TWI496816B - Polyimide precursor aqueous composition and method for preparing the same - Google Patents

Description

Polyimine precursor aqueous solution composition and polyylidene precursor aqueous solution composition manufacturing method

The present invention relates to a composition of an aqueous solution of a polyimide intermediate precursor and a method for producing a composition of an aqueous solution of a polyimide precursor. The polyazonia precursor aqueous solution composition is preferred because it has a higher environmental suitability than the polyamidimide precursor solution composition using an organic solvent. According to the production method of the present invention, since a solvent other than water is not required, an aqueous solution composition of a polyimine precursor having a smaller organic solvent content than a conventional one can be obtained, and a higher environmental compatibility can be obtained. An aqueous solution of a polyimine precursor precursor containing an aqueous solvent of an organic solvent. Further, the polyiminoimine is desirably obtained by using the aqueous solution of the polyimide intermediate precursor. In particular, the aromatic polyimine obtained by using the specific aqueous solution of the polyimine precursor of the present invention has high crystallinity and thus has excellent properties such as heat resistance, mechanical strength, electrical properties, solvent resistance and the like. .

Further, the present invention relates to a method for producing an aromatic polyimine seamless belt using the aqueous solution of the polyimide intermediate precursor. Further, the present invention relates to a binder resin composition for an electrode of an electrochemical element such as a lithium ion secondary battery or an electric double layer capacitor (a composition of a polyimine precursor aqueous solution for a binder resin). Furthermore, the present invention relates to a composition of a polyimine precursor aqueous solution for a flexible device substrate, such as a liquid crystal display, an organic EL display, a display device such as an electronic paper, or a substrate for a light receiving device such as a thin film solar cell. Polyimine precursor aqueous solution composition.

Polyimine obtained from tetracarboxylic dianhydride and diamine, especially aromatic polyimine obtained from aromatic tetracarboxylic dianhydride and aromatic diamine, due to heat resistance, mechanical strength, electrical properties, resistance It is excellent in properties such as solvent and is widely used in the field of electrochemical electronics. However, since polyimine is inferior in solubility in an organic solvent, a solution composition in which a polyamidene precursor of a polyimine precursor is dissolved in an organic solvent is usually applied to, for example, a surface of a substrate, followed by The polyimine is obtained by heating at a high temperature and subjecting the dehydration to ring closure (imidization). The polyamine liquid solution composition for producing the polyimine contains an organic solvent and must be heated at a high temperature, so that it is not necessarily ideal for the environmental surface, and may be limited in use depending on circumstances.

Therefore, a water-soluble polyimine precursor has been proposed. For example, Patent Document 1 proposes to polymerize a tetracarboxylic dianhydride and a diamine in an organic solvent to obtain a poly-proline, and if necessary, hydrolyze the varnish into water and pulverize the poly-proline, and Extracting and removing the reaction solvent contained in the polyamic acid, drying it to obtain poly-proline, and secondly, reacting the polyamine in water with a specific amine compound such as 2-methylaminodiethanol. The water-soluble polyamidate is obtained to obtain a polyacetate aqueous solution composition. However, the polyammonium carbonate aqueous solution composition (polyimine precursor composition) is difficult to be polymerized, and there is still room for improvement in the properties of the obtained polyimine. Further, the water-soluble polyimide precursor proposed in Patent Document 1 is suitable for use as a varnish for forming an insulating layer of an electronic device such as a multi-wafer module, a thin film magnetic head, or a semiconductor device.

Patent Document 2 proposes a polyglycine (polyimine precursor) obtained by reacting a tetracarboxylic acid component with an aromatic diamine component in an organic solvent, and 1,2-dimethylimidazole and/or 1 After the reaction of methyl-2-ethylimidazole, the water-soluble polyimine precursor obtained by separation from the reaction mixture is obtained. However, the water-soluble polyimine precursor obtained in the examples of Patent Document 2, the aromatic polyimine obtained using the same, is only non-crystalline. Furthermore, after the aqueous solution composition of the polyimide precursor is prepared in an organic solvent to prepare a water-soluble polyimide precursor, the separation and dissolution of the separated water-soluble polyimide precursor are first dissolved. Obtained in a water solvent process requires extremely complicated operations. Moreover, since the organic solvent cannot be completely removed from the water-soluble polyimine precursor prepared in an organic solvent (if it is to be completely removed, heat treatment is required, so that the oxime imidization causes no solubility to water), The obtained aqueous solution of the polyimide intermediate precursor may contain an organic solvent. Further, the water-soluble polyimine precursor obtained in Patent Document 2 is obtained by using a polyimine which is amorphous and has thermal fusion properties, and is suitable for use as a binder for organic or inorganic fiber woven fabrics or non-woven fabrics. By.

On the other hand, Non-Patent Document 1 shows that the smaller the degree of swelling of the electrode binder resin with respect to the electrolyte, the better the discharge capacity retention rate accompanying the charge and discharge cycle is.

In addition, Non-Patent Document 2 analyzes the reductive decomposition reaction of the electrolytic solution in the lithium battery, and confirms that lithium methoxide or the like is formed on the surface of the electrode. That is, in a battery environment, the electrolyte may contain lithium methoxide which is strongly alkaline and may adversely affect the binder resin.

Further, Patent Document 3 proposes that the solvent is an organic solvent, specifically, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or the like. A method for producing a flexible device substrate of a polyimide intermediate resin composition. On the other hand, from the viewpoint of environmental adaptability, there is also a demand for a water solvent.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 8-59832

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-226582

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-202729

[Non-patent literature]

[Non-Patent Document 1] Hitachi Chemical Technology Report No. 45 (July 2005)

[Non-Patent Document 2] Yoshida Hama et al., Decomposition Reaction of Carbonate Mixed Electrolyte for Lithium Batteries, Lectures for the 35th Battery Symposium, Nissan Electrochemical Association Battery Technology Committee, November 14, 1994, p.75 -76

A first object of the present invention is to provide a process for producing a polyimine precursor aqueous solution composition which can easily produce a polyisimide precursor aqueous solution composition having higher environmental compatibility without using a solvent other than water. Further, an aqueous solution of a polyimine precursor precursor containing an aqueous solvent having a small organic solvent content or no organic solvent is provided.

A second object of the present invention is to provide a polyimine precursor aqueous solution composition which uses an aqueous solvent and has good environmental compatibility, and the aromatic polyamidene obtained by using the same has high crystallinity, and thus has heat resistance. It is excellent in characteristics such as mechanical strength, electrical properties, and solvent resistance, and is preferably an organic solvent having a high molecular weight and a solvent other than water.

A third object of the present invention is to provide a method for producing an aromatic polyimine seamless belt which is capable of producing a fragrance by using an aqueous solution of a polyimine precursor having a good environmental compatibility using an aqueous solvent. The polyamidimide seamless belt is preferably made of high crystallinity, heat resistance, mechanical strength, electrical properties, solvent resistance, etc., and is suitable for use as an intermediate transfer or fixing for electrophotographic devices. Belt.

A fourth object of the present invention is to provide a binder resin composition for an electrode which is excellent in environmental compatibility by using an aqueous solvent, preferably a high molecular weight, an organic solvent other than a solvent, and aroma obtained therefrom. Since the polyamidimide has high crystallinity, it is excellent in properties such as heat resistance, mechanical strength, electrical properties, and solvent resistance, and has a low degree of swelling even in a battery environment and excellent bismuth.

A fifth object of the present invention is to provide a polyimine precursor resin composition for a flexible device substrate, which is excellent in environmental compatibility by using an aqueous solvent, and preferably contains a high molecular weight polylysine, a solvent. The substrate for an aromatic polyimine flexible device obtained by using the organic solvent other than the water has high crystallinity, and has excellent properties such as heat resistance, mechanical strength, low linear expansion, electrical properties, and solvent resistance. A flexible device substrate that is suitable as a display device such as a substrate for a liquid crystal display, a substrate for an organic EL display, or a substrate for an electronic paper, or a flexible device substrate that is a light-receiving device such as a substrate for a thin film solar cell.

The present invention relates to the following matters.

A method for producing a polyhydrazide precursor aqueous solution composition, characterized in that water is used as a reaction solvent, and the solubility of tetracarboxylic dianhydride and water at 25 ° C in the presence of imidazole is 0.1 g / The diamine is reacted with L or more to produce an aqueous solution composition of the polyimide precursor.

2. The method for producing a polyhydrazide precursor aqueous solution composition according to the above 1, wherein the amount of the imidazole used is 1.6 times or more relative to the tetracarboxylic dianhydride.

3. The method for producing a polyhydrazide precursor aqueous solution composition according to the above 1, or 2. wherein the imidazole has two or more alkyl groups as a substituent.

4. The method for producing a polyhydrazide precursor aqueous solution composition according to the above 3. wherein the imidazole is selected from the group consisting of 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 4 a group consisting of -ethyl-2-methylimidazole and 1-methyl-4-ethylimidazole.

5. The method for producing a polyhydrazide precursor aqueous solution composition according to any one of the above items 1 to 4, wherein the obtained polyamidene precursor has a logarithmic viscosity of 0.2 or more.

A polyaminimide precursor aqueous solution composition characterized by reacting a tetracarboxylic dianhydride with a diamine having a solubility of 0.1 g/L or more for water at 25 ° C. It is dissolved in a water solvent together with the imidazole, and the content of the organic solvent is less than 5%.

7. The composition of the aqueous solution of the polyimide intermediate precursor according to the above 6, wherein the organic solvent is substantially absent.

An aqueous solution of a polyimine precursor precursor obtained by reacting a tetracarboxylic acid component with a diamine component, which is obtained by reacting a repeating unit represented by the following chemical formula (1), with respect to the aforementioned poly The tetracarboxylic acid component of the proline is one or more than 1.6 moles of an imidazole having two or more alkyl groups as a substituent, and is dissolved in a water solvent.

In the chemical formula (1), A is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid having 2 to 3 aromatic rings, and B is a water having 1 to 2 aromatic rings and for 25 ° C. A divalent group obtained by removing an amine group from an aromatic diamine having a solubility of 0.1 g/L or more. 9. The aqueous solution of the polyimine precursor precursor according to the above 8, wherein the imidazole having two or more alkyl groups as a substituent is selected from the group consisting of 1,2-dimethylimidazole and 2-B. A group consisting of benzyl-4-methylimidazole, 4-ethyl-2-methylimidazole, and 1-methyl-4-ethylimidazole.

10. The aqueous solution of the polyimine precursor precursor according to the above 8. or 9. wherein A of the chemical formula (1) is any one of the following chemical formulae (2) to (7).

11. The polyhydrazide precursor aqueous solution composition according to any one of the above items 8, wherein B of the chemical formula (1) is any one of the following chemical formulas (8) to (9).

12. The aqueous solution of the polyimine precursor precursor according to any one of the above items 8, wherein the logarithmic viscosity is 0.2 or more.

13. The aqueous solution of a polybendimimine precursor according to any one of the preceding items 8, wherein the content of the organic solvent is less than 5%.

14. The aqueous solution of a polybendimimine precursor according to any one of the preceding items, wherein the organic solvent is substantially absent.

A method for producing an aromatic polyimine seamless belt, which comprises the steps of: a polymerization unit obtained by reacting a tetracarboxylic acid component with a diamine component and having a repeating unit represented by the following chemical formula (1) The hydrazide acid and the polyimine precursor aqueous solution composition in which the imidazole of 1.6 times or more of the tetracarboxylic acid component of the polyamic acid is dissolved in an aqueous solvent is heat-treated.

In the chemical formula (1), A is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid, and B is an amine group obtained by removing an amine group from an aromatic diamine having a solubility of water of 25 ° C or more of 0.1 g/L or more. 2 valence base.

16. The method for producing an aromatic polyimine seamless belt according to the above 15, wherein the imidazole has two or more alkyl groups as a substituent.

17. The method for producing an aromatic polyimine seamless belt according to the above 15. or 16. wherein the A of the chemical formula (1) is obtained by removing a carboxyl group from an aromatic tetracarboxylic acid having 2 to 3 aromatic rings. The 4 valence base.

18. The method for producing an aromatic polyimine seamless belt according to any one of the above items 15, wherein the B of the chemical formula (1) is removed from the aromatic diamine having 1 to 2 aromatic rings. A divalent group formed by an amine group.

19. The method for producing an aromatic polyimine seamless belt according to any one of the preceding items, wherein the polyacetamide precursor aqueous solution composition is substantially free of an organic solvent.

