JP5691273B2 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a polyimide-based solution. Specifically, at least one selected from the group consisting of a soluble polyimide and a polyimide precursor is dissolved in an organic solvent, the solution is applied onto a support substrate, and heat treatment is performed. To a polyimide-based solution capable of forming a smooth polyimide coating film on a support substrate.

  More specifically, the present invention relates to a liquid crystal aligning agent containing polyimide and / or a polyimide precursor, a liquid crystal aligning film formed from the liquid crystal aligning agent, and a liquid crystal display element including the same.

  Polyimide is widely used as a protective material and insulating material in the electric / electronic field because of its high mechanical strength, heat resistance, and solvent resistance. In such applications, for example, a polyimide is prepared by dissolving a solution obtained by dissolving polyamic acid or soluble polyimide in an appropriate organic solvent on a support substrate by a method such as spin coating, offset printing, or gravure printing, and heating. It is generally used by forming a film after processing.

  Specifically, when a polyimide film is used as an insulating film for a semiconductor, a coating film of a polyimide-based solution having a thickness of 1 to 10 μm is formed on a wiring-processed silicon support substrate. Moreover, when using a polyimide film as a liquid crystal aligning film, the coating film of a 0.05-0.2 micrometer polyimide-type solution is formed on the transparent support substrate with a transparent electrode. Thus, in the above applications, polyimide is generally used by forming a thin polyimide-based solution coating film on various supporting substrates.

  When a coating film of a polyimide-based solution is formed on a substrate, the fluidity of the solution after coating is important for forming a smooth film. It is because the unevenness | corrugation of the coating-film surface becomes smooth because a solution flows. For this purpose, a method of adding butyl cellosolve to a polyimide-based solution is mentioned (for example, see Patent Document 1). However, since butyl cellosolve has a weak dissolving power for film forming polyimide components such as polyamic acid and soluble polyimide, the film forming polyimide component may be precipitated by addition. In addition to such problems, development of an alternative component of butyl cellosolve is also desired from the viewpoint of safety to the human body.

Japanese Examined Patent Publication No. 4-81167

  This invention provides the polyimide-type solution in which precipitation of the film-forming polyimide-type component contained in this solution is suppressed more in the polyimide-type solution used for formation of a coating film.

  In the polyimide-based solution for forming a coating film, the inventors replaced the butyl cellosolve conventionally used as a coating property improving agent for improving the fluidity of the solution on the surface of the coating film with the following formula (A ), The same coating property improvement effect as that of butyl cellosolve is obtained, and the deposition of dissolved film-forming polyimide is suppressed. The inventors found that a whitening prevention effect by precipitation of polyimide in the film was obtained, and completed the present invention. The present invention comprises the following aspects.

(1) In the liquid crystal aligning agent containing the film-forming polyimide type | system | group component which is 1 or more types selected from the group which consists of a polyimide and a polyimide precursor, and the solvent which melt | dissolves this, the said solvent is following formula (A). The liquid crystal aligning agent characterized by including the compound represented.

In formula (A), Q ¹ represents —CH ₃ , —CH ₂ —OH, or — (CH ₂ ) ₂ —OH, Q ² represents —H, —CH ₃ , or —CH ₂ —OH, Q ³ independently represents —H, —CH ₃ , or —CH (CH ₃ ) ₂ , n represents 0 or 1, and one of Q ¹ and Q ² is a group having —OH; When n = 0, Q ¹ is —CH ₃ , Q ² is —CH ₂ —OH, and when n = 1, Q ¹ is —CH ₂ —OH or — (CH ₂ ) ₂ —OH. Yes, Q ² is —H, and Q ³ includes one or both of —CH ₃ and —CH (CH ₃ ) ₂ .

(2) The compound represented by the formula (A) is one or more selected from the group consisting of the following formulas (A-1), (A-2), and (A-3) (1 ) Liquid crystal aligning agent.

(3) The film-forming polyimide component is polyamic acid or a derivative thereof having a structure of a reaction product of diamine or a derivative thereof and tetracarboxylic acid or a derivative thereof (1) or (2 ) Liquid crystal aligning agent.

(4) The liquid crystal according to any one of (1) to (3), wherein the solvent is a mixed solvent of two or more compounds including the compound represented by the formula (A). Alignment agent.

(5) A liquid crystal alignment film formed by firing the coating film of the liquid crystal aligning agent according to any one of (1) to (4).

(6) A pair of opposed substrates, electrodes formed on one or both of the opposed surfaces of the pair of substrates, and formed on the opposed surfaces of the pair of substrates. A liquid crystal display element having a liquid crystal alignment film and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to (5).

(7) In a polyimide-based solution containing at least one film-forming polyimide-based component selected from the group consisting of polyimide and a polyimide precursor, and a solvent for dissolving the component, the solvent is represented by the formula (A). A polyimide-based solution comprising the compound represented.

(8) The film-forming polyimide component is a polyamic acid or a derivative thereof having a structure of a reaction product of diamine or a derivative thereof and tetracarboxylic acid or a derivative thereof. Polyimide solution.

(9) The polyimide solution according to (7) or (8), wherein the solvent is a mixed solvent of two or more compounds including the compound represented by the formula (A).

(10) The polyimide solution according to any one of (7) to (9), which is a coating material.

(11) The polyimide solution according to any one of (7) to (9), which is an insulating material.

(12) The polyimide solution according to any one of (7) to (9), which is an adhesive.

(13) The polyimide solution according to any one of (7) to (9), which is a sealing material.

(14) The polyimide-based solution according to any one of (7) to (9), which is a printed wiring board material.

(15) The polyimide solution according to any one of (7) to (9), which is a molding material.

(16) A method for producing a polyimide-based solution comprising obtaining a solution in which a film-forming polyimide-based component that is one or more selected from the group consisting of polyimide and a polyimide precursor is dissolved in a solvent that dissolves the component. Wherein the solvent contains a compound represented by the formula (A).

(17) The film-forming polyimide-based component is a polyamic acid or a derivative thereof having a structure of a reaction product of a diamine or a derivative thereof and a tetracarboxylic acid or a derivative thereof. A method for producing a polyimide-based solution.

(18) The method for producing a polyimide-based solution according to (16) or (17), wherein the solvent is a mixed solvent of two or more compounds including the compound represented by the formula (A). .

(19) A step of forming a coating film of a polyimide-based solution containing a film-forming polyimide-based component which is one or more selected from the group consisting of a soluble polyimide and a polyimide precursor and a solvent for dissolving the component. And a step of forming a polyimide film comprising a film-formable polyimide component in the coating film, and the solvent contains the compound represented by the formula (A) A method for producing a polyimide film, comprising:

(20) The film-forming polyimide-based component is a polyamic acid or a derivative thereof having a structure of a reaction product of diamine or a derivative thereof and tetracarboxylic acid or a derivative thereof. A method for producing a polyimide film.

(21) The method for producing a polyimide film according to (19) or (20), wherein the solvent is a mixed solvent of two or more compounds including the compound represented by the formula (A).

(22) A compound represented by the formula (A-2) or (A-3).

  According to the present invention, since the compound of the formula (A) is used as the solvent of the polyimide solution, the deposition of the film forming polyimide component contained in the solution in the polyimide solution used for forming the coating film. Can be suppressed.

  Moreover, since this invention uses the compound of said Formula (A) for the solvent of a polyimide-type solution, the outstanding applicability | paintability of a polyimide-type solution is obtained and the unevenness | corrugation in the surface of a coating film can be suppressed.

  Moreover, in this invention, using the mixed solvent of 2 or more types of compounds containing the compound represented by the said Formula (A) is still more from a viewpoint of suppressing precipitation of the film-forming polyimide type component from a polyimide type solution. It is effective.

  In the present invention, it is possible to use polyamic acid or a derivative thereof, which is a reaction product of diamine or a derivative thereof and tetracarboxylic acid or a derivative thereof, as the film-forming polyimide-based component. From the viewpoint of providing a polyimide-based solution used in a technical field where both excellent effects are required, it is even more effective.

4 is a diagram showing a ¹ H-NMR chart of a compound (A-2) obtained in Synthesis Example 2. FIG. It is a figure which shows the < ¹ > H-NMR chart of the compound (A-3) obtained by the synthesis example 3. FIG.

  The polyimide-based solution of the present invention contains a film-forming polyimide-based component and a solvent for dissolving it. The polyimide-based solution of the present invention can use various components used in this technical field in ordinary applications except that the solvent contains a compound represented by the following formula (A). The compound represented by the formula (A) may be one kind or two or more kinds.

In formula (A), Q ¹ represents —CH ₃ , —CH ₂ —OH, or — (CH ₂ ) ₂ —OH, Q ² represents —H, —CH ₃ , or —CH ₂ —OH, Q ³ independently represents —H, —CH ₃ , or —CH (CH ₃ ) ₂ , and n represents 0 or 1. However, ^one of Q ¹ and Q ² is a group having —OH. When n = 0, Q ¹ is —CH ₃ , Q ² is —CH ₂ —OH, and n = 1. When Q ¹ is —CH ₂ —OH or — (CH ₂ ) ₂ —OH, Q ² is —H, and Q ³ includes one or both of —CH ₃ and —CH (CH ₃ ) _2. .

  Examples of such a compound represented by the formula (A) include compounds represented by the following formulas (A-1) to (A-3).

  The content of the compound represented by the formula (A) in the polyimide-based solution of the present invention is sufficient to prevent precipitation of the film-forming polyimide in the obtained polyimide-based solution, and sufficient on the surface of the coating film by the polyimide-based solution. From the viewpoint of obtaining smoothness, it is preferably 1 to 80% by weight of the solvent, more preferably 2 to 70% by weight, and particularly preferably 5 to 60% by weight.

  Some of the compounds represented by the formula (A) can be obtained as commercial products. For example, the compound represented by the formula (A-1) can be obtained as a product “SOLKETAL” manufactured by Kanto Chemical Co., Inc.

  The compound represented by the formula (A) can be obtained by a dehydration ring-closing reaction between a polyol and a ketone. For example, in the compound represented by the formula (A-2), 2,2,4-trimethyl-1,3-pentanediol and hydroxyacetone are reacted in the presence of an acid catalyst while removing generated water. Can be obtained by: Similarly, the compound represented by the formula (A-3) produces 2,2,4-trimethyl-1,3-pentanediol and 4-hydroxy-2-butanone in the presence of an acid catalyst. It can be obtained by reacting while removing water.

  In the above reaction, the molar ratio of the ketone to the diol is preferably 1 or more from the viewpoint of preventing the diol from remaining and separating the target product from the reaction product by distillation. More preferably, it is more preferably 1.0 to 1.5, and still more preferably 1.0 to 1.2.

  The above reaction can be performed under reflux conditions of a solvent (entrainer) that is phase-separated from water and azeotropes with water. One or more entrainers may be used. Such entrainers include, for example, cyclohexane, toluene, xylene, and methylcyclopentane. The amount of the entrainer used is preferably 3 to 300 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the diol and ketone as raw materials.

  The acid catalyst can be selected from acid catalysts usually used in dehydration condensation. Examples of such an acid catalyst include p-toluenesulfonic acid or its monohydrate, sulfuric acid, and phosphoric acid. The acid catalyst is preferably p-toluenesulfonic acid or a monohydrate thereof. The amount of the acid catalyst used is preferably 0.01 to 10% by weight, more preferably 0.02 to 5% by weight, based on the total amount of diol and ketone as raw materials.

  The above reaction is preferably performed under reduced pressure from the viewpoint of suppressing dehydration from the raw material polyol or hydroxyketone itself, which is an embodiment of the ketone, which may occur during the reaction. For example, the synthesis reaction of the compound represented by the formula (A-2) can be performed under conditions where the entrainer is refluxed in the range of 26.66 kPa, 53 ° C. to 9.33 kPa, 48 ° C. In addition, the synthesis reaction of the compound represented by the formula (A-3) can be performed under conditions where the entrainer is refluxed in the range of 10.67 kPa, 30 ° C. to 8.00 kPa, 38 ° C.

  The compound represented by the formula (A-2) or (A-3) obtained by the above reaction can be taken out by vacuum distillation of the reaction product. For example, the boiling point of the compound represented by Formula (A-2) is 76 to 78 ° C. at 1.33 kPa, and the boiling point of the compound represented by Formula (A-3) is 123 to 125 at 0.67 kPa. ° C.

  The film-forming polyimide component is a component that can form a polyimide film by baking a coating film of the solution, and is selected from the group consisting of polyimide and a polyimide precursor. The film forming polyimide component may be one kind or two or more kinds.

  The content of the film forming polyimide component in the polyimide solution of the present invention is preferably 0.5 to 50% by weight, and 1 to 30% by weight from the viewpoint of workability such as appropriate viscosity. More preferably, the content is 2 to 20% by weight.

