阅读说明：本技术 化合物、聚合物、液晶取向剂、液晶取向膜、液晶显示元件、以及制造方法 (Compound, polymer, liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and production method ) 是由 小林修 一条洋树 砂川彩 小関洋平 大木洋一郎 尾崎刚史 北野文萌 小鹿瑞歩 于 2021-05-13 设计创作，主要内容包括：提供一种化合物、聚合物、液晶取向剂、液晶取向膜、液晶显示元件、以及制造方法。一种二胺化合物,由下述通式(1)表示。进而一种液晶取向剂,含有聚合物,所述聚合物是使包含含有所述二胺化合物的二胺类与四羧酸二酐类的原料组合物聚合而成。通式(1)中,R～(1)及R～(2)各自独立地表示氢原子、卤素原子、碳数1至6的烷基、碳数1至6的卤代烷基或碳数1至6的烷氧基。R～(1)与R～(2)可成为一体而形成可经取代的亚甲基。X各自独立地表示卤素原子、碳数1至6的烷基、碳数1至6的卤代烷基或碳数1至6的烷氧基,n表示0至4的整数。(Provided are a compound, a polymer, a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a manufacturing method. A diamine compound represented by the following general formula (1). Further disclosed is a liquid crystal aligning agent containing a polymer obtained by polymerizing a raw material composition containing a diamine containing the diamine compound and a tetracarboxylic acid dianhydride. In the general formula (1), R 1 And R 2 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R 1 And R 2 Can be integrated to form methylene which can be substituted. X each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4.)

1. A diamine compound represented by the following general formula (1),

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; x each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4.

2. The diamine compound according to claim 1, represented by the following general formula (1-1),

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; x is respectively independent earth surfaceRepresents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4.

3. The diamine compound according to claim 1 or 2, represented by the following general formula (1-2),

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form methylene which can be substituted.

4. Diamine compound according to any of claims 1 to 3, wherein both esters are substituted in the cyclopropane ring in trans configuration.

5. A polymer obtained by polymerizing a raw material composition containing a diamine and a tetracarboxylic acid dianhydride, wherein,

at least one of the diamines is the diamine compound according to any one of claims 1 to 4.

6. A liquid crystal aligning agent comprising the polymer according to claim 5.

7. A liquid crystal alignment film formed from the liquid crystal aligning agent according to claim 6.

8. A liquid crystal display element having the liquid crystal alignment film according to claim 7.

9. A method for manufacturing a liquid crystal alignment film, comprising: a step of applying the liquid crystal aligning agent according to claim 6 to a substrate to form a coating film; and irradiating the coating film with polarized ultraviolet rays.

10. A process for producing a diamine compound, which comprises reducing a dinitro compound represented by the following general formula (2) to obtain a diamine compound represented by the following general formula (1),

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; x each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, n represents an integer of 0 to 4,

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; x each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4.

11. A process for producing a diamine compound, which comprises deprotecting a protected diamino compound represented by the following general formula (7-1) to obtain a diamine compound represented by the following general formula (1-1),

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; x each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4; boc represents a tert-butoxycarbonyl group,

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; x each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4.

12. A process for producing a diamine compound, which comprises subjecting a cyclopropane derivative represented by the following general formula (3) and a protected aminophenol compound represented by the following general formula (6-1) to condensation reaction to synthesize a protected diamino compound represented by the following general formula (7-1), and then deprotecting the compound to obtain a diamine compound represented by the following general formula (1-1),

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; y represents a leaving group, and Y represents a leaving group,

wherein X represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4; when n is 2 or more, X's may be the same or different from each other; boc represents a tert-butoxycarbonyl group,

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; x each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4; boc represents a tert-butoxycarbonyl group,

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; x each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4.

13. A dinitro compound represented by the following general formula (2),

in the formula, R¹And R²Each independentlyRepresents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; x each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4.

14. The dinitro compound according to claim 13, which is represented by the following general formula (2-1),

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; x each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4.

15. The dinitro compound according to claim 13 or 14, which is represented by the following general formula (2-2),

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form methylene which can be substituted.

16. The dinitro compound according to any one of claims 13 to 15 wherein both esters are substituted in the cyclopropane ring in the trans configuration.