The method for producing an aromatic polyimine seamless belt according to any one of the above items, wherein the polyacetamide precursor aqueous solution composition is as described in any one of the above 8. to 14. An aqueous solution of a polyimine precursor precursor.

The method for producing an aromatic polyimine seamless belt according to any one of the preceding items, wherein the seamless belt obtained is an intermediate transfer belt.

The method for producing an aromatic polyimine seamless belt according to any one of the preceding items, wherein the seamless belt obtained is a fixed belt.

23. The method for producing an aromatic polyimine seamless belt according to any one of the preceding items, wherein the aromatic polyimine seamless belt is produced by a rotational molding method.

24. A binder resin composition for an electrode obtained by reacting a tetracarboxylic acid component with a diamine component to obtain a polylysine composed of a repeating unit represented by the following chemical formula (1), and a polyamine The acid tetracarboxylic acid component is 1.6 times or more of an imidazole, and is dissolved in a water solvent.

In the chemical formula (1), A is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid, and B is an amine group obtained by removing an amine group from an aromatic diamine having a solubility of water of 25 ° C or more of 0.1 g/L or more. 2 valence base.

25. The adhesive resin composition for an electrode according to the above item 24. wherein the imidazole has two or more alkyl groups as a substituent.

26. The electrode composition for an electrode according to the above item 24. or 25. wherein A of the chemical formula (1) is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid having 2 to 3 aromatic rings.

27. The electrode binder resin composition according to any one of the above items 24 to 26, wherein the B of the chemical formula (1) is obtained by removing an amine group from an aromatic diamine having 1 or 2 aromatic rings. 2 valence base.

28. The electrode binder resin composition according to any one of the above items 24 to 27, which is substantially free of an organic solvent.

29. The adhesive resin composition for an electrode according to any of the above-mentioned items, wherein the composition of the present invention is the aqueous solution of the polyimine precursor precursor according to any one of the above items 8. to 14.

30. The electrode resin composition for an electrode according to any one of the above items 24 to 29, wherein the binder resin obtained by heat treatment is immersed in dimethyl carbonate at 25 ° C for 24 hours, and the mass is increased to 2 masses. %the following.

An electrode mixture paste comprising: an electrode active material, and the electrode binder resin composition according to any one of the above items 24. to 30.

32. The electrode mixture paste according to the above 31, wherein the electrode active material is carbon powder, cerium powder, tin powder, or an alloy powder containing bismuth or tin.

33. An electrode obtained by coating an electrode mixture paste as described in the above 31. or 32. on a current collector and heat-treating to remove a solvent, and simultaneously performing a hydrazine imidization reaction.

34. The electrode according to the aforementioned 33, wherein the heat treatment temperature is 250 ° C or lower.

35. The electrode according to the aforementioned 33. or 34., which is a negative electrode for a lithium ion secondary battery.

A polyimine precursor resin composition for a flexible device substrate, which is obtained by reacting a tetracarboxylic acid component with a diamine component, and which is obtained by repeating units represented by the following chemical formula (1) The acid is formed by dissolving it in an aqueous solvent with respect to the imidazole of 1.6 times or more with respect to the tetracarboxylic acid component of the polyamic acid.

In the chemical formula (1), A is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid, and B is obtained by removing an amine group from an aromatic diamine having a solubility of water of 25 ° C or more of 0.1 g/L or more. 2 valence base.

37. The polyiminoimine precursor resin composition for a flexible device substrate according to the above 36, wherein the imidazole has two or more alkyl groups as a substituent.

38. The polyamidene precursor resin composition for a flexible device substrate according to the above 36, wherein the A of the chemical formula (1) is removed from the aromatic tetracarboxylic acid having 2 to 3 aromatic rings. a tetravalent group formed by a carboxyl group.

39. The polyimine precursor resin composition for a flexible device substrate according to any one of the preceding paragraphs 36 to 38, wherein the B of the chemical formula (1) is derived from an aromatic having 1 or 2 aromatic rings. A divalent group obtained by removing an amine group from a diamine.

The polyimine precursor resin composition for a flexible device substrate according to any one of the preceding paragraphs 36 to 39, which is substantially free of an organic solvent.

The polyimine precursor resin composition for a flexible device substrate according to any one of the preceding paragraphs, wherein the polyimine precursor of any one of the above items 8. to 14. Aqueous composition.

42. A method of manufacturing a flexible device, which is a method of manufacturing a flexible device for a display device or a light-receiving device, characterized by comprising the steps of: being flexible as described in any one of the aforementioned 36. to 41. The substrate of the device is coated on the carrier substrate with a polyimide precursor resin composition and heat-treated to form a solid polyimide film; a circuit is formed on the polyimide film; and A polyimide film having a circuit formed on the surface thereof is peeled off from the carrier substrate.

43. The method of producing a flexible device according to the above item 42, wherein the polyimide film of the polyimide film has a glass transition temperature of 250 ° C or higher.

A flexible device which is a display device or a light-receiving device manufactured by the method for manufacturing a flexible device according to the aforementioned 42. or 43.

45. The flexible device of the aforementioned 44., which is a light receiving element of an electronic paper, a display or a solar cell.

According to the present invention, it is possible to provide a method of easily preparing an aqueous solution of a polyimine precursor precursor having a higher environmental compatibility without using a solvent other than water. According to the manufacturing method, the polyhydrazide precursor aqueous solution composition can be obtained very simply (directly), especially the polyfluorene imide precursor aqueous solution containing the organic solvent in an amount of less than 5% or even no organic solvent. Things. The polyhydrazide precursor aqueous solution composition having a very small content of such an organic solvent is conventionally obtained, and can be produced by reacting a tetracarboxylic acid component with a diamine component in an aqueous solvent according to the production method of the present invention. Imine precursor (polyproline).

Further, a polyimine having excellent properties can be obtained by using a composition containing the imidazole, preferably a high molecular weight polyimine precursor aqueous solution.

According to the present invention, it is possible to provide a composition of an aqueous solution of a polyimide precursor, which uses an aqueous solvent and has good environmental compatibility, and the aromatic polyamidene obtained by using the same has high crystallinity, so it is heat resistance and mechanical strength. Among them, those having excellent properties such as electrical properties and solvent resistance are preferably organic solvents having a high molecular weight and a solvent other than water. A polyiminoimine precursor aqueous solution composition which can obtain an aromatic polyimine having such excellent characteristics has not been conventionally used.

In particular, the aromatic polyimine obtained from the aqueous solution composition of the polyimine precursor of the specific composition obtained according to the present invention is excellent in heat resistance, mechanical strength, electrical properties, solvent resistance and the like, and is suitable. It is used as a part for various precision equipment such as electric ‧ electronic equipment or photocopying machines, such as various materials such as flexible printed wiring boards, and a seamless belt for intermediate transfer, fixing, or transport of photocopiers. Moreover, even if the degree of swelling in a battery environment is small and excellent in enthalpy, it is also suitable for use as a binder of an electrode of a battery. Further, it is also suitable as a substrate of a flexible device such as a light receiving device such as a liquid crystal display, an organic EL display, or an electronic paper, or a light receiving element of a thin film solar cell.

According to the present invention, there is provided a method for producing an aromatic polyimine seamless belt which is an aqueous solution composition of a polyimide intermediate precursor which is excellent in environmental compatibility using an aqueous solvent. The polyhydrazide precursor aqueous solution composition used is preferably an organic solvent having a high molecular weight and a solvent other than water. A method for producing an aromatic polyimine seamless belt using the aqueous solution of the polyimide precursor aqueous solution, which is obtained by dissolving polyacrylamide which is a polyimide precursor in an organic solvent. In the case of an amine precursor solution composition, it is preferred because of its high environmental adaptability. Further, the aromatic polyimine seamless belt of the specific composition obtained by the production method of the present invention preferably has high crystallinity, and has excellent properties such as heat resistance, mechanical strength, electrical properties, solvent resistance, and the like. It is used as a seamless belt for intermediate transfer or a seamless belt for fixing for electrophotographic devices requiring heat resistance, electrical resistance stability, and high strength and toughness.

Further, according to the present invention, it is possible to provide a binder resin composition for an electrode which is excellent in environmental compatibility using an aqueous solvent, preferably a high molecular weight, and an organic solvent other than a solvent. The electrode binder resin composition is preferred because it has a higher environmental suitability than the polyimide solvent precursor solution composition using an organic solvent. Further, since the aromatic polyimine which has a specific composition obtained by using the electrode binder resin composition has high crystallinity, it is excellent in heat resistance, mechanical strength, electrical properties, solvent resistance and the like. The swelling degree in the environment is still small and has excellent bismuth property, and is suitable as a binder resin composition for electrodes of electrochemical elements such as lithium ion secondary batteries and electric double layer capacitors.

Moreover, according to the present invention, it is possible to provide a polyimine precursor resin composition for a flexible device substrate which is excellent in environmental compatibility by using an aqueous solvent, and is preferably composed of a high molecular weight polylysine, and The solvent is an organic solvent other than water. The polyimine precursor resin composition for a flexible device substrate is preferred because it has a higher environmental compatibility than a polyimide polyimide precursor solution composition using an organic solvent. Further, the substrate for an aromatic polyimine flexible device obtained according to the present invention preferably has high crystallinity, and has excellent properties such as heat resistance, mechanical strength, low linear expansion, electrical properties, solvent resistance, and the like. It is flexible as a light-receiving device such as a substrate for a liquid crystal display, a substrate for an organic EL display, or a substrate for an electronic paper, which is required for heat resistance, low thermal expansion, high strength and toughness, and a light-receiving device such as a substrate for a thin film solar cell. A device substrate or the like is particularly suitable as a substrate for a flexible display.

(Formation of the invention)

The present invention uses water as a reaction solvent to react a tetracarboxylic dianhydride with a diamine having a solubility of 0.1 g/L or more in water in the presence of an imidazole to produce a polythenimine precursor aqueous solution. Composition.

"Use water as a reaction solvent" means using water as a main component of a solvent. Therefore, the organic solvent other than water may be used in a proportion of 50% by mass or less, preferably 30% by mass or less, and more preferably 10% by mass or less based on the total solvent. Further, the organic solvent referred to herein does not include a tetracarboxylic acid component such as tetracarboxylic dianhydride, a diamine component, a polyimine precursor such as polyglycolic acid, or an imidazole.

The aforementioned organic solvent, such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, N-B Base-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphonium triamine, 1,2-dimethoxyethane, bis ( 2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, tetrahydrofuran, bis[2-(2-methoxyethoxy)ethyl]ether, 1 , 4-two Alkane, dimethyl hydrazine, dimethyl hydrazine, diphenyl ether, cyclobutyl hydrazine, diphenyl hydrazine, tetramethyl urea, anisole, m-cresol, phenol, γ-butyrolactone, and the like.

In the method for producing an aqueous solution of the polyimine precursor of the present invention, the solvent is preferably a solvent having a content of less than 5% of the organic solvent, and a solvent of an organic solvent other than water is preferred because of high environmental compatibility. . The composition of the reaction solvent is appropriately selected depending on the desired solvent composition of the aqueous solution of the polyimine precursor precursor to be produced, and it may be preferably the same as the desired solvent composition of the aqueous solution of the polyimide intermediate precursor.

The imidazole (compound) used in the present invention is preferably, for example, a compound of the following chemical formula (10).

In the chemical formula (10), each of X ₁ to X _{4 is} independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The imidazole used in the present invention has a solubility in water of at least 0.1 g/L at 25 ° C, particularly preferably 1 g/L or more.

Further, in the imidazole of the chemical formula (10), X ₁ to X ₄ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and at least two of X ₁ to X ₄ have a carbon number of 1 The imidazoles of the alkyl group of ~5, that is, the imidazoles having two or more alkyl groups as a substituent are more preferable.

Since the imidazole having two or more alkyl groups as a substituent has high solubility in water, it can be easily used to produce an aqueous solution composition of a polyimide precursor. The imidazoles are preferably 1,2-dimethylimidazole (the solubility in water at 25 ° C is 239 g / L, the same below), 2-ethyl-4-methylimidazole (1000 g / L), 4- Ethyl-2-methylimidazole (1000 g/L), and 1-methyl-4-ethylimidazole (54 g/L), and the like.

The imidazoles used may be one or a mixture of plural kinds.