The average molecular weight of the film-forming polyimide-based component is not particularly limited, but the polyimide and the polyimide precursor are not evaporated by firing in the formation of the polyimide film, and preferable physical properties (components of the obtained film) From the viewpoint of obtaining uniformity and the like, the weight average molecular weight is preferably 5 × 10 ³ or more, and more preferably 1 × 10 ⁴ or more. The weight average molecular weight is preferably 1 × 10 ⁶ or less from the viewpoint of easy handling as a polyimide-based solution such as viscosity.

  The weight average molecular weight of the film-forming polyimide component is measured by gel permeation chromatography (GPC). For example, the obtained polyamic acid or derivative thereof is diluted with dimethylformamide (DMF) so that the concentration of polyamic acid or derivative thereof is about 1% by weight, and Chromatopack C-R7A (manufactured by Shimadzu Corporation) is used. It is calculated | required by measuring by a gel permeation chromatograph analysis (GPC) method, using DMF as a developing solvent, and converting into polystyrene. Furthermore, from the viewpoint of improving the accuracy of GPC measurement, a developing solvent in which an inorganic acid such as phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid or the like or an inorganic salt such as lithium bromide or lithium chloride is dissolved in a DMF solvent may be prepared and used. . In the present invention, the molecular weight is measured by liquid chromatography using Alliance 2695, manufactured by WATERS, as the measuring instrument, N, N-dimethylformamide containing 1% phosphoric acid as the developing solvent, and polystyrene as the standard sample. Perform analysis. Examples of the column used here include HSPgel (registered trademark) RTMB-M, manufactured by WATERS. Moreover, the molecular weight as used in the field of this invention means a weight average molecular weight.

  Examples of the polyimide in the film forming polyimide component include, for example, a polyimide in which all amino acids and carboxyls of polyamic acid are subjected to dehydration ring-closing reaction, and a partial polyimide in which amino and carboxyl groups of polyamic acid are partially subjected to dehydration ring-closing reaction, Is mentioned. Moreover, as a polyimide precursor in the said film-forming polyimide type component, a polyamic acid or its derivative (s) is mentioned, for example.

  The polyimide can be obtained by a known method. For example, the polyimide is a polyamic acid solution together with acetic anhydride as a dehydrating agent, an acid anhydride such as propionic anhydride and trifluoroacetic anhydride, and a tertiary amine such as triethylamine, pyridine and collidine as dehydrating ring closure catalysts. It can be obtained by an imidization reaction at a temperature of 20 to 150 ° C.

  Alternatively, the polyimide is prepared by precipitating polyamic acid from a polyamic acid solution using a large amount of poor solvent (alcohol solvent or glycol solvent such as methanol, ethanol, isopropanol, etc.). It is also possible to obtain an imidization reaction at a temperature of 20 to 150 ° C. together with the same dehydrating agent and dehydrating ring closure catalyst as described above in a solvent such as the above.

  In the imidization reaction, the ratio of the dehydrating agent to the dehydrating ring-closing catalyst is preferably 0.1 to 10 (molar ratio). The total amount used of both is preferably 1.5 to 10 times the total molar amount of the acid dianhydride contained in the tetracarboxylic dianhydride used in the polyamic acid. By adjusting the dehydrating agent, catalyst amount, reaction temperature and reaction time of this chemical imidization, the degree of imidization can be controlled to obtain a partial polyimide.

  As said polyamic acid or its derivative (s), the compound which has the structure of the reaction product of diamine or its derivative (s) and tetracarboxylic acid or its derivative (s) is mentioned, for example. Examples of such polyamic acid or derivatives thereof include polyamic acid, polyamic acid ester, polyamic acid amide, and polyamideimide. Examples of the polyamic acid ester include a polyamic acid ester in which carboxyl of the polyamic acid is converted to an ester, and examples of the polyamic acid amide include, for example, a part of an acid dianhydride contained in a tetracarboxylic dianhydride compound. A polyamic acid-polyamide copolymer obtained by reacting with a dicarboxylic acid is exemplified. As the polyamideimide, for example, a polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closing reaction is used. Can be mentioned.

  In the case where the polyimide precursor of the present invention is used as a liquid crystal aligning agent for forming a liquid crystal alignment film in a liquid crystal display element, the polyimide precursor is a viewpoint that realizes desired characteristics in a polyimide film as a liquid crystal alignment film. Therefore, a polyamic acid or a derivative thereof is preferable.

  In the polyamic acid or derivative thereof, the tetracarboxylic acid or derivative thereof and the diamine or derivative thereof are preferably 0.8: 1.2 to 1.2: 0.8 in molar ratio, : 1.1 to 1.1: 0.9 is more preferable.

  The diamine or derivative thereof may be one type or two or more types. Examples of the diamine or derivatives thereof include diamines represented by the following general formulas (A) to (D).

In general formula (A), n is an integer of 1-12. Formula (B1), alkyl of (B2) and (B3) in, -Y ^1, -Y ^2, and Y ³ each is -H or C1-30. In General Formula (D), A ¹ independently represents — (CH ₂ ) _m — or —N (CH ₃ ) — (CH ₂ ) _m —N (CH ₃ ) —. Here, m represents an integer of 1 to 12.

  Examples of the diamine represented by the general formula (A) include diamines represented by the following structural formula (A1).

  Examples of the diamine represented by the general formulas (B1) to (B3) include diamines represented by the following structural formulas (B1-1) to (B3-1).

  Examples of the diamine represented by the general formula (C) include diamines represented by the following structural formulas (C1) to (C3).

  Examples of the diamine represented by the general formula (D) include diamines represented by the following structural formulas (D1) to (D4).

  Moreover, as said diamine or its derivative (s), the linear diamine represented by the following general formula (II)-(VIII) is also mentioned.

In the general formula (II), A ¹ is, - (CH _{2) m} - represents a. A ¹ in the general formula (IV) is a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO—, —C (CH _{3) 2 -, - C (} CF 3) 2 -, - (CH 2) m -, - O- (CH 2) m -O -, - N (CH 3) - (CH 2) m -N (CH ₃₎ -, or -S- (CH ₂₎ represents an _m -S-. A ¹ ′ in the general formula (VI) is a single bond, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —. _{, -C (CF 3) 2 -} , - O- (CH 2) m -O-, or -S- (CH ₂₎ represents an _m -S-. Note that m represents an integer of 1 to 12.

In general formula (VII), A ² independently represents —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or alkylene having 1 to 3 carbon atoms. .

In the general formula (VIII), A ¹ is independently —S—, —SS—, —SO ₂ —, —CO—, —CONH—, —NHCO—, —C (CF ₃ ) ₂ —. _{, -O- (CH 2) m -O} -, - S- (CH 2) represents an _m -S-. Here, m represents an integer of 1 to 12. In General Formula (VIII), A ² is a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or C 1 to C 3. Represents alkylene.

Hydrogen which is further coupled to the general formula (III) ~ (VIII) cyclohexane ring or a benzene ring in is independently _{-F, -Cl, -CH 3, -OH} , -COOH, -SO 3 H, - It may be replaced with PO ₃ H ₂ or 4-hydroxybenzyl.

  Examples of the linear diamine represented by the general formula (II) include diamines represented by the following structural formulas (II-1) to (II-3).

  Examples of the linear diamine represented by the general formula (III) include diamines represented by the following structural formulas (III-1) and (III-2).

  Examples of the linear diamine represented by the general formula (VI) include diamines represented by the following structural formulas (IV-1) to (IV-3).

  Examples of the linear diamine represented by the general formula (V) include diamines represented by the following structural formulas (V-1) to (V-14).

  Examples of the linear diamine represented by the general formula (VI) include diamines represented by the following structural formulas (VI-1) to (VI-29).

  Examples of the linear diamine represented by the general formula (VII) include diamines represented by the following structural formulas (VII-1) to (VII-6).

  Examples of the linear diamine represented by the general formula (VIII) include diamines represented by the following structural formulas (VIII-1) to (VIII-6).

  Furthermore, as said diamine or its derivative (s), the diamine which has a side chain structure is mentioned, for example. Examples of the diamine having such a side chain structure include side chain diamines represented by the following general formulas (IX) to (XIII).

In General Formula (IX), A ³ represents a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, or — (CH ₂ ) _m —. Here, m represents an integer of 1 to 6. R ⁷ represents a group having a steroid skeleton, a group represented by the following general formula (XIV), or alkyl having 1 to 30 carbon atoms. In the alkyl, any —CH ₂ — may be independently replaced by —CF ₂ —, —CHF—, —O—, —CH═CH— or —C≡C—, ₃ may be replaced by —CH ₂ F, —CHF ₂ or —CF ₃ . However, -O- is not adjacent in the alkyl.

In general formula (XIV), A ⁴ and A ⁵ are each independently a single bond, —O—, —COO—, —OCO—, —CONH—, —CH═CH—, or alkylene having 1 to 20 carbon atoms. Represents. R ⁸ and R ⁹ each independently represents —F or —CH ₃ . Ring S is independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene- It represents 1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl. R ¹⁰ represents -F, alkyl having 1 to 30 carbon atoms, a fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, -CN, a -OCH ₂ F, -OCHF ₂ or -OCF _3. A and b each independently represent an integer of 0 to 4, and when a or b is 2 to 4, adjacent A ⁴ or A ⁵ are different groups, and c, d and e are each independently Represents an integer of 0 to 3, f and g each independently represent an integer of 0 to 2, and c + d + e ≧ 1.

In general formula (X), the hydrogen bonded to the carbon forming the steroid skeleton may be independently replaced with —CH ₃ . In the general formulas (X) and (XI), R ¹¹ each independently represents —H or —CH ₃ , and R ¹² represents —H or C 1-20 alkyl or alkenyl, respectively. A ⁶ each independently represents a single bond, —C (═O) — or —CH ₂ —. In General Formula (XI), R ¹³ and R ¹⁴ each independently represent —H, C 1-20 alkyl or phenyl.

In the general formula (XII), R ¹⁵ represents —H or alkyl having 1 to 30 carbons. Arbitrary —CH ₂ — in the alkyl having 2 to 30 carbon atoms out of the alkyl may be independently replaced by —O—, —CH═CH— or —C≡C—. However, -O- is not adjacent in the alkyl. In the general formulas (XII) and (XIII), A ⁷ each independently represents —O— or alkylene having 1 to 6 carbon atoms. In General Formula (XII), A ⁸ represents a single bond or alkylene having 1 to 3 carbon atoms. Ring T represents 1,4-phenylene or 1,4-cyclohexylene. h represents 0 or 1; In General Formula (XIII), R ¹⁶ represents alkyl having 6 to 22 carbon atoms, and R ¹⁷ represents —H or alkyl having 1 to 22 carbon atoms.

In the side chain diamine represented by the general formula (IX), it is preferable that the bonding position relationship between the two amino groups in which the two amino groups are bonded to the carbon of the phenyl ring is meta or para. Further binding positional relationship between the two amino groups, "R ⁷ -A ³ -" 3-position when the 1-position of the bond position of the 5-position, or is preferably 2-position and 5-position.

  Examples of the side chain diamine represented by the general formula (IX) include diamines represented by the following general formulas (IX-1) to (IX-9).

In the general formulas (IX-1), (IX-2), (IX-5) and (IX-6), R ¹⁸ is preferably alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, and carbon C3-C30 alkyl or C3-C30 alkoxy is more preferable, C5-C25 alkyl or C5-C25 alkoxy is still more preferable. In the general formulas (IX-3), (IX-4) and (IX-7) to (IX-9), R ¹⁹ is preferably alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, More preferred is alkyl having 3 to 25 carbon atoms or alkoxy having 3 to 25 carbon atoms. Among the diamines represented by the general formula (IX), diamines represented by the general formulas (B1) to (B3) are particularly preferable, and are represented by the structural formulas (B1-1) to (B3-1). Particularly preferred are diamines.

  Examples of the side chain diamine represented by the general formula (IX) include diamines represented by the following general formulas (IX-10) to (IX-15).

In the general formulas (IX-10) to (IX-13), R ²⁰ is preferably an alkyl having 4 to 30 carbon atoms, and more preferably an alkyl having 6 to 25 carbon atoms. In the general formulas (IX-14) and (IX-15), R ²¹ is preferably an alkyl having 6 to 30 carbon atoms, more preferably an alkyl having 8 to 25 carbon atoms.

  Examples of the side chain diamine represented by the general formula (IX) include diamines represented by the following general formulas (IX-16) to (IX-36).

The general formulas (IX-16), (IX-17), (IX-20), (IX-22), (IX-23), (IX-26), (IX-28), (IX-29) In (IX-34) and (IX-35), R ²² is preferably alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons. Is more preferable.

