TETRACARBOXYLIC DIANHYDRIDE, CARBONYL COMPOUND, POLYIMIDE PRECURSOR RESIN, AND POLYIMIDE

Abstract

A tetracarboxylic dianhydride which is a compound represented by the following general formula (1):

##STR00001##

[in the formula (1), A represents one selected from the group consisting of optionally substituted divalent aromatic groups in each of which the number of carbon atoms forming an aromatic ring is 6 to 30, and R.sup.as each independently represent a hydrogen atom or the like], wherein 60% by mass or more of a stereoisomer contained in the compound is an exo/exo type stereoisomer represented by a specific general formula.

Claims

1. A tetracarboxylic dianhydride which is a compound represented by the following general formula (1): ##STR00024## [in the formula (1), A represents one selected from the group consisting of optionally substituted divalent aromatic groups in each of which the number of carbon atoms forming an aromatic ring is 6 to 30, and R.sup.as each independently represent one selected from the group consisting of a hydrogen atom and alkyl groups having 1 to 10 carbon atoms], wherein 60% by mass or more of a stereoisomer contained in the compound is an exo/exo type stereoisomer represented by the following general formula (2): ##STR00025## [A and R.sup.a in the formula (2) have the same definitions as A and R.sup.a in the above general formula (1)].

2. A carbonyl compound which is a compound represented by the following general formula (3): ##STR00026## [in the formula (3), A represents one selected from the group consisting of optionally substituted divalent aromatic groups in each of which the number of carbon atoms forming an aromatic ring is 6 to 30, R.sup.as each independently represent one selected from the group consisting of a hydrogen atom and alkyl groups having 1 to 10 carbon atoms, and R.sup.1s each independently represent one selected from the group consisting of a hydrogen atom, alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms], wherein 60% by mass or more of a stereoisomer contained in the compound is an exo/exo type stereoisomer represented by the following general formula (4): ##STR00027## [A, R.sup.a, and R.sup.1 in the formula (4) have the same definitions as A, R.sup.a, and R.sup.1 in the above general formula (3), respectively].

3. A polyimide precursor resin comprising a repeating unit (I) represented by the following general formula (5): ##STR00028## [in the formula (5), A represents one selected from the group consisting of optionally substituted divalent aromatic groups in each of which the number of carbon atoms forming an aromatic ring is 6 to 30, R.sup.as each independently represent one selected from the group consisting of a hydrogen atom and alkyl groups having 1 to 10 carbon atoms, R.sup.10 represents an arylene group having 6 to 50 carbon atoms, Ys each independently represent one selected from the group consisting of a hydrogen atom, alkyl groups having 1 to 6 carbon atoms, and alkylsilyl groups having 3 to 9 carbon atoms, one of the bonder represented by *1 and the bonder represented by *2 is bonded to the carbon atom a forming the norbornane ring, the other of the bonder represented by *1 and the bonder represented by *2 is bonded to the carbon atom b forming the norbornane ring, one of the bonder represented by *3 and the bonder represented by *4 is bonded to the carbon atom c forming the norbornane ring, and the other of the bonder represented by *3 and the bonder represented by *4 is bonded to the carbon atom d forming the norbornane ring], wherein 60% by mass or more of the repeating unit (I) contained in the polyimide precursor resin is a repeating unit having an exo/exo type three-dimensional structure represented by the following general formula (6): ##STR00029## [in the formula (6), A, R.sup.a, R.sup.10, and Y have the same definitions as A, R.sup.a, R.sup.10, and Y in the general formula (5), respectively, one of the bonder represented by *1 and the bonder represented by *2 is bonded to the carbon atom a forming the norbornane ring, the other of the bonder represented by *1 and the bonder represented by *2 is bonded to the carbon atom b forming the norbornane ring, one of the bonder represented by *3 and the bonder represented by *4 is bonded to the carbon atom c forming the norbornane ring, the other of the bonder represented by *3 and the bonder represented by *4 is bonded to the carbon atom d forming the norbornane ring, and the bonders represented by *1 to *4 have an exo conformation with respect to the norbornane ring to be bonded].

4. A polyimide comprising a repeating unit (A) represented by the following general formula (7): ##STR00030## [in the formula (7), A represents one selected from the group consisting of optionally substituted divalent aromatic groups in each of which the number of carbon atoms forming an aromatic ring is 6 to 30, R.sup.as each independently represent one selected from the group consisting of a hydrogen atom and alkyl groups having 1 to 10 carbon atoms, and R.sup.10 represents an arylene group having 6 to 50 carbon atoms], wherein 60% by mass or more of the repeating unit (A) contained in the polyimide is a repeating unit having an exo/exo type three-dimensional structure represented by the following general formula (8): ##STR00031## [A, R.sup.a, and R.sup.10 in the formula (8) have the same definitions as A, R.sup.a, and R.sup.10 in the above general formula (7), respectively].

Description

EXAMPLES

[0076] Hereinafter, the present invention is described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Synthesis Example 1

[0077] To a 1 L reaction vessel, cis-5s-norbornene-exo-2,3-dicarboxylic anhydride (100 g, 0.609 mol, exo form:endo form=98:2) manufactured by Mancherster Organics, methanol (500 mL), and concentrated hydrochloric acid (5.0 mL) having a concentration of 37% by mass were sequentially added under an argon stream to obtain a mixture liquid. Then, the mixture liquid was stirred under reflux conditions (internal temperature: 65° C.) for 4 hours to obtain a reaction liquid. After the reaction under reflux conditions for 4 hours in this way (after completion of the reaction), GC measurement was performed on the reaction liquid to confirm the disappearance of the raw material cis-5s-norbornene-exo-2,3-dicarboxylic anhydride.

[0078] Then, methanol was distilled off from the reaction liquid under reduced pressure using a rotary evaporator to obtain a liquid product. Next, the liquid product was dissolved in ethyl acetate (500 mL) and transferred to a separatory funnel. The liquid product was washed twice with saturated sodium hydrogen carbonate aqueous solution (200 mL) and then once with water (200 mL) to obtain an organic layer. Then, ethyl acetate was distilled off from the organic layer under reduced pressure using a rotary evaporator, thereby obtaining cis-5-norbornene-exo-2,3-dimethyl dicarboxylate (120 g, yield: 94%, exo form:endo form=100:0). The structure of the product was identified by .sup.1H-NMR and .sup.13C-NMR. Note that, regarding the above product, the “exo form” means that all the groups represented by the formula: —COOMe have an exo conformation with respect to the norbornene ring to be bonded, and on the other hand, the “endo form” means that all the groups represented by the formula: —COOMe have an endo conformation with respect to the norbornene ring to be bonded. The reaction formula of the reaction used in the production of such a product is presented below.

##STR00015##

Example 1

[0079] Into a 3 L reaction vessel, palladium acetate (118 mg, 0.524 mmol), tri-o-tolylphosphine (159 mg, 0.524 mmol), and N,N-dimethylformamide (596 mL) were sequentially charged under an argon stream, followed by stirring at an internal temperature of 50 to 56° C. for 30 minutes. Next, to the inside of the reaction vessel, cis-5-norbornene-exo-2,3-dimethyl dicarboxylate (110 g, 0.523 mol, ratio of exo form: 100 mol %) obtained in Synthesis Example 1, 1, 4-dibromobenzene (143 g, 0.262 mol), triethylamine (106 g, 1.05 mol), formic acid (48.3 g, 0.262 mol), and N,N-dimethylformamide (660 mL) were further added to obtain a mixture liquid. Then, the mixture liquid was heated to an internal temperature of 80° C. and stirred for 8 hours to obtain a reaction liquid. After the reaction while stirring for 8 hours in this way (after the completion of the reaction), the reaction liquid was allowed to cool until the temperature thereof reached room temperature.