Further, the solubility in water at 25 ° C means the limit amount (g) of the substance dissolved in 1 L (liter) of water at 25 ° C. This value can be easily retrieved by the well-known SciFinder (registered trademark) which is based on a search service based on a database such as Chemical Abstract. Here, among the solubility under various conditions, the value at pH 7 calculated by Advanced Chemistry Development (ACD/Labs) Software V11.02 (Copyright 1994-2011 ACD/Labs) was used.

The amount of the imidazole used in the present invention is preferably 0.8 times by weight or more, more preferably 1.0 times or more, based on the carboxyl group of the polyglycolic acid formed by the reaction of the tetracarboxylic dianhydride of the starting material with the diamine. More preferably, it is 1.2 times or more. When the amount of the imidazole used is less than 0.8 equivalents based on the carboxyl group of the polylysine, the uniformly dissolved aqueous solution of the polyimide precursor solution may not be easily obtained. Further, the upper limit of the amount of the imidazole to be used is not particularly limited, but is usually less than 10 equivalents, preferably less than 5 equivalents, and more preferably less than 3 equivalents. If the amount of the imidazole used is too large, it becomes uneconomical, and the storage stability of the aqueous solution of the polyimide intermediate precursor may be deteriorated.

In the present invention, the equivalent amount of the imidazole to the carboxyl group of the polyglycolic acid is defined as a ratio of several (several molecules) to the carboxyl group of one of the proline groups forming the polyaminic acid. Use imidazoles. Further, the number of carboxyl groups forming the proline group of the poly-proline is calculated by forming two carboxyl groups by one molecule of the tetracarboxylic acid component of the starting material.

Therefore, the amount of the imidazole used in the present invention is preferably 1.6 times or more, more preferably 2.0 times or less, based on the tetracarboxylic dianhydride (relative to the tetracarboxylic acid component of polyphthalic acid) of the starting material. Above the ear, it is more preferably 2.4 times more than the ear.

The imidazole used in the present invention is characterized in that it forms a salt with a carboxyl group of a poly-proline (polyimine precursor) formed by reacting a tetracarboxylic dianhydride of a raw material with a diamine to improve water solubility. Moreover, when the polyimine precursor is subjected to hydrazine imidization (dehydration ring closure) to polyimine, it has an extremely high catalytic action. As a result, if the aqueous solution of the polythenimine precursor of the present invention is used, for example, even at a relatively low temperature and for a short period of time, it is easy to produce a polyimide having a very high physical property or a polyimide. A binder resin for belts and electrodes, and a substrate for a flexible device.

As described above, in the present invention, it is preferred to use water as a reaction solvent, and in the presence of an imidazole, it is preferred to have a tetracarboxylic acid component in the presence of an imidazole having two or more alkyl groups as a substituent. The diamine component reacts, and the polyaluminine precursor aqueous solution composition is extremely (directly) produced.

This reaction is carried out using a tetracarboxylic acid component (tetracarboxylic dianhydride) having substantially the same molar amount, and is carried out at a lower temperature of 100 ° C or lower, preferably 80 ° C or lower, in order to suppress the oxime imidization reaction. The reaction temperature is not limited, but the reaction temperature is usually 25 ° C to 100 ° C, preferably 40 ° C to 80 ° C, more preferably 50 ° C to 80 ° C, and the reaction time is about 0.1 to 24 hours, preferably about 2 to 2. 12 hours. By making the reaction temperature and the reaction time fall within the above range, the production efficiency is good, and a high molecular weight polyazinium precursor aqueous solution composition can be easily obtained. Further, the reaction can be carried out under an air atmosphere, but it is usually carried out under a nitrogen atmosphere, preferably under a nitrogen atmosphere.

Further, the tetracarboxylic acid component (tetracarboxylic dianhydride) and the diamine component are substantially equal to each other, and specifically, the molar ratio [tetracarboxylic acid component/diamine component] is about 0.90 to 1.10, preferably About 0.95~1.05.

The tetracarboxylic dianhydride used in the present invention is not particularly limited, but from the viewpoint of the properties of the obtained polyimine, aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic acid are preferred. The anhydride is better. The tetracarboxylic dianhydride used in the present invention, for example, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2, 2',3,3'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, diphenyl ketone tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenylphosphonium tetracarboxylic acid Anhydride, conjugated triphenyltetracarboxylic dianhydride, meta-triphenyltetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1,2,4,5-cyclohexane Tetracarboxylic dianhydride or the like is preferred.

The tetracarboxylic acid component is not necessarily one type, and may be a mixture of a plurality of types.

The diamine used in the present invention is a diamine having a solubility in water of 25 ° C of 0.1 g / L or more. The diamine has a solubility in water of at least 0.1 g/L at 25 ° C, which is a particularly necessary property for obtaining a homogeneously dissolved aqueous solution of a polyimide precursor aqueous solution, and if the solubility for water at 25 ° C is less than 0.1 g / L, it is difficult to obtain a uniformly dissolved polyiminoimine precursor aqueous solution composition.

The diamine is not particularly limited as long as it has a solubility in water of at least 0.1 g/L at 25 ° C, but an aromatic diamine or an alicyclic diamine is preferred from the viewpoint of the properties of the obtained polyfluorene imide. The amine is better.

The aromatic diamine is preferably an aromatic diamine having 1 or 2 aromatic rings. When the aromatic diamine has more than two aromatic rings, the solubility in water may be less than 0.1 g/L.

Preferred aromatic diamine components used in the present invention, for example, p-phenylenediamine (120 g/L in water at 25 ° C, the same below), phenyldiamine (77 g / L), 4 , 4'-diaminodiphenyl ether (0.19g/L), 3,4'-diaminodiphenyl ether (0.24g/L), 4,4'-diaminodiphenylmethane (0.54g) /L), 2,4-toluenediamine (62 g/L), 3,3'-dihydroxy-4,4'-diaminobiphenyl (1.3 g/L), bis(4-amino-3) -carboxyphenyl)methane (200 g/L), 2,4-diaminotoluene (62 g/L), etc., but the high crystallinity of the obtained polyimine is high in crystallinity and can obtain excellent characteristics. , p-phenylenediamine, meta-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and mixtures thereof are preferred, and benzene is extended. The diamine, 4,4'-diaminodiphenyl ether, and mixtures thereof are more preferred.

Further, an alicyclic diamine, for example, 1,4-diaminocyclohexane (1000 g/L) or the like.

The diamine component is not necessarily one type, and may be a mixture of plural kinds. These diamines having a high solubility in water may be combined with other diamines so that the solubility in water at 25 ° C is 0.1 g/L or more as a whole of the diamine component.

Further, the diamine having a solubility in water at 25 ° C (solubility in water at 25 ° C) of 0.1 g/L or more means that the diamine is dissolved in 1 L (1000 ml) of water at 25 ° C in an amount of 0.1 g or more. The solubility in water at 25 ° C refers to the limit (g) of the substance dissolved in 1 L (liter) of water at 25 ° C. This value can be easily retrieved by the well-known SciFinder (registered trademark) which is based on a search service based on a database such as Chemical Abstract. Here, among the solubility under various conditions, the value at pH 7 calculated by Advanced Chemistry Development (ACD/Labs) Software V11.02 (Copyright 1994-2011 ACD/Labs) was used.

The polyamic acid constituting the composition of the aqueous solution of the polyimine precursor of the present invention is preferably composed of a repeating unit represented by the above chemical formula (1) from the viewpoint of the properties of the obtained polyimine.

A of the chemical formula (1) is a chemical structure derived from a tetracarboxylic acid component of polyamic acid, and is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid, preferably having 2 to 3 aromatic groups. A tetravalent group obtained by removing a carboxyl group from a tetracarboxylic acid of a ring.

A of the chemical formula (1), in order to make the obtained polylysine sufficiently soluble in water and at the same time obtain higher crystallinity of the aromatic polyimine, and easily obtain high-characteristic aromatic polyimide. The substrate for the belt, the electrode binder resin, or the aromatic polyimine flexible device is preferably a tetravalent group obtained by removing a carboxyl group from a tetracarboxylic acid having 2 to 3 aromatic rings, and the above chemical formula It is preferable that any one of (2) to (7) is more preferably one or more of the above chemical formulas (2), (3), and (5), and any one of the above chemical formulas (2) to (3) is further Better.

Such an aromatic tetracarboxylic acid component, for example, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2 ',3,3'-biphenyltetracarboxylic dianhydride, diphenyl ketone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, diphenylphosphonium tetracarboxylic dianhydride, couplet Triphenyltetracarboxylic dianhydride, cross-linked triphenyltetracarboxylic dianhydride, and the like are preferred. Among them, 3,3',4,4'-biphenyltetracarboxylic dianhydride, diphenyl ketone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, and mixtures thereof Preferably, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, and mixtures thereof are more preferred. When a tetracarboxylic acid component other than these is used, it may become difficult to obtain a water-soluble polyimide precursor, or the obtained polyimine may have low crystallinity and high characteristics may not be obtained.

B of the chemical formula (1) is a chemical structure derived from a diamine component of polylysine, and is a divalent product obtained by removing an amine group from an aromatic diamine having a solubility of water of 25 ° C or more of 0.1 g/L or more. The base is preferably a divalent group obtained by removing an amine group from an aromatic diamine having 1 to 2 aromatic rings and having a solubility in water of 25 ° C of 0.1 g/L or more. That is, the aromatic diamine component of the polyglycolic acid used in the present invention is an aromatic diamine having a solubility in water of 0.1 g/L or more at 25 ° C, preferably having 1 or 2 aromatic rings. .

As described above, the solubility of the aromatic diamine to water at 25 ° C is 0.1 g / L or more, in order to obtain a particularly necessary characteristic of the composition of the aqueous solution of the uniformly dissolved polyimine precursor, if the solubility for water at 25 ° C is less than At 0.1 g/L, it is difficult to obtain a uniformly dissolved polyiminoimine precursor aqueous solution composition.

Further, when the aromatic diamine has more than two aromatic rings, the aromatic diamine molecule usually contains a plurality of highly bendable bonds, and thus the aromatic polyimine obtained from such an aromatic diamine Crystallinity is low, and it is sometimes difficult to obtain high characteristics.

B of the chemical formula (1), in order to obtain a polyacrylamide having sufficient solubility in water and at the same time making the obtained aromatic polyimide having higher crystallinity and easily obtaining high-characteristic aromatic polyimide The substrate for a belt, an electrode binder resin, or an aromatic polyimine flexible device is preferably an aromatic compound having one or two aromatic rings and having a solubility of 0.1 g/L or more for water at 25 ° C. The divalent group obtained by removing the amine group of the diamine is preferable, and any one of the above chemical formulas (8) to (9) is more preferable.

Such an aromatic diamine component, for example, p-phenylenediamine (120 g/L in water at 25 ° C, the same below), phenyldiamine (77 g / L), 4, 4'- Diaminodiphenyl ether (0.19 g/L), 3,4'-diaminodiphenyl ether (0.24 g/L), 4,4'-diaminodiphenylmethane (0.54 g/L), 2,4-toluenediamine (62 g/L), 3,3'-dihydroxy-4,4'-diaminobiphenyl (1.3 g/L), bis(4-amino-3-carboxyphenyl) ) methane (200 g/L), 2,4-diaminotoluene (62 g/L), etc., but because of high water solubility and high crystallinity of the obtained polyimine, excellent properties can be obtained. An amine, an exophenylene diamine, a 4,4'-diaminodiphenyl ether, a 3,4'-diaminodiphenyl ether, and a mixture thereof, preferably a phenylenediamine, 4, 4'-diaminodiphenyl ether, and mixtures thereof are preferred.

Especially when used as a flexible device substrate, the glass transition temperature of the obtained aromatic polyimine is increased, so the main component of the tetracarboxylic acid component is 3,3',4,4'-biphenyltetracarboxylic acid Anhydride, and/or diphenyl ketone tetracarboxylic dianhydride, and the main component of the diamine component is p-phenylenediamine, and/or meta-phenylenediamine, and/or 4,4'-diamine The diphenyl ether is preferred, and the main component of the tetracarboxylic acid component is 3,3',4,4'-biphenyltetracarboxylic dianhydride, and the main component of the diamine component is more preferably p-phenylenediamine.