Formulas (IX-18), (IX-19), (IX-21), (IX-24), (IX-25), (IX-27), (IX-30) to (IX-33) and (IX-36) in, R ²³ is -H, -F, alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, -CN, are -OCH ₂ F, -OCHF ₂ or -OCF ₃ preferably Further, alkyl having 3 to 25 carbon atoms or alkoxy having 3 to 25 carbon atoms is more preferable. In the general formulas (IX-31) and (IX-32), A ⁹ represents alkylene having 1 to 20 carbon atoms.

  Examples of the side chain diamine represented by the general formula (IX) include diamines represented by the following structural formulas (IX-37) to (IX-46).

  The side chain type diamine represented by the general formula (IX) is preferably a diamine represented by the general formulas (IX-1) to (IX-9), and is represented by the general formula (IX-2) or (IX-4). The diamine represented by these is more preferable.

In the side chain diamine represented by the general formula (X), one of two “NH ₂ —Ph—A ⁶ —O—” is bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position. It is preferable. Further, the two amino groups bonded to the two phenyl groups are preferably bonded to the meta position or the para position with respect to the bonding position of A ⁶ .

  Examples of the side chain diamine represented by the general formula (X) include diamines represented by the following structural formulas (X-1) to (X-4).

In the side chain type diamine represented by the general formula (XI), two “NH ₂ — (R ¹⁴ —) Ph—A ⁶ —O—” are bonded to the carbon of phenyl, respectively, It is preferable that it is couple | bonded with the meta position or the para position with respect to the carbon in the phenyl which has couple | bonded. Further, the two amino groups bonded to the two phenyl groups are preferably bonded to the meta position or the para position with respect to the bonding position of A ⁶ .

  Examples of the side chain diamine represented by the general formula (XI) include diamines represented by the following structural formulas (XI-1) to (XI-8).

In the side chain diamine represented by the general formula (XII), it is preferable that two amino groups bonded to two phenyl groups are bonded to A ^{7 in} a meta position or a para position.

  Examples of the side chain diamine represented by the general formula (XII) include diamines represented by the following general formula (XII-A).

In General Formula (XII-A), Y ⁴ represents an alkyl having 1 to 30 carbon atoms or a group represented by the following General Formula, and X ² is independently —CH ₂ — or —O—. Represents. Moreover, in the following general formula, Y < ⁵ > and Y < ⁶ > represent a C1-C30 alkyl, respectively.

  Moreover, as a side chain type diamine represented by the said general formula (XII), the diamine represented by the following general formula (XII-1)-(XII-9) is mentioned, for example.

In the general formulas (XII-1) to (XII-3), R ²⁴ is preferably —H or an alkyl group having 1 to 30 carbon atoms. In the general formulas (XII-4) and (XII-5), R ²⁵ is preferably —H or an alkyl group having 1 to 30 carbon atoms, and the general formulas (XII-6) to (XII-9) Among them, R ²⁵ is preferably —H or an alkyl group having 1 to 20 carbon atoms.

  As the diamine represented by the general formula (XII), for example, diamines represented by the following structural formulas (XII-2-1), (XII-4-1) and (XII-7-1) are preferably used.

In the side chain diamine represented by the general formula (XIII), it is preferable that two amino groups bonded to two phenyl groups are bonded to A ^{7 in} a meta position or a para position.

  Examples of the side chain diamine represented by the general formula (XIII) include diamines represented by the following general formulas (XIII-1) to (XIII-3).

In the general formula, R ²⁶ is preferably an alkyl group having 6 to 20 carbon atoms, and R ²⁷ is preferably —H or an alkyl group having 1 to 10 carbon atoms.

  Furthermore, the diamine or derivative thereof is represented by a naphthalene diamine having a naphthalene structure, a fluorene diamine having a fluorene structure, a siloxane diamine having a siloxane bond, and the general formulas (IX) to (XIII). Examples thereof include diamines having a side chain structure other than the side chain structure.

  For example, examples of the siloxane diamine include diamines represented by the following general formula (XV).

In the general formula (XV), R ²⁸ and R ²⁹ independently represent alkyl having 1 to 3 carbon atoms or phenyl, and A ¹⁰ independently represents methylene, phenylene, or alkyl-substituted phenylene. i represents an integer of 1 to 6, and j represents an integer of 1 to 10.

  Examples of the diamine represented by the general formula (XV) include diamines represented by the following structural formulas (XV-1) to (XV-7).

  Furthermore, as said diamine or its derivative (s), the diamine represented by the following general formula (1 ')-(8') is mentioned, for example.

In the general formula, R ³⁰ and R ³¹ each independently represents an alkyl group having 3 to 30 carbon atoms.

  Examples of the diamine derivative include a silylated diamine compound obtained by silylating a diamine using a silylating agent.

  The silylating agent may be one type or two or more types. Examples of the silylating agent include trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, triethylchlorosilane, triethylbromosilane, tripropylchlorosilane, tributylchlorosilane, trihexylchlorosilane, dimethylpropylchlorosilane, dimethylpropylchlorosilane, dimethyloctylchlorosilane, and dimethyl. Trialkyl halogenated silanes such as octadecylchlorosilane and t-butyldimethylchlorosilane; vinyl group-containing halogenated silanes such as dimethylvinylchlorosilane; dimethylphenylchlorosilane, diphenylmethylchlorosilane, dimethylphenylchlorosilane, diphenylmethylchlorosilane, methylphenylvinylchlorosilane, etc. Phenyl group-containing halogenated silane; Halogenated alkyl group-containing halogenated silanes such as methyldimethylchlorosilane, 3-chloropropyldimethylchlorosilane, dichloromethyldimethylchlorosilane; alkoxy group-containing halogenated silanes such as trimethoxychlorosilane, triethoxychlorosilane, dimethoxymethylchlorosilane; dimethyldichlorosilane, Dihalogenated silanes such as diethyldichlorosilane, dipropyldichlorosilane, dibutyldichlorosilane, and dihexyldichlorosilane; disilanes such as hexamethyldisilane, hexaethyldisilane, and hexaphenyldisilane; bis (trimethylsilyl) acetamide, bis (triethylsilyl) ) Silylated acetamides such as acetamide and bis (triphenylsilyl) acetamide; hexamethyldisila Disilazane of emissions, and the like.

  The silylated diamine compound can be obtained by a known method. For example, the silylated diamine compound can be obtained by a method described in JP-A-1-217420, wherein a silyl is silylated to obtain a silylated diamine compound.

In addition, the diamine or its derivative can use various other forms of diamine as long as the intended purpose such as the use of the polyimide film is achieved.

  The tetracarboxylic acid or its derivative may be one kind or two or more kinds. As said tetracarboxylic acid or its derivative (s), tetracarboxylic dianhydride is mentioned, for example. Examples of the tetracarboxylic dianhydride include aromatic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and silsesquioxane dianhydrides derivatives. It is done.

  Examples of the aromatic tetracarboxylic dianhydride include compounds represented by the following structural formulas (1) to (13).

  Examples of the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride include compounds represented by the following structural formulas (14) to (62).

  Examples of the silsesquioxane dianhydride derivative include compounds represented by the following structural formula (i).

  Further, examples of the tetracarboxylic dianhydride include a tetracarboxylic dianhydride having a side chain structure. Examples of the tetracarboxylic dianhydride having a side chain structure include compounds having a steroid skeleton represented by the following structural formulas (63) and (64).

  Examples of the monohydric alcohol and monohydric alcohol derivative that esterify tetracarboxylic dianhydride include methanol, ethanol, propanol, and butanol. A method of obtaining a dicarboxylic acid diester compound by esterifying tetracarboxylic dianhydride is carried out according to the method described in JP-A-61-72022.

  As the tetracarboxylic dianhydride, various other forms of tetracarboxylic dianhydride can be used as long as the intended purpose such as use of the polyimide film is achieved. .

  The polyamic acid or a derivative thereof can be produced using a known method. For example, the diamine is charged into a reaction vessel equipped with a raw material inlet, a nitrogen inlet, a thermometer, a stirrer, and a condenser, and a desired amount of monoamine is charged as necessary.

  Next, a solvent (for example, amide polar solvent such as N-methyl-2-pyrrolidone or dimethylformamide) and the tetracarboxylic dianhydride are added, and a desired amount of carboxylic acid anhydride is added as necessary. To do. At this time, it is preferable that the total charge amount of tetracarboxylic dianhydride is approximately equal to the total number of moles of diamine (molar ratio of about 0.9 to 1.1).

  A solution of polyamic acid can be suitably obtained by reacting at a temperature of 0 to 70 ° C. for 1 to 48 hours under stirring. Moreover, polyamic acid with small molecular weight can also be obtained by heating and raising reaction temperature (for example, 50-80 degreeC). The produced polyamic acid is obtained by precipitating with a large amount of a poor solvent and completely separating the solid and the solvent by filtration or the like.

  In order to adjust the obtained polyamic acid to a desired viscosity, it can be used after diluted with a solvent described later.

  The obtained polyamic acid can be separated from the solvent and re-dissolved in the solvent described later together with various additives described later, and used as a polyimide-based solution, or various additives can be used without being separated from the solvent. It can also be added and used as a polyimide-based solution.

  In the polyamic acid or derivative thereof, a part of the diamine may be replaced with a monoamine. Replacing a part of the diamine with a monoamine causes the termination of the polymerization reaction that produces the polyamic acid or its derivative and suppresses the progress of the further reaction, so the molecular weight of the resulting polyamic acid or its derivative can be easily controlled. From the viewpoint of The ratio of the monoamine to the diamine may be within a range in which the effects of the present invention can be obtained, and as a guideline, it is preferably 10 mol% or less of the total amine.

  Similarly, in the polyamic acid or derivative thereof, a part of the tetracarboxylic dianhydride may be replaced with a carboxylic acid anhydride. Replacing a part of the tetracarboxylic dianhydride with a carboxylic acid anhydride causes termination of the polymerization reaction to produce the polyamic acid or a derivative thereof, and suppresses further progress of the reaction. This is preferable from the viewpoint of easily controlling the molecular weight of the derivative. The ratio of the carboxylic acid anhydride to the tetracarboxylic dianhydride may be within a range in which the effect of the present invention can be obtained, and is preferably 10 mol% or less of the tetracarboxylic dianhydride as a guide.

  The polyamic acid ester can be obtained as a polyimide precursor from a dicarboxylic acid diester compound and a diamine. As a method for producing such a polyamic acid ester, for example, a method using carbodiimide as a condensing agent (Japanese Patent Laid-Open No. 61-72022), a method using a carbonic acid diester (Japanese Patent Laid-Open No. 62-72724), phosphorus-based Examples thereof include a method using a compound (Japanese Patent Laid-Open No. 2002-356554) and a method of heating in a phenol solvent (Japanese Patent Laid-Open No. 53-124596).

  The polyamic acid amide is, for example, by replacing a part of the tetracarboxylic dianhydride with an organic dicarboxylic acid derivative, or by replacing a part or all of the tetracarboxylic dianhydride with a tricarboxylic acid derivative. It can be obtained as a polyamic acid-polyamide copolymer. Here, the ratio of the organic dicarboxylic acid to the tetracarboxylic dianhydride may be within a range in which the effects of the present invention can be obtained, and as a guideline, it is preferably 10 mol% or less of the tetracarboxylic dianhydride. .

  Furthermore, the polyamide-imide can be obtained, for example, by chemically imidizing the polyamic acid-polyamide copolymer.

  The polyamic acid or derivative thereof can be identified by analyzing by IR or NMR. Furthermore, after decomposing solid polyamic acid or its derivatives with an aqueous solution of strong alkali such as KOH or NaOH, the monomer used is identified by extracting with an organic solvent and analyzing by GC, HPLC or GC-MS. can do.

  The film-forming polyimide component can be selected from the viewpoint of solubility in a solvent. As the film-forming polyimide component, it is preferable to use a component that is relatively easily precipitated from the polyimide solution from the viewpoint of more remarkably obtaining the effects of the present invention. For example, a polyamic acid having a structure with high linearity and having no substituent has a tendency to easily precipitate when made into a solution in a solvent not containing the compound of the formula (A). Here, the structure with high linearity is a linear structure, which means a state in which a bent structure is not included in the structure. Examples of the polyamic acid having such a specific partial structure include a structure in which the structure between two amino groups or two dicarboxylic anhydride groups does not have a substituent, and an aliphatic ring. , An aromatic ring, a condensed ring of these rings, or a structure in which two or more of these rings are bonded by a single bond, 1,2-ethylene, 1,4-butylene, etc. The compound which has the structure of the reaction product of tetracarboxylic acid or its derivative (s) is mentioned.

  For example, in the polyamic acid having the partial structure, when the partial structure is a diamine, examples of the partial structure of the diamine include the following.

  For example, in the polyamic acid having the partial structure, when the partial structure is a tetracarboxylic dianhydride, examples of the partial structure of the tetracarboxylic acid include the following.