[0080] Next, the reaction liquid was moved to a separatory funnel, toluene (2.62 L) and water (1.05 L) were added, and liquid separation washing was performed. Next, the organic layer thus obtained was washed twice with hydrochloric acid (520 mL) having a concentration of 5% by mass, twice with a saturated sodium hydrogen carbonate aqueous solution (520 mL), and further washed twice with water (520 mL). Then, the black insoluble matter in the intermediate layer was removed by Celite filtration. The obtained filtrate was heated under the condition of a water bath temperature of 60° C. and concentrated to obtain a crude product.

[0081] Next, the crude product (135.4 g) thus obtained was added with ethyl acetate (108 mL) to obtain a mixture liquid, and then, the mixture liquid was added with cyclohexane (1.05 L) while heating and stirring under the condition of a water bath temperature of 60° C. to prepare a solution, and crystallization was carried out as follows. Specifically, the solution was prepared as described above, which was heated and stirred under the condition of a water bath temperature of 50° C., and the crystals were precipitated as a precipitation product by gradual cooling to room temperature while continuing the stirring (crystallization). After filtering the precipitation product obtained by such a crystallization step, the obtained filtrate was washed with cyclohexane (211 mL) and then dried under reduced pressure at 80° C. for 5 hours to obtain a white product. In order to analyze the absolute structure of the product thus obtained, one-dimensional NMR (.sup.1H and .sup.13C) and two-dimensional NMR (DEPT 135, DQF COSY, HMQC, HMBC, NOESY) measurements were preformed, and the product was found to be an ester compound having a structure represented by the following formula (yield 49%):

##STR00016##

[0082] As described above, analysis of the absolute structure revealed that the product obtained was an exo/exo type ester compound (tetramethyl exo,exo-5,5′-(1,4-phenylene)bis(bicyclo[2.2.1]heptane-2,3-exo-dicarboxylate) in which each methyl ester group had a structure taking an exo conformation with respect to the norbornane ring to be bonded. Note that it was also found that, in the exo/exo type ester compound, the benzene ring had an exo conformation with respect to both norbornane rings.

Example 2

[0083] Into a 300 mL reaction vessel, the exo/exo type ester compound (13.0 g, 26.1 mmol) obtained in Example 1, acetic acid (185 g), and acetic acid solution of 10 mass % trifluoromethanesulfonic acid prepared in advance (1.96 g, trifluoromethanesulfonic acid: 1.30 mmol) were sequentially charged under an argon stream to obtain a reaction solution. Then, while heating and refluxing the reaction solution, an operation of adding 18 g of acetic acid while extracting 18 g of the distillate was carried out every hour using a Dean-Stark tube. Such an operation continued until 6 hours had passed since the extraction of 18 g of the distillate was started. After operating for 6 hours in this manner, the heating and refluxing were stopped, and the reaction solution was allowed to cool to room temperature, and allowed to stand overnight because no precipitation product was precipitated. The next day, when the reaction solution after allowed to stand overnight was confirmed again, a white precipitation product had been precipitated in the reaction solution, so that it was filtered and washed once with acetic acid (20 mL) and once with ethyl acetate (20 mL) to obtain a filtrate. Next, the filtrate was dried under reduced pressure at 80° C. for 5 hours to obtain a white product. In order to analyze the absolute structure of the white product thus obtained, one-dimensional NMR (.sup.1H and .sup.13C) and two-dimensional NMR (DEPT 135, DQF COSY, HMQC, HMBC, NOESY) measurements were preformed, and the product was found to be an acid dianhydride having a structure represented by the following formula (yield 58%):

##STR00017##

[0084] As described above, analysis of the absolute structure revealed that the product was an exo/exo type tetracarboxylic dianhydride (exo,exo-5,5′-(1,4-phenylene)bis(bicyclo[2.2.1]heptane-2,3-exo-dicarboxylic anhydride) in which each acid anhydride group had a structure taking an exo conformation with respect to the norbornane ring to be bonded. Note that it was also found that, in the exo/exo type tetracarboxylic dianhydride, the benzene ring had an exo conformation with respect to both norbornane rings. Moreover, when liquid chromatography (LC) analysis was performed, the LC purity of the product (tetracarboxylic dianhydride) was 96 area %.

[0085] Next, the exo/exo type tetracarboxylic dianhydride (16.9 g) thus obtained was charged into a glass tube oven, and then the pressure was reduced, and heating was started after the degree of vacuum reached 6.5×10.sup.−4 Pa. By such heating, the acid dianhydride was first melted when the temperature reached 250° C., and then, evaporation started when the temperature reached 270° C., and the degree of vacuum increased to 4.3×10.sup.−3 Pa. Then, a distillation operation was carried out to obtain 15.3 g of a purified product (yield: 98%). Note that it was confirmed by .sup.1H-NMR measurement and LC analysis that there were no impurities (LC purity: >99 area %). In this way, a purified exo/exo type tetracarboxylic dianhydride was obtained. Hereinafter, the tetracarboxylic dianhydride thus obtained is sometimes referred to as “exo/exo type BzDA.”

Synthesis Example 2

[0086] To a 1 L reaction vessel, 5-norbornene-2,3-dicarboxylic anhydride (1,150 g, 7.01 mol, exo form:endo form=0:100) manufactured by Wako Pure Chemical Industries, Ltd., methanol (5.75 mL), and concentrated hydrochloric acid (57.5 mL) having a concentration of 37% by mass were sequentially added under an argon stream to obtain a mixture liquid. Then, the mixture liquid was stirred under reflux conditions (internal temperature: 65° C.) for 4 hours to obtain a reaction liquid. After the reaction under reflux conditions for 4 hours in this way (after completion of the reaction), GC measurement was performed on the reaction liquid to confirm the disappearance of the raw material 5-norbornene-2,3-dicarboxylic anhydride.

[0087] Then, methanol was distilled off from the reaction liquid under reduced pressure using a rotary evaporator to obtain a liquid product. Next, the liquid product was dissolved in ethyl acetate (5.8 L) and transferred to a separatory funnel. The liquid product was washed twice with saturated sodium hydrogen carbonate aqueous solution (2.3 L) and then once with water (2.3 L) to obtain an organic layer. Then, ethyl acetate was distilled off from the organic layer under reduced pressure using a rotary evaporator, thereby obtaining cis-5-norbornene-endo-2,3-dimethyl dicarboxylate (1,404 g, yield: 95%, exo form: endo form=0:100). Regarding the above product, the “exo form” means that all the groups represented by the formula: —COOMe have an exo conformation with respect to the norbornene ring to be bonded, and on the other hand, the “endo form” means that all the groups represented by the formula: —COOMe have an endo conformation with respect to the norbornene ring to be bonded. Note that the structure of the product was also identified by .sup.1H-NMR.

##STR00018##

Comparative Example 1

[0088] Into a 3 L reaction vessel, palladium acetate (1.20 g, 5.35 mmol), tri-o-tolylphosphine (1.63 g, 5.35 mmol), and N,N-dimethylformamide (4.28 L) were sequentially charged under an argon stream, followed by stirring at an internal temperature of 50 to 56° C. for 30 minutes. Next, to the inside of the reaction vessel, cis-5-norbornene-endo-2,3-dimethyl dicarboxylate (1,125 g, 5.35 mol) obtained in Synthesis Example 2, 1,4-dibromobenzene (757 g, 3.21 mol), triethylamine (1,083 g, 10.7 mol), formic acid (493 g, 10.7 mol), and N,N-dimethylformamide (4.28 L) were further added to obtain a mixture liquid. Then, the mixture liquid was heated to an internal temperature of 80° C. and stirred for 8 hours to obtain a reaction liquid. After the reaction while stirring for 8 hours in this way (after the completion of the reaction), the reaction liquid was allowed to cool until the temperature thereof reached room temperature.