The aqueous solution of the polythenimine precursor obtained according to the present invention has a solid concentration of 30 μC at a concentration of 0.5 g/100 mL depending on the concentration of the solid component derived from the polyimide precursor (essentially poly-proline). The logarithmic viscosity measured by water dissolution is 0.2 or more, preferably 0.4 or more, more preferably 0.6 or more, still more preferably 0.8 or more, and particularly preferably a high molecular weight of 1.0 or more or higher. When the logarithmic viscosity is lower than the above range, the molecular weight of the polyimine precursor is low, and therefore, it is difficult to obtain a highly characteristic polyimine or polypyrene using the aqueous solution of the polyimine precursor of the present invention. An imide seamless belt, a binder resin for electrodes, and a substrate for an aromatic polyimide flexible device.

The aqueous solution composition of the polythenimine precursor of the present invention is caused by the solid content concentration of the polyimide precursor (essentially poly-proline), and is not particularly limited, but is relative to the polyimide precursor. The total amount of the solvent is preferably 5% by mass to 45% by mass, more preferably 7% by mass to 40% by mass, still more preferably 9% by mass to 30% by mass. When the solid content concentration is less than 5% by mass, the workability and the workability at the time of use may be deteriorated, and if it is more than 45% by mass, the solution may have no fluidity.

Further, the solution viscosity of the aqueous solution of the polyimine precursor of the present invention at 30 ° C is not particularly limited, but is preferably 1000 Pa sec or less, more preferably 0.5 to 500 Pa sec, and still more preferably 1 ～. 300Pa sec, especially preferably 3 to 200 Pa sec, is preferable in terms of operation. When the viscosity of the solution exceeds 1000 Pa sec, there is no fluidity, and it may be difficult to apply it uniformly to a metal (collector foil or the like) or glass, and if it is less than 0.5 Pa sec, it may be applied to a metal (collecting electricity). When foil or the like, or glass, etc., liquid or water repellency may occur, and it may be difficult to obtain a high-performance polyimine or a polyimide-based seamless belt, an electrode binder resin, or an aromatic polymer. A substrate for an imide flexible device.

The aqueous solution of the polyimine precursor precursor of the present invention is an aqueous solvent, but an organic solvent other than water may be used. For example, a known organic solvent used in the preparation of polyamic acid is 50% by mass or less of the total solvent. It is preferably used in a proportion of 30% by mass or less, more preferably 10% by mass or less. That is, the aqueous solution of the polyimine precursor of the present invention is obtained by dissolving the polyamidene precursor polyamine and imidazole in water alone or in a ratio of 50% by mass or more. It is preferably 70% by mass or more, more preferably 90% by mass or more of a mixture of water and an organic solvent, that is, an aqueous solvent (aqueous solvent).

The aforementioned organic solvent, such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, N-B Base-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphonium triamine, 1,2-dimethoxyethane, bis ( 2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, tetrahydrofuran, bis[2-(2-methoxyethoxy)ethyl]ether, 1 , 4-two Alkane, dimethyl hydrazine, dimethyl hydrazine, diphenyl ether, cyclobutyl hydrazine, diphenyl hydrazine, tetramethyl urea, anisole, m-cresol, phenol, γ-butyrolactone, and the like.

The aqueous solution of the polyimine precursor of the present invention has a solvent content of less than 5% of the organic solvent, more preferably an organic solvent other than water, which is a separate solvent of water, and is environmentally compatible. The point of view is especially good.

The polyhydrazide precursor aqueous solution composition of the present invention can be obtained by the following methods, etc. according to the methods of Patent Documents 1 and 2, and the like:

(i) using an organic solvent as a reaction solvent, and a polyphthalic acid obtained by reacting a tetracarboxylic acid component with a diamine component is put into water to obtain a poly-proline powder, and the poly-proline powder is dissolved in an aqueous solvent. a method of obtaining an aqueous solution by simultaneously mixing and dissolving with an imidazole (preferably an imidazole having two or more alkyl groups),

(ii) using an organic solvent as a reaction solvent to react a tetracarboxylic acid component with a diamine component in the presence of an imidazole (preferably an imidazole having two or more alkyl groups) to obtain a water-soluble polyimine precursor a method of separating it and dissolving it in a water solvent, or

(iii) using an organic solvent as a reaction solvent to react a tetracarboxylic acid component with a diamine component to obtain a poly-proline acid, and using an organic solvent as a reaction solvent, the polyamic acid and the imidazole (preferably having 2 The above-mentioned alkyl imidazoles are reacted to obtain a water-soluble polyimine precursor, which is separated and dissolved in an aqueous solvent. However, as described above, in order to obtain a very small content of the organic solvent, it is further a composition of an aqueous solution of a polyimine precursor which does not contain an organic solvent, and a precursor system for preparing a polyimine in an organic solvent is not preferable.

The polyhydrazide precursor aqueous solution composition of the present invention can be usually obtained by heat treatment to remove the aqueous solvent while performing hydrazine imidization (dehydration ring closure) to obtain a polyimine. The heat treatment conditions are not particularly limited, but are preferably about 100 ° C or higher, preferably 120 ° C to 600 ° C, more preferably 150 ° C to 500 ° C, still more preferably 150 ° C to 350 ° C, preferably a stepwise increase in temperature. The state is heated for 0.01 to 30 hours, preferably 0.01 to 10 hours.

This heat treatment is preferably carried out under normal pressure, but it may be carried out under reduced pressure in order to remove the water solvent with good efficiency. Further, it is also possible to carry out heat treatment at a lower temperature and defoaming treatment under reduced pressure in the initial stage. If the heat treatment temperature is suddenly increased, problems such as foaming may occur.

The aqueous solution of the polyimine precursor of the present invention is heat-treated only at a relatively low temperature (for example, 150 ° C to 300 ° C, preferably 200 ° C to 280 ° C), so that it can be easily obtained compared to the usual use of an organic solvent. The polyimine which has excellent properties of adhesion to, for example, metals or the like, which is not inferior in the composition of the polyimine precursor (polyglycine) solution. Therefore, by using the aqueous solution of the polyimine precursor of the present invention, not only a polyimide film but also a polyimide belt can be obtained.

In the method for producing an aromatic polyimine seamless belt of the present invention, the polyimine precursor aqueous solution composition, specifically, the polyamine contained in the repeating unit represented by the above chemical formula (1), An aqueous solution of a polyimine precursor precursor which is uniformly dissolved in an aqueous solvent with respect to the tetracarboxylic acid component of the polyamic acid tetrachloride described above, and is coated or blown to the substrate. A coating film composed of a layer of a polyimine precursor aqueous solution is formed on the surface, and the polyimine precursor aqueous solution composition is subjected to heat treatment.

In the present invention, the aqueous solution of the polyimine precursor precursor can be obtained by heat treatment to remove the aqueous solvent and simultaneously carry out hydrazine imidization (dehydration ring closure), and an aromatic polyimine seamless belt is desirably obtained. The heat treatment conditions are not particularly limited, and are preferably about 100 ° C or higher, preferably 120 ° C to 600 ° C, more preferably 150 ° C to 500 ° C, still more preferably 150 ° C to 350 ° C, preferably a stepwise increase in temperature. The state is heated for 0.01 to 30 hours, preferably 0.01 to 10 hours.

This heat treatment is preferably carried out under normal pressure. However, in order to remove the water solvent with good efficiency, it may be carried out under reduced pressure. Further, the heat treatment may be carried out at a lower temperature and at a lower temperature in the initial stage to carry out a defoaming treatment. If the heat treatment temperature is suddenly increased, problems such as foaming may occur, and a polyimide belt having a good property may not be obtained in some cases.

In the method for producing an aromatic polyimine seamless belt of the present invention, heat treatment is performed only at a relatively low temperature (for example, 150 ° C to 300 ° C, preferably 200 ° C to 280 ° C), which can be easily obtained compared to usual The polyimine precursor seamless belt having excellent properties is not inferior in the case of using a polyacetimimine precursor (polyglycine) solution composition of an organic solvent.

As a method of forming a seamless belt, a conventionally known method can be preferably used. For example, a rotary forming method, that is, a state in which a cylindrical mold which functions as a substrate is rotated, and a surface of a mold (inside or outside) is formed by coating or blowing to form a composition of an aqueous solution of a polyimide intermediate precursor. The film is coated and heated at a lower temperature to remove the water solvent to form a self-supporting film (the film does not flow, and the polymerization and partial hydrazide reaction are carried out while the water solvent is removed), followed by self-supporting It is preferable to obtain a seamless belt by performing a heat treatment in a state in which the film is peeled off from the substrate as needed, and a method of dehydrating and imidizing. As used herein, "water solvent removal" or "dehydration / hydrazine imidization" does not mean that only water solvent removal or dehydration only is carried out in this step. In the aqueous solvent removal step, the dehydration ‧ 醯 imidization is also carried out to a considerable extent, and in the dehydration ‧ 醯 imidization step, the removal of the residual water solvent is also carried out.

The aqueous solution of the polyimine precursor of the present invention may contain other added components depending on the use of the obtained aromatic polyimide-seam seamless belt. Further, the obtained aromatic polyimide polyimide seamless belt may be a laminate of another resin layer or a metal layer.

The thickness of the aromatic polyimine seamless belt of the present invention can be appropriately selected depending on the purpose of use, but it is usually about 20 to 200 μm.

The aromatic polyimine seamless belt obtained according to the present invention is suitable for use as an intermediate transfer of an electrophotographic apparatus because it has high crystallinity, excellent heat resistance, mechanical strength, electrical properties, solvent resistance and the like. Seamless belt for printing or fixing.

When the aromatic polyimide polyimide seamless belt is used as an intermediate transfer belt for an electrophotographic apparatus, it is preferable to contain a conductive filler to give a surface resistivity of 10 ⁸ to 10 ¹⁶ Ω/□ and a volume resistivity of 10 ^{8 .} Semi-conductivity of ~10 ¹⁶ Ω‧cm.

The conductive filler may be a conductive or semiconductive fine powder used in a usual intermediate transfer seamless belt, and is not particularly limited, and examples thereof include carbon black such as Ketchen Black and acetylene black, metal such as aluminum or nickel, and tin oxide. An oxidized metal compound, potassium titanate or the like. The conductive fillers may be used singly or in combination. In the present invention, carbon black is preferably used as the conductive filler, and particularly preferably an average primary particle diameter of 5 to 100 nm, particularly preferably 10 to 50 nm. When the average primary particle diameter exceeds 100 nm, the uniformity of mechanical properties or resistance values tends to be insufficient.

The blending amount of the conductive filler varies depending on the type, particle diameter, and dispersion state of the filler, and is usually in the range of 1 to 50 parts by weight, preferably 2 to 30 parts by weight based on 100 parts by weight of the polyimine (solid content). Better. In the present invention, the surface resistivity (10 ⁸ to 10 ¹⁶ Ω/□) and the volume resistivity (10 ⁸ to 10 ¹⁶ ) suitable for the intermediate transfer belt can be adjusted by selecting the conductive filler and combining the appropriate blending amount. Ω‧cm) range.

When the aromatic polyimine seamless belt is used as a fixing belt for an electrophotographic apparatus, in order to impart thermal conductivity, it is preferable to add a filler such as cerium oxide, boron nitride, aluminum nitride, tantalum nitride, or aluminum oxide, or In order to impart rubber elasticity, for example, a fluororesin powder or a metal foil which is a heat generating body is preferably laminated. The amount of the filler to be added is preferably in the range of 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, per 100 parts by weight of the polyimine (solid content).

When used as a fixing belt for an electrophotographic apparatus, the aromatic polyimine seamless belt has a thermal conductivity of 0.15 W/mK or more, preferably 0.20 W/mK or more.

Further, when the aromatic polyimine seamless belt is used as a fixing belt for an electrophotographic apparatus, it is preferable to form a seamless belt having a rubber elastic layer or a release layer laminated on the surface. The release layer (peeling layer) is not particularly limited as long as it can improve the peeling property of the surface of the seamless belt, and tetrafluoroethylene which is known per se, such as polytetrafluoroethylene (PTFE), or a modified substance thereof, can be used. - perfluoroalkyl vinyl ether interpolymer (PFA), tetrafluoroethylene-ethylene interpolymer (ETFE), tetrafluoroethylene-hexafluoropropylene interpolymer (FEP), tetrafluoroethylene-vinylidene copolymer (TFE/ VdF), tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (EPA), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), chlorotrifluoroethylene-fluorine The vinylene copolymer (CTFE/VdF), polyvinylidene fluoride (PVdF), and polyvinyl fluoride (PVF) are preferably formed. Further, the rubber elastic layer may be made of the same material, and it is also preferable that the surface layer contains a conductive filler.

The aqueous solution of the polyimine precursor of the present invention can also be suitably used as a binder resin composition for electrodes.