  Examples of the diamine or derivatives thereof include the structural formulas (V-1), (VI-4), (VI-8), (VI-16), and (VI-28), and the tetracarboxylic acid or Examples of the derivatives include the structural formulas (1), (2), (10), (13), and (14).

  The film-forming polyimide component can be further selected from the viewpoint of the use of a polyimide solution or a polyimide film. For example, in the case of a polyimide-based solution for forming a liquid crystal alignment film, that is, a liquid crystal aligning agent, a film-forming polyimide component having a structure capable of obtaining desired characteristics in the liquid crystal alignment film can be selected.

  For example, in the case of a liquid crystal aligning agent, the polyamic acid or a derivative thereof is appropriately adjusted to have a pretilt angle in a liquid crystal display device by using a diamine having a side chain structure such as the side chain diamine or a tetracarboxylic dianhydride. It can be adjusted and can be applied to any kind of liquid crystal display element. As the pretilt angle, in the case of a VA liquid crystal display element, a large pretilt angle of about 80 to 90 °, and in the case of an OCB liquid crystal display element, a pretilt angle of about 7 to 20 ° is used. In the case of an STN type liquid crystal display element, a pretilt angle of about 3 to 10 ° is often required, and in the case of an IPS type liquid crystal display element, a small pretilt angle of about 0 to 3 ° is often required.

  In applications requiring a large pretilt angle, such as a VA liquid crystal display element, an OCB liquid crystal display element, a TN type liquid crystal display element, and an STN type liquid crystal display element, from the viewpoint of expressing a desired pretilt angle in the liquid crystal alignment film, The diamine or derivative thereof preferably contains a diamine having a side chain structure.

  Moreover, from the viewpoint of obtaining appropriate orientation and an appropriate pretilt angle when a liquid crystal display device is obtained, in TN, VA, and IPS, the diamine or derivative thereof preferably contains the linear diamine. The molar ratio of the linear diamine in the diamine or derivative thereof is preferably 1 to 90%, and more preferably 5 to 80%.

  Further, from the viewpoint of making the polyamic acid or derivative thereof soluble in a solvent, the tetracarboxylic acid or derivative thereof is preferably selected from the tetracarboxylic dianhydride as appropriate.

  Also in the tetracarboxylic dianhydride, from the viewpoint of increasing the pretilt angle in the liquid crystal display element, the tetracarboxylic acid or a derivative thereof preferably includes a tetracarboxylic dianhydride having a side chain structure.

  Furthermore, the tetracarboxylic dianhydride includes the aromatic tetracarboxylic dianhydride and one or both of an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride, This is preferable from the viewpoint of reducing the residual voltage in the display element.

  The characteristics expressed by the structure of the monomer of the polyamic acid or its derivative, such as the pretilt angle, can be obtained by producing the polyamic acid or its derivative using a monomer that provides such a characteristic. The characteristics of the monomer can be obtained from one kind of polyamic acid obtained by using a plurality of types of monomers that provide such characteristics, or derivatives thereof, and two types of characteristics that can be obtained by using a plurality of types of monomers that provide such characteristics. It can be obtained from more than one polyamic acid or derivative thereof.

  It is preferable that two or more kinds of polyamic acids or derivatives thereof in which some or all of the monomers are different are contained in the polyimide-based solution from the viewpoint of imparting preferable characteristics as the polyimide-based solution of the present invention. The mixing ratio of two or more kinds of polyamic acids or derivatives thereof may be such that desired characteristics corresponding to the use of the polyimide-based solution can be obtained.

  More specifically, by appropriately selecting the type of diamine or derivative thereof, tetracarboxylic acid or derivative thereof, and a combination thereof, further required reduction in residual voltage, suitable pretilt angle, etc. Desired properties can be imparted and improved.

  From the viewpoints of the use and properties of the liquid crystal aligning agent described above, more preferable linear diamines include the structural formulas (V-1) to (V-5), (VI-1) to (VI-10), ( VI-21), (VI-22), (VI-26), (VII-1), (VII-2), (VII-6), and diamines represented by (VIII-1). More preferable linear diamines include diamines represented by the structural formulas (V-1), (V-2), (VI-1) to (VI-10) and (VI-26).

  Further, from the viewpoint of the use and characteristics of the liquid crystal aligning agent described above, more preferable aromatic tetracarboxylic dianhydrides include the structural formulas (1), (2), (5), (6) and (7 ), And more preferable examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride represented by the structural formula (1).

  Furthermore, from the viewpoints of the use and properties of the liquid crystal aligning agent described above, more preferable examples of the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride include the structural formulas (14) to (29), And the compound represented by (60), and more preferable examples of the aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride include 1,2 represented by the structural formula (14). 3,4-cyclobutanetetracarboxylic dianhydride.

  Further, from the viewpoint of constituting a polyamic acid for producing a soluble polyimide, more preferable examples of the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride include the structural formulas (19) and (20 ), (27) to (29), and compounds represented by (60).

  The solvent contains a compound represented by the formula (A). The solvent may be composed only of the compound of the formula (A), but from the viewpoint of improving the solubility of the film-forming polyimide-based component and improving the desired properties based on the use of the polyimide film. A mixed solvent with other solvents is preferable. The content of the compound of the formula (A) in the solvent is preferably 1% by weight or more and more preferably 2% by weight or more from the viewpoint of obtaining the effect of smoothing the coating film of the polyimide-based solution. It is preferably 5% by weight or more. Further, the content of the compound of the formula (A) in the solvent is preferably 80% by weight or less, and preferably 70% by weight or less from the viewpoint of obtaining the effect of suppressing the deposition of the film-forming polyimide component. More preferably, it is particularly preferably 60% by weight or less.

  Among the solvents, solvents other than the compound represented by the formula (A) are used from among the solvents usually used in the production process and applications of polymer components such as polyamic acid, polyimide, and polyamideimide. It can be appropriately selected according to the purpose. Such other solvents can be used, for example, from the viewpoints of adjusting physical properties such as the viscosity of the polyimide-based solution, ease of handling, and simplification of the process. The other solvent may be one kind or two or more kinds. Examples of the other solvent include an aprotic polar organic solvent that is easily soluble in polyamic acid or a derivative thereof, and a coating property improving solvent for improving coating property by changing the surface tension. The other solvent is preferably a mixed solvent containing them.

  Examples of the aprotic polar organic solvent include N-methyl-2-pyrrolidone, N, N′-dimethylimidazolidinone, N-methylcaprolactam, N, N-dimethylpropionamide, N, N-dimethylacetamide, and dimethyl. Examples include sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N, N ′, N′-tetramethylurea, γ-butyrolactone, and γ-valerolactone. The aprotic polar organic solvent is preferably at least one selected from N-methyl-2-pyrrolidone, N, N′-dimethylimidazolidinone, γ-butyrolactone, and γ-valerolactone.

  Examples of the coating property improving solvent include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ether such as ethylene glycol monobutyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol Monoalkyl or phenyl acetate, propylene glycol monoalkyl ether such as triethylene glycol monoalkyl ether, propylene glycol monobutyl ether, dialkyl malonate such as diethyl malonate, dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether, and the like Examples include ester compounds such as acetates. The coating property improving solvent is preferably at least one selected from ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether.

  The types and ratios of the aprotic polar solvent and the coatability improving solvent can be appropriately set in consideration of the printability, coatability, solubility, storage stability, and the like of the polyimide-based solution. The aprotic polar solvent is relatively superior in solubility and storage stability to the applicability improving solvent, and the applicability improving solvent tends to be excellent in printability and applicability.

  The polyimide-based solution of the present invention may further contain components other than the film-forming polyimide-based component and the solvent described above. Examples of such other components include additives. The said additive should just be a component used in order to improve the specific property of a polyimide-type solution, and may be 1 type, or 2 or more types. Examples of the additive include high-molecular compounds and low-molecular compounds other than the film-forming polyimide-based component that are used in accordance with the respective purposes.

  The polymer compound is preferably a polymer compound that is soluble in the solvent from the viewpoint of controlling the electrical properties and orientation of a liquid crystal alignment film formed from a polyimide-based solution. Examples of such a polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

  Examples of the low molecular weight compound include surfactants, antistatic agents, silane coupling agents, titanium-based coupling agents, and imidization catalysts. The surfactant is preferable from the viewpoint of improving the applicability of the polyimide-based solution. The antistatic agent is preferable from the viewpoint of improving the antistatic property of the polyimide-based solution and the liquid crystal alignment film formed therefrom. A silane coupling agent and a titanium-based coupling agent are preferable from the viewpoint of improving adhesion and rubbing resistance of the liquid crystal alignment film formed from the polyimide-based solution to the substrate. The imidization catalyst is preferable from the viewpoint of proceeding imidization at a low temperature in the formation of the liquid crystal alignment film from the polyimide-based solution.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3-aminopropylmethyl. Trimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloro Propyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N , N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine.

  Examples of the imidization catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline. And cyclic amines such as pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, and hydroxy-substituted imidazole. . The imidation catalyst is preferably one or more selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline.

  The addition amount of the silane coupling agent is usually 0 to 30 parts by weight and preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the film-forming polyimide component.

  The amount of the imidation catalyst added is usually 0 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the film forming polyimide component.

  The addition amount of other additives varies depending on the application, but is usually 0 to 30 parts by weight, and 0.1 to 20 parts by weight with respect to 100 parts by weight of the film-forming polyimide component. preferable.

  When the polyimide-based solution of the present invention is used for forming a liquid crystal alignment film, that is, when it is a liquid crystal alignment agent, a component that improves the characteristics of the liquid crystal alignment film is used for the additive. be able to. For example, the polyimide-based solution of the present invention may further contain an alkenyl-substituted nadiimide compound from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element over a long period of time. The alkenyl-substituted nadiimide compound may be a single compound or two or more compounds. From the above viewpoint, the content of the alkenyl-substituted nadiimide compound is preferably 0.01 to 1.00 as a weight ratio with respect to the film forming polyimide component in the polyimide solution, and 0.01 to 0.70. It is more preferable that it is 0.01 to 0.50.

  The alkenyl-substituted nadiimide compound is preferably a compound that can be dissolved in the solvent. Examples of such alkenyl-substituted nadiimide compounds include compounds represented by the following general formula (Ina).

In the general formula (Ina), L ¹ and L ² each independently represent hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl or benzyl. , N represents 1 or 2.

When n = 1, W is alkyl of 1 to 12 carbon atoms, alkenyl having 2 to 6 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, having 6 to 12 carbon atoms aryl, benzyl, -Z ¹ - (O) _{^{q - (Z 2 O) r}} -Z 3 -H (Z 1, Z 2 and Z ³ each independently represents an alkylene having 2 to 6 carbon atoms, q represents 0 or 1, and r is 1 -(Z ⁴ ) _s -BZ ⁵ -H (wherein Z ⁴ and Z ⁵ are each an alkylene having 1 to 4 carbon atoms or a cycloalkylene having 5 to 8 carbon atoms, each represents an integer of 30). , B represents phenylene, and s represents 0 or 1,) -B-T-B-H (B represents phenylene, and T represents —CH ₂ —, —C _{(CH 3) 2 -, -} O -, - CO -, - S- or SO ₂ -. a group represented by representative), or 1 to 3 hydrogens of these groups It represents a substituted group with an acid group.

  At this time, preferable W is alkyl having 1 to 8 carbons, alkenyl having 3 to 4 carbons, cyclohexyl, phenyl, benzyl, poly (ethyleneoxy) ethyl having 4 to 10 carbons, phenyloxyphenyl, phenylmethylphenyl, Phenyl isopropylidene phenyl and groups in which one or two hydrogens of these groups are replaced by hydroxyl groups.

Formula when n = 2 in (Ina), W is an alkylene of 2 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, arylene having 6 to 12 carbon ^{atoms, -Z 1 -O- (Z 2 O} ) a group represented by _r— Z ³ — (the meanings of Z ^{1 to} Z ³ and r are as described above), —Z ⁴ —B—Z ⁵ — (the meanings of Z ⁴ , Z ⁵ and B are are as described above. groups represented by), -B- (O-B) s -T- (B-O) s -B- (B represents a phenylene, T is alkylene of 1 to 3 carbon atoms , -O- or -SO ₂ - represents, s represents a group represented by, or one to three hydrogen is replaced with a hydroxyl group of these groups represent) 0 or 1..

In this case, preferable W is alkylene having 2 to 12 carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, —C ₃ H ₆ —O— (Z ² —O) _r —O—C ₃ H ₆ — (Z ² is A group independently represented by alkylene having 2 to 6 carbon atoms, r represents 1 or 2, and -B-T-B- (B represents phenylene, and T represents -CH ₂ -,- O— or —SO ₂ —), a group represented by —B—O—B—C ₃ H ₆ —B—O—B— (B represents phenylene), and these A group in which one or two hydrogens of a group are replaced by a hydroxyl group.