17. A process for producing a dinitro compound, which comprises synthesizing a dinitro compound represented by the following general formula (2) by condensation reaction of a cyclopropane derivative represented by the following general formula (3) with a nitro compound represented by the following general formula (4),

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; y represents a leaving group, and Y represents a leaving group,

wherein X represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4; when n is 2 or more, X's may be the same or different from each other,

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; x each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4.

18. A protected diamino compound represented by the following general formula (7-1),

in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r¹And R²Can be integrated to form a methylene group which can be substituted; x each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4; boc represents tert-butoxycarbonyl.

19. A protected diamino compound according to claim 18 wherein both esters are substituted on the cyclopropane ring in the trans configuration.

Technical Field

The present invention relates to a diamine compound which is effectively used as a raw material monomer of a polymer used for a liquid crystal aligning agent, a method for producing the same, a polymer using the diamine compound as a raw material monomer, a dinitro compound which is effectively used as a synthesis intermediate of the diamine compound, a method for producing the same, and a protected diamino compound. Further, the present invention relates to a liquid crystal aligning agent containing the polymer, a liquid crystal alignment film (photo-alignment film) of a photo-alignment type formed using the liquid crystal aligning agent, a method for producing the same, and a liquid crystal display element having the liquid crystal alignment film.

Background

As liquid crystal display elements, various driving methods such as a Twisted Nematic (TN) mode, a Super Twisted Nematic (STN) mode, an In-Plane Switching (IPS) mode, a Fringe Field Switching (FFS) mode, and a Vertical Alignment (VA) mode are known. These liquid crystal display elements are used in image display devices of various electronic apparatuses such as televisions and cellular phones, and are being developed with the aim of further improving display quality. Specifically, the performance of the liquid crystal display element can be improved not only by improving the driving method and the element structure, but also by using a structural member used in the element. Among the structural members used in liquid crystal display devices, particularly, liquid crystal alignment films are one of important materials for display quality, and studies have been actively conducted to meet the demand for high quality of liquid crystal display devices.

Here, the liquid crystal alignment film is provided on a pair of substrates provided on both sides of a liquid crystal layer of the liquid crystal display element so as to be in contact with the liquid crystal layer, and has a function of aligning liquid crystal molecules constituting the liquid crystal layer with respect to the substrates in a certain regularity. By using a liquid crystal alignment film having high liquid crystal alignment properties, a liquid crystal display element having high contrast and improved image sticking characteristics can be realized (see, for example, patent documents 1 and 2).

In the formation of such a liquid crystal alignment film, a solution (varnish) in which polyamic acid, soluble polyimide, or polyamic acid ester is dissolved in an organic solvent has been mainly used. When a liquid crystal alignment film is formed using these varnishes, various liquid crystal alignment films are formed by applying the varnish to a substrate and then curing the coating film by heating or the like, and alignment treatment suitable for the display mode is performed as necessary.

Specifically, for example, as a method for forming a polyimide film for forming a liquid crystal alignment film on a substrate, there is known a method for forming a polyimide film by applying a liquid crystal alignment agent containing a polyamic acid as a polyimide precursor on a substrate and then calcining the applied liquid crystal alignment agent, or a method for applying a liquid crystal alignment agent containing a solvent-soluble polyimide on a substrate and removing the solvent to form a polyimide film, and a method for applying a liquid crystal alignment agent containing a polyamic acid containing an imide group obtained from a diamine containing an imide group on a substrate (for example, see patent document 3).

Further, as an alignment treatment method, there are known: a rubbing method of rubbing the surface of the alignment film with cloth or the like to adjust the direction of polymer molecules; and a photo-alignment method in which the alignment film is irradiated with linearly polarized ultraviolet light to cause photochemical changes such as photoisomerization and dimerization in the polymer molecules, thereby imparting anisotropy to the film. Among them, the photo-alignment method has higher uniformity of alignment than the rubbing method, and is a non-contact alignment treatment method, and thus has advantages such as not damaging a film and reducing causes of display defects of a liquid crystal display element due to dust, static electricity, and the like.

As one of the above-described photo-alignment methods, a decomposition type photo-alignment method is known. The decomposition type photo-alignment method is a method in which a polyimide film is irradiated with polarized ultraviolet light, so that anisotropic decomposition is caused by the polarization direction dependency of ultraviolet absorption of a molecular structure, and liquid crystals are aligned by polyimide remaining without being decomposed (for example, see patent document 4).