In this case, the aqueous solution of the polyimine precursor precursor of the present invention (the binder resin composition for an electrode of the present invention) can be usually removed by heat treatment to remove the aqueous solvent, and at the same time, the hydrazine imidization (dehydration ring closure) is ideal. Aromatic polyimine is obtained. The heat treatment conditions are not particularly limited, and are preferably about 100 ° C or higher, preferably 120 ° C to 600 ° C, more preferably 150 ° C to 500 ° C, and preferably 0.01 to 30 hours, preferably 0.01 to 10 hours. .

The characteristics of the aromatic polyimine obtained by using the binder resin composition for an electrode of the present invention are only heat-treated at a relatively low temperature (for example, 150 ° C to 300 ° C, preferably 200 ° C to 280 ° C), that is, It is preferable to obtain a binder resin composition for an electrode which is usually used in an organic solvent, and it is preferably a polyimide having such excellent properties as adhesion to a metal.

In the adhesive resin composition for an electrode of the present invention, when the polyimide resin obtained by the above heat treatment is immersed in dimethyl carbonate at 25 ° C for 24 hours, the mass thereof is preferably 3% by mass or less. More preferably, it is 2% by mass or less, and more preferably 1% by mass or less, so it is preferable to use it as a resin composition for a battery. Further, dimethyl carbonate is a compound which is often used as an electrolyte component of a battery, and the mass of the binder resin due to swelling due to the electrolyte in the electrolyte (incubation rate when immersed at 25 ° C for 24 hours) When the amount is 5 mass% or less, more preferably 3% by mass or less, and particularly preferably 2 mass% or less, the influence of the volume change of the electrode can be satisfactorily suppressed.

Further, lithium methoxide is often formed in a battery environment, but the polyimine resin obtained from the binder resin composition for an electrode of the present invention has an increased mass even in an electrolyte containing lithium methoxide (when The swelling ratio at 25 ° C for 24 hours is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less.

In the electrode resin composition for an electrode of the present invention, at least the electrode active material is mixed in a temperature range in which the temperature range is not limited, but preferably 10 ° C to 60 ° C, and an electrode mixture paste can be preferably prepared. The electrode active material is preferably a known one, but a lithium-containing metal composite oxide, carbon powder, cerium powder, tin powder, or an alloy powder containing bismuth or tin is preferred. The amount of the electrode active material in the electrode mixture paste is not particularly limited, and is usually 0.1 to 1000 times, preferably 1 to 1000 times, based on the mass of the solid content of the polyaminic acid. The best is 5 to 1000 times, and more preferably 10 to 1000 times. If the mass of the living material is too small, the blunt portion formed in the active material layer of the current collector becomes large, and sometimes the function as an electrode becomes insufficient. Moreover, if the mass of the living material is too large, the living material may not sufficiently adhere to the current collector and become easy to fall off. Further, in the electrode mixture paste, an additive such as a surfactant, a viscosity adjuster or a conductive auxiliary agent may be added as needed. Further, the solid content of the polyamic acid is preferably from 1 to 15% by mass based on the total solid content of the electrode mixture paste. Outside of this range, electrode performance may sometimes be low.

An electrode mixture paste containing the electrode composition for an electrode of the present invention and an electrode active material such as a lithium-containing metal composite oxide which can be reversibly inserted and released by charge and discharge, for example, a lithium-containing metal composite oxide, is cast or It is applied to a conductive collector such as aluminum, and is heat-treated at 80 to 400 ° C, more preferably 120 to 380 ° C, and more preferably 150 to 350 ° C, and the solvent is removed and simultaneously iridized. The reaction can obtain an electrode. When the heat treatment temperature is outside the above range, the oxime imidization reaction may not proceed sufficiently, or the physical properties of the electrode molded body may be lowered. The heat treatment is carried out in a plurality of stages in order to prevent foaming or powdering. Further, the heat treatment time is preferably in the range of 3 minutes to 48 hours. When the heat treatment time is more than 48 hours, it is not preferable from the viewpoint of productivity, and if it is shorter than 3 minutes, the oxime imidization reaction or solvent removal may be insufficient, which is not preferable.

The electrode obtained in this manner is particularly suitable as a positive electrode of a lithium ion secondary battery.

Further, the resin composition containing the electrode binder of the present invention and the alloy powder which can reversibly insert and release lithium ions by charge and discharge, for example, carbon powder, cerium powder, tin powder, or alloy powder containing bismuth or tin The electrode mixture paste of the electrode active material is cast or coated on a conductive collector such as copper, and is preferably in a temperature range of 80 to 300 ° C, more preferably 120 to 280 ° C, and particularly preferably 150 to 250 ° C. The electrode can be obtained by heat treatment and removal of the solvent while carrying out the oxime imidization reaction. When the heat treatment temperature is lower than 80 ° C, the oxime imidization reaction may not proceed sufficiently, and the physical properties of the electrode molded body may be lowered. If the heat treatment is performed at a temperature higher than 300 ° C, copper deformation or the like may occur, and sometimes it may not be used as an electrode. In this case, the heat treatment may be carried out in multiple stages in order to prevent foaming or powdering. Further, the heat treatment time is preferably in the range of 3 minutes to 48 hours. When the heat treatment time exceeds 48 hours, it is not preferable from the viewpoint of productivity, and if it is shorter than 3 minutes, the hydrazine imidization reaction or the removal of the solvent may be insufficient, which is not preferable.

The electrode obtained in this manner is particularly suitable as a negative electrode of a lithium ion secondary battery.

The polyhydrazide precursor aqueous solution composition of the present invention is also suitable as a polyimide intermediate precursor resin composition for a flexible device substrate.

In the method for producing a flexible device of the present invention, the polyilylimide precursor aqueous solution composition, specifically, the polyamic acid composed of the repeating unit represented by the above chemical formula (1) and the polyfluorene The polycarboxylic acid tetracarboxylic acid component is 1.6 times mole of imidazole and is uniformly dissolved in an aqueous solvent to form a polyimine precursor aqueous solution composition, which is coated or blown onto the surface of the substrate to form a polyazide. A coating film composed of an amine precursor aqueous solution composition layer is formed, and the polyhydrazide precursor aqueous solution composition is subjected to heat treatment to obtain a substrate for an aromatic polyimine flexible device.

In the present invention, the aqueous solution of the polyimine precursor precursor can be removed by heat treatment and simultaneously subjected to hydrazine imidization (dehydration ring closure), and the substrate for an aromatic polyimine flexible device is desirably obtained. . The heat treatment conditions are not particularly limited, but are preferably about 100 ° C or higher, preferably 120 ° C to 600 ° C, more preferably 150 ° C to 500 ° C, still more preferably 150 ° C to 350 ° C, preferably in stages. The state of the temperature is heat-treated for 0.01 to 30 hours, preferably 0.01 to 10 hours.

This heat treatment is preferably carried out under normal pressure, but it may be carried out under reduced pressure in order to remove the water solvent with good efficiency. Further, it is also possible to carry out heat treatment at a lower temperature and defoaming treatment under reduced pressure in the initial stage. If the heat treatment temperature is suddenly increased, a problem such as foaming may occur, and a good substrate for a flexible device may not be obtained.

In the method for producing a substrate for an aromatic polyimine flexible device of the present invention, heat treatment can be easily carried out only at a relatively low temperature (for example, 150 ° C to 300 ° C, preferably 200 ° C to 280 ° C). A substrate for an aromatic polyimine flexible device having excellent properties compared to a composition of a polyimine precursor (polyglycine) solution in which an organic solvent is usually used.

In the method for producing a flexible device of the present invention, a polyimide composition precursor resin composition (a polyimine precursor aqueous solution composition) is applied onto a support substrate as a support and heat-treated to form The solid polyimine resin film is formed by forming a circuit on the polyimide film, and the polyimide substrate film having a circuit formed on the surface of the carrier substrate is peeled off.

The coating of the polyimine precursor aqueous solution composition can be applied as long as it can form a coating film having a uniform thickness on the carrier substrate (support). For example, it can be applied by screen printing or spin coating using screen printing.

A coating film composed of a composition of a polyimine precursor aqueous solution is formed on the carrier substrate, and is heated at a lower temperature to remove the aqueous solvent to form a self-supporting film (the film does not flow, and is removed by water solvent). At the same time, the polymerization and a part of the oxime imidization reaction are carried out, and then the method of heat-treating the self-supporting film in this state or if it is peeled off from the substrate as needed, and performing the dehydration method can be preferably obtained. A substrate for a flexible device. As used herein, "water solvent removal" or "dehydration / hydrazine imidization" does not mean that only water solvent removal or dehydration only is carried out in this step. In the aqueous solvent removal step, the dehydration ‧ 醯 imidization is also carried out to a considerable extent, and in the dehydration ‧ 醯 imidization step, the removal of the residual water solvent is also carried out.

The polyhydrazide precursor aqueous solution composition of the present invention may contain other additives in addition to the use of the substrate for the aromatic polyimine flexible device obtained. Moreover, the obtained substrate for an aromatic polyimine flexible device may be further laminated with another resin layer.

In the method for producing a flexible device of the present invention, the thickness of the polyimide film is preferably 1 to 20 μm. When the thickness is less than 1 μm, the polyimide film does not have sufficient resistance, and when used as a flexible device substrate, it may not be able to withstand stress and break. Further, when the thickness of the polyimide film is more than 20 μm, the thickness of the flexible device becomes difficult. The thickness of the polyimide film is more preferably 2 to 10 μm in order to maintain a film which is more resistant to the sufficient resistance of the flexible device.

In the method for producing a flexible device of the present invention, a circuit necessary for a display device or a light receiving device is formed on the polyimide film formed as described above. This step varies depending on the type of device. For example, in the manufacture of a TFT liquid crystal display device, a TFT such as an amorphous germanium is formed on a polyimide film. The TFT includes a gate metal layer, a nitride gate dielectric layer, and an ITI pixel electrode. Further, a configuration necessary for the liquid crystal display can be formed by a known method. The polyimine resin film obtained in the present invention is excellent in various properties such as heat resistance and enthalpy, and thus the method of forming an electric circuit or the like is not particularly limited.

The polyimide film having a circuit or the like formed on the surface thereof is peeled off from the carrier substrate as described above. The peeling method is not particularly limited, and for example, peeling can be performed by irradiating a laser or the like from the side of the carrier substrate. Since the polyimine resin film obtained according to the present invention has high toughness, it can be physically peeled off from the carrier substrate (support).

In the method for producing a flexible device of the present invention, in many cases, the polyimide film is heated to 250 ° C or higher and further 300 ° C or higher in the step of forming a circuit or the like. Therefore, the glass transition temperature of the polyimide film is preferably 250 ° C or more, more preferably 300 ° C or more.

In the present invention, a flexible device such as a liquid crystal display, an organic EL display, an electronic paper display device, a solar cell, a CMOS or the like is used. The present invention is particularly applicable to devices that are intended to be thinned and flexible.

[Examples]

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the Examples.

The measurement method of the characteristics used in the following examples is shown below.

<solid content concentration>

The sample solution (the mass of which was set to w1) was heat-treated in a hot air dryer at 120 ° C for 10 minutes, heated at 250 ° C for 10 minutes, and then heat treated at 350 ° C for 30 minutes, and the quality after heat treatment was measured. (The quality is set to w2). The solid content concentration [% by mass] was calculated by the following formula.

Solid content concentration [% by mass] = (w2/w1) × 100

<logarithmic viscosity>

The sample solution was diluted so that the concentration according to the solid content concentration was 0.5 g/dl (solvent was water). The dilution was measured at 30 ° C using a Cannon-Fenske No. 100 to measure the flow time (T ₁ ). The logarithmic viscosity is calculated by the following equation using the water flow time (T ₀ ) which is the background value.

Logarithmic viscosity = {ln(T ₁ /T ₀ )}/0.5

<Solid viscosity (rotational viscosity)>

It was measured at 30 ° C using an E-type viscometer manufactured by Tokyo Keiki Co., Ltd.

<Production of Polyimine Film Sample>

The obtained polyimine precursor aqueous solution composition is applied to a glass plate of a substrate by a bar coater, and the coating film is defoamed and pre-dried at 25° C. for 30 minutes under reduced pressure, and then subjected to atmospheric pressure. The mixture was placed in a hot air dryer, heated at 80 ° C for 30 minutes, heated at 120 ° C for 30 minutes, heated at 200 ° C for 10 minutes, and then heat treated at 250 ° C for 10 minutes to form a polythene having a thickness of 50 μm. Amine film. The properties were evaluated using the polyimide film.