  Such an alkenyl-substituted nadiimide compound, as described in, for example, Japanese Patent No. 2729565, holds an alkenyl-substituted nadic acid anhydride derivative and a diamine at a temperature of 80 to 220 ° C. for 0.5 to 20 hours. A compound obtained by synthesis by the method or a commercially available compound can be used. Specific examples of the alkenyl-substituted nadiimide compound include the following compounds.

  N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-methallylmethylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,

  N- (2-ethylhexyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-allylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-methallylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl- Allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboxyl N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-cyclohexyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-phenyl-allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide,

  N-phenyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-methallylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (2-hydroxyethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2- Hydroxyethyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-hydroxyethyl) -methallylbicyclo [2.2.1] hept -5-ene- , 3-dicarboximide,

  N- (2,2-dimethyl-3-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2,2-dimethyl-3-hydroxy Propyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2,3-dihydroxypropyl) -allylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (2,3-dihydroxypropyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-hydroxy-1-propenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxycyclohexyl) -allyl (methyl) bicycle [2.2.1] hept-5-ene-2,3-dicarboximide,

  N- (4-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxyphenyl) -allyl (methyl) bicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxyphenyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-hydroxyphenyl) -allylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide, N- (3-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide , -(P-hydroxybenzyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (2-hydroxyethoxy) ethyl} -allylbicyclo [2. 2.1] hept-5-ene-2,3-dicarboximide,

  N- {2- (2-hydroxyethoxy) ethyl} -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (2-hydroxyethoxy) ) Ethyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (2-hydroxyethoxy) ethyl} -methallylmethylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- 2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {4- (4-hydroxyphenyl) Isopropylidene) phenyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -allyl (methyl) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide and oligomers thereof,

  N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene Bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5- Ene-2,3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′— Cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

  1,2-bis {3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethane, 1,2-bis {3 ′-(allylmethylbicyclo) [2.2.1] Hept-5-ene-2,3-dicarboximido) propoxy} ethane, 1,2-bis {3 ′-(methallylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximido) propoxy} ethane, bis [2 '-{3'-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] Ether, bis [2 ′-{3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether, 1,4-bis {3 ′ -(Allylbicyclo [2.2.1] he To-5-ene-2,3-dicarboximido) propoxy} butane, 1,4-bis {3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido) propoxy} butane,

  N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide),

  2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- {4- (methallylbicyclo [2] 2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,

  Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4 -(Ant Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} sulfone,

  Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, 1,6-bis (allylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide) -3-hydroxy-hexane, 1,12-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)- 3,6-dihydroxy-dodecane, 1,3-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-cyclohexane, 1,5-bis { 3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} -3-hydroxy-pentane, 1,4-bis (allylbicyclo [2.2.1 ] Hept-5-ene 2,3-dicarboximide) -2-hydroxy - benzene,

  1,4-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2,5-dihydroxy-benzene, N, N′-p- (2-hydroxy ) Xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p- (2-hydroxy) xylylene-bis (allylmethylcyclo [2] 2.1] hept-5-ene-2,3-dicarboximide), N, N′-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide), N, N'-m- (2-hydroxy) xylylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) , N, N′-p- (2,3-dihi Proxy) xylylene - bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

  2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) -2-hydroxy-phenoxy} phenyl] propane, bis {4- (Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2-hydroxy-phenyl} methane, bis {3- (allylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide) -4-hydroxy-phenyl} ether, bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-phenyl} sulfone, 1,1,1-tri {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)} phenoxymethylpropane, N , N , N "- tri (ethylene methallyl ruby [2.2.1] hept-5-ene-2,3-dicarboximide) isocyanurate, and the like of these oligomers.

  Furthermore, the alkenyl-substituted nadiimide compound used in the present invention may be a compound represented by the following structural formula containing an asymmetric alkylene / phenylene group.

Among the alkenyl-substituted nadiimide compounds, preferred compounds are shown below.
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene-bis (a) Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-cyclohexylene- Bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

  N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide), 2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane 2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4 -{4- (methallylbicyclo 2.2.1] Hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3- Dicarboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,

  Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4 -(Ant Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-Dicarboximido) phenyl} sulfone.

Further preferred alkenyl-substituted nadiimide compounds are shown below.
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene-bis (a) Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-cyclohexylene- Bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

  N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide),

  2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- {4- (methallylbicyclo [2] 2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylbicyclo [2] 2.1] Hept 5-ene-2,3-dicarboximide) phenyl} methane, bis {4- (methallyl methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} methane.

  As a particularly preferred alkenyl-substituted nadiimide compound, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy represented by the following structural formula (Ina-1) Imido) phenyl} methane, N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide represented by the structural formula (Ina-2) And N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the structural formula (Ina-3). .

  For example, the polyimide-based solution as the liquid crystal aligning agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond from the viewpoint of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The compound having a radical polymerizable unsaturated double bond may be a single compound or two or more compounds. The compound having a radically polymerizable unsaturated double bond does not include the alkenyl-substituted nadiimide compound. From the above viewpoint, the content of the compound having a radical polymerizable unsaturated double bond is preferably 0.01 to 1.00 as a weight ratio with respect to the film-forming polyimide component, and 0.01 to 0 .70 is more preferable, and 0.01 to 0.50 is still more preferable.

  The ratio of the compound having a radical polymerizable unsaturated double bond to the alkenyl-substituted nadiimide compound is from the viewpoint of reducing the ion density of the liquid crystal display element, suppressing the increase in ion density over time, and further suppressing the afterimage. The weight ratio is preferably 0.1 to 10, and more preferably 0.5 to 5.

  Examples of the compound having a radical polymerizable unsaturated double bond include (meth) acrylic acid esters, (meth) acrylic acid derivatives such as (meth) acrylic acid amide, and bismaleimide. The compound having a radically polymerizable unsaturated double bond is more preferably a (meth) acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

  Specific examples of the (meth) acrylic acid ester include, for example, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Examples include oxyethyl, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

Specific examples of the bifunctional (meth) acrylic acid ester include, for example, ethylene bisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200, which are products of Toa Synthetic Chemical Industry, Nippon Kayaku Co., Ltd. ) Products KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD
R-684, Osaka Organic Chemicals Co., Ltd. products V260, V312 and V335HP, and Kyoeisha Oil Chemical Co., Ltd. products Light acrylate BA-4EA, Light acrylate BP-4PA and Light acrylate BP-2PA Is mentioned.

  Specific examples of the trifunctional or higher polyfunctional (meth) acrylic acid ester include, for example, 4,4′-methylenebis (N, N-dihydroxyethylene acrylate aniline), Aronix M-400, Aronix M-405, Aronix M-450. , Aronix M-7100, Aronix M-8030, Aronix M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and Osaka Organic Chemical Co., Ltd. There is a certain VGPT.

  Specific examples of the (meth) acrylic acid amide derivative include, for example, N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropyl. Methacrylamide, N-ethoxyethylacrylamide, N-ethoxyethylmethacrylamide, N-tetrahydrofurfurylacrylamide, N-tetrahydrofurfurylmethacrylamide, N-ethylacrylamide, N-ethyl-N-methylacrylamide, N, N-diethyl Acrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acryloylpyrrolidine, N, N′-me Renbisacrylamide, N, N′-ethylenebisacrylamide, N, N′-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N- (iso -Butoxymethyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethylmethacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- ( Methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N′-methylenebismethacrylamide.

  Among the above (meth) acrylic acid derivatives, N, N′-methylenebisacrylamide, N, N′-dihydroxyethylene-bisacrylamide, ethylenebisacrylate, and 4,4′-methylenebis (N, N-dihydroxyethyleneacrylate) Aniline) is particularly preferred.

  Examples of the bismaleimide include BMI-70 and BMI-80 manufactured by Kay Kasei Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI- manufactured by Daiwa Kasei Kogyo Co., Ltd. 7000.

  Further, for example, the polyimide-based solution as the liquid crystal aligning agent of the present invention may further contain an oxazine compound from the viewpoint of long-term stability of electrical characteristics in the liquid crystal display element. The oxazine compound may be a kind of compound or two or more kinds of compounds. From the above viewpoint, the content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight with respect to the film-forming polyimide component, More preferably, it is 20% by weight.

  The oxazine compound is soluble in the solvent, and in addition, an oxazine compound having ring-opening polymerizability is preferable.

  Further, the number of oxazine structures in the oxazine compound is not particularly limited.

  Various structures are known for the structure of oxazine. In the present invention, the structure of oxazine is not particularly limited, and examples of the oxazine structure in the oxazine compound include an oxazine structure having an aromatic group containing a condensed polycyclic aromatic group such as benzoxazine and naphthoxazine.

  Examples of the oxazine compound include compounds represented by the following general formulas (a) to (f). In the following general formula, the bond displayed toward the center of the ring indicates that it is bonded to any carbon that forms the ring and can be bonded to a substituent.

In the general formulas (a) to (c), R ¹ and R ² each represent an organic group having 1 to 30 carbon atoms. Moreover, in said general formula (a)-(f), R < ³ > -R < ⁶ > represents hydrogen or a C1-C6 hydrocarbon group, respectively. In the general formulas (c), (d), and (f), X represents a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, — (CH ₂ ) _m —, —O— (CH ₂ ) _m —O—, or —S— (CH ₂ ). _m represents -S-. Here, m is an integer of 1-6. In the general formulas (e) and (f), Y is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) _2. -Or C1-C3 alkylene is represented. The benzene ring of the Y, hydrogen bonded to the naphthalene ring, -F _{independently, -CH 3, -OH, -COOH,} -SO 3 H, may be replaced with -PO ₃ H _2.

  The oxazine compound includes an oligomer or polymer having an oxazine structure in the side chain, and an oligomer or polymer having an oxazine structure in the main chain.

  Examples of the oxazine compound represented by the general formula (a) include the following oxazine compounds.

In the formula, R ¹ is preferably alkyl having 1 to 30 carbons, and more preferably alkyl having 1 to 20 carbons.

  Examples of the oxazine compound represented by the general formula (b) include the following oxazine compounds.

In the formula, R ¹ is independently preferably an alkyl having 1 to 30 carbon atoms, more preferably an alkyl having 1 to 20 carbon atoms.

  Examples of the oxazine compound represented by the general formula (c) include an oxazine compound represented by the following general formula (I).

In the general formula (I), R ¹ and R ² each represents an organic group having 1 to 30 carbon atoms, R ^{3 to} R ⁶ each represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and X represents a single group. It represents a bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—, —SO ₂ — or —C (CF ₃ ) ₂ —. Examples of the oxazine compound represented by the general formula (I) include the following oxazine compounds.

In the formula, R ¹ is independently preferably an alkyl having 1 to 30 carbon atoms, more preferably an alkyl having 1 to 20 carbon atoms.

  Examples of the oxazine compound represented by the general formula (d) include the following oxazine compounds.

  Examples of the oxazine compound represented by the general formula (e) include the following oxazine compounds.

  Examples of the oxazine compound represented by the general formula (f) include the following oxazine compounds.

  Of these, more preferably, the formula (b-1), the formula (c-1), the formula (c-3), the formula (c-5), the formula (c-7), the formula (c-9), Oxazine compounds represented by formula (d-1) to formula (d-6), formula (e-3), formula (e-4), and formula (f-2) to formula (f-4) can be given. .

  The oxazine compound can be produced by the same method as described in International Publication No. 2004/009708, JP-A-11-12258, and JP-A-2004-352670.

  For example, the oxazine compound represented by the general formula (a) is obtained by reacting a phenol compound, a primary amine, and an aldehyde (see International Publication No. 2004/009708 pamphlet).

  The oxazine compound represented by the general formula (b) is obtained by reacting by adding a primary amine to formaldehyde gradually, and then adding and reacting a compound having a naphthol-based hydroxyl group (International Publication 2004 / 009708 pamphlet).

  The oxazine compound represented by the general formula (c) is a secondary aliphatic compound in which an organic solvent contains 1 mole of a phenol compound, at least 2 moles of aldehyde, and 1 mole of primary amine per 1 phenolic hydroxyl group. It can be obtained by reacting in the presence of an amine, a tertiary aliphatic amine, or a basic nitrogen-containing heterocyclic compound (see International Publication No. 2004/009708 and JP-A-11-12258).

  The oxazine compounds represented by the general formulas (d) to (f) are diamines such as 4,4′-diaminodiphenylmethane, diamines having a plurality of benzene rings and an organic group that binds them, aldehydes such as formalin, and the like. It can be obtained by dehydrating and condensing phenol in n-butanol at a temperature of 90 ° C. or higher (see JP 2004-352670 A).