[0089] Next, the reaction liquid was moved to a separatory funnel, toluene (26.9 L) and water (10.7 L) were added, and liquid separation washing was performed. The organic layer obtained was washed twice with hydrochloric acid (5.3 L) having a concentration of 5% by mass, twice with a saturated sodium hydrogen carbonate aqueous solution (5.3 L), and further washed twice with water (5.3 L). Then, the black insoluble matter in the intermediate layer was removed by Celite filtration. The obtained filtrate was heated under the condition of a water bath temperature of 60° C., and the reaction solution was concentrated under reduced pressure to 2,000 g to obtain a concentrated liquid. Then, toluene was added to the concentrated liquid and diluted to obtain a solution. The total amount of the solution thus obtained was 2,940 g.

[0090] Next, the solution was divided into two (1,470 g×2), and when cyclohexane (14.8 L) was added to each solution while heating each solution under the condition of a water bath temperature of 60° C., a white precipitation product was formed in each solution. Each of the above solutions with a precipitation product thus produced therein was then stirred for 30 minutes while heating under the condition of a water bath temperature of 50° C., and then allowed to cool to room temperature. Next, the precipitation product was filtered from each of the resulting solutions, the resulting filtrate was washed with cyclohexane (1.07 L) and then dried under reduced pressure at 80° C. for 5 hours to obtain a white product. In order to analyze the absolute structure of the product obtained, one-dimensional NMR (.sup.1H and .sup.13C) and two-dimensional NMR (DEPT 135, DQF COSY, HMQC, HMBC, NOESY) measurements were preformed, and the product was found to be an ester compound having a structure represented by the following formula (yield 51%):

##STR00019##

[0091] As described above, analysis of the absolute structure revealed that the product was an endo/endo type ester compound (tetramethyl exo,exo-5,5′-(1,4-phenylene)bis(bicyclo[2.2.1]heptane-2,3-endo-dicarboxylate) in which each methyl ester group had a structure taking an endo conformation with respect to the norbornane ring to be bonded. Note that it was also found that, in the endo/endo type ester compound, the benzene ring had an exo conformation with respect to both norbornane rings.

Comparative Example 2

[0092] Into a 20 L reaction vessel, the endo/endo type ester compound (650 g, 1.30 mol) obtained in Comparative Example 1, acetic acid (9.34 kg), and acetic acid solution of 10 mass % trifluoromethanesulfonic acid prepared in advance (9.78 g, trifluoromethanesulfonic acid: 65.2 mmol) were sequentially charged under an argon stream to obtain a reaction solution. Then, while heating and refluxing the reaction solution, an operation of adding 1100 g of acetic acid while extracting 1100 g of the distillate was carried out every hour using a Dean-Stark tube. Such an operation continued until 6 hours had passed since the extraction of the distillate was started. Note that 1 hour after the start of heating and refluxing, a white precipitate product was formed in the reaction solution. In this way, after continuing the above operation for 6 hours, the heating and refluxing were stopped, and the reaction solution was allowed to cool to room temperature, and allowed to stand overnight. The next day, the white precipitate was filtered from the reaction solution that had been allowed to stand overnight, and was washed once with acetic acid (1.9 L) and five times with ethyl acetate (1.9 L) to obtain a filtrate. Next, the filtrate was dried under reduced pressure at 80° C. for 5 hours to obtain a white product. In order to analyze the absolute structure of the product thus obtained, one-dimensional NMR (.sup.1H and .sup.13C) and two-dimensional NMR (DEPT 135, DQF COSY, HMQC, HMBC, NOESY) measurements were preformed, and the product was found to be an acid dianhydride having a structure represented by the following formula (yield 86%):

##STR00020##

[0093] As described above, analysis of the absolute structure revealed that the product was an endo/endo type tetracarboxylic dianhydride in which each acid anhydride group had a structure taking an endo conformation with respect to the norbornane ring to be bonded. Note that it was also found that, in the endo/endo type tetracarboxylic dianhydride, the benzene ring had an exo conformation with respect to both norbornane rings. In addition, when liquid chromatography (LC) analysis was performed, the LC purity of the product was 99%. The endo/endo type tetracarboxylic dianhydride thus obtained is hereinafter referred to as “endo/endo type BzDA” in some cases.

[On Solubility of Tetracarboxylic Dianhydride in Organic Solvent]

[0094] As the samples, the tetracarboxylic dianhydride (exo/exo type BzDA) obtained in Example 2 and the tetracarboxylic dianhydride (endo/endo type BzDA) obtained in Comparative Example 2 were separately used to confirm the solubility of each tetracarboxylic dianhydride in an organic solvent as follows. Specifically, after 50 mg of the sample was added to a screw tube, an organic solvent was added little by little into the screw tube, and the amount of the sample dissolved was visually confirmed. Note that, as the organic solvents, N,N′-dimethylacetamide and N-methyl-2-pyrrolidone were used to confirm the solubility in the solvents. As a result of the test, the exo/exo type BzDA obtained in Example 2 was easily dissolved in each solvent (N,N′-dimethylacetamide, N-methyl-2-pyrrolidone), and it was found that the use of these solvents (N,N′-dimethylacetamide, N-methyl-2-pyrrolidone) made it possible to sufficiently prepare a solution having a concentration of 5% by mass or more. On the other hand, it was found that the endo/endo type BzDA obtained in Comparative Example 2 had low solubility in each solvent (N,N′-dimethylacetamide, N-methyl-2-pyrrolidone), the use of N,N′-dimethylacetamide did not make it possible to prepare a solution having a concentration of 1% by mass or more, and even the use of N-methyl-2-pyrrolidone did not make it possible to prepare a solution having a concentration of 3.5% by mass or more. From these results, it was found that the tetracarboxylic dianhydride having an exo/exo type three-dimensional structure (exo/exo type BzDA: Example 2) has extremely high solubility in organic solvents.

Example 3

[0095] Under a nitrogen atmosphere, into a 15 mL screw tube, 0.560 g (2.46 mmol) of 4,4′-diaminobenzanilide (DABAN) was introduced as an aromatic diamine, and also, 1.01 g (2.46 mmol) of the exo/exo type BzDA obtained in Example 2 was introduced as a tetracarboxylic dianhydride. Next, 6.2 g of tetramethylurea (TMU) as a solvent was added into the screw tube to obtain a mixture liquid. Next, the obtained mixture liquid was stirred under a nitrogen atmosphere and under a temperature condition of room temperature for 5 days to obtain a reaction liquid (varnish) (the step of obtaining such a reaction liquid (varnish) is hereinafter referred to as the “varnish preparation step”). Note that it is found that the varnish contains a polyamic acid in which a repeating unit (I) is contained represented by the general formula (5) derived from the exo/exo type BzDA used, and in which, in the repeating unit (I), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (6) is 100% by mass (note that, in the formulas (5) and (6), A is a p-phenylene group, R.sup.10 is a divalent group obtained by removing two amino groups from DABAN, and R.sup.a and Y are both hydrogen atoms).

[0096] Next, the reaction liquid (varnish) was applied to a glass substrate having a size of 76 mm in length and 52 mm in width using a spin coater to form a coating film of the varnish on the glass substrate. Then, the glass plate having the coating film formed thereon was dried under reduced pressure at 70° C. for 30 minutes. Next, the glass plate having the coating film formed thereon was set in an inert oven, and nitrogen purging was performed. Next, under a nitrogen stream, the temperature was raised to 135° C. and held for 1 hour, and the temperature was further raised to 350° C. and held for 1 hour, and then a polyimide was formed on the glass substrate by operating the inert oven so as to cool to room temperature, and a glass substrate coated with a film made of polyimide was obtained. Next, the film made of polyimide was peeled off from the glass substrate to obtain a colorless and transparent film made of polyimide (the step of obtaining such a film is hereinafter referred to as the “film preparation step”). Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the following general formula (101) derived from the exo/exo type BzDA used:

##STR00021##

[0097] and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the following general formula (102):

##STR00022##

[0098] is 100% by mass (each imide ring bonded to the norbornane ring in the formula is a repeating unit taking an exo conformation with respect to the norbornane ring to be bonded) (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from DABAN).