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent application laid-open No. 2010-197999

[ patent document 2] International publication No. 2013/157463

[ patent document 3] Japanese patent laid-open No. Hei 9-185064

[ patent document 4] Japanese patent laid-open No. Hei 9-297313

Disclosure of Invention

[ problems to be solved by the invention ]

In addition, with the recent change in the use form of liquid crystal display elements, there is a demand for liquid crystal display elements that can further achieve high contrast. Here, in order to realize a high contrast, it is necessary that liquid crystal molecules of the liquid crystal layer be regularly aligned, and for this reason, it is important that a liquid crystal alignment film that imparts alignment properties to the liquid crystal layer has high liquid crystal alignment properties. However, since the liquid crystal alignment film obtained by the conventional photo-alignment method has insufficient liquid crystal alignment properties, it is not practical to sufficiently satisfy the recent demand for improvement in contrast.

In order to solve the problems of the conventional techniques, the present inventors have made studies with an object of providing a material and a raw material thereof capable of forming a liquid crystal alignment film having high liquid crystal alignment properties.

[ means for solving problems ]

The present inventors have made diligent studies to solve the above problems and, as a result, have found that: a liquid crystal alignment film having high liquid crystal alignment properties can be obtained by using a polyamic acid or a derivative thereof synthesized by using a diamine compound having a specific cyclopropane structure as a diamine monomer, as a liquid crystal alignment agent, and a liquid crystal display element having high contrast can be realized by using the liquid crystal alignment film. The present invention has been completed based on such findings, and specifically has the following structure.

[1] A diamine compound represented by the following general formula (1).

[ solution 1]

(in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R¹And R²Can be integrated to form methylene which can be substituted. X each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4)

[2] The diamine compound according to [1], which is represented by the following general formula (1-1).

[ solution 2]

(in the formula, R¹、R²X and n are each independently of R of the general formula (1)¹、R²X and n are the same meaning

[3] The diamine compound according to [1] or [2], which is represented by the following general formula (1-2).

[ solution 3]

(in the formula, R¹And R²Are each independently of R of the general formula (1)¹And R²To the same extent)

[4] The diamine compound according to any one of [1] to [3], wherein two esters are substituted at a cyclopropane ring in a trans configuration.

[5] A polymer obtained by polymerizing a raw material composition containing diamines and tetracarboxylic acid dianhydrides, wherein at least one of the diamines is the diamine compound according to any one of [1] to [4], or a derivative thereof.

[6] A liquid crystal aligning agent comprising the polymer according to [5 ].

[7] A liquid crystal alignment film formed from the liquid crystal aligning agent according to [6 ].

[8] A liquid crystal display element having the liquid crystal alignment film according to [7 ].

[9] A method for manufacturing a liquid crystal alignment film, comprising: a step of applying the liquid crystal aligning agent according to [6] to a substrate to form a coating film; and irradiating the coating film with polarized ultraviolet rays.

[10] A process for producing a diamine compound, which comprises reducing a dinitro compound represented by the following general formula (2) to obtain a diamine compound represented by the following general formula (1).

[ solution 4]

(in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R¹And R²Can be integrated to form methylene which can be substituted. X each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen having 1 to 6 carbon atomsAlkyl or alkoxy having 1 to 6 carbon atoms, n represents an integer of 0 to 4)

[ solution 5]

(in the formula, R¹、R²X and n are each independently of R of the general formula (1)¹、R²X and n are the same meaning

[11] A process for producing a diamine compound, which comprises deprotecting a protected diamino compound represented by the following general formula (7-1) to obtain a diamine compound represented by the following general formula (1-1).

[ solution 6]

(in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R¹And R²Can be integrated to form methylene which can be substituted. X each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4. Boc represents tert-butoxycarbonyl group)

[ solution 7]

(in the formula, R¹、R²X and n are each independently of R of the general formula (1)¹、R²X and n are the same meaning

[12] A process for producing a diamine compound, which comprises subjecting a cyclopropane derivative represented by the following general formula (3) and a protected aminophenol compound represented by the following general formula (6-1) to a condensation reaction to synthesize a protected diamino compound represented by the following general formula (7-1), and then deprotecting the compound to obtain a diamine compound represented by the following general formula (1-1).