  Further, for example, the polyimide-based solution as the liquid crystal aligning agent of the present invention may further contain an oxazoline compound from the viewpoint of long-term stability of electrical characteristics in the liquid crystal display element. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be a kind of compound or two or more kinds of compounds. From the above viewpoint, the content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 40% by weight. It is preferably 20% by weight. Alternatively, the content of the oxazoline compound is 0.1 to 40% by weight based on the film-forming polyimide component when the oxazoline structure in the oxazoline compound is converted to oxazoline, from the above viewpoint. preferable.

  The oxazoline compound may have only one oxazoline structure in one compound, or may have two or more kinds. Moreover, the said oxazoline compound should just have one said oxazoline structure in one compound, but it is preferable to have 2 or more. The oxazoline compound may be a polymer having an oxazoline ring structure in the side chain, or may be a copolymer. The polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in the side chain, or a copolymer of a monomer having an oxazoline structure in the side chain and a monomer having no oxazoline structure It may be. The copolymer having an oxazoline structure in the side chain may be a copolymer of two or more monomers having an oxazoline structure in the side chain, or two or more monomers having an oxazoline structure in the side chain and an oxazoline structure It may also be a copolymer with a monomer that does not have.

  The oxazoline structure is preferably a structure present in the oxazoline compound so that one or both of oxygen and nitrogen in the oxazoline structure can react with the carbonyl group of the polyamic acid.

  Examples of the oxazoline compound include 2,2′-bis (2-oxazoline), 1,2,4-tris- (2-oxazolinyl-2) -benzene, 4-furan-2-ylmethylene-2-phenyl-4H. -Oxazol-5-one, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 2,3-bis (4 -Isopropenyl-2-oxazolin-2-yl) butane, 2,2′-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl-2-oxazolin-2-yl) pyridine, 2,2 '-Isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl-2-oxazoline), 2,2'-methyle Bis (4-tert-butyl-2-oxazoline), and 2,2'-methylenebis (4-phenyl-2-oxazoline) and the like. In addition to these, polymers and oligomers having oxazolyl such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.) are also included.

  Further, for example, the polyimide-based solution as the liquid crystal aligning agent of the present invention may further contain an epoxy compound from the viewpoint of long-term stability of electrical characteristics in the liquid crystal display element. The epoxy compound may be a kind of compound or two or more kinds of compounds. From the above viewpoint, the content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight with respect to the film-forming polyimide component, More preferably, it is 20% by weight.

  Examples of the epoxy compound include various compounds having one or more epoxy rings in the molecule. Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, N-glycidyl phthalimide, (Nonafluoro-N-butyl) epoxide, perfluoroethylglycidyl ether, epichlorohydrin, epibromohydrin, N, N-diglycidylaniline, and 3- [2- (perfluorohexyl) ethoxy] -1,2 -Epoxy propane.

  Examples of the compound having two or more epoxy rings in the molecule include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic Type epoxy compounds.

  Examples of the glycidyl ether include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol type epoxy compounds, hydrogenated bisphenol-A type epoxy compounds, hydrogenated bisphenol-F type epoxy compounds, and hydrogenated compounds. Bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, phenol novolac type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolak type epoxy Compounds, brominated cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, naphthalene skeleton-containing epoxy compounds, aromatic Polyglycidyl ether compounds, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compounds, aliphatic polyglycidyl ether compound, a polysulfide-type diglycidyl ether compound, and biphenol type epoxy compound.

  Examples of the glycidyl ester include diglycidyl ester compounds and glycidyl ester epoxy compounds.

  Examples of the glycidylamine include polyglycidylamine compounds and glycidylamine type epoxy resins.

  Examples of the epoxy group-containing acrylic compound include homopolymers and copolymers of monomers having oxiranyl.

  Examples of the glycidyl amide include glycidyl amide type epoxy compounds.

  Examples of the chain aliphatic epoxy compound include a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of an alkene compound.

  Examples of the cycloaliphatic epoxy compound include a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound.

  Examples of the bisphenol A type epoxy compound include 828, 1001, 1002, 1003, 1004, 1007, 1010 (all manufactured by Mitsubishi Chemical Corporation), Epototo YD-128 (manufactured by Nippon Steel Chemical Co., Ltd.), DER. -331, DER-332, DER-324 (all manufactured by Dow Chemical Co.), Epicron 840, Epicron 850, Epicron 1050 (all manufactured by DIC Corporation), Epomic R-140, Epomic R-301, and Epomic R-304 (both manufactured by Mitsui Chemicals, Inc.) can be mentioned.

  Examples of the bisphenol F type epoxy compound include 806, 807, 4004P (all manufactured by Mitsubishi Chemical Corporation), Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001 (all Nippon Steel Chemical Co., Ltd.) Product), DER-354 (manufactured by Dow Chemical Co.), Epicron 830, and Epicron 835 (all manufactured by DIC Corporation).

  Examples of the bisphenol type epoxy compound include epoxidized products of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

  Examples of the hydrogenated bisphenol-A type epoxy compound include Santoto ST-3000 (manufactured by Nippon Steel Chemical Co., Ltd.), Rica Resin HBE-100 (manufactured by Shin Nippon Rika Co., Ltd.), and Denacol EX-252 (Nagase Chem) Tex Co., Ltd.).

  Examples of the hydrogenated bisphenol type epoxy compound include epoxidized products of hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

  Examples of the brominated bisphenol-A type epoxy compound include 5050, 5051 (all manufactured by Mitsubishi Chemical Corporation), Epototo YDB-360, Epototo YDB-400 (all manufactured by Nippon Steel Chemical Co., Ltd.), DER. -530, DER-538 (all manufactured by Dow Chemical Company), Epicron 152, and Epicron 153 (all manufactured by DIC Corporation).

  Examples of the phenol novolac type epoxy compound include 152, 154 (all manufactured by Mitsubishi Chemical Corporation), YDPN-638 (manufactured by Nippon Steel Chemical Co., Ltd.), DEN431, DEN438 (all manufactured by Dow Chemical Co., Ltd.). , Epicron N-770 (manufactured by DIC Corporation), EPPN-201, and EPPN-202 (all manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the cresol novolac type epoxy compound include 180S75 (manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all manufactured by Nippon Steel Chemical Co., Ltd.), Epicron N-665, and Epicron N-695 ( DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the bisphenol A novolac type epoxy compound include 157S70 (manufactured by Mitsubishi Chemical Corporation) and Epicron N-880 (manufactured by DIC Corporation).

  Examples of the naphthalene skeleton-containing epoxy compound include Epicron HP-4032, Epicron HP-4700, Epicron HP-4770 (all manufactured by DIC Corporation), and NC-7000 (manufactured by Nippon Kayaku Co., Ltd.). .

  Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (the following structural formula 101), catechol diglycidyl ether (the following structural formula 102), resorcinol diglycidyl ether (the following structural formula 103), 2- [4- (2 , 3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane (Structural Formula 104 below), Tris (4 -Glycidyloxyphenyl) methane (the following structural formula 105), 1031S, 1032H60 (all manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), Denacol EX-201 (manufactured by Nagase ChemteX Corporation) ), DPPN-503, DPPN-502H, DPPN-501H NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), (manufactured by Mitsui Chemicals, Inc.) Techmore VG3101L, a compound represented by the following structural formula 106, and compounds represented by the following structural formula 107.

  Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (manufactured by Dow Chemical Co.) and Epicron HP-7200 (manufactured by DIC Corporation).

  Examples of the alicyclic diglycidyl ether compound include cyclohexane dimethanol diglycidyl ether compound and licarresin DME-100 (manufactured by Shin Nippon Rika Co., Ltd.).

  Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (the following structural formula 108), diethylene glycol diglycidyl ether (the following structural formula 109), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (the following structural formula 110). ), Tripropylene glycol diglycidyl ether (the following structural formula 111), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (the following structural formula 112), 1,4-butanediol diglycidyl ether (the following structural formula 113), 1,6-hexanediol diglycidyl ether (the following structural formula 114), dibromoneopentyl glycol diglycidyl ether (the following structural formula 115), Denaco EX-810, Denacol EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX-313 (all Nagase ChemteX Co., Ltd.), DD-503 (manufactured by ADEKA Co., Ltd.), Rica Resin W-100 (manufactured by Shin Nippon Rika Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4-hexanediol (below) Structural formula 116), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321, and Denacol EX-41 (Both manufactured by Nagase Chemtex Co., Ltd.) and the like.

  Examples of the polysulfide-type diglycidyl ether compound include FLEP-50 and FLEP-60 (both manufactured by Toray Fine Chemical Co., Ltd.).

  Examples of the biphenol type epoxy compound include YX-4000, YL-6121H (all manufactured by Mitsubishi Chemical Corporation), NC-3000P, and NC-3000S (all manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the diglycidyl ester compound include diglycidyl terephthalate (the following structural formula 117), diglycidyl phthalate (the following structural formula 118), bis (2-methyloxiranylmethyl) phthalate (the following structural formula 119), and diglycidyl hexa. Examples include hydrophthalate (the following structural formula 120), a compound represented by the following structural formula 121, a compound represented by the following structural formula 122, and a compound represented by the following structural formula 123.

  Examples of the glycidyl ester epoxy compound include 871, 872 (all manufactured by Mitsubishi Chemical Corporation), Epicron 200, Epicron 400 (all manufactured by DIC Corporation), Denacol EX-711, and Denacol EX-721 (all Also manufactured by Nagase ChemteX Corporation).

  Examples of the polyglycidylamine compound include N, N-diglycidylaniline (the following structural formula 124), N, N-diglycidyl-o-toluidine (the following structural formula 125), N, N-diglycidyl-m-toluidine (the following). Structural formula 126), N, N-diglycidyl-2,4,6-tribromoaniline (the following structural formula 127), 3- (N, N-diglycidyl) aminopropyltrimethoxysilane (the following structural formula 128), N, N, O-triglycidyl-p-aminophenol (the following structural formula 129), N, N, O-triglycidyl-m-aminophenol (the following structural formula 130), N, N, N ′, N′-tetraglycidyl -4,4'-diaminodiphenylmethane (the following structural formula 131), N, N, N ', N'-tetraglycidyl-m-xylylenediamine (T TRAD-X (Mitsubishi Gas Chemical Co., Ltd.), the following structural formula 132), 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.)), the following structural formula 133), 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane (the following structural formula 134), 1,3-bis (N, N-diglycidylamino) cyclohexane (the following structural formula 135), 1, 4-bis (N, N-diglycidylamino) cyclohexane (the following structural formula 136), 1,3-bis (N, N-diglycidylamino) benzene (the following structural formula 137), 1,4-bis (N, N-diglycidylamino) benzene (the following structural formula 138), 2,6-bis (N, N-diglycidylaminomethyl) bicyclo [2.2.1] heptane (the following structural formula 139), , N, N ′, N′-tetraglycidyl-4,4′-diaminodicyclohexylmethane (the following structural formula 140), 2,2′-dimethyl- (N, N, N ′, N′-tetraglycidyl) -4 , 4′-diaminobiphenyl (the following structural formula 141), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenyl ether (the following structural formula 142), 1,3,5-tris (4- (N, N-diglycidyl) aminophenoxy) benzene (the following structural formula 143), 2,4,4′-tris (N, N-diglycidylamino) diphenyl ether (the following structural formula 144), tris (4- (N, N-diglycidyl) aminophenyl) methane (the following structural formula 145), 3,4,3 ′, 4′-tetrakis (N, N-diglycidylamino) biphenyl (the following structural formula 146), 3 , 4,3 ′, 4′-tetrakis (N, N-diglycidylamino) diphenyl ether (the following structural formula 147), a compound represented by the following structural formula 148, and a compound represented by the following structural formula 149. .

  Examples of the homopolymer of the monomer having oxiranyl include polyglycidyl methacrylate. Examples of the copolymer of monomers having oxiranyl include, for example, N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer. Examples include polymers, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymers, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymers, and styrene-glycidyl methacrylate copolymers.

  Examples of the monomer having oxiranyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

  Examples of the monomer other than the oxiranyl-containing monomer in the oxiranyl-containing monomer copolymer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl ( (Meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Examples include styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

  Examples of the glycidyl isocyanurate include 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (the following structural formula 150), 1,3. -Diglycidyl-5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (the following structural formula 151), and glycidyl isocyanurate type epoxy resin.

  Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and epolide PB3600 (manufactured by Daicel Chemical Industries, Ltd.).

  Examples of the cycloaliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd.), the following structural formula 152), 2 -Methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (the following structural formula 153), 2,3-epoxycyclopentane-2', 3'-epoxycyclopentane Ether (the following structural formula 154), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2: 8,9-diepoxy limonene (Celoxide 3000 (Daicel Chemical Industries ( Co., Ltd.), structural formula 155), structural formula 56, CY-175, CY-177, CY-179 (all manufactured by CIBA-GEIGY), EHPD-3150 (manufactured by Daicel Chemical Industries), and a cyclic aliphatic epoxy resin. It is done.