Comparative Example 3

[0099] Into a 50 mL flask, 2.70 g (11.9 mmol) of DABAN as an aromatic diamine and 4.88 g (12.0 mmol) of the endo/endo type BzDA obtained in Comparative Example 2 as a tetracarboxylic dianhydride were introduced. Next, into the flask, 10.1 g of dimethylacetamide (N,N-dimethylacetamide) as an organic solvent, 7.6 g of y-butyrolactone as an organic solvent, and 0.061 g (0.50 mmol) of triethylamine as a reaction accelerator were introduced to obtain a mixture liquid. Then, the mixture liquid thus obtained was stirred while heating under a nitrogen atmosphere under a temperature condition of 180° C. for 6 hours to obtain a viscous and uniform pale yellow reaction liquid (varnish). Next, the varnish was applied to a glass substrate having a size of 76 mm in length and 52 mm in width using a spin coater to form a coating film of the varnish on the glass substrate. Then, the glass substrate having the coating film formed thereon was set in an inert oven, and nitrogen purging was performed. Next, in the inert oven, under a nitrogen stream, the temperature was raised to 60° C. and held for 4 hours, and the temperature was then raised to 250° C. and held for 1 hour, and then a polyimide was formed on the glass substrate by operating the inert oven so as to cool to room temperature, and a glass substrate coated with a film made of polyimide was obtained. Next, the film made of polyimide was peeled off from the glass substrate to obtain a colorless and transparent film made of polyimide. It is found that the thus-obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the endo/endo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an endo/endo type three-dimensional structure represented by the following formula (103):

##STR00023##

[0100] is 100% by mass (each imide ring bonded to the norbornane ring in the formula is a repeating unit taking an endo conformation with respect to the norbornane ring to be bonded) (note that R.sup.10s in the formulas (101) and (103) are each a divalent group obtained by removing two amino groups from DABAN).

[Evaluation of Characteristics of Polyimides Obtained in Example 3 and Comparative Example 3]

[0101] The following measurement methods were employed to subject the polyimides (films) obtained in Example 3 and Comparative Example 3 to the measurement of linear expansion coefficient, glass transition temperature, total luminous transmittance, 5% weight loss temperature (Td5%), HAZE, and YI (note that the polyimides (films) obtained in Examples 4 to 18 and Comparative Examples 4 to 8 described later were also measured by employing the following measurement methods, respectively). Table 1 presents the results obtained together with the film thickness of each film.

<Method of Measuring Linear Expansion Coefficient (CTE)>

[0102] The linear expansion coefficient was measured as follows. Specifically, a film in a size of 20 mm in length and 5 mm in width (the thickness of the sample was the same as the thickness of the film obtained in each of Examples and the like) was cut out from the polyimide (film) obtained in each of Examples and the like. By using this film as a measurement sample, the change in length of the sample was measured from 50° C. to 200° C. under a nitrogen atmosphere in a tensile mode (49 mN) by employing a condition of a rate of temperature rise of 5° C./minute with a thermomechanical analyzer (manufactured by Rigaku Corporation under the trade name of “TMA 8311”) being used as a measuring apparatus. Then, the average value of the changes in length per Celsius degree in the temperature range from 100° C. to 200° C. was determined.

<Method of Measuring Glass Transition Temperature (Tg)>

[0103] The glass transition temperature (unit: ° C.) was measured as follows. Specifically, a film in a size of 20 mm in length and 5 mm in width (the thickness of the sample was the same as the thickness of the film obtained in each of Examples and the like) was cut out from the polyimide (film) obtained in each of Examples and the like. By using this film as a measurement sample, the TMA curve was determined by performing measurement under a nitrogen atmosphere in a tensile mode (49 mN) by employing a condition of a rate of temperature rise of 5° C./minute with a thermomechanical analyzer (manufactured by Rigaku Corporation under the trade name of “TMA 8311”) being used as a measuring apparatus. The curves before and after the inflection point of the TMA curve due to the glass transition were extrapolated, thereby determining the value (unit: ° C.) of the glass transition temperature (Tg) of the resin constituting the film obtained in each of Examples and the like.

<Method of Measuring Total Luminous Transmittance>

[0104] The value of the total luminous transmittance (unit: %) was determined as follows. The polyimide (film) obtained in each of Examples and the like was used as it was as a sample for measurement, and the trade name “Haze Meter NDH-5000” manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD. was used as a measuring apparatus to perform measurement in accordance with JIS K7361-1 (issued in 1997).

<Measurement of 5% Weight Loss Temperature (Td5%)>

[0105] The 5% weight loss temperature (unit: ° C.) was measured as follows using the polyimide film obtained in each of Examples and the like. Specifically, first, 2 to 4 mg of a sample was prepared from the polyimide film obtained in each of Examples, and the sample was placed in an aluminum sample pan. A thermogravimetric analyzer (under the trade name of “TG/DTA7200” manufactured by SII Nanotechnology Inc.) was used as the measuring apparatus. The scanning temperature was set from 40° C. to 200° C. under a nitrogen gas atmosphere, and the sample was heated from room temperature at a heating rate of 10° C./minute and held at 200° C. for 1 hour. The weight at this point was set as the zero point. After that, the scanning temperature was set from 200° C. to 550° C., and heating was performed from 200° C. under the condition of a rate of temperature rise of 10° C./minute to measure the temperature at which the weight of the sample used was reduced by 5%.

<Method of Measuring HAZE>

[0106] The HAZE (turbidity) was determined as follows. The polyimide (film) obtained in each of Examples and the like was used as it was as a sample for measurement, and the trade name “Haze Meter NDH-5000” manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD. was used as a measuring apparatus to perform measurement in accordance with JIS K7136 (issued in 2000).

<Measurement of YI>

[0107] The yellowness index (YI) was determined as followed. The trade name “Spectrophotometer SD6000” manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD. was used as a measuring apparatus to perform measurement in accordance with ASTM E313-05 (issued in 2005).

TABLE-US-00001 TABLE 1 Film Tg Total Luminous Tetracarboxylic Aromatic Thickness CTE (TMA) Transmittance Td5% HAZE Dianhydride Diamine (μm) (ppm/K) (° C.) (%) (° C.) (%) YI Example 3 Exo/Exo Type DABAN 12 34 392 87 460 0.96 3.4 BzDA Comparative Endo/Endo Type DABAN 30 55 401 89 464 0.87 1.3 Example 3 BzDA

[0108] As is clear from the results presented in Table 1, it was confirmed that the polyimides obtained in Example 3 and Comparative Example 3 both had a total luminous transmittance of 80% or more, and the transparency was at a sufficiently high level. In addition, it was confirmed that the polyimide obtained in Example 3 had a Tg of 449° C., a very high value, and the heat resistance based on Tg was at a very high level. In addition, in the case where the repeating unit of the polyimide was composed of a repeating unit having an exo/exo type three-dimensional structure (Example 3), it was confirmed that the polyimide had a lower linear expansion coefficient as compared with the case where the repeating unit of the polyimide was a repeating unit having an endo/endo type three-dimensional structure (Comparative Example 3).