<Mechanical properties (tensile test)>

A tensile test was carried out in accordance with ASTM D882 using a tensile tester (RTC-1225A manufactured by Orientec Co., Ltd.) to obtain tensile modulus, tensile elongation at break, and tensile strength at break.

<Measurement of glass transition temperature>

A solid viscoelastic analyzer RSAIII (compression mode dynamic measurement, frequency 62.8 rad/sec (10 Hz), deformation amount set to 3% of the sample height) manufactured by TA Instruments was used, from -140 ° C in a nitrogen gas stream. 450 ° C with a temperature gradient of 3 ° C, 30 seconds after the arrival of each temperature is measured, the temperature is raised to the next temperature and repeated measurements, to determine the maximum point of loss elastic modulus (E"), the temperature is taken as glass Transfer point (Tg).

<Manufacture of Aromatic Polyimine Seamless Belt>

The polyimine precursor aqueous solution composition was uniformly applied to the inner surface of a cylindrical mold having an inner diameter of 150 mm and a length of 300 mm which was rotated at a number of revolutions of 100 rpm, and then the coating film was allowed to stand at 80 ° C for 30 minutes at a rotation speed of 200 rpm. The mixture was subjected to heat treatment at 120 ° C for 30 minutes, 200 ° C for 10 minutes, and further at 250 ° C for 10 minutes to obtain an aromatic polyimine seamless belt having a thickness of 50 μm.

The obtained aromatic seamless belt was visually observed. Further, the characteristics of the aromatic polyimine seamless belt were evaluated.

<Status observation of aromatic polyimine seamless belt>

Those who have no problems such as blistering or cracking are rated as ○, and those with adverse phenomena such as blistering or cracking account for 30% or less of all, and △, and areas with undesirable phenomena such as blistering or cracking are more than 30% of the total. Appraised as ×.

<Production of a polyimide polyimide film sample for electrode>

The obtained electrode binder resin composition was applied to a glass plate of a substrate by a bar coater, and the coating film was defoamed and preliminarily dried at 25 ° C for 30 minutes under reduced pressure, and then placed under normal pressure. The hot air dryer was subjected to heat treatment at 80 ° C for 30 minutes, at 120 ° C for 30 minutes, at 200 ° C for 10 minutes, and further at 250 ° C for 10 minutes to form a polyimide film having a thickness of 25 μm. The properties were evaluated using the polyimide film.

<Swelling test>

A sample of 5 cm square (thickness: 25 μm) was cut out from the polyimide film obtained from the electrode binder resin composition as a sample. The mass after vacuum drying at 60 ° C for 24 hours is regarded as the dry mass (Wd), and the mass after immersion in a dimethyl carbonate (DMC) solution or a 10% by mass methanol solution of lithium methoxide at 25 ° C for 24 hours As the swelling quality (Ww), the swelling ratio S is calculated according to the following formula.

S[% by mass]=(Ww-Wd)/Ww×100

<Observation of the state of the substrate for a flexible device>

Those who have no problems such as blistering or cracking are rated as ○, and those with adverse phenomena such as blistering or cracking account for 30% or less of all, and △, and areas with undesirable phenomena such as blistering or cracking are more than 30% of the total. Appraised as ×.

The abbreviations of the compounds used in the following examples are explained.

s-BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

ODPA: 4,4'-oxydiphthalic dianhydride

a-BPDA: 2,3',3,4'-biphenyltetracarboxylic dianhydride

i-BPDA: 2,2',3,3'-biphenyltetracarboxylic dianhydride

DSDA: 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride

BTDA: 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride

PPD: p-phenylenediamine (solubility to water at 25 ° C: 120 g / L, the same below)

ODA: 4,4'-diaminodiphenyl ether (0.19 g/L)

MPD: phenyldiamine (77g/L)

2,4-TDA: 2,4-diaminotoluene (62g/L)

HAB: 3,3'-dihydroxy-4,4'-diaminobiphenyl (1.3 g/L)

MBAA: bis(4-amino-3-carboxyphenyl)methane (200g/L)

BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane (0.000019 g/L)

TPE-R: 1,3-bis(4-aminophenoxy)benzene (0.0018g/L)

1,2-DMZ: 1,2-dimethylimidazole (239g/L)

2E4MZ: 2-ethyl-4-methylimidazole (1000g/L)

DBU: 1,8-diazabicyclo[5,4,0]undec-7-ene

NMP: N-methyl-2-pyrrolidone

DMAc: N,N-dimethylacetamide

[Example A1]

Into a glass reaction vessel having a 500 mL internal volume of a stirrer, a nitrogen gas introduction, and a discharge tube, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 1,2-DMZ 29.87 g (1.25 with respect to the carboxyl group) were added thereto. The mixture was stirred at 25 ° C for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to the solution, and the mixture was stirred at 25 ° C for 12 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 9.0% by mass, a solution viscosity of 16.3 Pa s, and a logarithmic viscosity of 0.95.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution and the polyimide film are shown in Table 1.

[Example A2]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction, and a discharge tube of 500 mL, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 1,2-DMZ 29.87 g (different to carboxyl group 1.25) were added thereto. The mixture was stirred at 25 ° C for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to the solution, and the mixture was stirred at 50 ° C for 8 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 9.1% by mass, a solution viscosity of 35.5 Pa s, and a logarithmic viscosity of 1.25.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution and the polyimide film are shown in Table 1.

[Example A3]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction, and a discharge tube of 500 mL, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 1,2-DMZ 29.87 g (1.25 with respect to the carboxyl group) were added thereto. The mixture was stirred at 25 ° C for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 9.1% by mass, a solution viscosity of 63.0 Pa s, and a logarithmic viscosity of 1.86.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution and the polyimide film are shown in Table 1.

[Example A4]

A 500 mL reaction vessel equipped with a stirrer, a nitrogen gas introduction, and a discharge tube was placed, and 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 2E4MZ 34.23 g (1.25 equivalents relative to the carboxyl group) were added thereto. Stir at 25 ° C for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 9.6% by mass, a solution viscosity of 10.3 Pa s, and a logarithmic viscosity of 0.64.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution and the polyimide film are shown in Table 1.

[Example A5]

Add 450 g of water as a solvent to a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction, and a discharge tube of 500 mL, and add ODA 20.25 g (0.101 mol) and 1,2-DMZ 24.31 g (1.25 with respect to the carboxyl group). The mixture was stirred at 25 ° C for 1 hour to dissolve. 29.75 g (0.101 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 8.7% by mass, a solution viscosity of 32.0 Pa‧s, and a logarithmic viscosity of 0.42.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution and the polyimide film are shown in Table 1.

[Example A6]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and MPD 13.44 g (0.124 mol) and 1,2-DMZ 29.87 g (relative to the carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 8.9% by mass, a solution viscosity of 13.5 Pa s, and a logarithmic viscosity of 0.75.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution and the polyimide film are shown in Table 1.

[Example A7]

To a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge pipe and a 500 mL internal volume, 450 g of water was added as a solvent, and 2,4-TDA 14.67 g (0.120 mol) and 1,2-DMZ 28.86 g (2,4-TDA) were added thereto. It was stirred at 25 ° C for 1 hour to dissolve in 1.25 times equivalent of the carboxyl group. 35.33 g (0.120 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 8.8% by mass, a solution viscosity of 1.0 Pa ‧ and a logarithmic viscosity of 0.21.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution are shown in Table 1.

[Example A8]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and HAB 21.18 g (0.098 mol) and 1,2-DMZ 47.09 g (relative to the carboxyl group) were added thereto. 2.50 equivalents), stirred at 25 ° C for 1 hour to dissolve. 28.82 g (0.098 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 9.4% by mass, a solution viscosity of 1.5 Pa‧s, and a logarithmic viscosity of 0.50.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution are shown in Table 1.

[Example A9]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction, and a discharge tube of 500 mL, 450 g of water was added as a solvent, and MBA 24.66 g (0.086 mol) and 1,2-DMZ 41.41 g (relative to the carboxyl group) were added thereto. It was 2.50 times equivalent) and stirred at 25 ° C for 1 hour to dissolve. To the solution was added 25.34 g (0.086 mol) of s-BPDA, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 9.5% by mass, a solution viscosity of 2.0 Pa ‧ and a logarithmic viscosity of 0.75.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution are shown in Table 1.

[Example A10]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 12.93 g (0.120 mol) and 1,2-DMZ 28.73 g (relative to the carboxyl group) were added thereto. It was 1.25 times equivalent) and stirred at 25 ° C for 1 hour to dissolve. To the solution was added 37.07 g (0.120 mol) of ODPA, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 8.9% by mass, a solution viscosity of 2.0 Pa ‧ and a logarithmic viscosity of 0.58.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution are shown in Table 1.

[Example A11]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 1,2-DMZ 29.87 g (relative to the carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. 36.56 g (0.124 mol) of i-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 8.6% by mass, a solution viscosity of 0.8 Pa ‧ and a logarithmic viscosity of 0.22.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution are shown in Table 1.

[Example A12]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 11.59 g (0.107 mol) and 1,2-DMZ 25.77 g (relative to the carboxyl group) were added thereto. It was 1.25 times equivalent) and stirred at 25 ° C for 1 hour to dissolve. 38.41 g (0.107 mol) of DSDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 8.7% by mass, a solution viscosity of 1.2 Pa‧s, and a logarithmic viscosity of 0.35.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution are shown in Table 1.

[Example A13]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 12.57 g (0.116 mol) and 1,2-DMZ 27.93 g (relative to the carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. 37.43 g (0.116 mol) of BTDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain a water-soluble polyimine precursor solution having a solid concentration of 8.8% by mass, a solution viscosity of 73.8 Pa s, and a logarithmic viscosity of 0.45.

The characteristics of the obtained aqueous solution of the polyimide precursor aqueous solution are shown in Table 1.

[Reference Example A1]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 1,2-DMZ 17.92 g (relative to the carboxyl group) were added thereto. 0.75 times equivalent), stirred at 25 ° C for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours, but was not uniformly dissolved, and a polyhydrazide precursor aqueous solution composition could not be obtained.

The results are shown in Table 2.

[Comparative Example A1]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and DBU 47.29 g (1.25 equivalents relative to the carboxyl group) were added thereto. It was stirred at 25 ° C for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours, but was not uniformly dissolved, and a polyhydrazide precursor aqueous solution composition could not be obtained.

The results are shown in Table 2.

[Reference Example A2]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and BAPP 29.13 g (0.071 mol) and 1,2-DMZ 17.05 g (relative to the carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. To the solution, 20.87 g (0.071 mol) of s-BPDA was added, and the mixture was stirred at 70 ° C for 4 hours, but was not uniformly dissolved, and a polyhydrazide precursor aqueous solution composition could not be obtained.

The results are shown in Table 2.

[Reference Example A3]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and TPE-R 24.92 g (0.085 mol) and 1,2-DMZ 20.49 g were added thereto (relative to The carboxyl group was 1.25 equivalents, and the mixture was stirred at 25 ° C for 1 hour to dissolve. To the solution was added 25.08 g (0.085 mol) of a-BPDA, and the mixture was stirred at 70 ° C for 4 hours, but was not uniformly dissolved, and a polyhydrazide precursor aqueous solution composition could not be obtained.

The results are shown in Table 2.

[Reference Example A4]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL glass container, 450 g of water was added as a solvent, and TPE-R 24.26 g (0.083 mol) and 2E4 MZ 22.86 g (1.25 times relative to the carboxyl group) were added thereto. Equivalent), stirred at 25 ° C for 1 hour to dissolve. To the solution was added 25.74 g (0.083 mol) of ODPA, and the mixture was stirred at 70 ° C for 4 hours, but was not uniformly dissolved, and a polyhydrazide precursor aqueous solution composition could not be obtained.

The results are shown in Table 2.

[Reference Example A5]

TPE-R 29.23 g (0.1 mol) and DMAc 234.60 g were added to a 1000 mL glass reaction vessel equipped with a stirrer, a reflux condenser (with a water separator), a thermometer, and a nitrogen introduction tube at 25 ° C, and mixed in the mixture. 29.42 g (0.1 mol) of a-BPDA was added to the liquid while stirring under a nitrogen gas flow, and the reaction was allowed to proceed for 2 hours to obtain a polyimide precursor solution. Further, the solution was diluted with DMAc 293.25 g to be 1.3 poise at 30 °C. 1,2-DMZ 5.87 g (0.06 mol) was added to the solution, and the solution was slowly added to acetone (6.5 L) equipped with a homogenizer to precipitate a polyimine precursor powder. The suspension was filtered, acetone was washed, and vacuum-dried at 40 ° C for 10 hours to obtain a powder of 60.52 g of a polyimide precursor.