  The epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A novolac epoxy compound, a cresol novolac epoxy compound, and a cyclic aliphatic epoxy compound, and N, N, N ′, N′-tetra Glycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolak Type epoxy compounds and It is preferably one or more of sol novolak type epoxy compounds.

  Among these examples, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′— Tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L”, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate and N-phenylmaleimide-glycidyl methacrylate copolymer are particularly preferred preferable.

  Further, for example, the polyimide-based solution of the present invention is within the range in which the effects of the present invention can be obtained (preferably within 20% by weight of the film-forming polyimide-based component), and other polymers such as acrylic acid polymer and acrylate polymer It may further contain components.

  Furthermore, the polyimide-based solution of the present invention can be prepared so as to have characteristics according to its use. For example, when the use of the polyimide solution is a liquid crystal aligning agent for forming a liquid crystal alignment film, the content of the film forming polyimide component in the polyimide solution of the present invention is the method of applying the polyimide solution to the substrate. Can also be selected. For example, a polyimide-based solution (liquid crystal aligning agent) used in a printing machine (including an offset printing machine and an inkjet printing machine, hereinafter may be abbreviated as “printing machine”) used in a manufacturing process of a normal liquid crystal display element. ), The content of the film-forming polyimide-based component is preferably 0.5 to 30% by weight, and more preferably 1 to 15% by weight. The content of the film forming polyimide component can be adjusted as appropriate in relation to the viscosity of the polyimide solution described later.

  The viscosity of the polyimide-based solution of the present invention varies widely depending on the coating method, the content of the film-forming polyimide-based component, the type of film-forming polyimide-based component used, and the type and ratio of the solvent. For example, in the case of application by a printing press, the viscosity of the polyimide-based solution is preferably 5 to 100 mPa · s, and more preferably 10 to 80 mPa · s. The viscosity of the polyimide solution is preferably 5 mPa · s or more from the viewpoint of obtaining a sufficient film thickness of the liquid crystal alignment film, and the viscosity of the polyimide solution is 100 mPa · s or less is a liquid crystal having a uniform film thickness. It is preferable from the viewpoint of obtaining an alignment agent. In the case of application by spin coating, the viscosity of the polyimide-based solution is preferably 5 to 200 mPa · s, and more preferably 10 to 100 mPa · s.

  The viscosity of the polyimide solution is measured by a rotational viscosity measurement method, and is measured (measurement temperature: 25 ° C.) using, for example, a rotational viscometer (TVE-20L type manufactured by Toki Sangyo Co., Ltd.).

  The polyimide-based solution of the present invention is a method for producing a polyimide-based solution that includes obtaining a solution in which the film-forming polyimide-based component is dissolved in a solvent that dissolves the film-forming polyimide-based component. It can manufacture by using the compound represented by these. For example, the polyimide-based solution of the present invention can be produced by dissolving the film-forming polyimide-based component in the compound of the formula (A), or the solvent in a solvent other than the compound of the formula (A). It can be produced by dissolving a film forming polyimide component and adding the compound of the formula (A) to the obtained solution, or a mixed solvent of the compound of the formula (A) and another solvent. Can be produced by dissolving the film-forming polyimide-based component in the solvent, or by forming the film-forming polyimide-based component by reaction in a solvent other than the compound of the formula (A). The reaction product solution can be prepared by adding the compound of the formula (A). The polyimide-based solution of the present invention can be used for a normal application of a solution containing a film-forming polyimide-based component such as a liquid crystal aligning agent by adding other components depending on the application and adjusting the physical properties. Can do.

  For example, the polyimide-based solution of the present invention includes a colorant, mineral oil, filler, elastomer, antioxidant, stabilizer, antifoaming agent, extender, plasticizer, catalyst, pigment, pigment paste, reinforcing material as necessary. By adding known additives according to the use of the polyimide-based solution, such as flow control agents, leveling agents, thickening agents, flame retardants, curing agents, curable compounds, and other resins , A coating material, an insulating material, an adhesive, a sealing material, a printed wiring board material, or a molding material. Examples of other resins include polyamide and polyimide. Examples of the coating material include coating agents such as paints, printing inks, surfaces, and protective materials. Moreover, as a molding material, the material for FRP (fiber reinforced plastic) is mentioned, for example.

  The content of the film-forming polyimide component in the polyimide-based solution of the present invention for the above uses is 0.5 to 70% by weight based on the total amount of the polyimide-based solution, although it varies depending on each use. Is preferably 0.5 to 50% by weight from the viewpoint of workability. The polyimide-based solution of the present invention for the above-mentioned use is prepared by using a solution of a film-forming polyimide-based component and the solvent as a raw material, adding the additive, and then performing an appropriate mixing operation such as stirring and kneading. Can be obtained.

  The polyimide film of the present invention can be formed by an ordinary method of forming a polyimide film from such a coating film, except that the polyimide-based solution of the present invention is used as the coating film forming solution. That is, the polyimide film of the present invention includes a step of forming a coating film of a polyimide-based solution containing the film-forming polyimide-based component and a solvent for dissolving the film-forming polyimide component, and firing the formed coating film. In the method for producing a polyimide film including a step of forming a polyimide film comprising a film-forming polyimide-based component, the compound represented by the formula (A) is used as the solvent. The polyimide film of the present invention can be used for a normal use of a polyimide film formed by baking a coating film of a solution such as a liquid crystal alignment film by using an appropriate polyimide-based solution according to the use.

  For example, the liquid crystal alignment film of the present invention is formed by baking a coating film of the polyimide-based solution (liquid crystal alignment agent) of the present invention described above. Formation of the coating film of the polyimide-based solution and its baking can be performed by a usual method in a photoresist.

  The said liquid crystal aligning film apply | coats the polyimide-type solution of this invention to the board | substrate for liquid crystal display elements, or the measurement board | substrates, such as a calcium fluoride and silicon | silicone, for example, The coating film of this polyimide-type solution is 150-400 degreeC, for example. Preferably, it can be formed by heating to 180 to 280 ° C. Here, the film thickness of the liquid crystal alignment film is preferably 10 to 300 nm, and more preferably 30 to 100 nm. In addition, the liquid crystal alignment film is preferably rubbed when it is used for a horizontal electric field type liquid crystal display element such as an IPS liquid crystal display element.

  The film thickness of the liquid crystal alignment film can be adjusted by the viscosity of the polyimide solution or the application method of the polyimide solution. The film thickness of the liquid crystal alignment film can be measured by a known film thickness measuring device such as a step meter or an ellipsometer. Furthermore, the components in the liquid crystal alignment film can be analyzed using a normal analysis means such as IR or MS after performing a treatment such as hydrolysis as necessary. For example, “Performance improvement of polybenzoxazine by alloying with polyimide: effect of preparation method on the properties” (Tsutomu Takeichi et al., Polymer, 2005, 46, p.4909-4916).

  The liquid crystal display element of the present invention includes a pair of opposed substrates, electrodes formed on one or both of the opposed surfaces of the pair of substrates, and the pair of substrates facing each other. And a liquid crystal layer formed between the pair of substrates.

  The pair of substrates with electrodes arranged opposite to each other is preferably a transparent substrate (for example, a glass substrate).

  An electrode is provided on the surface of at least one or both of the pair of substrates according to the form of the liquid crystal display element. The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such electrodes include ITO and metal vapor deposition films. The electrode may be formed on the entire surface of the substrate, or may be formed in a predetermined shape that is patterned, for example. Further, the electrode may be provided on only one of the pair of substrates, or may be provided on both. For example, the liquid crystal alignment film of the present invention is formed on the surface of the substrate on which the electrode is not provided, and the liquid crystal alignment film of the present invention is formed on the electrode on the substrate on which the electrode is provided. The formation of the liquid crystal alignment film of the present invention is as described above.

  The liquid crystal layer sandwiched between the pair of substrates includes a liquid crystal composition. Here, the liquid crystal composition is not particularly limited, and either a liquid crystal composition having a positive dielectric anisotropy or a liquid crystal composition having a negative dielectric anisotropy may be used depending on the driving mode. it can.

  Examples of preferable liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 8-157826, Japanese Patent Laid-Open No. 8- No. 231960, JP-A-9-241644 (EP882722A1), JP-A-9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-255556. JP, 9-241643 (EP882711A1), JP 10-204016 (EP844229A1), JP 10-204436, JP 10-231482, JP 2000-087040, JP It is disclosed in 2001-48822 gazette etc. .

  The liquid crystal composition used in the VA liquid crystal display element can be various liquid crystal compositions having negative dielectric anisotropy. Examples of preferred liquid crystal compositions include JP-A-57-141432, JP-A-2-4725, JP-A-4-224858, JP-A-8-40953, JP-A-8-104869, Japanese Laid-Open Patent Publication No. 10-168076, Japanese Laid-Open Patent Publication No. 10-168453, Japanese Laid-Open Patent Publication No. 10-236989, Japanese Laid-Open Patent Publication No. 10-236990, Japanese Laid-Open Patent Publication No. 10-236992, Japanese Laid-Open Patent Publication No. 10-236993, Japanese Laid-open Patent Publication No. -236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076 JP, 10-237448, (EP967261A1), JP 10-28787. JP-A-10-287875, JP-A-10-291945, JP-A-11-029581, JP-A-11-080049, JP-A-2000-256307, JP-A-2001-019965, JP 2001-072626 A, JP 2001-192657 A, and the like.

  One or more optically active compounds may be added to the liquid crystal composition having a positive or negative dielectric anisotropy.

  Of course, the liquid crystal display element of the present invention may have other members. For example, in a color display TFT type liquid crystal element using a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal electrode, a pixel electrode, and the like are formed on a first transparent substrate, and the second transparent substrate is formed. A black matrix, a color filter, a planarization film, a pixel electrode, and the like that block light outside the pixel region may be included.

  Further, in a VA liquid crystal display element, in particular, an MVA liquid crystal display element, a minute protrusion called a domain is formed on a first transparent substrate. A spacer may be formed for adjusting the cell gap between the substrates.

  The liquid crystal display element of the present invention can be manufactured by any method. For example, 1) a step of applying a polyimide solution on the two transparent substrates, 2) a step of drying the applied polyimide solution, 3 ) A step of performing heat treatment necessary for dehydration and ring-closing reaction of the dried polyimide solution, 4) a step of aligning the obtained liquid crystal alignment film, 5) after bonding the two substrates, It is manufactured by a method including a step of encapsulating a liquid crystal composition in between, or a step of dropping a liquid crystal composition on one substrate and then bonding it to the other substrate.

  As a coating method in the step of applying the polyimide-based solution, a spinner method, a printing method, a dipping method, a dropping method, an ink jet method and the like are generally known. These methods are also applicable in the present invention.

  Further, as a method of the drying step and the step of performing the heat treatment necessary for the dehydration reaction, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are also applicable in the present invention. The drying step is preferably performed at a relatively low temperature (50 to 140 ° C.) within a range where the solvent can be evaporated. In general, the heat treatment step is preferably performed at a temperature of about 150 to 300 ° C.

  The alignment treatment for the liquid crystal alignment film is usually a rubbing treatment for IPS liquid crystal display elements, OCB liquid crystal display elements, TN liquid crystal display elements, and STN liquid crystal display elements. In many cases, the VA liquid crystal display element is not subjected to the rubbing treatment.

  Next, an adhesive is applied onto one of the substrates, and the liquid crystal is injected in a bonding vacuum. In the case of the dropping injection method, the liquid crystal composition is dropped on the substrate before bonding, and then bonded on the other substrate. The liquid crystal display element of the present invention is produced by curing the adhesive used for bonding with heat or ultraviolet rays.

  A polarizing plate (polarizing film), a wave plate, a light scattering film, a driving circuit, and the like may be mounted on the liquid crystal display element of the present invention.

  The polyimide-based solution of the present invention is applied to various support substrates and subjected to heat treatment to form a polyimide-based solution coating film, which is used as an insulating film / protective film or liquid crystal alignment film for electric / electronic elements. Since the film-forming polyimide is less likely to precipitate during storage, whitening of the coating film can be suppressed, and the fluidity of the solution after application is good, the unevenness is improved. A smooth coating film can be formed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. The compounds used in the examples are as follows.

<Tetracarboxylic dianhydride>
Compound (1): pyromellitic dianhydride

<Diamine>
Compound (VI-4): 1,2-bis (4-aminophenyl) ethane

<Solvent>
Compound (A-1): SOLKETAL (manufactured by Kanto Chemical Co., Inc.)
Compound (A-2): Compound of formula (A-2) Compound (A-3): Compound of formula (A-3) NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve (ethylene glycol monobutyl ether)

<Acid catalyst>
PTS: p-toluenesulfonic acid monohydrate

[Synthesis Example 1]
A 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet is charged with 1.726 g (8.130 mmol) of compound (VI-4) and 50.0 g of dehydrated NMP and dried. The solution was stirred and dissolved under a nitrogen stream. Next, 1.774 g (8.133 mmol) of compound (1) and 16.5 g of dehydrated NMP were added, and the mixture was reacted for 30 hours in a room temperature environment. When the reaction temperature rose during the reaction, the reaction temperature was kept at about 70 ° C. or lower for the reaction. To the resulting reaction mixture, 30.0 g of dehydrated NMP was added to obtain a polyimide solution having a concentration of 3% by weight. This polyimide solution is designated as PA1.

