JP5252338B2 - Diamine compound, polyamic acid and imidized polymer produced using the same - Google Patents

Description

  The present invention relates to a novel diamine compound, and polyamic acid and imidized polymer produced using the same.

  Polyimides have many higher-order structures consisting of cyclic structures such as heterocycles and aromatic rings, molecular chains are difficult to move even at high temperatures, have many higher-order bonds such as double bonds, and interatomic bond energy The heat resistance of polyimide is different from that of various plastics for the reasons that the heterocycle and aromatic ring interact with each other in the polymer molecule and form a CT (Charge Transfer) complex and the cohesion is large. Among them, it is ranked highest.

  Furthermore, polyimide not only has excellent heat resistance, but also has high strength, high elasticity, excellent mechanical properties, high insulation, low dielectric properties, and excellent electrical properties, as well as chemical resistance, radiation resistance, and flame resistance. Is also excellent.

  In recent years, photosensitive polyimides have also been developed. Ultra-highly integrated semiconductors, tough and strong adhesive polyimides are used in space transportation machines, highly transparent polyimides are used in optical communication equipment, and injection moldable polyimides are used in automobiles. Used in heat-resistant sliding parts such as parts.

  As an example of using a polyimide having the above characteristics for an optical application, an example using a polyimide using a dianhydride containing a sulfur atom and a diamine not containing a sulfur atom as an optical waveguide (Patent Document 1) ; Example using a polyimide using a diacid anhydride containing no sulfur atom and a diamine containing a sulfur atom as a liquid crystal alignment film (Patent Document 2); Highly refracting a mixture of polyimide having a specific structure and titanium oxide particles Example (Patent Document 3) used as a rate material; and Example using a mixture of polyamic acid not containing a sulfur atom, titanium oxide particles and other specific compounds as a positive photosensitive resin composition (Patent Document 4) Etc. are known.

JP 2004-131684 A JP-A-5-263077 JP 2001-354853 A JP 2005-208465 A

  It is an object of the present invention to provide a novel diamine compound for producing a polyimide having a higher refractive index and excellent transparency and heat resistance, a polyamic acid and an imidized polymer produced using the same. To do.

That is, the present invention provides the following novel diamine compound, and a novel polyamic acid and imidized polymer comprising it and tetracarboxylic dianhydride.
1. A diamine compound represented by the following general formula (1).
2. A polyamic acid having a structure represented by the following general formula (3).
[In Formula (3), R shows a tetravalent aliphatic group, a tetravalent alicyclic group, or a tetravalent aromatic group, and m shows the number of 1-100000. ]
3. An imidized polymer having a structure represented by the following general formula (4).
[In Formula (4), R shows a tetravalent aliphatic group, a tetravalent alicyclic group, or a tetravalent aromatic group, and m shows the number of 1-100,000. ]

By using the novel diamine compound of the present invention, it is possible to provide a polyamic acid and an imidized polymer having a high refractive index and excellent transparency and heat resistance.
The novel polyamic acid and imidized polymer of the present invention are particularly suitable for optical applications that require a high refractive index, excellent transparency and heat resistance.
In the present invention, by using a novel diamine compound into which a sulfur atom is introduced, a high refractive index material capable of achieving both a high refractive index and high heat resistance can be provided.
By combining a novel diamine compound and an aliphatic or alicyclic tetracarboxylic dianhydride, an imidized polymer having a high refractive index and high transparency and excellent heat resistance can be obtained.

  Hereinafter, the novel diamine compound of the present invention, the polyamic acid produced using the diamine compound, and the imidized polymer will be specifically described.

I. Diamine Compound The diamine compound of the present invention is a compound having a fluorene skeleton and a sulfur atom (sulfide group) in the molecule and having a structure represented by the following general formula (1). By having a fluorene skeleton and a sulfur atom in the molecule, the polyamic acid and imidized polymer produced using the fluorene skeleton and the sulfur atom can have a high refractive index.
The substitution positions of the two sulfide groups are preferably the p-position of the phenyl group substituted at the 9-position of the fluorene skeleton and the 4-position of phthalic dianhydride, respectively.