To 3 g of the polyimine precursor powder, 26.10 g of water and 0.9 g of 1,2-DMZ (0.0094 mol) were added, and the mixture was stirred at 60 ° C for 2 hours to dissolve, thereby obtaining a uniform polyimine precursor. Aqueous solution. The generated solution was analyzed for gas by GC-MS, and as a result, 6.28% of DMAc was detected, and it was confirmed that the organic solvent remained.

【Table 1】

[Example B1]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 1,2-DMZ 29.87 g (relative to the carboxyl group) were added thereto. It was 1.25 times equivalent) and stirred at 25 ° C for 1 hour to dissolve. 36.56g (0.124 mol) of s-BPDA was added to the solution, and stirred at 70 ° C for 4 hours to obtain a polythenimine precursor aqueous solution having a solid concentration of 9.1% by mass, a solution viscosity of 63.0 Pa ‧ and a logarithmic viscosity of 1.86. Things.

The aromatic polyimide polyimide seamless belt was produced in accordance with the production of the above-mentioned aromatic polyimide polyimide seamless belt using the polyimine precursor aqueous solution composition.

The evaluation results of the state observation and characteristics of the obtained polyimine precursor aqueous solution composition and the polyimine seamless belt are shown in Table 3.

[Example B2]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 2E4MZ 34.23 g (1.25 equivalents to the carboxyl group) were added thereto. ), stirred at 25 ° C for 1 hour to dissolve. 36.56g (0.124 mol) of s-BPDA was added to the solution, and stirred at 70 ° C for 4 hours to obtain a polythenimine precursor aqueous solution having a solid concentration of 9.6% by mass, a solution viscosity of 10.3 Pa s, and a logarithmic viscosity of 0.64. Things.

The aromatic polyimine seamless belt was produced in accordance with the production of the above-mentioned aromatic polyimide coating seamless belt using the polyimine precursor aqueous solution composition.

The evaluation results of the state observation and characteristics of the obtained polyimine precursor aqueous solution composition and the polyimine seamless belt are shown in Table 3.

[Example B3]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and ODA 20.25 g (0.101 mol) and 1,2-DMZ 24.31 g (relative to carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. 29.75 g (0.101 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 8.7% by mass, a solution viscosity of 32.0 Pa s, and a logarithmic viscosity of 0.42. Things.

The aromatic polyimine seamless belt was produced in accordance with the production of the above-mentioned aromatic polyimide coating seamless belt using the polyimine precursor aqueous solution composition.

The evaluation results of the state observation and characteristics of the obtained polyimine precursor aqueous solution composition and the polyimine seamless belt are shown in Table 3.

[Example B4]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction, and a discharge tube of 500 mL, 450 g of water was added as a solvent, and ODA 10.97 g (0.055 m) and PPD 5.92 g (0.055 m) and 1, 2 were added thereto. -DMZ 20.43 g (1.25 equivalents relative to the carboxyl group), and stirred at 25 ° C for 1 hour to dissolve. s-BPDA 16.12g (0.055 mole) and ODPA 16.99g (0.055 mole) were added to the solution, and stirred at 70 ° C for 4 hours to obtain a solid concentration of 9.1% by mass, a solution viscosity of 6.5 Pa‧s, and a logarithmic viscosity of 0.50. The aqueous solution of the polyimide precursor aqueous solution.

The aromatic polyimine seamless belt was produced in accordance with the production of the above-mentioned aromatic polyimide coating seamless belt using the polyimine precursor aqueous solution composition.

The evaluation results of the state observation and characteristics of the obtained polyimine precursor aqueous solution composition and the polyimine seamless belt are shown in Table 3.

[Example B5]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge pipe and a 500 mL internal volume, 450 g of water was added as a solvent, and ODA 14.86 g (0.074 mol) and PPD 3.44 g (0.032 mol) and 1, 2 were added thereto. -DMZ 20.43 g (1.25 equivalents relative to the carboxyl group), and stirred at 25 ° C for 1 hour to dissolve. To the solution, 21.83 g (0.074 mol) and ODPA 9.87 g (0.032 mol) of s-BPDA were added, and the mixture was stirred at 70 ° C for 4 hours to obtain a solid concentration of 9.0% by mass, a solution viscosity of 5.2 Pa‧s, and a logarithmic viscosity of 0.46. The aqueous solution of the polyimide precursor aqueous solution.

The aromatic polyimine seamless belt was produced in accordance with the production of the above-mentioned aromatic polyimide coating seamless belt using the polyimine precursor aqueous solution composition.

The evaluation results of the state observation and characteristics of the obtained polyimine precursor aqueous solution composition and the polyimine seamless belt are shown in Table 3.

[Example C1]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 1,2-DMZ 29.87 g (relative to the carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to the solution, and the mixture was stirred at 25 ° C for 12 hours to obtain an aqueous solution of a binder resin composition having a solid concentration of 9.0% by mass, a solution viscosity of 16.3 Pa s, and a logarithmic viscosity of 0.95. .

The characteristics of the obtained binder resin composition for electrodes and the binder for electrodes for polyimides are shown in Table 4.

Further, 8.89 g of the electrode binder resin composition obtained in the electrode (0.8 g of the solid content of the imidized niobium) and 9.2 g of a 300 mesh tantalum powder were mixed in a mortar to prepare an electrode mixture paste. Agent. The obtained paste can be thinly spread on the copper foil with a glass rod. The copper foil coated with the paste is fixed on the substrate, and is heated at 120 ° C for 1 hour, at 200 ° C for 10 minutes, at 220 ° C for 10 minutes, and at 250 ° C for 10 minutes. The active material layer has an electrode thickness of 100 μm.

[Example C2]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 1,2-DMZ 29.87 g (relative to the carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to the solution, and the mixture was stirred at 50 ° C for 8 hours to obtain an aqueous solution of a binder resin composition having a solid concentration of 9.1% by mass, a solution viscosity of 35.5 Pa‧s, and a logarithmic viscosity of 1.25. .

The characteristics of the obtained binder resin composition for electrodes and the binder for electrodes for polyimides are shown in Table 4.

Further, the obtained electrode binder resin composition was treated in the same manner as in Example C1, and an electrode was preferably produced.

[Example C3]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 1,2-DMZ 29.87 g (relative to the carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. To the solution, 36.56 g (0.124 mol) of s-BPDA was added, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a binder resin composition for an electrode having a solid concentration of 9.1% by mass, a solution viscosity of 63.0 Pa s, and a logarithmic viscosity of 1.86.

The characteristics of the obtained binder resin composition for electrodes and the binder for electrodes for polyimides are shown in Table 4.

Further, the obtained electrode binder resin composition was treated in the same manner as in Example C1, and an electrode was preferably obtained.

[Example C4]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 2E4MZ 34.23 g (1.25 equivalents relative to the carboxyl group) were added thereto. It was stirred at 25 ° C for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a binder resin composition having a solid concentration of 9.6% by mass, a solution viscosity of 10.3 Pa s, and a logarithmic viscosity of 0.64. .

The characteristics of the obtained binder resin composition for electrodes and the binder for electrodes for polyimides are shown in Table 4.

Further, the obtained electrode binder resin composition was treated in the same manner as in Example C1, and an electrode was preferably produced.

[Example C5]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction, and a discharge tube of 500 mL, 450 g of water was added as a solvent, and ODA 10.97 g (0.055 m) and PPD 5.92 g (0.055 m) and 1, 2 were added thereto. -DMZ 20.43 g (1.25 equivalents relative to the carboxyl group), and stirred at 25 ° C for 1 hour to dissolve. s-BPDA 16.12g (0.055 mole) and ODPA 16.99g (0.055 mole) were added to the solution, and stirred at 70 ° C for 4 hours to obtain a solid concentration of 9.1% by mass, a solution viscosity of 6.5 Pa‧s, and a logarithmic viscosity of 0.50. The electrode is composed of an aqueous solution of a binder resin composition.

The characteristics of the obtained binder resin composition for electrodes and the binder for electrodes for polyimides are shown in Table 4.

Further, the obtained electrode binder resin composition was treated in the same manner as in Example C1, and an electrode was preferably produced.

[Example C6]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge pipe and a 500 mL internal volume, 450 g of water was added as a solvent, and ODA 14.86 g (0.074 mol) and PPD 3.44 g (0.032 mol) and 1, 2 were added thereto. -DMZ 20.43 g (1.25 equivalents relative to the carboxyl group), and stirred at 25 ° C for 1 hour to dissolve. To the solution, 21.83 g (0.074 mol) and ODPA 9.87 g (0.032 mol) of s-BPDA were added, and the mixture was stirred at 70 ° C for 4 hours to obtain a solid concentration of 9.0% by mass, a solution viscosity of 5.2 Pa‧s, and a logarithmic viscosity of 0.46. The electrode is composed of an aqueous solution of a binder resin composition.

The characteristics of the obtained binder resin composition for electrodes and the binder for electrodes for polyimides are shown in Table 4.

Further, the obtained electrode binder resin composition was treated in the same manner as in Example C1, and an electrode was preferably produced.

[Example C7]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and ODA 20.25 g (0.101 mol) and 1,2-DMZ 24.31 g (relative to the carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. 29.75 g (0.101 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of an adhesive resin composition for an electrode having a solid concentration of 8.7% by mass, a solution viscosity of 32.0 Pa s, and a logarithmic viscosity of 0.42. .

The characteristics of the obtained binder resin composition for electrodes and the binder for electrodes for polyimides are shown in Table 4.

Further, the obtained electrode binder resin composition was treated in the same manner as in Example C1, and an electrode was preferably produced.

[Example C8]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and MPD 13.44 g (0.124 mol) and 1,2-DMZ 29.87 g (relative to the carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. 36.56 g (0.124 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of an adhesive resin composition for an electrode having a solid concentration of 8.9% by mass, a solution viscosity of 13.5 Pa s, and a logarithmic viscosity of 0.75. .

The characteristics of the obtained binder resin composition for electrodes and the binder for electrodes for polyimides are shown in Table 4.

Further, the obtained electrode binder resin composition was treated in the same manner as in Example C1, and an electrode was preferably produced.

[Example D1]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 1,2-DMZ 29.87 g (relative to the carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. 36.56g (0.124 mol) of s-BPDA was added to the solution, and stirred at 70 ° C for 4 hours to obtain a polythenimine precursor aqueous solution having a solid concentration of 9.1% by mass, a solution viscosity of 63.0 Pa ‧ and a logarithmic viscosity of 1.86. Things.

The obtained aqueous solution of the polyimide precursor aqueous solution is applied to a glass plate of a substrate by a bar coater, and the coated film is defoamed and preliminarily dried at 25 ° C for 30 minutes under reduced pressure at atmospheric pressure. The mixture was placed in a hot air dryer, heated at 80 ° C for 30 minutes, heated at 120 ° C for 30 minutes, heated at 200 ° C for 10 minutes, and further heat treated at 250 ° C for 10 minutes to form a polyimide having a thickness of 10 μm. Amine film.

Table 5 shows the results of evaluation of the state and characteristics of the obtained polyimine precursor aqueous solution composition and the polyimide substrate for a flexible device.

[Example D2]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and PPD 13.44 g (0.124 mol) and 2E4MZ 34.23 g (1.25 equivalents relative to the carboxyl group) were added thereto. It was stirred at 25 ° C for 1 hour to dissolve. 36.56g (0.124 mol) of s-BPDA was added to the solution, and stirred at 70 ° C for 4 hours to obtain a polythenimine precursor aqueous solution having a solid concentration of 9.6% by mass, a solution viscosity of 10.3 Pa s, and a logarithmic viscosity of 0.64. Things.

The obtained aqueous solution of the polyimide precursor aqueous solution is applied to a glass plate of a substrate by a bar coater, and the coated film is defoamed and pre-dried at 25 ° C for 30 minutes under reduced pressure, and then dried. The mixture was placed in a hot air dryer, heated at 80 ° C for 30 minutes, heated at 120 ° C for 30 minutes, heated at 200 ° C for 10 minutes, and heat treated at 250 ° C for 10 minutes to form a polythene having a thickness of 10 μm. Imine film.

