180860 discloses an aromatic diamine represented by the following formula:

Embedded image And a polyimide obtained by reacting an aromatic diamine of Chemical formula 9 with tetracarboxylic dianhydride. However, the aromatic diamine of Chemical formula 9 has a methylene group of a hydrocarbon having a weak intermolecular bonding force between the benzene ring and the perfluoroalkyl group, so that the bond is easily broken when heated, and therefore, the aromatic diamine is The polyimide obtained by using an aromatic diamine was not satisfactory in heat resistance.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to create a novel fluorine-containing polyimide and to provide a polyimide resin having a low dielectric constant, high moisture resistance and high heat resistance.

[0007]

Means for Solving the Problems The inventors of the present invention have focused on the fact that it is necessary to introduce more fluorine atoms into the molecular structure of polyimide in order to satisfy the above requirements, and have conducted various studies. Succeeded in introducing a large number of fluorine atoms, and created novel fluorinated aromatic diamines, novel fluorinated polyimides and fluorinated polyamic acids. The fluorinated polyimide in the present invention is represented by the following formula (I):

Embedded image [In the formula (I), R represents a tetravalent residue of a tetracarboxylic acid dianhydride, Rf is -C _n F _2n-1 (where, n is a integer from 6-12, which is two the double bond viewed one contains may be in branches.) shows the hydrogen of the benzene ring may be substituted with a substituent, a nitrogen atom of the two imide group to each ester bond At the ortho, meta or para position. ] It is a fluorine-containing polyimide containing the structural unit represented by these. Here, the substituent that may be substituted on the hydrogen of the benzene ring is a lower alkyl group,
There are a lower alkoxy group, fluorine, chlorine, bromine and the like.

[0008] The fluorine-containing polyimide further comprises
[Formula (I ')]

Embedded image [Wherein, in the formula (I ′), R ′ is a tetravalent residue of tetracarboxylic dianhydride which may be the same or different from R in the formula (I), and X is A divalent diamine residue other than the formula (A)

Embedded image Wherein (A), Rf is the same meaning as in In formula (I), hydrogen of the benzene ring may be substituted with location substituent. ] May be included.

In the present invention, the fluorine-containing polyamic acid is
Chemical formula 13 [Formula (II)]

Embedded image [However, in the formula (II), R and Rf have the same meanings as in the formula (I), and the hydrogen of the benzene ring may be substituted by a substituent, and the nitrogen atom of the two imide groups Are each bonded to the ortho, meta or para position with respect to the ester bond. ] Is included. Here, examples of the substituent which may be substituted on the hydrogen of the benzene ring include a lower alkyl group, a lower alkoxy group, fluorine, chlorine, and bromine.

The fluorinated polyamic acid further comprises
4 [Formula (II ')]

Embedded image [However, in formula (II '), R' and X have the same meaning as in formula (I '). ] May be included.

The fluorine-containing polyimide has a constitutional unit of the formula (I) and a constitutional unit of the formula (I ′) in a molar ratio of the latter / the former of 0 /.
It is preferably contained so as to be 100 to 95/5, particularly preferably 0/100 to 90/10. Similarly, the fluorinated polyamic acid has the formula (II)
It is preferable that the structural unit of the formula (II ′) and the structural unit of the formula (II ′) are contained so that the latter / former has a molar ratio of 0/100 to 95/5, particularly 0/100 to 90/10. Is preferred. A polyimide obtained from a fluorinated polyimide having a small number of structural units of the formula (I) and a fluorinated polyamic acid having a small number of structural units of the formula (II) tends to have low moisture resistance and a high dielectric constant.

In the present invention, the term "polyimide resin" refers to a fluorine-containing polyimide and a precursor thereof. The precursor of the fluorinated polyimide refers to a fluorinated polyamic acid and a substance obtained by partially imidating the fluorinated polyamic acid. The polyimide resin includes (a) a tetracarboxylic dianhydride; and (b) a diamine compound containing a fluorinated aromatic diamine represented by Formula 15 (Formula (III));

Embedded image [In the formula (III), Rf is the same meaning as in In formula (I), hydrogen of the benzene ring may be substituted with a substituent. Here, the substituent which may be substituted on the hydrogen of the benzene ring includes a lower alkyl group, a lower alkoxy group, fluorine, chlorine, bromine and the like. ] To react with each other. Further, the fluorinated polyimide can be produced by subjecting the fluorinated polyamic acid to a dehydration ring-closing reaction.

The (a) tetracarboxylic dianhydride includes pyromellitic dianhydride, 3,3 ', 4,4'
-Diphenyltetracarboxylic dianhydride, 2,2 ',
3,3'-diphenyltetracarboxylic dianhydride, 2,
2-bis (3,4, -dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-di Carboxyphenyl) 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'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3-benzophenonetetracarboxylic acid Dianhydride, 2,3,3 ', 4'-
Benzophenonetetracarboxylic dianhydride, 1,2,2
5,6-naphthalenetetracarboxylic dianhydride, 2,
3,6,7, -naphthalenetetracarboxylic dianhydride,
1,2,4,5-naphthalene-tetracarboxylic dianhydride, 1,4,5,8-naphthalene-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8
-Tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8, tetracarboxylic dianhydride,
2,3,6,7-tetrachloronaphthalene-1,4
5,8-tetracarboxylic dianhydride, phenanthrene-
1,8,9,10-tetracarboxylic dianhydride, 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'-biphenyl Tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-di Carboxyphenyl) 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 anhydride) ethylene glycol bis (trimellitic anhydride), propanediol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), Pentanediol bis (trimellitic anhydride), hexanediol bis (trimellitic anhydride), octanediol bis (trimellitic anhydride), decanediol bis (trimellitic anhydride), 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, pyrrolidine-
2,3,4,5-tetracarboxylic dianhydride, 1,2,2
3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-
Dicarboxylic anhydride) sulfone bicyclo- (2,2,2) -oct (7) -ene-2,
3,5,6-tetracarboxylic 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 and the like, and two or more kinds may be used as a mixture.

The fluorinated aromatic diamine of the formula (III) is a novel compound and has a long-chain or bulky perfluoroalkenyl group in the molecule. The fluorinated aromatic diamine of the formula (III) is added in an amount of 5 to the total amount of the diamine compound.
It is preferably used in an amount of from 100 to 100 mol%, particularly preferably from 10 to 100 mol%. If the amount of the fluorine-containing aromatic diamine is too small, the effect of improving the moisture resistance and the effect of lowering the dielectric constant tend to decrease.