The diamine compound of the present invention can be produced as follows.
Step 1: Production of dinitro compound In an aprotic polar solvent, anhydrous potassium carbonate and 9,9′-bis (4-mercaptophenyl) fluorene are reacted to form 9,9′-bis (4-mercaptophenyl) in the system. ) Synthesize the potassium salt of fluorene. The dinitro compound shown by General formula (5) can be manufactured by adding p-chloronitrobenzene there. In addition, the manufacturing method of a fluorene skeleton is well-known, It can manufacture according to a well-known method. Moreover, a fluorene derivative can also be obtained as a commercial item.

Step 2: Manufacture of a diamine compound By using palladium carbon and hydrazine monohydrate in a protic polar solvent, the dinitro compound (5) synthesized in Step 1 is reduced to give a general formula (6). A diamine compound can be produced.

II. Polyamic acid The polyamic acid of the present invention is a polymer obtained by polycondensation reaction of the diamine compound of the present invention and tetracarboxylic dianhydride, preferably the following general formula (2)
It is a polymer which has a structure shown by following General formula (3) obtained by polycondensation reaction with the tetracarboxylic dianhydride which has a structure shown by these.

R in the above general formulas (2) and (3) is a tetravalent aliphatic group, a tetravalent alicyclic group or a tetravalent group corresponding to the residue obtained by removing the anhydride group from tetracarboxylic dianhydride. An aromatic group of
M in the said General formula (3) shows the number of 1-100,000, and it is preferable that it is 10-10000.

  The tetracarboxylic dianhydride represented by the general formula (2) is selected from the group consisting of aliphatic, alicyclic or aromatic tetracarboxylic dianhydrides, and has excellent transparency required for optical applications. An aliphatic or alicyclic tetracarboxylic dianhydride is more preferable because a cured product having properties can be obtained.

Specific examples of the aliphatic or alicyclic tetracarboxylic dianhydride include, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 ^2,7 ] dodecane-3,5,9,11-tetraone Meso-1,2,3,4-butanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dihydrate, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro -2,5 Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic Aliphatic and alicyclic tetracarboxylic dianhydrides such as acid dianhydrides and bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydrides be able to. Among these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 ^2,7 ] dodecane- 3,5,9,11-tetraone, meso-1,2,3,4-butanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-di- Oxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3. 1.0 ^2,7 ] Dodecane-3,5,9,11-tetraone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, meso-1,2,3,4-butanetetracarboxylic dianhydride are particularly preferred.

  Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl Sulfonetetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenylsulfonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyl Diphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′- Screw (3 4-Dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane Dianhydride, 4,4 ′-(hexafluoroisopropylidene) bis (phthalic acid) dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide Dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride , Aromatic tetracarboxylic dianhydrides such as bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride It can be mentioned. Among these, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 2 , 3 ′, 3,4′-biphenylsulfonetetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) bis (phthalic acid) dianhydride and 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydrides are preferred.

  In addition, since a polyamic acid having a higher refractive index can be obtained, it is also preferable to use a tetracarboxylic dianhydride containing a sulfur atom. Examples of sulfur atom-containing acid anhydrides include 4,4 '-[p-thiobis (phenylene-sulfanyl)] diphthalic anhydride.

  In addition, in manufacture of the polyamic acid of this invention, other diamine can also be used together in the range which does not impair the effect of this invention other than the diamine compound shown by the said General formula (1). Examples of such a diamine compound include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4,4′- Diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 3,4′-diaminodiphenyl ether, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-Aminophenoxy) phenyl] hexafluoropropane, 2 2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino- 5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 - it can be exemplified (m-phenylene-isopropylidene) bisaniline.