Example 4

[0109] Under a nitrogen atmosphere, into a 15 mL screw tube, 0.495 g (2.46 mmol) of 4,4′-diaminodiphenyl ether (DDE) was introduced as an aromatic diamine, and also, 1.01 g (2.46 mmol) of the exo/exo type BzDA obtained in Example 2 was introduced as a tetracarboxylic dianhydride. Next, 5.97 g of N,N′-dimethylacetamide (DMAc) as a solvent was added into the screw tube to obtain a mixture liquid. Next, the obtained mixture liquid was stirred under a nitrogen atmosphere and under a temperature condition of room temperature for 2 days to obtain a reaction liquid (varnish) (the step of obtaining such a reaction liquid (varnish) is hereinafter referred to as the “varnish preparation step”). Note that it is found that the varnish contains a polyamic acid in which a repeating unit (I) is contained represented by the general formula (5) derived from the exo/exo type BzDA used, and in which, in the repeating unit (I), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (6) is 100% by mass (note that, in the formulas (5) and (6), A is a p-phenylene group, R.sup.10 is a divalent group obtained by removing two amino groups from DDE, and R.sup.a and Y are both hydrogen atoms).

[0110] Next, the reaction liquid (varnish) was applied to a glass substrate having a size of 76 mm in length and 52 mm in width using a spin coater to form a coating film of the varnish on the glass substrate. Then, the glass plate having the coating film formed thereon was set in an inert oven, and nitrogen purging was performed. Next, in the inert oven, under a nitrogen stream, the temperature was raised to 70° C. and held for 3 hours, the temperature was then raised to 135° C. and held for 1 hour, and the temperature was further raised to 350° C. and held for 1 hour, and then a polyimide was formed on the glass substrate by operating the inert oven so as to cool to room temperature, and a glass substrate coated with a film made of polyimide was obtained. Next, the film made of polyimide was peeled off from the glass substrate to obtain a colorless and transparent film made of polyimide (the step of obtaining such a film is hereinafter referred to as the “film preparation step”). Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from DDE).

Comparative Example 4

[0111] A reaction liquid (varnish) was produced in the same manner as in the varnish preparation step employed in Example 4 except that the endo/endo type BzDA obtained in Comparative Example 2 was used as the tetracarboxylic dianhydride instead of the exo/exo type BzDA obtained in Example 2. In addition, a colorless and transparent film made of polyimide was obtained in the same manner as in the film preparation step employed in Example 4 except that the reaction liquid (varnish) thus obtained was used, and the condition for operating the inert oven at the time of forming the polyimide was changed to the condition of “under a nitrogen stream, the temperature is raised to 60° C. and held for 4 hours, and then the temperature is raised to 350° C. and held for 1 hour, and then cooled to room temperature.” Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the endo/endo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an endo/endo type three-dimensional structure represented by the above general formula (103) is 100% by mass (note that R.sup.10s in the formulas (101) and (103) are each a divalent group obtained by removing two amino groups from DDE).

[Evaluation of Characteristics of Polyimides Obtained in Example 4 and Comparative Example 4]

[0112] The above-described measurement methods were employed to subject the polyimides (films) obtained in Example 4 and Comparative Example 4 to the measurement of linear expansion coefficient, glass transition temperature, total luminous transmittance, 5% weight loss temperature (Td5%), HAZE, and YI. Table 2 presents the results obtained together with the film thickness of each film.

TABLE-US-00002 TABLE 2 Film Tg Total Luminous Tetracarboxylic Aromatic Thickness CTE (TMA) Transmittance Td5% HAZE Dianhydride Diamine (μm) (ppm/K) (° C.) (%) (° C.) (%) YI Example 4 Exo/Exo Type DDE 18 56 340 89 457 0.83 2.6 BzDA Comparative Endo/Endo Type DDE 15 67 343 90 475 1.3 1.6 Example 4 BzDA

[0113] As is clear from the results presented in Table 2, it was confirmed that the polyimides obtained in Example 4 and Comparative Example 4 both had a total luminous transmittance of 80% or more, and the transparency was at a sufficiently high level. In addition, it was confirmed that the polyimides obtained in Example 4 and Comparative Example 4 had a Tg of 250° C. or higher (as is clear from the description in Table 2, both have a Tg of 340° C. or higher), and the heat resistance based on Tg was at a sufficiently high level for both cases. Moreover, in the case where the repeating unit of the polyimide was composed of a repeating unit having an exo/exo type three-dimensional structure (Example 4), it was confirmed that the polyimide had a lower linear expansion coefficient as compared with the case where the repeating unit of the polyimide was a repeating unit having an endo/endo type three-dimensional structure (Comparative Example 4).

Example 5

[0114] Under a nitrogen atmosphere, into a 15 mL screw tube, 0.719 g (2.46 mmol) of 1,3-bis(4-aminophenoxy)benzene (TPE-R) was introduced as an aromatic diamine, and also, 1.01 g (2.46 mmol) of the exo/exo type BzDA obtained in Example 2 was introduced as a tetracarboxylic dianhydride. Next, 6.90 g of N,N′-dimethylacetamide (DMAc) as a solvent was added into the screw tube to obtain a mixture liquid. Next, the obtained mixture liquid was stirred under a nitrogen atmosphere and under a temperature condition of room temperature for 2 days to obtain a reaction liquid (varnish) (the step of obtaining such a reaction liquid (varnish) is hereinafter referred to as the “varnish preparation step”). Note that it is found that the varnish contains a polyamic acid in which a repeating unit (I) is contained represented by the general formula (5) derived from the exo/exo type BzDA used, and in which, in the repeating unit (I), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (6) is 100% by mass (note that, in the formulas (5) and (6), A is a p-phenylene group, R.sup.10 is a divalent group obtained by removing two amino groups from TPE-R, and R.sup.a and Y are both hydrogen atoms).

[0115] Next, the reaction liquid (varnish) was applied to a glass substrate having a size of 76 mm in length and 52 mm in width using a spin coater to form a coating film of the varnish on the glass substrate. Then, the glass plate having the coating film formed thereon was set in an inert oven, and nitrogen purging was performed. Next, in the inert oven, under a nitrogen stream, the temperature was raised to 70° C. and held for 3 hours, and the temperature was then raised to 300° C. and held for 1 hour, and then a polyimide was formed on the glass substrate by operating the inert oven so as to cool to room temperature, and a glass substrate coated with a film made of polyimide was obtained. Next, the film made of polyimide was peeled off from the glass substrate to obtain a colorless and transparent film made of polyimide (the step of obtaining such a film is hereinafter referred to as the “film preparation step”). Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from TPE-R).

Comparative Example 5

[0116] A reaction liquid (varnish) was produced in the same manner as in the varnish preparation step employed in Example 5 except that the endo/endo type BzDA obtained in Comparative Example 2 was used as the tetracarboxylic dianhydride instead of the exo/exo type BzDA obtained in Example 2. In addition, a colorless and transparent film made of polyimide was obtained in the same manner as in the film preparation step employed in Example 5 except that the reaction liquid (varnish) thus obtained was used, and the condition for operating the inert oven at the time of forming the polyimide was changed to the condition of “under a nitrogen stream, the temperature is raised to 60° C. and held for 4 hours, and then the temperature is raised to 350° C. and held for 1 hour, and then cooled to room temperature.” Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the endo/endo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an endo/endo type three-dimensional structure represented by the above general formula (103) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from TPE-R).

[Evaluation of Characteristics of Polyimides Obtained in Example 5 and Comparative Example 5]

[0117] The above-described measurement methods were employed to subject the polyimides (films) obtained in Example 5 and Comparative Example 5 to the measurement of linear expansion coefficient, glass transition temperature, total luminous transmittance, 5% weight loss temperature (Td5%), HAZE, and YI. Table 3 presents the results obtained together with the film thickness of each film.