As the fluorine-containing aromatic diamine represented by the formula (III), 5- (perfluorononenyloxy) isophthalic acid bis (4-aminophenyl ester),
Bis (perfluorononenyloxy) isophthalate (2
-Methyl-4-aminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-methoxy-4-aminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-fluoro -4-aminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-chloro-4-
Aminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-bromo-4-aminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (3-aminophenyl ester), 5 -(Perfluorononenyloxy) isophthalic acid bis (3-amino-5-methylphenyl ester),
5- (perfluorononenyloxy) isophthalic acid bis (3-amino-5-methoxyphenyl ester), 5-
Bis (perfluorononenyloxy) isophthalate (3
-Amino-5-fluorophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (3-amino-chlorophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (3-amino-5-
Bromophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-aminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-amino-4-methylphenyl ester), 5 -(Perfluorononenyloxy) isophthalic acid bis (2-amino-4-methoxyphenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-amino-4-fluorophenyl ester), 5- ( Perfluorononenyloxy) isophthalic acid bis (2-amino-4-chlorophenyl ester),
5- (perfluorononenyloxy) isophthalic acid bis (2-amino-4-bromophenyl ester) and the like. 5- (perfluorononenyloxy) isophthalic acid bis (4-aminophenyl ester),

Bis (2-methyl-4-aminophenyl ester) 5- (perfluorohexenyloxy) isophthalate, bis (2-methoxy-4-aminophenyl ester) 5- (perfluorohexenyloxy) isophthalate, 5 -(Perfluorohexenyloxy) isophthalic acid bis (2-fluoro-4-aminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-chloro-4-aminophenyl ester), 5- (perfluoro Hexenyloxy) isophthalic acid bis (2-bromo-4-aminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (3-aminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (3 -Amino-5-methylphenyle Ether), 5- (perfluoro hexenyloxy) isophthalic acid bis (3-amino-5-methoxyphenyl ester), 5- (perfluoro hexenyloxy) isophthalic acid bis (3-amino -
5- (fluorophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (3-amino-chlorophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (3-amino-5-bromophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-aminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-amino-4-methylphenyl ester), 5- (perfluorohexenyloxy) Bis (2-amino-4-methoxyphenyl ester) isophthalate, bis (2-amino-4-fluorophenyl ester) isophthalate, bis (2-amino-4-fluorophenyl ester) isophthalate, bis (2-amino-4-fluorophenyl ester) isophthalate ( 2-amino-4- Lolo phenyl ester), 5- (perfluoro hexenyloxy) isophthalic acid bis (2-amino-4-bromo-phenyl ester)
Etc.

In these compounds, the perfluorononenyl group has Rf of —C ₉ F ₁₇ , the perfluorohexenyl group has Rf of —C ₆ F ₁₁ , and the same applies to the following. 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.

The fluorine-containing aromatic diamine represented by the formula (III) in the present invention is represented by the following formula (IV):

Embedded image [However, in the formula (IV), Rf has the same meaning as in the formula (I), and hydrogen on the benzene ring is a lower alkyl group,
It may be appropriately substituted with a substituent such as a lower alkoxy group, fluorine, chlorine and bromine. R ¹ represents a monovalent organic group, R ² represents hydrogen or a divalent organic group combining R ¹ and R ² , and the nitrogen atom is bonded to the ortho, meta or para position with respect to the ester group. ing. And a deprotection reaction of a fluorine-containing diamine having an amino group protected.

[0021] In the above formulas (IV), 2-valent organic group combined monovalent organic group or R ¹ and R ² as R ¹ is a group protecting the amino group, e.g., R ³ OC There is a (＝ O)-group (where R ³ represents a monovalent organic group), specifically, a benzyloxycarbonyl group, a t-butylcarbonyl group, a p-methoxybenzyloxycarbonyl group,
Examples include a p-nitrobenzyloxycarbonyl group, a p-biphenylisopropyloxycarbonyl group, and a 9-fluorenylmethyloxycarbonyl group. As a group for protecting an amino group, an R ⁴ C (＝ O) — group (here, R ⁴
Represents a hydrogen, an alkyl group or an aryl group), a trityl group, a p-toluenesulfonyl group, a group represented by the following formula 17, and the like.

Embedded image

Examples of the fluorine-containing diamine represented by the formula (IV) in which the amino group is protected include 5- (perfluorononenyloxy) isophthalic acid bis (4-benzyloxycarbonylaminophenyl ester), Bis (2-methyl-4-fluorononenyloxy) isophthalate
Benzyloxycarbonylaminophenyl ester),
5- (perfluorononenyloxy) isophthalic acid bis (4-methoxy-4-benzyloxycarbonylaminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-fluoro-4-benzyloxycarbonylamino) Phenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-chloro-4-benzyloxycarbonylaminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-bromo-4-) Benzyloxycarbonylaminophenyl ester), bis (3-benzyloxycarbonylaminophenyl ester) 5- (perfluorononenyloxy) isophthalate, bis (3-benzyloxycarbonylamido) 5- (perfluorononenyloxy) isophthalate 5-methylphenyl ester),
5- (perfluorononenyloxy) isophthalic acid bis (3-benzyloxycarbonylamino-5-methoxyphenyl ester),

Bis (3-benzyloxycarbonylamino) 5- (perfluorononenyloxy) isophthalate
5- (fluorophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (3-benzyloxycarbonylamino-5-chlorophenyl ester),
5- (perfluorononenyloxy) isophthalic acid bis (3-benzyloxycarbonylamino-5-bromophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-benzyloxycarbonylaminophenyl ester), 5- (perfluorononenyloxy) isophthalic acid bis (2-benzyloxycarbonylamino-4-methylphenyl ester), 5-
Bis (perfluorononenyloxy) isophthalate (2
-Benzyloxycarbonylamino-4-methoxyphenyl ester), 5- (perfluorononenyloxy)
Bis (2-benzyloxycarbonylamino-4-fluorophenyl ester) isophthalate, 5- (perfluorononenyloxy) bis (2-benzyloxycarbonylamino-4-chlorophenyl ester) isophthalate, 5- (perfluorononene) Nyloxy) isophthalic acid bis (2-benzyloxycarbonylamino-4-bromophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (4-benzyloxycarbonylaminophenyl ester),