[Synthesis Example 2] Synthesis of Compound (A-2) 2,2,4-trimethyl-1,3 in a 1 L reaction vessel equipped with a thermometer, stirrer, raw material charging inlet, Dean-Stark trap, reflux condenser -146 g of pentanediol and 81 g of hydroxyacetone were added. Further, 0.12 g of PTS as a catalyst and 50 g of cyclohexane as an entrainer (a solvent for azeotropically removing water generated by the reaction) were added to the reaction vessel. The reaction vessel was heated and reacted for 3 hours while removing water at reflux. After completion of the reaction, purification was performed by rectification to obtain 190 g of a compound (A-2) having a purity of 98% or more.

The obtained compound (A-2) was identified by a nuclear magnetic resonance spectrum obtained by ¹ H-NMR analysis. DRX-500 (manufactured by Bruker BioSpin Co., Ltd.) was used as the measuring device. In the measurement, the sample obtained in Synthesis Example 2 is dissolved in a deuterated solvent in which a sample such as CDCl ₃ is soluble, and ¹ H-NMR analysis is performed at room temperature at 500 MHz and 24 times. It was. Tetramethylsilane (TMS) was used as a reference material for the zero point of the chemical shift δ value. The obtained ¹ H-NMR chart is shown in FIG.

  The purity of the obtained compound (A-2) was determined by measurement by gas chromatography. A GC-14A gas chromatograph manufactured by Shimadzu Corporation was used as the measuring device. The column used was a capillary column G-100-309-170 (length 40 m, inner diameter 1.2 mm, film thickness 5 μm) manufactured by Shimadzu GL; the fixed liquid phase was dimethylpolysiloxane; Helium was used as the carrier gas, and the flow rate was adjusted to 1 mL / min. The temperature of the sample vaporizing chamber was set to 300 ° C., and the temperature of the detector (FID) portion was set to 300 ° C.

  The sample was dissolved in toluene to prepare a 1% by weight solution, and 1 μL of the resulting solution was injected into the sample vaporization chamber. As a recorder, C-R6A type Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof was used. When the above-described column is used, the weight% of each component in the sample substantially corresponds to the area% of each peak in the sample. From the peak area of the obtained gas chromatogram, the compound (A− The purity of 2) was determined. As a sample dilution solvent, for example, chloroform or hexane may be used.

[Synthesis Example 3] Synthesis of Compound (A-3) 2,2,4-Trimethyl-1,3 in a 1 L reaction vessel equipped with a thermometer, stirrer, raw material charging inlet, Dean-Stark trap, reflux condenser -146 g of pentanediol and 132 g of 4-hydroxy-2-butanone were added. Further, 0.30 g of PTS as a catalyst and 50 g of cyclohexane as an entrainer were added to the reaction vessel. The reaction vessel was heated and reacted for 3 hours while removing water at reflux. After completion of the reaction, purification was performed by rectification to obtain 200 g of a compound (A-3) having a purity of 98% or more. Confirmation of the structure of compound (A-3) and measurement of purity were carried out in the same manner as for compound (A-2). The obtained ¹ H-NMR chart is shown in FIG.

[Example 1]
30 parts by weight of compound (A-1) was mixed with 3 parts by weight of PA1 obtained in Synthesis Example 1 with respect to 100 parts by weight of PA1 to obtain a polyimide-based solution. The obtained polyimide-based solution was stored at room temperature for 24 hours, and the storage stability of the solution was observed. As a result, no change was observed and the storage stability was good.

[Example 2]
30% by weight of the compound (A-2) obtained in Synthesis Example 2 was mixed with 3% by weight of PA1 obtained in Synthesis Example 1 with respect to 100 parts by weight of PA1 to obtain a polyimide-based solution. The obtained polyimide-based solution was stored at room temperature for 24 hours, and the storage stability of the solution was observed. As a result, no change was observed and the storage stability was good.

[Example 3]
30% by weight of the compound (A-3) obtained in Synthesis Example 3 was mixed with 3% by weight of PA1 obtained in Synthesis Example 1 with respect to 100 parts by weight of PA1 to obtain a polyimide-based solution. The obtained polyimide-based solution was stored at room temperature for 24 hours, and the storage stability of the solution was observed. As a result, no change was observed and the storage stability was good.

[Comparative Example 1]
30 parts by weight of BC was mixed with 3 parts by weight of PA1 obtained in Synthesis Example 1 with respect to 100 parts by weight of PA1 to obtain a polyimide-based solution. The obtained polyimide solution was stored at room temperature for 24 hours, and the storage stability of the solution was observed. As a result, the solution became cloudy and the storage stability was poor.

  As shown in Examples 1 to 3 and Comparative Example 1, in the polyimide-based solutions of Examples 1 to 3 to which the compound (A-1), (A-2), or (A-3) was added, BC Storage stability can be improved as compared with the polyimide-based solution of Comparative Example 1 to which is added.

  In an optical element such as a liquid crystal display element, a polyimide film may be used in various forms. Changes in the properties of the polyimide-based solution for forming such a polyimide film over time may affect the physical properties of the polyimide film and the quality of optical elements using the polyimide film. The present invention can improve the storage stability of a polyimide-based solution compared to a polyimide-based solution containing butyl cellosolve, and is excellent in coating properties as with a polyimide-based solution containing butyl cellosolve. Therefore, according to the present invention, in a technique using a polyimide-based solution for forming a coating film containing butyl cellosolve, it is expected to provide a more excellent technique from the viewpoint of storage stability of the polyimide-based solution.

Claims (21)

In a liquid crystal aligning agent containing a film-forming polyimide-based component that is one or more selected from the group consisting of polyimide and a polyimide precursor, and a solvent that dissolves the component,
The said solvent contains the compound represented by a following formula (A), The liquid crystal aligning agent characterized by the above-mentioned.

(In the formula (A),
Q ¹ represents —CH ₃ , —CH ₂ —OH, or — (CH ₂ ) ₂ —OH,
Q ² represents —H, —CH ₃ , or —CH ₂ —OH,
Q ³ independently represents —H, —CH ₃ , or —CH (CH ₃ ) ₂ ;
n represents 0 or 1,
Any ^one of Q ¹ and Q ² is a group having —OH;
When n = 0, Q ¹ is —CH ₃ , Q ² is —CH ₂ —OH,
When n = 1, Q ¹ is —CH ₂ —OH or — (CH ₂ ) ₂ —OH, Q ² is —H,
Q ³ includes one or both of —CH ₃ and —CH (CH ₃ ) ₂ . ) The compound represented by the formula (A) is one or more selected from the group consisting of the following formulas (A-1), (A-2), and (A-3). Liquid crystal aligning agent.

  3. The liquid crystal according to claim 1, wherein the film forming polyimide component is a polyamic acid or a derivative thereof having a structure of a reaction product of a diamine or a derivative thereof and a tetracarboxylic acid or a derivative thereof. Alignment agent.   The said solvent is a mixed solvent of 2 or more types of compounds containing the compound represented by the said formula (A), The liquid crystal aligning agent as described in any one of Claims 1-3 characterized by the above-mentioned. The method of baking the coating film of the liquid crystal aligning agent as described in any one of Claims 1-4, and forming a liquid crystal aligning film . A pair of substrates disposed opposite to each other, electrodes formed on one or both of the opposed surfaces of the pair of substrates, and liquid crystal formed on the opposed surfaces of the pair of substrates. In the manufacturing method of the liquid crystal display element which has an orientation film and the liquid crystal layer formed between the said pair of board | substrates, the said liquid crystal orientation film is a manufacturing method of the liquid crystal display element formed with the method of Claim 5. In a polyimide-based solution containing a film-forming polyimide-based component that is one or more selected from the group consisting of polyimide and a polyimide precursor, and a solvent for dissolving the component,
The polyimide-based solution, wherein the solvent contains a compound represented by the following formula (A).

(In the formula (A),
Q ¹ represents —CH ₃ , —CH ₂ —OH, or — (CH ₂ ) ₂ —OH,
Q ² represents —H, —CH ₃ , or —CH ₂ —OH,
Q ³ independently represents —H, —CH ₃ , or —CH (CH ₃ ) ₂ ;
n represents 0 or 1,
Any ^one of Q ¹ and Q ² is a group having —OH;
When n = 0, Q ¹ is —CH ₃ , Q ² is —CH ₂ —OH,
When n = 1, Q ¹ is —CH ₂ —OH or — (CH ₂ ) ₂ —OH, Q ² is —H,
Q ³ includes one or both of —CH ₃ and —CH (CH ₃ ) ₂ . )   The polyimide-based solution according to claim 7, wherein the film-forming polyimide component is a polyamic acid or a derivative thereof having a structure of a reaction product of diamine or a derivative thereof and tetracarboxylic acid or a derivative thereof. .   The polyimide solvent according to claim 7 or 8, wherein the solvent is a mixed solvent of two or more kinds of compounds including the compound represented by the formula (A).   The polyimide-based solution according to any one of claims 7 to 9, which is a coating material.   The polyimide-based solution according to any one of claims 7 to 9, which is an insulating material.   The polyimide-based solution according to any one of claims 7 to 9, which is an adhesive.   The polyimide-based solution according to any one of claims 7 to 9, which is a sealing material.   The polyimide-based solution according to any one of claims 7 to 9, which is a printed wiring board material.   The polyimide-based solution according to any one of claims 7 to 9, which is a molding material. In a method for producing a polyimide-based solution, including a film-formable polyimide-based component that is one or more selected from the group consisting of polyimide and a polyimide precursor, obtaining a solution obtained by dissolving it in a solvent that dissolves the component,
The said solvent contains the compound represented by a following formula (A), The manufacturing method of the polyimide-type solution characterized by the above-mentioned.

(In the formula (A),
Q ¹ represents —CH ₃ , —CH ₂ —OH, or — (CH ₂ ) ₂ —OH,
Q ² represents —H, —CH ₃ , or —CH ₂ —OH,
Q ³ independently represents —H, —CH ₃ , or —CH (CH ₃ ) ₂ ;
n represents 0 or 1,
Any ^one of Q ¹ and Q ² is a group having —OH;
When n = 0, Q ¹ is —CH ₃ , Q ² is —CH ₂ —OH,
When n = 1, Q ¹ is —CH ₂ —OH or — (CH ₂ ) ₂ —OH, Q ² is —H,
Q ³ includes one or both of —CH ₃ and —CH (CH ₃ ) ₂ . )   The polyimide-based solution according to claim 16, wherein the film-forming polyimide component is a polyamic acid or a derivative thereof having a structure of a reaction product of a diamine or a derivative thereof and a tetracarboxylic acid or a derivative thereof. Manufacturing method.   The method for producing a polyimide-based solution according to claim 16 or 17, wherein the solvent is a mixed solvent of two or more kinds of compounds including the compound represented by the formula (A). A step of forming a coating film of a polyimide-based solution containing a film-forming polyimide-based component which is one or more selected from the group consisting of polyimide and a polyimide precursor and a solvent for dissolving the component, and the formed coating film In the manufacturing method of a polyimide film including a step of baking and forming a polyimide film composed of a film forming polyimide component in the coating film,
The said solvent contains the compound represented by a following formula (A), The manufacturing method of the polyimide film characterized by the above-mentioned.

(In the formula (A),
Q ¹ represents —CH ₃ , —CH ₂ —OH, or — (CH ₂ ) ₂ —OH,
Q ² represents —H, —CH ₃ , or —CH ₂ —OH,
Q ³ independently represents —H, —CH ₃ , or —CH (CH ₃ ) ₂ ;
n represents 0 or 1,
Any ^one of Q ¹ and Q ² is a group having —OH;
When n = 0, Q ¹ is —CH ₃ , Q ² is —CH ₂ —OH,
When n = 1, Q ¹ is —CH ₂ —OH or — (CH ₂ ) ₂ —OH, Q ² is —H,
Q ³ includes one or both of —CH ₃ and —CH (CH ₃ ) ₂ . )   The polyimide film component according to claim 19, wherein the film forming polyimide component is a polyamic acid or a derivative thereof having a structure of a reaction product of a diamine or a derivative thereof and a tetracarboxylic acid or a derivative thereof. Production method.   The method for producing a polyimide film according to claim 19 or 20, wherein the solvent is a mixed solvent of two or more kinds of compounds including the compound represented by the formula (A).

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