TABLE-US-00003 TABLE 3 Film Tg Total Luminous Tetracarboxylic Aromatic Thickness CTE (TMA) Transmittance Td5% HAZE Dianhydride Diamine (μm) (ppm/K) (° C.) (%) (° C.) (%) YI Example 5 Exo/Exo Type TPE-R 37 66 274 89 457 0.60 2.5 BzDA Comparative Endo/Endo Type TPE-R 13 74 274 89 465 1.3 1.4 Example 5 BzDA

[0118] As is clear from the results presented in Table 3, it was confirmed that the polyimides obtained in Example 5 and Comparative Example 5 both had a total luminous transmittance of 80% or more, and the transparency was at a sufficiently high level. In addition, it was confirmed that the polyimides obtained in Example 5 and Comparative Example 5 had a Tg of 250° C. or higher, and the heat resistance based on Tg was at a sufficiently high level for both cases. Moreover, in the case where the repeating unit of the polyimide was composed of a repeating unit having an exo/exo type three-dimensional structure (Example 5), it was confirmed that the polyimide had a lower linear expansion coefficient as compared with the case where the repeating unit of the polyimide was a repeating unit having an endo/endo type three-dimensional structure (Comparative Example 5).

Example 6

[0119] A reaction liquid (varnish) was produced in the same manner as in the varnish preparation step used in Example except that 0.788 g (2.46 mmol) of 2,2′-bis(trifluoromethyl)benzidine (TFMB) was used as the aromatic diamine instead of using DABAN, and 4.17 g of N,N′-dimethylacetamide (DMAc) was used as the solvent instead of TMU. In addition, a colorless and transparent film made of polyimide was obtained in the same manner as in the film preparation step employed in Example 3 except that the reaction liquid (varnish) thus obtained was used. Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from TFMB). The film thickness of the polyimide (film) obtained in Example 6 was 13 μm. Moreover, the polyimide (film) obtained in Example 6 was subjected to measurement of various characteristics by employing the above-mentioned measuring method, and the linear expansion coefficient (CTE) was 54 ppm/K, the glass transition temperature was 357° C., the total luminous transmittance was 90%, Td5% was 443° C., HAZE was 0.84%, and YI was 3.3.

Example 7

[0120] Into a 50 mL flask, 3.20 g (10.0 mmol) of TFMB as an aromatic diamine and 4.06 g (10.0 mmol) of the exo/exo type BzDA obtained in Example 2 as a tetracarboxylic dianhydride were introduced. Next, into the flask, 14.5 g of N,N-dimethylacetamide (DMAc) as an organic solvent, 14.5 g of γ-butyrolactone as an organic solvent, and 0.051 g (0.509 mmol) of triethylamine as a reaction accelerator were introduced to obtain a mixture liquid. Then, the mixture liquid thus obtained was stirred while heating under a nitrogen atmosphere under a temperature condition of 180° C. for 6 hours to obtain a viscous and uniform pale yellow reaction liquid (varnish). Next, the varnish was applied to a glass substrate having a size of 76 mm in length and 52 mm in width using a spin coater to form a coating film of the varnish on the glass substrate. Then, the glass substrate having the coating film formed thereon was dried at 70° C. for 30 minutes under reduced pressure. Next, the glass substrate having the coating film formed thereon was set in an inert oven, and nitrogen purging was performed. Next, in the inert oven, the temperature was raised to 350° C. and held for 1 hour under a nitrogen stream, and then a polyimide was formed on the glass substrate by operating the inert oven so as to cool to room temperature, and a glass substrate coated with a film made of polyimide was obtained. Next, the film made of polyimide was peeled off from the glass substrate to obtain a colorless and transparent film made of polyimide. Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from TFMB).

Example 8

[0121] A colorless and transparent film made of polyimide was obtained in the same manner as in Example 7 except that a mixture of 2.44 g (6.00 mmol) of exo/exo type BzDA obtained in Example 2 and 1.63 g (4.00 mmol) of endo/endo type BzDA obtained in Comparative Example 2 (mixture having an exo/exo type BzDA content of 60% by mass) was used as the tetracarboxylic dianhydride instead of using the exo/exo type BzDA obtained in Example 2 alone, the amount of DMAc used in obtaining the mixture liquid was changed to 5.45 g, the amount of γ-butyrolactone used in obtaining the mixture liquid was changed to 5.45 g, a solution diluted by adding 3.05 g each of DMAc and γ-butyrolactone after completion of the reaction was used as a reaction liquid (varnish) instead of using the solution obtained after completion of the reaction (mixture liquid after the reaction) (after stirring while heating the mixture liquid under a nitrogen atmosphere under a temperature condition of 180° C. for 6 hours) as it was as a reaction liquid (varnish), and the time for holding at 350° C. in the inert oven was changed from 1 hour to 1.5 hours. Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the tetracarboxylic dianhydride used (content of exo/exo type BzDA: 60% by mass), and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 60% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from TFMB).

Comparative Example 6

[0122] A colorless and transparent film made of polyimide was obtained in the same manner as in Example 7 except that a mixture of 2.03 g (5.00 mmol) of exo/exo type BzDA obtained in Example 2 and 2.03 g (5.00 mmol) of endo/endo type BzDA obtained in Comparative Example 2 (mixture having an exo/exo type BzDA content of 50% by mass) was used as the tetracarboxylic dianhydride instead of using the exo/exo type BzDA obtained in Example 2 alone, the amount of DMAc used was changed to 8.5 g, and the amount of γ-butyrolactone used was changed to 8.5 g. Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the tetracarboxylic dianhydride used (content of exo/exo type BzDA: 50% by mass), and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 50% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from TFMB).

Comparative Example 7

[0123] A colorless and transparent film made of polyimide was obtained in the same manner as in Example 8 except that 8.13 g (20.0 mmol) of endo/endo type BzDA obtained in Comparative Example 2 was used alone as a tetracarboxylic dianhydride instead of using a mixture of the exo/exo type BzDA obtained in Example 2 and the endo/endo type BzDA obtained in Comparative Example 2, the amount of TFMB used was 6.40 (20.0 mmol) g, 7.3 g of N-methylpyrrolidone was used instead of DMAc in obtaining the mixture liquid, the amount of γ-butyrolactone used in obtaining the mixture liquid was changed to 7.3 g, the amount of triethylamine used was changed to 0.202 g (2.00 mmol), 18.7 g of y-butyrolactone was added and diluted after completion of the reaction instead of adding DMAc and γ-butyrolactone and diluting after completion of the reaction (after stirring while heating the mixture liquid under a nitrogen atmosphere under a temperature condition of 180° C. for 6 hours). Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the tetracarboxylic dianhydride used (content of endo/endo type BzDA: 100% by mass), and in which, in the repeating unit (A), the content of the repeating unit having an endo/endo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from TFMB).

Evaluation of Characteristics of Polyimides Obtained in Examples 7 and 8 and Comparative Examples 6 and 7

[0124] The above-described measurement methods were employed to subject the polyimides (films) obtained in Examples 7 and 8 and Comparative Examples 6 and 7 to the measurement of linear expansion coefficient, glass transition temperature, total luminous transmittance, 5% weight loss temperature (Td5%), HAZE, and YI. Table 4 presents the results obtained together with the film thickness of each film.