Bis (2-methyl-4-benzyloxycarbonylaminophenyl ester) 5- (perfluorohexenyloxy) isophthalate, bis (2-methoxy-isophthalic acid) 5- (perfluorohexenyloxy) isophthalate
4- (benzyloxycarbonylaminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-fluoro-4-benzyloxycarbonylaminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2- Chloro-4-benzyloxycarbonylaminophenyl ester), 5
-(Perfluorohexenyloxy) isophthalic acid bis (2-bromo-4-benzyloxycarbonylaminophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (3-benzyloxycarbonylaminophenyl ester), 5- ( Perfluorohexenyloxy) isophthalic acid bis (3-benzyloxycarbonylamino-5-methylphenyl ester), 5-
(Perfluorohexenyloxy) isophthalic acid bis (3-benzyloxycarbonylamino-5-methoxyphenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (3-benzyloxycarbonylamino-5-fluorophenyl ester), Bis (3- (perfluorohexenyloxy) isophthalate
Benzyloxycarbonylamino-5-chlorophenyl ester),

Bis (3-benzyloxycarbonylamino-5-bromophenyl ester) 5- (perfluorohexenyloxy) isophthalate, bis (2-benzyloxycarbonylaminophenyl ester) 5- (perfluorohexenyloxy) isophthalate Bis (2-benzyloxycarbonylamino-4-methylphenyl ester), 5- (perfluorohexenyloxy) isophthalic acid, bis (2-benzyloxycarbonylamino) 5- (perfluorohexenyloxy) isophthalate
4-methoxyphenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-benzyloxycarbonylamino-4-fluorophenyl ester), 5- (perfluorohexenyloxy) isophthalic acid bis (2-benzyloxycarbonyl) Amino-4-
Chlorophenyl ester) and bis (2-benzyloxycarbonylamino-4-bromophenyl ester) 5- (perfluorohexenyloxy) isophthalate. In the compounds exemplified above, a t-butyloxycarbonyl group, a p-methoxybenzyloxycarbonyl group, a p-nitrobenzyloxycarbonyl group, a p-biphenylisopropyloxy group is used instead of the benzyloxycarbonyl group which is a protecting group for an amino group. Carbonyl group,
9-fluorenylmethyloxycarbonyl group, the R ⁴
Compounds having a group such as a C (ＯO) — group, a trityl group, a p-toluenesulfonyl group, and a group represented by the above formula (17) can also be exemplified.

In the above deprotection reaction, the compound represented by the formula (IV) is dissolved in an organic solvent such as ethyl acetate, dimethylformamide, dimethylacetamide, benzene, xylene, acetone, tetrahydrofuran, and the like. Hydrogen gas may be passed in the presence at 0 to 100 ° C., preferably at around room temperature. At this time, the amount of catalyst used is
The amount of the compound represented by the formula (IV) is preferably 1 to 50% by weight, and the time for passing hydrogen gas may be determined as appropriate, but usually 1 to 10 hours is sufficient.

Alternatively, the deprotection reaction is carried out by dissolving the compound represented by the formula (IV) in an organic solvent as described above,
Hydrogen acid such as F, HBr, HC1, H ₂ SO ₄ or the like can be added and reacted. At this time, it is preferable to use 1 to 50 times equivalent of the hydrogen acid to the compound represented by the formula (IV), and when using HF, it is preferable to react at room temperature or lower, particularly 0 ° C. or lower, Other hydrogen acids are 0-10
The reaction is preferably carried out at 0 ° C., particularly around room temperature. The reaction time is appropriately determined.
1 to 1 hour and 1 to 10 hours when other hydrogen acids are used are sufficient.

Further, the reaction may be carried out by reacting the compound represented by the above formula (IV) in the presence of water and a basic compound such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide and potassium hydroxide. . At this time, the basic compound and water are each 1 to 50 with respect to the compound represented by the formula (IV).
It is preferable to use a double equivalent, and as a solvent for the reaction, water, an alcohol such as methanol or ethanol, cresol, or the like is used in addition to the organic solvent described above.

The fluorine-containing diamine represented by the formula (IV) and having a protected amino group is represented by the following formula (V).

Embedded image [However, in the formula (V), Rf has the same meaning as in the formula (I), and the hydrogen of the benzene ring is appropriately substituted with a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, and bromine. Is also good. And an acid chloride compound represented by the following formula (VI):

Embedded image [However, in the formula (VI), R ¹ and R ² have the same meanings as in the formula (IV), and the hydrogen of the benzene ring is a substituent such as a lower alkyl group, a lower alkoxy group, fluorine, chlorine, and bromine. The nitrogen atom may be optionally substituted and is bonded to the hydroxy group at the ortho, meta or para position. And an aminohydroxybenzene compound having an amino group protected.

Examples of the acid chloride compound represented by the above formula (V) include 5- (perfluorononenyloxy) isophthalic acid dichloride, 4-methyl-5- (perfluorononenyloxy) isophthalic acid dichloride, −
Methoxy-5- (perfluorononenyloxy) isophthalic acid dichloride, 4-fluoro-5- (perfluorononenyloxy) isophthalic acid dichloride, 4-chloro-5- (perfluorononenyloxy) isophthalic acid dichloride, -Bromo-5- (perfluorononenyloxy) isophthalic acid dichloride, 5- (perfluorohexenyloxy) isophthalic acid dichloride,
-Methyl-5- (perfluorohexenyloxy) isophthalic acid dichloride, 4-methoxy-5- (perfluorohexenyloxy) isophthalic acid dichloride,
Fluoro-5- (perfluorohexenyloxy) isophthalic acid dichloride, 4-chloro-5- (perfluorohexenyloxy) isophthalic acid dichloride, 4-
Bromo-5- (perfluorohexenyloxy) isophthalic acid dichloride and the like.

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.

[0032] In the above formulas (VI), 2-valent organic group combined monovalent organic group or R ¹ and R ² as R ¹ is a group protecting the amino group, such protecting group Is the above formula (I
There is one described in V).