In addition, aromatic diamines having hetero atoms such as diaminotetraphenylthiophene; 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylene Diamine, Nonamethylenediamine, 4,4-Diaminoheptamethylenediamine, 1,4-Diaminocyclohexane, Isophoronediamine, Tetrahydrodicyclopentadienylenediamine, Hexahydro-4,7-methanoindanylene methylenediamine, Tricyclo [6 , 2,1,0 ^2.7 ] -undecylenedimethyldiamine and the like can also include aliphatic or alicyclic diamines.

  Of the diamines used in the production of the polyamic acid of the present invention, the proportion of the diamine compound of the present invention represented by the general formula (1) is preferably 50 mol% or more, more preferably 80 mol% or more. In order to achieve a high refractive index, it is particularly preferably 100 mol%.

The polycondensation reaction between the diamine compound represented by the general formula (1) and the tetracarboxylic dianhydride can be carried out under known methods and conditions. For example, the following method is preferred.
The polyamic acid of the present invention can be obtained as a solution by stirring and mixing the diamine compound and the acid dianhydride in an aprotic organic solvent such as N-methyl-2-pyrrolidone. For example, a diamine compound may be dissolved in an organic solvent, and acid dianhydride may be added thereto and mixed with stirring. Alternatively, a mixture of a diamine compound and acid dianhydride may be added to an organic solvent and mixed with stirring. May be. The reaction is usually performed at a temperature of 100 ° C. or lower, preferably 80 ° C. or lower, under normal pressure. However, the reaction may be performed under pressure or under reduced pressure as necessary. The reaction time varies depending on the diamine compound and acid dianhydride used, the organic solvent, the reaction temperature, etc., but is usually in the range of 4 to 24 hours.

III. Imidized polymer The imidized polymer of the present invention is obtained by imidizing the polyamic acid of the present invention, and preferably has a structure represented by the following general formula (4).
In the formula (4), R and m are as described in the general formula (3).

  The method and reaction conditions for imidizing the polyamic acid of the general formula (3) are not particularly limited, and known methods and reaction conditions can be used. For example, as a heating imidation method, a method of heating to 250 to 350 ° C. for 1 to 6 hours to convert to an imidized polymer, 100 ° C. for 1 hour, 200 ° C. for 1 hour, and further 300 ° C. for 1 hour And a method of heating in stages. Furthermore, a dehydrating cyclization reagent such as a carboxylic acid anhydride and a tertiary amine can also be used as chemical imidization. Examples of the dehydrating cyclization reagent include acetic anhydride-pyridine, acetic anhydride-triethylamine, and trifluoroacetic anhydride.

  The polyamic acid of the present invention has a high refractive index, and the imidized polymer of the present invention obtained by imidizing this also has a high refractive index, excellent transparency and heat resistance, and has a high refractive index and transparency. And is useful as a material for producing articles that require heat resistance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples.

Production Example 1
4,4 ′-[p-thiobis (phenylene-sulfanyl)] diphthalic anhydride
In a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, 4,4′-thiobisbenzenethiol (5.00 g, 0.02 mol) and 4-bromophthalic anhydride (10.00 g, 0.044 mol) , Anhydrous potassium carbonate (6.08 g, 0.044 mol), and N, N-dimethylformamide (DMF) (100 ml) were added and reacted at 120 ° C. for 12 hours. The reaction solution was returned to room temperature, and a white solid was collected by filtration and dried under reduced pressure at 160 ° C. for 24 hours. Distilled water (100 ml) and concentrated hydrochloric acid (100 ml) were added to the obtained white solid, and the mixture was heated and stirred for 3 hours. The obtained white solid was collected by filtration and heated at 180 to 190 ° C. for 3 hours to obtain a yellow solid.