TABLE-US-00004 TABLE 4 Film Tg Total Luminous Tetracarboxylic Aromatic Thickness CTE (TMA) Transmittance Td5% HAZE Dianhydride Diamine (μm) (ppm/K) (° C.) (%) (° C.) (%) YI Example 7 Exo/Exo Type TFMB 28 49 372 91 455 0.50 1.6 BzDA (100 Mass %) Example 8 Exo/Exo Type TFMB 28 57 366 90 455 0.95 2.8 BzDA (60 Mass %) Endo/Endo Type BzDA (40 Mass %) Comparative Exo/Exo Type TFMB 70 66 358 89 454 0.93 — Example 6 BzDA (50 Mass %) Endo/Endo Type BzDA (50 Mass %) Comparative Endo/Endo Type TFMB 15 73 324 91 475 0.49 1.5 Example 7 BzDA (100 Mass %)

[0125] As is clear from the results presented in Table 4, it was confirmed that the polyimides obtained in Examples 7 and 8 and Comparative Examples 6 and 7 both had a total luminous transmittance of 80% or more, and the transparency was at a sufficiently high level. In addition, it was confirmed that the polyimides obtained in Examples 7 and 8 and Comparative Examples 6 and 7 had a Tg of 250° C. or higher, and the heat resistance based on Tg was at a sufficiently high level for both cases. Moreover, from the results presented in Table 4, it was confirmed that the polyimides (Examples 7 to 8) containing 60% by mass or more of the repeating unit having an exo/exo type three-dimensional structure was a polyimide having a lower linear expansion coefficient than the polyimides (Comparative Examples 6 to 7) in which the content of the repeating unit having an exo/exo type three-dimensional structure was 50% by mass or less, and it was found that, by containing 60% by mass or more of the repeating unit having an exo/exo type three-dimensional structure, it was possible to lower the value of linear expansion coefficient.

Example 9

[0126] A reaction liquid (varnish) was produced in the same manner as in the varnish preparation step used in Example except that 0.901 g (2.46 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (Bis-AP-AF) was used as the aromatic diamine instead of using DABAN, and 4.4 g of DMAc was used as a solvent instead of TMU. In addition, a colorless and transparent film made of polyimide was obtained in the same manner as in the film preparation step employed in Example 3 except that the reaction liquid (varnish) thus obtained was used, and the condition for operating the inert oven at the time of forming the polyimide was changed to the condition of “under a nitrogen stream, the temperature is raised to 300° C. and held for 1 hour, and then cooled to room temperature.” Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from Bis-AP-AF).

Example 10

[0127] A colorless and transparent film made of polyimide was obtained in the same manner as in Example 7 except that 1.82 g (4.91 mmol) of Bis-AP-AF was used as the aromatic diamine instead of using TFMB, the amount of exo/exo type BzDA obtained in Example 2 was changed to 2.02 g (4.92 mmol), the amount of DMAc used in obtaining the mixture liquid was changed to 4.4 g, the amount of γ-butyrolactone used in obtaining the mixture liquid was changed to 4.4 g, the amount of tri ethyl amine used as a reaction accelerator was changed to 0.0249 g (0.247 mmol), a solution diluted by adding 12.7 g of DMAc after completion of the reaction was used as a reaction liquid (varnish) instead of using the solution obtained after completion of the reaction (mixture liquid after the reaction) (after stirring while heating the mixture liquid under a nitrogen atmosphere under a temperature condition of 180° C. for 6 hours) as it was as a reaction liquid (varnish), and the condition for operating the inert oven was changed to “under a nitrogen stream, the temperature is raised to 250° C. and held for 1 hour, and then cooled to room temperature.” Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from Bis-AP-AF).

Comparative Example 8

[0128] A colorless and transparent film made of polyimide was obtained in the same manner as in Example 10 except that 4.07 g (10.0 mmol) of the endo/endo type BzDA obtained in Comparative Example 2 was used as the tetracarboxylic dianhydride instead of the exo/exo type BzDA obtained in Example 2, the amount of Bis-AP-AF used was changed to 3.66 g (10.0 mmol), the amount of DMAc used in obtaining the mixture liquid was changed to 3.8 g, the amount of γ-butyrolactone used in obtaining the mixture liquid was changed to 3.8 g, the amount of triethylamine used was changed to 0.051 g (0.500 mmol), and the amount of DMAc added after completion of the reaction was changed from 12.7 g to 15.6 g. Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the endo/endo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an endo/endo type three-dimensional structure represented by the above general formula (103) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from Bis-AP-AF).

Evaluation of Characteristics of Polyimides Obtained in Examples 9 and 10 and Comparative Example 8

[0129] The above-described measurement methods were employed to subject the polyimides (films) obtained in Examples 9 and 10 and Comparative Example 8 to the measurement of linear expansion coefficient, glass transition temperature, total luminous transmittance, 5% weight loss temperature (Td5%), HAZE, and YI. Table 5 presents the results obtained together with the film thickness of each film.

TABLE-US-00005 TABLE 5 Film Tg Total Luminous Tetracarboxylic Aromatic Thickness CTE (TMA) Transmittance Td5% HAZE Dianhydride Diamine (μm) (ppm/K) (° C.) (%) (° C.) (%) YI Example 9 Exo/Exo Type Bis-AP-AF 38 50 336 90 430 2.2 1.9 BzDA Example 10 Exo/Exo Type Bis-AP-AF 23 41 345 91 418 0.64 0.8 BzDA Comparative Endo/Endo Type Bis-AP-AF 32 55 316 91 414 0.64 1.5 Example 8 BzDA

[0130] As is clear from the results presented in Table 5, it was confirmed that the polyimides obtained in Examples 9 and 10 and Comparative Example 8 both had a total luminous transmittance of 80% or more, and the transparency was at a sufficiently high level. In addition, it was confirmed that the polyimides obtained in Examples 9 and 10 and Comparative Example 8 had a Tg of 250° C. or higher, and the heat resistance based on Tg was at a sufficiently high level. Moreover, in the case where the repeating unit of the polyimide was composed of a repeating unit having an exo/exo type three-dimensional structure (Examples 9 and 10), it was confirmed that the polyimide had a lower linear expansion coefficient as compared with the case where the repeating unit of the polyimide was a repeating unit having an endo/endo type three-dimensional structure (Comparative Example 8).

Example 11

[0131] A reaction liquid (varnish) was produced in the same manner as in the varnish preparation step used in Example 3 except that a mixture of 0.373 g (1.64 mmol) of DABAN and 0.089 g (0.82 mmol) of p-diaminobenzene (PPD) was used as the aromatic diamine instead of using DABAN alone, the amount of TMU used in obtaining the mixture liquid was changed to 5.7 g, and a solution diluted by adding 2.3 g of TMU after completion of the reaction was used as a reaction liquid (varnish) instead of using the solution obtained after completion of the reaction (mixture liquid after the reaction) (after stirring the mixture liquid under a nitrogen atmosphere under a temperature condition of room temperature for 5 days) as it was as a reaction liquid (varnish). In addition, a colorless and transparent film made of polyimide was obtained in the same manner as in the film preparation step employed in Example 3 except that the reaction liquid (varnish) thus obtained was used. Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that, in all repeating units, 50 mol % of the repeating units are such that R.sup.10 is a divalent group obtained by removing two amino groups from DABAN, and the remaining 50 mol % of the repeating units are such that R.sup.10 is a divalent group obtained by removing two amino groups from PPD).

Example 12

[0132] A reaction liquid (varnish) was produced in the same manner as in the varnish preparation step used in Example 3 except that a mixture of 0.394 g (1.23 mmol) of TFMB and 0.133 g (1.23 mmol) of PPD was used as the aromatic diamine instead of using DABAN alone, the amount of TMU used in obtaining the mixture liquid was changed to 3.6 g, and a solution diluted by adding 5.1 g of TMU after completion of the reaction was used as a reaction liquid (varnish) instead of using the solution obtained after completion of the reaction (mixture liquid after the reaction) (after stirring the mixture liquid under a nitrogen atmosphere under a temperature condition of room temperature for 5 days) as it was as a reaction liquid (varnish). In addition, a colorless and transparent film made of polyimide was obtained in the same manner as in the film preparation step employed in Example 11 except that the reaction liquid (varnish) thus obtained was used. Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that, in all repeating units, 50 mol % of the repeating units are such that R.sup.10 is a divalent group obtained by removing two amino groups from TFMB, and the remaining 50 mol % of the repeating units are such that R.sup.10 is a divalent group obtained by removing two amino groups from PPD).