Examples of the aminohydroxybenzene compound represented by the formula (VI) in which the amino group is protected include 1-hydroxy-4- (benzyloxycarbonylamino) benzene and 1-hydroxy-4- (t-butyloxycarbonyl). Amino) benzene, 1-hydroxy-4- (p-methoxybenzyloxycarbonylamino) benzene, 1-
Hydroxy-4- (p-nitrobenzyloxycarbonylamino) benzene, 1-hydroxy-4- (p-biphenylisopropyloxycarbonylamino) benzene, 1-hydroxy-4- (9-fluorenylmethyloxycarbonylamino) benzene , 1-hydroxy-4
-(Acetylamino) benzene, 1-hydroxy-4-
(4-toluenesulfonylamino) benzene, 1-hydroxy-4- (tritylamino) benzene, 1-hydroxy-3-methyl-4- (benzyloxycarbonylamino) benzene, 1-hydroxy-3-methoxy-4-
(Benzyloxycarbonylamino) benzene, 1-hydroxy-3-fluoro-4- (benzyloxycarbonylamino) benzene, 1-hydroxy-3-chloro-
4- (benzyloxycarbonylamino) benzene, 1
-Hydroxy-3-bromo-4- (benzyloxycarbonylamino) benzene, 1-hydroxy-3-methyl-4- (t-butyloxycarbonylamino) benzene, 1-hydroxy-3-methoxy-4- (t- Butyloxycarbonylamino) benzene, 1-hydroxy-
3-fluoro-4- (t-butyloxycarbonylamino) benzene,

1-hydroxy-3-chloro-4- (t-
Butyloxycarbonylamino) benzene, 1-hydroxy-3-bromo-4- (t-butyloxycarbonylamino) benzene, 1-hydroxy-3- (benzyloxycarbonylamino) benzene, 1-hydroxy-3
-(T-butyloxycarbonylamino) benzene, 1
-Hydroxy-3- (p-methoxybenzyloxycarbonylamino) benzene, 1-hydroxy-3- (p-
Nitrobenzyloxycarbonylamino) benzene, 1
-Hydroxy-3- (p-biphenylisopropyloxycarbonylamino) benzene, 1-hydroxy-3-
(9-fluorenylmethyloxycarbonylamino) benzene, 1-hydroxy-3- (benzyloxycarbonylamino) -5-methylbenzene, 1-hydroxy-
3- (benzyloxycarbonylamino) -5-methoxybenzene, 1-hydroxy-3- (benzyloxycarbonylamino) -5-fluorobenzene, 1-hydroxy-3- (benzyloxycarbonylamino) -5
Chlorobenzene, 1-hydroxy-3- (benzyloxycarbonylamino) -5-bromobenzene, 1-hydroxy-3- (t-butyloxycarbonylamino)-
5-methylbenzene, 1-hydroxy-3- (t-butyloxycarbonylamino) -5-methoxybenzene,
1-hydroxy-3- (t-butyloxycarbonylamino) -5-fluorobenzene,

1-hydroxy-3- (t-butyloxycarbonylamino) -5-chlorobenzene, 1-hydroxy-3- (t-butyloxycarbonylamino) -5
-Bromobenzene, 1-hydroxy-2- (benzyloxycarbonylamino) benzene, 1-hydroxy-2
-(T-butyloxycarbonylamino) benzene, 1
-Hydroxy-2- (p-methoxybenzyloxycarbonylamino) benzene, 1-hydroxy-2- (p-
Nitrobenzyloxycarbonylamino) benzene, 1
-Hydroxy-2- (p-biphenylisopropyloxycarbonylamino) benzene, 1-hydroxy-2-
(9-fluorenylmethyloxycarbonylamino) benzene, 1-hydroxy-2- (benzyloxycarbonylamino) -4-methylbenzene, 1-hydroxy-
2- (benzyloxycarbonylamino) -4-methoxybenzene, 1-hydroxy-2- (benzyloxycarbonylamino) -4-fluorobenzene, 1-hydroxy-2- (benzyloxycarbonylamino) -4-
Chlorobenzene, 1-hydroxy-2- (benzyloxycarbonylamino) -4-bromobenzene, 1-hydroxy-2- (t-butyloxycarbonylamino)-
4-methylbenzene, 1-hydroxy-2- (t-butyloxycarbonylamino) -4-methoxybenzene,
1-hydroxy-2- (t-butyloxycarbonylamino) -4-fluorobenzene, 1-hydroxy-2-
(T-butyloxycarbonylamino) -4-chlorobenzene, 1-hydroxy-2- (t-butyloxycarbonylamino) -4-bromobenzene and the like.

The formulas (I), (II), (III) and (I
In V) and (V), Rf in these formulas includes, for example, groups of formulas (a) to (i) shown in the following formula (20).

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As an example of the compound represented by the formula (V),
There is 5- (perfluorononenyloxy) isophthalic acid dichloride, which will be described below using this compound. However, for other compounds represented by the formula (V), the following description is essentially different. Absent. The reaction between 5- (perfluorononenyloxy) isophthalic acid dichloride and an aminohydroxybenzene compound having an amino group protected is described in Shinkagaku Koza Vol. 14 (II) (Maruzen Co., Ltd., issued on December 20, 1977). A publicly known method as shown on page 1020 and below can be employed. For example, a base such as pyridine, triethylamine, or dimethylaniline is used to capture the hydrochloric acid generated by the reaction in a nitrogen atmosphere. The base is preferably used in an amount of 1 molar equivalent to 3 molar equivalents with respect to the generated hydrochloric acid. If it is less than 1 molar equivalent, the capture of hydrochloric acid is insufficient, and if it is more than 3 molar equivalents, the yield may decrease due to side reactions and the like.

Further, as a catalyst for accelerating this reaction,
Strong bases such as N, N-dimethylaminopyridine, 4-pyrrolidinopyridine, diazabicyclononene (DBN), and diazabicycloundecene (DBU) can be used. The catalyst is preferably used in an amount of 0.5 mol% to 200 mol% with respect to the base added for capturing hydrochloric acid.

The above reaction is usually carried out in an organic catalyst. Solvents that can be used include toluene, benzene,
There are organic solvents that do not react with acid chloride or phenol, such as tetrahydrofuran ethyl ether. These organic solvents may be used as a mixture of two or more as long as they are compatible with each other. It is preferable to use a sufficiently dehydrated organic solvent. If water is present in the reaction system, the acid chloride is decomposed, and the yield may decrease.

By the above reaction, a fluorinated diamine represented by the formula (VI) in which the amino group is protected is obtained.
This may be separated by a method of distilling off the solvent or mixing with a poor solvent to cause precipitation, and then subjected to the next reaction. In some cases, the reaction solution may be directly used for the next reaction.

5- (Perfluorononenyloxy) isophthalic acid dichloride can be obtained by a known acid chloride synthesis method using 5- (perfluorononenyloxy) isophthalic acid using thionyl chloride, phosphorus pentachloride, phosphorus trichloride or the like. . Reaction conditions vary depending on the reagent used, and are not particularly limited.

The above-mentioned 5- (perfluorononenyloxy) isophthalic acid is represented by the following formula (VII):

Embedded image (However, in the formula, the —C ₉ F ₁₇ group contains one double bond,
It may be branched as appropriate. ).