Yield: 7.8g
Yield: 71.9%
Melting point: 175.2 ° C (DSC)
FT-IR (KBr, cm < ^-1 >): 1847.5, 1778.0, 1604.4, 1473.3, 1326.8, 1257.4, 902.5, 817.7, 732.0
¹ H-NMR (300 MHz, DMSO-d ₆ , ppm): 7.45-7.49 (d, 4H), 7.52 to 7.55 (d, 4H), 7.56 (s, 2H), 7.60-7.63 (d, 2H), 7.83-7.85 (d, 2H)
Calcd _{C 28 H 14 O 6 S 3} : C, 61.98%; H, 2.60%
Measured value C, 62.23%; H, 2.97%

Example 1
(1) Synthesis of 9,9′-bis [4- (p-nitrophenyl) sulfanylphenyl] fluorene
In a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, anhydrous potassium carbonate (4.50 g, 32.56 mmol) and 9,9′-bis (4-mercaptophenyl) fluorene (4.10 g, 10.72 mmol) ), P-chloronitrobenzene (4.37 g, 27.74 mmol) and dehydrated DMF (14 ml) were added and reacted at 180 ° C. for 24 hours. The reaction solution was poured into cold water, and the precipitate was collected by filtration and washed with a water / ethanol = 1/1 (volume) solution. The filtered product was dried at 160 ° C. for 12 hours. The crude product was purified by recrystallization using a DMF / ethanol mixed solution.
Yield: 5.72g
Yield: 86%
Melting point: 239.0 ° C. (DSC)
FT-IR (KBr, cm ⁻¹ ): 3089, 3070, 1674, 1577, 1334, 1083, 836, 740
¹ H-NMR (300 MHz, CDCl ₃ , ppm): 8.04 (d, 4H), 7.84-7.78 (m, 2H), 7.46-7.38 (m, 8H), 7. 34 (d, 2H), 7.28 (d, 4H), 7.18 (d, 4H)

(2) Synthesis of 9,9′-bis [4- (p-aminophenyl) sulfanylphenyl] fluorene
In a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, 9,9′-bis [4- (p-nitrophenyl) sulfanylphenyl] fluorene (2.59 g, 4.14 mmol) synthesized in the above (1) was added. ), Dehydrated ethanol (26 ml), and 10% palladium activated carbon (0.35 g) were added and heated to reflux. Thereafter, hydrazine monohydrate (26 ml) was added dropwise over 1.5 hours, and the reaction solution was heated to reflux for 3 to 24 hours. The reaction mixture was filtered hot, and the yellow precipitate was collected by filtration and washed with ethanol. The obtained yellow solid was recrystallized and purified using ethanol. FIG. 1 shows a ¹³ C-NMR chart, DEPT-135 ° chart and ¹ H-NMR chart of the obtained compound, and FIG. 2 shows ¹ H-NMR (COSY).

Yield: 1.92 g
Yield: 82%
Melting point: 216.3 ° C. (DSC)
FT-IR (KBr, cm ⁻¹ ): 3451, 3367, 3050, 3025, 1616, 1594, 1034, 825, 756
Calcd _{C 37 H 28 N 2 S 4} : C, 78.71%; H, 4.96%; N, 4.96%
Measurement C, 78.41%; H, 5.13%; N, 4.44%

<Production of polyamic acid>
Example 2
In a reaction vessel equipped with a nitrogen introduction tube, 9,9′-bis [4- (p-aminophenyl) sulfanylphenyl] fluorene (2.26 g, 4 mmol) (hereinafter referred to as 2SDAF) produced in Example 1 was added to NSD. -Methyl-2-pyrrolidone (10.16 g) (hereinafter referred to as NMP) was added and stirred at room temperature for complete dissolution. Next, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (0.78 g, 4 mmol) (hereinafter referred to as CBDA) and NMP (2 g) were added, and the mixture was stirred at room temperature for 24 hours. NMP solution A was obtained.

Examples 3-9
Polymerization was carried out in the same manner as in Example 2 except that acid anhydrides shown in Table 1 below were used instead of CBDA used in Example 2 to obtain NMP solutions of each polyamic acid.