Table 5 shows the results of evaluation of the state and characteristics of the obtained polyimine precursor aqueous solution composition and the polyimide substrate for a flexible device.

[Example D3]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and ODA 20.25 g (0.101 mol) and 1,2-DMZ 24.31 g (relative to carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. 29.75 g (0.101 mol) of s-BPDA was added to the solution, and the mixture was stirred at 70 ° C for 4 hours to obtain an aqueous solution of a polyimine precursor having a solid concentration of 8.7% by mass, a solution viscosity of 32.0 Pa s, and a logarithmic viscosity of 0.42. Things.

The obtained aqueous solution of the polyimide precursor aqueous solution is applied to a glass plate of a substrate by a bar coater, and the coated film is defoamed and preliminarily dried at 25 ° C for 30 minutes under reduced pressure at atmospheric pressure. The mixture was placed in a hot air dryer at 80 ° C for 30 minutes, at 120 ° C for 30 minutes, at 200 ° C for 10 minutes, and then at 250 ° C for 10 minutes for heat treatment to form a polyimide film having a thickness of 10 μm.

Table 5 shows the results of evaluation of the state and characteristics of the obtained polyimine precursor aqueous solution composition and the polyimide substrate for a flexible device.

[Example D4]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction, and a discharge tube of 500 mL, 450 g of water was added as a solvent, and ODA 10.97 g (0.055 m) and PPD 5.92 g (0.055 m) and 1, 2 were added thereto. -DMZ 20.43 g (1.25 equivalents relative to the carboxyl group), and stirred at 25 ° C for 1 hour to dissolve. s-BPDA 16.12g (0.055 mole) and ODPA 16.99g (0.055 mole) were added to the solution, and stirred at 70 ° C for 4 hours to obtain a solid concentration of 9.1% by mass, a solution viscosity of 6.5 Pa‧s, and a logarithmic viscosity of 0.50. The aqueous solution of the polyimide precursor aqueous solution.

The obtained polyimine precursor aqueous solution composition was applied onto a glass plate as a substrate by a bar coater, and the coated film was defoamed and preliminarily dried at 25 ° C for 30 minutes under reduced pressure. The mixture was placed in a hot air dryer and pressed at 80 ° C for 30 minutes, at 120 ° C for 30 minutes, at 200 ° C for 10 minutes, and then at 250 ° C for 10 minutes for heat treatment to form a polyimide film having a thickness of 10 μm.

Table 5 shows the results of evaluation of the state and characteristics of the obtained polyimine precursor aqueous solution composition and the polyimide substrate for a flexible device.

[Example D5]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge pipe and a 500 mL internal volume, 450 g of water was added as a solvent, and ODA 14.86 g (0.074 mol) and PPD 3.44 g (0.032 mol) and 1, 2 were added thereto. -DMZ 20.43 g (1.25 equivalents relative to the carboxyl group), and stirred at 25 ° C for 1 hour to dissolve. To the solution, 21.83 g (0.074 mol) and ODPA 9.87 g (0.032 mol) of s-BPDA were added, and the mixture was stirred at 70 ° C for 4 hours to obtain a solid concentration of 9.0% by mass, a solution viscosity of 5.2 Pa‧s, and a logarithmic viscosity of 0.46. The aqueous solution of the polyimide precursor aqueous solution.

The obtained polyimine precursor aqueous solution composition was applied onto a glass plate as a substrate by a bar coater, and the coated film was defoamed and preliminarily dried at 25 ° C for 30 minutes under reduced pressure. The mixture was placed in a hot air dryer, and dried at 80 ° C for 30 minutes, at 120 ° C for 30 minutes, at 200 ° C for 10 minutes, and further at 250 ° C for 10 minutes, to form a polyimide film having a thickness of 10 μm.

Table 5 shows the results of evaluation of the state and characteristics of the obtained polyimine precursor aqueous solution composition and the polyimide substrate for a flexible device.

[Example D6]

In a glass reaction vessel equipped with a stirrer, a nitrogen gas introduction ‧ discharge tube and a 500 mL internal volume, 450 g of water was added as a solvent, and MPD 13.44 g (0.124 mol) and 1,2-DMZ 29.87 g (relative to the carboxyl group) were added thereto. 1.25 times equivalent), stirred at 25 ° C for 1 hour to dissolve. 36.56g (0.124 mol) of s-BPDA was added to the solution, and stirred at 70 ° C for 4 hours to obtain a polythenimine precursor aqueous solution having a solid concentration of 8.9% by mass, a solution viscosity of 13.5 Pa s, and a logarithmic viscosity of 0.75. Things.

The obtained polyimine precursor aqueous solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was subjected to degassing and preliminary drying at 25° C. under reduced pressure for 30 minutes. The mixture was placed in a hot air dryer at normal pressure for 30 minutes at 120 ° C, 30 minutes at 120 ° C, 10 minutes at 200 ° C, and further heat treated at 250 ° C for 10 minutes to form a polyimide film having a thickness of 10 μm.

Table 5 shows the results of evaluation of the state and characteristics of the obtained polyimine precursor aqueous solution composition and the polyimide substrate for a flexible device.

(industrial use)

According to the present invention, it is possible to provide a method of easily preparing an aqueous solution composition of a polyimine precursor having a higher environmental compatibility without using a solvent other than water. According to this production method, it is extremely easy (directly) to obtain an aqueous solution composition of a polyimine precursor having an extremely small content of an organic solvent, and particularly a composition of an aqueous solution of a polyimide intermediate precursor containing an aqueous solvent containing no organic solvent.

Furthermore, according to the present invention, it is possible to provide a polyhydrazide precursor aqueous solution composition which uses an aqueous solvent and has good environmental compatibility, and the aromatic polyimine obtained by using the same has high crystallinity, so heat resistance, It is excellent in characteristics such as mechanical strength, electrical properties, and solvent resistance, and is preferably an organic solvent having a high molecular weight and a solvent other than water.

Further, according to the present invention, there is provided a method for producing an aromatic polyimine seamless belt which is an aqueous solution of a polyimine precursor precursor which is excellent in environmental compatibility using an aqueous solvent. Further, the aromatic polyimine seamless belt obtained by the production method of the present invention preferably has high crystallinity and excellent properties such as heat resistance, mechanical strength, electrical properties, solvent resistance, and the like, and is therefore suitable for use as an electron. A seamless belt for intermediate transfer of a photographic device or a seamless belt for fixing.

According to the present invention, it is possible to provide a binder resin composition for an electrode which is excellent in environmental compatibility using an aqueous solvent. Further, the aromatic polyimine obtained by using the electrode binder resin composition has excellent crystallinity, heat resistance, mechanical strength, electrical properties, solvent resistance, and the like, and is swelled even in a battery environment. The degree is still small and has excellent ambiguity.

According to the present invention, it is possible to provide a polyimide polyimide precursor resin composition for a flexible device substrate which is excellent in environmental compatibility using an aqueous solvent. Further, the substrate for an aromatic polyimine flexible device obtained according to the present invention preferably has high crystallinity and excellent properties such as heat resistance, mechanical strength, low linear expansion, electrical properties, solvent resistance, and the like. A flexible device substrate that is suitable as a display device such as a substrate for a liquid crystal display, a substrate for an organic EL display, or a substrate for an electronic paper, or a flexible device substrate that is a light-receiving device such as a substrate for a thin film solar cell.

Claims (17)

A method for producing a polyhydrazylene precursor aqueous solution composition, characterized in that water is used as a reaction solvent, and the solubility of tetracarboxylic dianhydride and water at 25 ° C in the presence of imidazole is 0.1 g / L or more The diamine reaction produces an aqueous solution composition of a polyimide precursor; the amount of the imidazole used is 1.6 times or more relative to the tetracarboxylic dianhydride. The method for producing a polyhydrazide precursor aqueous solution composition according to the first aspect of the invention, wherein the imidazole has two or more alkyl groups as a substituent. The method for producing a polyhydrazide precursor aqueous solution composition according to claim 2, wherein the imidazole is selected from the group consisting of 1,2-dimethylimidazole and 2-ethyl-4-methylimidazole. A group consisting of 4-ethyl-2-methylimidazole and 1-methyl-4-ethylimidazole. The method for producing an aqueous solution of a polythenimine precursor according to the first aspect of the invention, wherein the obtained polyamidene precursor has a logarithmic viscosity of 0.2 or more. An aqueous solution of a polyimine precursor precursor characterized by reacting a tetracarboxylic dianhydride with a diamine obtained by reacting a diamine having a solubility of 0.1 g/L or more with water at 25 ° C, and an imidazole At the same time, it is soluble in a water solvent, and the content of the organic solvent is less than 5%; the amount of the imidazole used is 1.6 times or more relative to the tetracarboxylic dianhydride. An aqueous solution of a polyimine precursor precursor solution according to claim 5, which does not contain an organic solvent. An aqueous solution of a polyimine precursor precursor obtained by reacting a tetracarboxylic acid component with a diamine component to obtain a polylysine composed of a repeating unit represented by the following chemical formula (1), and relative to the poly The tetracarboxylic acid component of the proline is 1.6 times or more of the imidazole having two or more alkyl groups as a substituent and dissolved in a water solvent: In the chemical formula (1), A is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid having 2 to 3 aromatic rings, and B is a water having 1 to 2 aromatic rings and for 25 ° C. A divalent group obtained by removing an amine group from an aromatic diamine having a solubility of 0.1 g/L or more. The aqueous solution of the polyimine precursor precursor of the seventh aspect of the patent application, wherein the chemical formula (1) A is one or more of the following chemical formulas (2) to (7): . The aqueous solution of the polyimine precursor precursor according to claim 7 or 8, wherein the chemical formula (1) B is any one of the following chemical formulas (8) to (9): . An aqueous solution of a polyimine precursor precursor according to claim 7 or 8 wherein the content of the organic solvent is less than 5%. A method for producing an aromatic polyimine seamless belt, comprising the steps of: reacting a tetracarboxylic acid component with a diamine component to obtain a polyamine which is composed of a repeating unit represented by the following chemical formula (1) The acid and the aqueous solution of the polyimine precursor precursor prepared by dissolving the imidazole of 1.6 times or more with respect to the tetracarboxylic acid component of the polyamic acid in an aqueous solvent are heat-treated: In the chemical formula (1), A is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid, and B is an amine group obtained by removing an amine group from an aromatic diamine having a solubility of water of 25 ° C or more of 0.1 g/L or more. 2 valence base. A binder resin composition for an electrode obtained by reacting a tetracarboxylic acid component with a diamine component to obtain a polylysine composed of a repeating unit represented by the following chemical formula (1), and relative to the polyamic acid The tetracarboxylic acid component is 1.6 times more molar than the imidazole and is dissolved in a water solvent: In the chemical formula (1), A is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid, and B is an amine group obtained by removing an amine group from an aromatic diamine having a solubility of water of 25 ° C or more of 0.1 g/L or more. 2 valence base. An electrode mixture paste comprising: an electrode active material; and a binder resin composition for an electrode according to claim 12 of the patent application. An electrode obtained by applying an electrode mixture paste as disclosed in claim 13 to a current collector, and performing heat treatment to remove the solvent, and simultaneously performing a ruthenium imidization reaction. A polyimine precursor resin composition for a flexible device substrate obtained by reacting a tetracarboxylic acid component with a diamine component to obtain a polylysine composed of repeating units represented by the following chemical formula (1) And the imidazole which is 1.6 times or more relative to the tetracarboxylic acid component of the polyamic acid is simultaneously dissolved in an aqueous solvent: In the chemical formula (1), A is a tetravalent group obtained by removing a carboxyl group from an aromatic tetracarboxylic acid, and B is an amine group obtained by removing an amine group from an aromatic diamine having a solubility of water of 25 ° C or more of 0.1 g/L or more. 2 valence base. A method for manufacturing a flexible device, which is a method for manufacturing a flexible device for a display device or a light-receiving device, comprising the steps of: using a polymerized substrate for a flexible device substrate according to claim 15 The imine precursor resin composition is coated on a carrier substrate and heat-treated to form a solid polyimide film; a circuit is formed on the polyimide film; and a circuit is formed on the surface The polyimide film of the polyimide is peeled off from the carrier substrate. A flexible device which is a display device or a light-receiving device manufactured by the method of manufacturing a flexible device according to claim 16 of the patent application.