The —C ₉ F ₁₇ group in the formula (VII) is introduced based on, for example, a trimer of hexafluoropropene as shown below. According to the method disclosed in JP-A-60-511146, a trimer of hexafluoropropene is reacted with 5-hydroxyisophthalic acid in an aprotic polar solvent at room temperature or lower in the presence of a base catalyst, A compound represented by the following formula (VIII) is obtained.

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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 represented by the formula (III) includes 4-aminophenyl-3-aminobenzoic acid, 2,2-bis (4 -Aminophenyl) propane, 2,6-diaminopyridine, bis (4-aminophenyl) diethylsilane, bis- (4-aminophenyl) diphenylsilane, bis- (4-aminophenyl)
Ethyl phosphine 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'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene,
2,4-bis (β-amino-t-butyl) toluene, bis (p-β-amino-t-butyl-phenyl) ether, bis (p-β-methyl-γ-amino-pentyl) benzene, bis- p- (1,1-dimethyl-5-aminopentyl) benzene,

Hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 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-diaminoicosadecane, 1,4-
Diaminocyclohexane, 1,10-diamino-1,1
0-dimethyldecane, 1,12-diaminooctadecane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenyl) phenyl) hexafluoropropane, 3,3′- Dimethyl-4,4'-diaminodiphenylmethane, 3,
3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'diethoxy-4,4'-diaminodiphenylmethane, 3, 3'-difluoro-4,4'-
Diaminodiphenylmethane, 3,3'-dichloro-4,
4'-diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane,

3,3'-di (trifluoromethyl)-
4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylether, 3,
3'-diisopropyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-4,4'-diaminodiphenyl ether, 3,3'-diethoxy-4,4 '
-Diaminodiphenyl ether, 3,3'-difluoro-4,4'-diaminodiphenyl ether, 3,3'-
Dichloro-4,4'-diaminodiphenyl ether,
3,3'-dibromo-4,4'-diaminodiphenyl ether, 3,3'-di (trifluoromethyl) -4,4 '
-Diaminodiphenyl ether, 3,3'-dimethyl-
4,4'-diaminodiphenylsulfone, 3,3'-dimethoxy-4,4'-diaminodiphenylsulfone,
3,3'-diethoxy-4,4'-diaminodiphenylsulfone, 3,3'-difluoro-4,4'-diaminodiphenylsulfone, 3,3'-dichloro-4,4'-
Diaminodiphenyl sulfone, 3,3'-dibromo-
4,4'-diaminodiphenylsulfone, 3,3'-di
(Trifluoromethyl) -4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-dimethoxy-4,4'-
Diaminodiphenylpropane, 3,3'-diethoxy-
4,4'-diaminodiphenylpropane, 3,3'-difluoro-4,4'-diaminodiphenylpropane,
3,3'-dichloro-4,4'-diaminodiphenylpropane, 3,3'-dibromo-4,4'-diaminodiphenylpropane, 3,3'-di (trifluoromethyl)-
4,4'-diaminodiphenylpropane, 3,3'-dimethyl-4,4'-diaminodiphenylsulfide,
3,3'-dimethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-difluoro-4,
4'-diaminodiphenyl sulfide, 3,3'-dichloro-4,4'-diaminodiphenyl sulfide, 3,
3'-dibromo-4,4'-diaminodiphenyl sulfide, 3,3'-di (trifluoromethyl) -4,4 '
-Diaminodiphenyl sulfide, 3,3'-dimethyl-4,4'-diaminodiphenylhexafluoropropane, 3,3'-dimethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3 ' -Diethoxy-4
4'-diaminodiphenylhexafluoropropane,
3,3'-difluoro-4,4'-diaminodiphenylhexafluoropropane, 3,3'-dichloro-4,4 '
-Diaminodiphenylhexafluoropropane, 3,
3'-dibromo-4,4'-diaminodiphenylhexafluoropropane, 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenylhexafluoropropane,

3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-dimethoxy-4,4'-diaminobenzophenone, 3,3'-diethoxy-4,
4'-diaminobenzophenone, 3,3'-difluoro-4,4'-diaminobenzophenone, 3,3'-dichloro-4,4'-diaminobenzophenone, 3,3'-
Dibromo-4,4'-diaminobenzophenone, 3,
3'-di (trifluoromethyl) -4,4'-diaminobenzophenone, 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'-tetrafluoro-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetrachloro-4,4'
-Diaminodiphenyl ether, 3,3 ', 5,5'-
Tetrabromo-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'-diaminodiphenyl ether,

3,3 ', 5,5'-tetramethyl-4,
4'-diaminodiphenylsulfone, 3,3 ', 5
5'-tetramethoxy-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetraethoxy-4,4'
-Diaminodiphenylsulfone, 3,3 ', 5,5'-tetrafluoro-4,4'-diaminodiphenylsulfone,
3,3 ', 5,5'-tetrachloro-4,4'-diaminodiphenylsulfone, 3,3', 5,5'-tetrabromo-4,4'-diaminodiphenylsulfone, 3,
3 ', 5,5'-tetra (trifluoromethyl) -4,
4'-diaminodiphenylsulfone, 3,3 ', 5
5'-tetramethyl-4,4'-diaminodiphenylpropane, 3,3 ', 5,5'-tetramethoxy-4,
4'-diaminodiphenylpropane, 3,3 ', 5
5'-tetraethoxy-4,4'-diaminodiphenylpropane, 3,3 ', 5,5'-tetrafluoro-4,
4'-diaminodiphenylpropane, 3,3 ', 5
5'-tetrachloro-4,4'-diaminodiphenylpropane, 3,3 ', 5,5'-tetrabromo-4,4'
-Diaminodiphenylpropane, 3,3 ', 5,5'-
Tetra (trifluoromethyl) -4,4'-diaminodiphenylpropane, 3,3 ', 5,5'-tetramethyl-
4,4'-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'-diaminodiphenylsulfide, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetramethoxy-
4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetraethoxy-4,4'-
Diaminodiphenylhexafluoropropane, 3,
3 ', 5,5'-tetrafluoro-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5
5'-tetrachloro-4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetrabromo-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5,5 '-Tetra (trifluoromethyl) -4,4'-diaminodiphenylhexafluoropropane,

3,3 ', 5,5'-tetramethyl-4,
4'-diaminobenzophenone, 3,3 ', 5,5'-
Tetramethoxy-4,4'-diaminobenzophenone,
3,3 ', 5,5'-tetraethoxy-4,4'-diaminobenzophenone, 3,3', 5,5'-tetrafluoro-4,4'-diaminobenzophenone, 3,3 ',
5,5'-tetrachloro-4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetrabromo-4,4'
-Diaminobenzophenone, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'-diaminobenzophenone, 3,3', 5,5'-tetraisopropyl-
4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5
5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-
4,4'-diaminodiphenyl ether, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenyl ether, 3,3'-diisopropyl-
5,5'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylpropane, 3,3 '
-Diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylsulfone, 1,3-diamino- There is 5- (perfluorononenyloxy) benzene and the like, and two or more kinds may be used in combination.