Example 13

[0133] A reaction liquid (varnish) was produced in the same manner as in the varnish preparation step used in Example except that 0.858 g (2.46 mmol) of bis(4-aminophenyl)ester of terephthalic acid (BPTP) was used as the aromatic diamine instead of using DABAN, 5.96 g of N-methylpyrrolidone (NMP) was used as a solvent instead of TMU, and a solution diluted by adding 4.96 g of NMP after completion of the reaction was used as a reaction liquid (varnish) instead of using the solution obtained after completion of the reaction (mixture liquid after the reaction) (after stirring the mixture liquid under a nitrogen atmosphere under a temperature condition of room temperature for 5 days) as it was as a reaction liquid (varnish). In addition, a colorless and transparent film made of polyimide was obtained in the same manner as in the film preparation step employed in Example 11 except that the reaction liquid (varnish) thus obtained was used, and the condition for operating the inert oven at the time of forming the polyimide was changed to the condition of “under a nitrogen stream, the temperature is raised to 135° C. and held for 30 minutes, and then the temperature is raised to 300° C. and held for 1 hour, and then cooled to room temperature.” Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from BPTP).

Example 14

[0134] A colorless and transparent film made of polyimide was obtained in the same manner as in Example 10 except that 2.16 g (5.00 mmol) of bis[4-(3-aminophenoxy)phenyl]sulfone (BAPS-M) was used as the aromatic diamine instead of using Bis-AP-AF, the amount of exo/exo type BzDA obtained in Example 2 was changed to 2.03 g (5.00), the amount of DMAc used to obtain the mixture liquid was changed to 8.4 g, the amount of γ-butyrolactone used in obtaining the mixture liquid was changed to 8.4 g, the amount of triethylamine used as a reaction accelerator was changed to 0.0253 g (0.250 mmol), and the solution obtained after completion of the reaction was used as it was as a reaction liquid (varnish) without adding DMAc (without diluting with DMAc) after completion of the reaction (after stirring while heating the mixture liquid under a nitrogen atmosphere under a temperature condition of 180° C. for 6 hours). Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10 s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from BAPS-M).

Example 15

[0135] A colorless and transparent film made of polyimide was obtained in the same manner as in Example 10 except that 1.46 g (5.00 mmol) of 1,3-bis(3-aminophenoxy)benzene (APB-N) was used as the aromatic diamine instead of using Bis-AP-AF, the amount of DMAc used in obtaining the mixture liquid was changed to 5.2 g, the amount of γ-butyrolactone used in obtaining the mixture liquid was changed to 5.2 g, and the solution obtained after completion of the reaction was used as it was as a reaction liquid (varnish) without adding DMAc (without diluting with DMAc) after completion of the reaction (after stirring while heating the mixture liquid under a nitrogen atmosphere under a temperature condition of 180° C. for 6 hours). Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from APB-N).

Example 16

[0136] A colorless and transparent film made of polyimide was obtained in the same manner as in Example 10 except that 1.01 g (5.14 mmol) of 3,4′-diaminodiphenyl ether (3,4-DDE) was used as the aromatic diamine instead of using Bis-AP-AF, the amount of exo/exo type BzDA obtained in Example 2 was changed to 2.09 g (5.14 mmol), 6.0 g of NMP was used in obtaining the mixture liquid instead of DMAc, the amount of γ-butyrolactone used in obtaining the mixture liquid was changed to 6.0 g, and the solution obtained after completion of the reaction was used as it was as a reaction liquid (varnish) without adding DMAc (without diluting with DMAc) after completion of the reaction (after stirring while heating the mixture liquid under a nitrogen atmosphere under a temperature condition of 180° C. for 6 hours). Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from 3,4-DDE).

Example 17

[0137] A colorless and transparent film made of polyimide was obtained in the same manner as in Example 10 except that 1.29 g (5.00 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAPA) was used as the aromatic diamine instead of using Bis-AP-AF, the amount of DMAc used in obtaining the mixture liquid was changed to 6.65 g, the amount of γ-butyrolactone used in obtaining the mixture liquid was changed to 6.65 g, and the amount of DMAc added after completion of the reaction (after stirring while heating the mixture liquid under a nitrogen atmosphere under a temperature condition of 180° C. for 6 hours) was changed from 12.7 g to 5.5 g. Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from BAPA).

Example 18

[0138] A colorless and transparent film made of polyimide was obtained in the same manner as in Example 10 except that 1.41 g (5.00 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)sulfone (BPS-DA) was used as the aromatic diamine instead of using Bis-AP-AF, the amount of the exo/exo type BzDA obtained in Example 2 was 2.03 g (5.00 mmol), and a silicon wafer was used instead of the glass substrate. Note that it is found that the obtained polyimide forming the film is a polyimide that contains a repeating unit (A) represented by the above general formula (101) derived from the exo/exo type BzDA used, and in which, in the repeating unit (A), the content of the repeating unit having an exo/exo type three-dimensional structure represented by the above general formula (102) is 100% by mass (note that R.sup.10s in the formulas (101) and (102) are each a divalent group obtained by removing two amino groups from BPS-DA).

Evaluation of Characteristics of Polyimides Obtained in Examples 11 to 18

[0139] The above-described measurement methods were employed to subject the polyimides (films) obtained in Examples 11 to 18 to the measurement of linear expansion coefficient, glass transition temperature, total luminous transmittance, 5% weight loss temperature (Td5%), HAZE, and YI. Table 6 presents the results obtained together with the film thickness of each film.

TABLE-US-00006 TABLE 6 Film Tg Total Luminous Tetracarboxylic Aromatic Thickness CTE (TMA) Transmittance Td5% HAZE Dianhydride Diamine (μm) (ppm/K) (° C.) (%) (° C.) (%) YI Example 11 Exo/Exo Type DABAN (50 mol %) 15 37 387 87 452 1.1 4.0 BzDA PPD (50 mol %) Example 12 Exo/Exo Type TFMB (50 mol %) 20 54 364 90 452 0.79 2.9 BzDA PPD (50 mol %) Example 13 Exo/Exo Type BPTP 15 21 431 86 438 1.1 — BzDA Example 14 Exo/Exo Type BAPS-M 20 55 257 89 461 0.85 0.8 BzDA Example 15 Exo/Exo Type APB-N 30 58 — 89 458 1.30 1.1 BzDA Example 16 Exo/Exo Type 3,4-DDE 22 52 296 88 453 0.74 3.4 BzDA Example 17 Exo/Exo Type BAPA 17 41 329 89 — 0.78 1.9 BzDA Example 18 Exo/Exo Type BPS-DA 16 41 363 86 — 0.96 — BzDA

INDUSTRIAL APPLICABILITY

[0140] As described above, the present invention makes it possible to provide a tetracarboxylic dianhydride that can be used as a raw material monomer for producing a polyimide having a lower linear expansion coefficient while having a sufficiently high level of light transmittance and heat resistance; a carbonyl compound that can be used as a raw material for efficiently producing the tetracarboxylic dianhydride and can be obtained as an intermediate during the production of the tetracarboxylic dianhydride; a polyimide precursor resin that can be suitably used for producing the polyimide having a lower linear expansion coefficient while having a sufficiently high level of light transmittance and heat resistance and can be efficiently produced by using the tetracarboxylic dianhydride; and a polyimide that can have a lower linear expansion coefficient while having a sufficiently high level of light transmittance and heat resistance. Therefore, the tetracarboxylic dianhydride of the present invention is useful as a monomer or the like for producing a polyimide for glass replacement. In addition, the tetracarboxylic dianhydride of the present invention can have sufficiently high solvent solubility, and is also useful as a compound or the like for use in applications such as an epoxy curing agent.