Comparative Example 1
To a reaction vessel equipped with a nitrogen introduction tube, N-methyl-2-pyrrolidone (80 g) (NMP) was added to bis (p-aminophenyl) ether (8.01 g, 40 mmol) (hereinafter referred to as ODA) at room temperature. Stir to dissolve completely. Next, CBDA (7.84 g, 40 mmol) and NMP (25 g) were added and stirred at room temperature for 24 hours to obtain an NMP solution of polyamic acid.

<Creation of cured film>
An NMP solution of polyamic acid produced in Examples and Comparative Examples was dispensed on a 3 inch diameter 3 mm thick fused quartz substrate, spin coated to a thickness of about 8-12 μm, and applied at 280 ° C. in a nitrogen atmosphere. Heated for 1.5 hours to obtain a cured film.
FIG. 3 shows an IR chart of the imidized polymer in the cured film obtained by curing the polyamic acid obtained in Examples 3, 4 and 9.

<Characteristic evaluation of cured film>
The following characteristics were evaluated about the cured film obtained above. The results are shown in Table 1.

(1) Refractive Index Using a Metricon PC-2000 type prism coupler, the refractive index at a wavelength of 633 nm of the cured film obtained above was measured.

(2) Transmittance Using a U-3500 self-recording spectrophotometer manufactured by Hitachi, Ltd., transmittance (%) at wavelengths of 400 nm and 450 nm per 1 μm thickness of the cured film obtained above was measured.

(3) Heat resistance Using a DSC6300 manufactured by Seiko Instruments Inc. (temperature increase rate: 10 ° C./min, under nitrogen stream), the 5% weight loss temperature of the cured film obtained above was measured. The case where the 5% weight loss temperature was 400 ° C. or higher was evaluated as heat resistance pass (◯).

Abbreviations in Table 1 represent the following.
2SDAF: 9,9′-bis [4- (p-aminophenyl) sulfanylphenyl] fluorene; prepared in Example 1 ODA: bis (p-aminophenyl) ether CBDA: 1,2,3,4-cyclobutanetetracarboxylic Acid dianhydride CHDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride MBDA: Meso-1,2,3,4-butanetetracarboxylic dianhydride TCA-AH: 4,10-dioxa Tricyclo [6.3.1.0 ^2,7 ] dodecane-3,5,9,11-tetraone sBPDA: 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride aBPDA: 2,3 ', 3,4'-biphenylsulfonetetracarboxylic dianhydride ODPA: 4,4'-oxydiphthalic dianhydride 3SDEA: 4,4'-[p-thiobis (F Prepared in Preparation Example 1; - ylene sulfanyl)] diphthalic acid anhydride

  From the results in Table 1, it is understood that the polyamic acid and imidized polymer made from the diamine compound represented by the general formula (1) have a high refractive index, excellent transparency, and excellent heat resistance. .

The diamine compound of the present invention is useful as a raw material for producing an imidized polymer having a high refractive index and excellent transparency and heat resistance.
The polyamic acid and imidized polymer of the present invention are suitable as materials for producing optical members that are required to have a high refractive index and excellent transparency and heat resistance at the same time. Specifically, examples of the optical member include a coating material of a high refractive index material and a high refractive index material of an antireflection film, an optical waveguide, various lenses, and a sensitivity improving material for an image sensor.

It is a ¹³ C-NMR (a) chart, a DEPT-135 ° chart (b) and a ¹ H-NMR chart (c) of the diamine compound obtained in Example 1. 2 is a ¹ H-NMR (COSY) chart of the diamine compound obtained in Example 1. FIG. 4 is an IR chart of the imidized polymer obtained in Examples 3, 4 and 9.