As a part of the diamine, silicon diamine may be used. Such silicon diamines include 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 silicon diamine is used, these amounts are preferably used in an amount of 0.1 to 10 mol% based on the total amount of diamine. By using silicon diamine, the resulting polyimide resin has improved adhesion.

In producing a polyimide resin, tetracarboxylic dianhydride and a diamine are reacted at an appropriate temperature. In this reaction, the degree of imidization can be appropriately adjusted by selecting appropriate conditions. For example, to produce a completely or almost completely imidized polyimide by reacting at 100 ° C. or higher, particularly 120 ° C. or higher, if necessary, in the presence of a catalyst such as tributylamine, triethylamine, and triphenyl phosphite. (The catalyst is 0 to 1 with respect to the total amount of the reaction components.
It is preferably used in an amount of 5% by weight, particularly preferably 0.01 to 15% by weight.
The following reaction can produce a polyamic acid which is a polyimide precursor and is completely or almost not imidized. Further, a polyimide precursor in which imidization has partially progressed can be produced.

Further, the above-mentioned polyamic acid or the polyimide precursor partially partially imidized is further heated to 100 ° C. or more, particularly 120 ° C. or more, to imidize it, or to acetic anhydride, propionic anhydride, benzoic anhydride. Chemical ring closure (imidization) (ring closure) in the presence of a ring closing agent such as an acid anhydride such as an acid, a carbodiimide such as dicyclohexylcarbodiimide, and, if necessary, a ring closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine and imidazole. It is preferable to use the agent and the ring-closing catalyst in the range of 1 to 8 mol per 1 mol of the acid anhydride.)
According to the method, a polyimide in which imidization is almost or completely completed can be produced. These reactions are
Preferably, the reaction is performed in the presence of an organic solvent.

The organic polar solvents usable in the above reaction include 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 thereof may be used as a mixture as long as they are compatible with each other. In addition, along with these organic polar solvents, toluene,
General-purpose solvents such as xylene, cellosolve acetate, and methyl cellosolve can be used in combination as long as the solubility of the polyimide resin or its precursor is not reduced. There are no particular restrictions on the order in which the reactants are added.

The polyimide resin such as polyimide or polyamic acid in the present invention can be used in the form of a varnish or powder dissolved in an organic solvent. In particular, a polyamic acid and a precursor of a polyimide having a low degree of imidization are soluble in an organic solvent and can be used in the form of a varnish.However, a polyimide resin which is almost completely imidized can be dissolved in an organic solvent. There are soluble ones and hardly soluble ones.
The latter is preferably used in powder form. Further, in order to prevent voids due to condensed water accompanying the imidation reaction,
It is preferable to use the polyimide after imidization is almost completed.

The polyimide resin varnish can be applied to the surface of a substrate such as a glass or silicon wafer by a commonly used method such as spin coating, spraying, brushing and the like, and then heated to form a polyimide film. In this case, when a polyimide precursor is used, it is imidized during the heat treatment.

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

The above polyimide film is made of hydrazine,
Through holes and the like can be easily processed with an etching solution usually used for a polyimide resin such as tetramethylammonium hydroxide.

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 more. Further, the polyimide can be adjusted to have a water absorption of 1% or less, particularly 0.5% or less. The compound obtained in each step can be purified by column separation, recrystallization from alcohol, and the like.

[0061]

EXAMPLES First, 5- (perfluorononenyloxy)
Isophthalic acid dichloride, 1-hydroxy-4- (benzyloxycarbonylamino) benzene, 5- (perfluorononenyloxy) isophthalic acid bis 4- (benzyloxycarbonylaminophenyl ester), and 5- (perfluorononenyloxy) ) Isophthalic acid bis (4-aminophenyl ester) was synthesized.

Synthesis Example 1 Synthesis of 5- (perfluorononenyloxy) isophthalic acid dichloride Thionyl chloride was added to 61.2 g (0.1 mol) of 5- (perfluorononenyloxy) isophthalic acid of formula (VIII). 120
g (0.1 mol) and heated at 80 ° C., and after 12 hours, the reaction system became a homogeneous solution. Then, excess thionyl chloride was distilled off under reduced pressure, and the mixture was distilled under reduced pressure. (Fluorononenyloxy) isophthalic acid dichloride was obtained.

Synthesis Example 2 Synthesis of 1-hydroxy-4- (benzyloxycarbonylamino) benzene 13.08 g (0.120 mol) of p-aminophenol
260 ml of dry tetrahydrofuran (THF) and 11.38 g (0.144 mol) of pyridine were added to the mixture, and benzyloxycarbonyl chloride was added in an ice bath under a nitrogen stream.
0% toluene solution was added dropwise over 1 hour.
For 5 hours and at room temperature for 16 hours. The resulting pyridine hydrochloride was filtered off, the filtrate was concentrated by evaporation, and the precipitate was poured into a large amount of water to precipitate. Drying yielded 1-hydroxy-4- (benzyloxycarbonylamino) benzene.

(Synthesis Example 3) Synthesis of bis (4- (benzyloxycarbonylaminophenyl) ester of 5- (perfluorononenyloxy) isophthalic acid 11.7 g of 1-hydroxy-4- (benzyloxycarbonylamino) benzene (48) 2.0 mmol) in dry T
Dissolved in 80 ml of HF and 3.79 g of pyridine (48.0
Mmol) and N, N-dimethylaminopyridine 0.4
9 g (4.0 mmol) was added, and 13.0 g (20.0 mmol) of 5- (perfluorononenyloxy) isophthalic acid dichloride in a dry THF solution (4
0 ml) was slowly added dropwise, followed by 5 hours at room temperature,
And reacted at 60 ° C. for 2 hours, the resulting pyridine hydrochloride was filtered off, the filtrate was evaporated and concentrated, then poured into a large amount of water, the resulting white precipitate was filtered, washed with water, and dried under reduced pressure. As a result, the following 5- (perfluorononenyloxy) isophthalic acid bis 4- (benzyloxycarbonylaminophenyl ester) represented by Chemical Formula 23 was obtained.

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(Synthesis Example 4) Synthesis of bis (4-aminophenyl ester) 5- (perfluorononenyloxy) isophthalate Bis 4- (benzyloxycarbonylaminophenyl ester) 5- (perfluorononenyloxy) isophthalate ) 10.6 g (0.010 mol) of THF 50 ml,
After adding 2.7 g of 5% palladium / carbon and stirring at room temperature for 7 hours under a hydrogen stream, the palladium / carbon was filtered off, the filtrate was distilled off, and the column was separated using ethyl acetate / hexane as a developing solvent. To give bis (4-aminophenyl ester) 5- (perfluorononenyloxy) isophthalate.

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Example 1 8 g of dried N, N-dimethylacetamide and 5- (perfluorononenyloxy) obtained above were placed in a four-necked flask equipped with a thermometer, a stirring device, a drying tube and a nitrogen introducing tube. 1.59 g (2 mmol) of bis (4-aminophenyl ester) isophthalate [Formula 24] was taken and stirred. After the diamine is dissolved, while cooling in an ice bath,
0.89 g (2 mmol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added in small portions. After the addition, cool in an ice bath for 5 minutes.
The reaction was carried out for a time to obtain a polyamic acid solution.

The above polyamic acid solution is poured into water,
The precipitated polyamic acid was filtered off and dried. FIG. 1 shows the infrared absorption spectrum (IR spectrum) of this polyamic acid. The polyamic acid was dissolved in N, N-dimethylacetamide at a concentration of 0.1 g / dl,
Table 1 shows the results obtained by measuring the reduced viscosity in the above.

Further, the above polyamic acid solution was applied on a glass substrate by spin coating, and the solution was sequentially heated at 150 ° C. and 20 ° C.
Heating was performed at 0 ° C., 250 ° C., and 300 ° C. for 30 minutes each to obtain a polyimide film. FIG. 2 shows the results of measuring the IR spectrum of the polyimide using the obtained polyimide film, and Table 1 shows the results of measuring the glass transition temperature, the thermal decomposition temperature, the water absorption and the dielectric constant.

The fluorinated polyimide obtained here contains a structural unit represented by the following chemical formula 25. In addition,
Rf 'represents a group of the formula (a) in the above formula (hereinafter the same).

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Example 2 8 g of dried N-methyl-2-pyrrolidone was placed in a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube, and 5- (perfluorononenyloxy) was added thereto. ) Bis (4-aminophenyl ester) isophthalate
[Formula 24] 1.59 g (2 mmol) was added and stirred. After the diamine was dissolved, 0.64 g (2 mmol) of 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride was added little by little. After completion of the addition, the mixture was reacted at room temperature for 5 hours to obtain a polyamic acid solution. Thereafter, the polyamic acid was isolated according to Example 1, and the reduced viscosity was measured. Furthermore, a polyimide film was prepared according to Example 1, and the glass transition temperature, the thermal decomposition temperature, and the water absorption were measured (Table 1).

The fluorinated polyamic acid obtained here is
It contains a structural unit represented by the following Chemical Formula 26.

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Example 3 8 g of dried N, N-dimethylacetamide was placed in a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube, and 5- (perfluorononenyloxy) was added thereto. 0.79 g (1 mmol) of bis (4-aminophenyl ester) isophthalate [formula 24] and 4,4 '
0.20 g (1 mmol) of diaminodiphenyl ether was added and stirred until a homogeneous solution was obtained. Then, at room temperature, 0.58 g (2 mmol) of 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride was added little by little,
The reaction was carried out at room temperature for 5 hours to obtain a polyamic acid. afterwards,
Polyamic acid was isolated according to Example 1, and the reduced viscosity was measured. Furthermore, a polyimide film was prepared according to Example 1, and the glass transition temperature, the thermal decomposition temperature, and the water absorption were measured (Table 1).

The fluorinated polyimide thus obtained contains 50 mol% of a structural unit represented by the following chemical formula 27 and
Is a unit containing 50 mol%.

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Example 4 8 g of N, N-dimethylformamide was placed in a four-necked flask equipped with a thermometer, a stirring device, a drying tube and a nitrogen inlet tube.
And bis (4-aminophenyl ester) 5- (perfluorononenyloxy) isophthalate [formula 2]
4] 1.59 g (2 mmol) was added and stirred until a homogeneous solution was obtained. Then, while cooling in an ice bath,
', 4'-biphenyltetracarboxylic dianhydride 0.5
8 g (2 mmol) were added in small portions. After the addition,
The reaction was carried out for 5 hours while cooling in an ice bath to obtain a polyamic acid. Thereafter, the polyamic acid was isolated according to Example 1,
The IR spectrum and reduced viscosity were measured. Furthermore, a polyimide film was prepared according to Example 1, and the IR spectrum, glass transition temperature, thermal decomposition temperature, and water absorption were measured. FIG. 3 shows an IR spectrum of the polyamic acid, FIG. 4 shows an IR spectrum of the polyimide, and Table 1 shows other measurement results.
It was shown to.

The fluorinated polyimide obtained here contains a structural unit represented by the following structural formula 29.

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Example 5 8 g of dried N, N-dimethylacetamide and bis (5- (perfluorononenyloxy) isophthalate) were placed in a four-necked flask equipped with a thermometer, a stirring device, a drying tube and a nitrogen inlet tube. 4-aminophenyl ester)
4] 1.59 g (2 mmol) was taken and stirred. After the diamine is dissolved, 1,2,3,
4-cyclobutanetetracarboxylic dianhydride 0.392
g (2 mmol) was added little by little, and after completion of the addition, the mixture was reacted 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 reduced viscosity was measured. Furthermore, a polyimide film was prepared according to Example 1, and the glass transition temperature, the thermal decomposition temperature, and the water absorption were measured (Table 1).

The fluorinated polyimide obtained here contains a structural unit represented by the following structural formula.

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Example 6 In a four-necked flask equipped with a thermometer, a stirring device, a drying tube and a nitrogen introducing tube, 8 g of dried N, N-dimethylacetamide and bis (5- (perfluorononenyloxy) isophthalate) were added. 4-aminophenyl ester)
4] 1.59 g (2 mmol) of 1.59 g was taken and stirred. After the diamine was dissolved, 0.396 g (2 mmol) of butanetetracarboxylic dianhydride was added little by little while cooling in an ice bath. After completion of the addition, the mixture was reacted 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 reduced viscosity was measured. Furthermore, a polyimide film was prepared according to Example 1, and the glass transition temperature, the thermal decomposition temperature, and the water absorption were measured (Table 1).