Claims (7)

Diamine compound represented by the following following formula (1).
A polyamic acid having a structure represented by the following general formula (3).
[In the formula (3), R represents 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 ^2,7 ] dodecane-3,5,9,11-tetraone, meso-1,2,3,4 -Butanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dihydrate, 3,5,6-tricarboxynorbornane 2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c -Furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenylsulfonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4'-dimethyldiphenylsilaneteto Lacarboxylic acid dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3 , 4-Dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl Propane dianhydride, 4,4 ′-(hexafluoroisopropylidene) bis (phthalic acid) dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine Oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) Acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, and 4,4 ′-[p-thiobis (phenylene-sulfanyl)] diphthalic anhydride The tetravalent group corresponding to the residue which removed the anhydride group from the tetracarboxylic dianhydride selected from the group which consists of a thing is shown, m shows the number of 1-100,000. ] R is butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 ^2,7 ] dodecane- 3,5,9,11-tetraone, meso-1,2,3,4-butanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-di- Oxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4 , 4'-biphenylsulfonate Carboxylic dianhydride, 2,3 ′, 3,4′-biphenylsulfone tetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) bis (phthalic acid) dianhydride, 3,3 ′, An anhydride group from a tetracarboxylic dianhydride selected from the group consisting of 4,4'-biphenyltetracarboxylic dianhydride and 4,4 '-[p-thiobis (phenylene-sulfanyl)] diphthalic anhydride The polyamic acid according to claim 2, which is a tetravalent group corresponding to the residue from which is removed . R is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, meso-1,2,3,4-butanetetracarboxylic acid Dianhydride, 4,10-dioxatricyclo [6.3.1.0 ^2,7 ] Dodecane-3,5,9,11-tetraone, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenylsulfonetetracarboxylic dianhydride An anhydride group from a tetracarboxylic dianhydride selected from the group consisting of 4,4′-oxydiphthalic dianhydride and 4,4 ′-[p-thiobis (phenylene-sulfanyl)] diphthalic anhydride The polyamic acid according to claim 2, which is a tetravalent group corresponding to the removed residue. An imidized polymer having a structure represented by the following general formula (4).
[In the formula (4), R represents 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 ^2,7 ] dodecane-3,5,9,11-tetraone, meso-1,2,3,4 -Butanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dihydrate, 3,5,6-tricarboxynorbornane 2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c -Furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenylsulfonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4'-dimethyldiphenylsilaneteto Lacarboxylic acid dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3 , 4-Dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl Propane dianhydride, 4,4 ′-(hexafluoroisopropylidene) bis (phthalic acid) dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine Oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) Acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, and 4,4 ′-[p-thiobis (phenylene-sulfanyl)] diphthalic anhydride The tetravalent group corresponding to the residue which removed the anhydride group from the tetracarboxylic dianhydride selected from the group which consists of a thing is shown, m shows the number of 1-100,000. ] R is butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,10-dioxatricyclo [6.3.1.0 ^2,7 ] dodecane- 3,5,9,11-tetraone, meso-1,2,3,4-butanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-di- Oxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4 , 4'-biphenylsulfonate Carboxylic dianhydride, 2,3 ′, 3,4′-biphenylsulfone tetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) bis (phthalic acid) dianhydride, 3,3 ′, An anhydride group from a tetracarboxylic dianhydride selected from the group consisting of 4,4'-biphenyltetracarboxylic dianhydride and 4,4 '-[p-thiobis (phenylene-sulfanyl)] diphthalic anhydride 6. The imidized polymer according to claim 5, which is a tetravalent group corresponding to the residue from which is removed . R is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, meso-1,2,3,4-butanetetracarboxylic acid Dianhydride, 4,10-dioxatricyclo [6.3.1.0 ^2,7 ] Dodecane-3,5,9,11-tetraone, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenylsulfonetetracarboxylic dianhydride An anhydride group from a tetracarboxylic dianhydride selected from the group consisting of 4,4′-oxydiphthalic dianhydride and 4,4 ′-[p-thiobis (phenylene-sulfanyl)] diphthalic anhydride 6. The imidized polymer according to claim 5, which is a tetravalent group corresponding to the removed residue.