The fluorinated polyimide obtained here contains a structural unit represented by the following structural formula.

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Example 7 8 g of dried N, N-dimethylacetamide and bis (5- (perfluorononenyloxy) isophthalate) were placed in a four-necked flask equipped with a thermometer, a stirring device, a drying tube and a nitrogen inlet tube. 4-aminophenyl ester)
4] 1.59 g (2 mmol) was taken and stirred. After the diamine was dissolved, 0.788 g (2 mmol) of bis (exo-bicyclo [2,2,1] hept-2,3-dicarboxylic anhydride) sulfone was added little by little while cooling in an ice bath. After completion of the addition, the mixture was reacted for 5 hours while cooling in an ice bath to obtain a polyamic acid solution. Thereafter, the first embodiment
The polyamic acid was isolated according to the method described in Example 1, and the reduced viscosity was measured.
Furthermore, a polyimide film was prepared according to Example 1, and the glass transition temperature, the thermal decomposition temperature, and the water absorption were measured (Table 1).

The obtained fluorinated polyimide contains a structural unit represented by the following formula (32).

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Comparative Example 1 In a four-necked flask equipped with a thermometer, a stirring device, a drying tube and a nitrogen introducing tube, 8 g of dried N, N-dimethylacetamide and 0.4 g of 4,4'-diaminodiphenyl ether ( 2 mmol) and stirred until a homogeneous solution was obtained. After the diamine is dissolved, while cooling in an ice bath,
0.89 g (2 mmol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added in small portions. After the addition, cool in an ice bath for 5 minutes.
The reaction was carried out for a period of time to obtain a polyamic acid. Then, Example 1
The polyamic acid was isolated according to the method described in the above, and the reduced viscosity was measured.
Further, a polyimide film was prepared according to Example 1,
The glass transition temperature, thermal decomposition temperature and water absorption were measured. The results of these measurements are also shown in Table 1.

Comparative Example 2 In place of 0.89 g (2 mmol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, benzophenone tetracarboxylic dianhydride was used instead of 0.89 g (2 mmol).
Except that 64 g (2 mmol) was used, the same operation as in Comparative Example 1 was carried out to isolate the polyamic acid, measure its reduced viscosity, further prepare a polyimide film, and obtain its glass transition temperature and thermal decomposition temperature. And the water absorption were measured (Table 1).

The conditions for measuring the glass transition temperature, the thermal decomposition temperature, the water absorption and the dielectric constant are as follows. 1) Glass transition temperature Using Perkin Elmer DSC-7, heating rate 10 ° C
/ Min Measured with a sample amount of about 10 mg. 2) Thermal decomposition temperature The thermal decomposition temperature was measured at a heating rate of 10 ° C./min using a differential thermal balance (TG-7000, manufactured by Vacuum Riko Co., Ltd.). 3) Water absorption The polyimide film was immersed in water at room temperature for 24 hours, and the water absorption was determined from the weight change before and after that. 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.

[0085]

[Table 1] Table 1 Measurement results of properties ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Polyamide polyimide Example or ───────────────────── 比較 is a comparative example Reduced viscosity Glass transition Thermal decomposition temperature Water absorption Dielectric constant (dl / g) Temperature ( ° C) degree (° C) (%)） Example 1 41 247 433 0.2 2.7 2 0.40 241 413 0.3 2.9 3 0.45 253 425 0.3 2.9 4 0.43 251 426 0.3 2.35 0.30 234 420 0.2 2.8 6 0.34 224 415 0.3 2.8 7 0.28 258 380 0.3 2.9 Comparative Example 1 0.55 175 450 1.1 3.6 2 0.63 29 463 1.3 3.5 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0086]

The fluorinated polyimide of claim 1 or 2 and the fluorinated polyamic acid of claim 3 or 4 are novel. These polyimides or polyimides obtained from these polyamic acids have a low dielectric constant, a low water absorption, excellent moisture resistance, and good heat resistance. According to the method of claim 5, the polyimide,
Alternatively, a polyimide resin containing the above polyamic acid can be easily produced.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of a 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 4.

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

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 73/00-73/26 C08L 79/00-79/08

Claims (5)

(57) [Claims] ## STR1 ## 1. The formula (I): ## STR1 ## [In the formula (I), R represents a tetravalent residue of a tetracarboxylic acid dianhydride, Rf is -C _n F _2n-1 (where, n is a integer from 6-12, which is two wherein one of the double bond, may be branched.) shows the hydrogen of the benzene ring is a lower alkyl group, lower alkoxycarbonyl
It may be substituted by a xy group, fluorine, chlorine or bromine, and the nitrogen atoms of the two imide groups are respectively bonded to the ortho, meta or para position with respect to the ester bond. ] The fluorine-containing polyimide containing the structural unit represented by these. (2) In addition to the structural unit represented by the above formula (I), a compound represented by the following formula (I ′): [Wherein, in the formula (I ′), R ′ is a tetravalent residue of tetracarboxylic dianhydride which may be different or the same as R in the formula (I), and X is A divalent diamine residue different from 3 (formula (A)); In formula (A), Rf has the same meaning as in formula (I), and hydrogen on the benzene ring is a lower alkyl group or a lower alcohol.
It may be substituted by a xy group, fluorine, chlorine or bromine . ] The fluorine-containing polyimide containing the structural unit represented by these. ## STR3 ## [Chem. 4] [Formula (II)] [However, in the formula (II), R and Rf have the same meanings as in the formula (I), and hydrogen on the benzene ring is a lower alkyl.
A nitrogen atom of the two imide groups may be ortho-, meta- or para-position to the ester bond, each of which may be substituted with a substituent such as a kill group, a lower alkoxy group, fluorine, chlorine or bromine. Is bound to. ] A fluorinated polyamic acid comprising a structural unit represented by the formula: 4. In addition to the structural unit represented by the above formula (II), a compound represented by the following formula (II ′): [However, in the formula (II ′), R ′ and X have the same meanings as in the formula (I ′). ] A fluorinated polyamic acid comprising a structural unit represented by the formula: 5. A diamine compound containing a fluorine-containing aromatic diamine represented by (a) an acid anhydride containing a tetracarboxylic dianhydride; and (b) a fluorinated 6 [formula (III)]. [Wherein, in the formula (III), Rf has the same meaning as in the formula (I), and hydrogen on the benzene ring is a lower alkyl.
Group, lower alkoxy group, fluorine, chlorine or bromine . A process for producing a fluorine-containing polyimide resin.