[ solution 8]

(in the formula, R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R¹And R²Can be integrated to form methylene which can be substituted. Y represents a leaving group)

[ solution 9]

(wherein X represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4. when n is 2 or more, X's may be the same or different from each other. Boc represents a tert-butoxycarbonyl group)

[ solution 10]

(in the formula, R¹、R²X, n and Boc with R of the general formula (7-1)¹、R²X, n and Boc are the same meaning

[ solution 11]

(in the formula, R¹、R²X and n are each independently of R of the general formula (1)¹、R²X and n are the same meaning

[13] A dinitro compound represented by the following general formula (2).

[ solution 12]

(in the formula, R¹、R²X and n are each independently of R of the general formula (2)¹、R²X and n are the same meaning

[14] The dinitro compound according to [13] is represented by the following general formula (2-1).

[ solution 13]

(in the formula, R¹、R²X and n are each independently of R of the general formula (2)¹、R²X and n are the same meaning

[15] The dinitro compound according to [13] or [14], which is represented by the following general formula (2-2).

[ solution 14]

(in the formula, R¹And R²Are each independently of R of the general formula (2)¹And R²To the same extent)

[16] The dinitro compound according to any one of [13] to [15], wherein two esters are substituted at a cyclopropane ring in a trans configuration.

[17] Disclosed is a method for producing a dinitro compound, wherein a cyclopropane derivative represented by the following general formula (3) and a nitro compound represented by the following general formula (4) are subjected to a condensation reaction to synthesize a dinitro compound represented by the following general formula (2).

[ solution 15]

(in the formula, R¹And R²Each independently representA hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R¹And R²Can be integrated to form methylene which can be substituted. Y represents a leaving group)

[ solution 16]

(wherein X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4. when n is 2 or more, X's may be the same or different)

[ solution 17]

(in the formula, R¹、R²X and n are each independently of R of the general formula (2)¹、R²X and n are the same meaning

[18] A protected diamino compound represented by the following general formula (7-1).

[ solution 18]

(in the formula, R¹、R²X, n and Boc with R of the general formula (7-1)¹、R²X, n and Boc are the same meaning

[19] A protected diamino compound according to [18], wherein both esters are substituted in the trans configuration at the cyclopropane ring.

For R of each formula¹、R²And a halogen atom in X, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a leaving group in Y are explained.

Examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, iodine atom.

The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic.

Specific examples of the alkyl group include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, 1-ethylpropyl, hexyl, isohexyl, 1-methylpentyl, 1-ethylbutyl, cyclopentyl, cyclohexyl and the like.

Examples of the haloalkyl group having 1 to 6 carbon atoms include groups in which an arbitrary number of hydrogen atoms at arbitrary positions in the alkyl group having 1 to 6 carbon atoms are substituted with halogen atoms. As specific examples of halogen atoms, reference may be made to R¹、R²And specific examples of the halogen atom in X. The number of halogen atoms in the haloalkyl group is preferably 1 to 5, more preferably 1 to 4, and further preferably 1 to 3. Specific examples of the haloalkyl group include: difluoromethyl, trifluoromethyl, 1-difluoroethyl, 2,2, 2-trifluoroethyl, 3-fluoropropyl, chloromethyl, dichloromethyl, trichloromethyl, and the like.

The alkoxy group having 1 to 6 carbon atoms may be any of straight, branched, and cyclic. Specific examples of the alkoxy group include: methoxy, ethoxy, propoxy, isopropyloxy, butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, pentyloxy, isopentyloxy, neopentyloxy, tert-pentyloxy, 1-methylbutyloxy, 1-ethylpropyloxy, hexyloxy, isohexyloxy, 1-methylpentyloxy, 1-ethylbutyloxy, cyclopentyloxy, cyclohexyloxy and the like.

Examples of the leaving group Y include: chlorine atom, hydroxyl group, 4-nitrophenyloxy group, 2, 4-dinitrophenyloxy group and the like.

[ Effect of the invention ]

The diamine compound of the present invention is effective as a raw material monomer of a polymer used in a liquid crystal aligning agent. By using a polymer synthesized using the diamine compound as a liquid crystal aligning agent, a liquid crystal alignment film having high liquid crystal alignment properties can be formed. Further, by applying the liquid crystal alignment film to a liquid crystal display element, a liquid crystal layer thereof can be provided with high alignment properties, and display can be performed with high contrast.

Detailed Description

The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments or specific examples, but the present invention is not limited to such embodiments. In the present specification, the numerical range expressed by the term "to" means a range including the numerical values described before and after the term "to" as the lower limit value and the upper limit value.

The "liquid crystal aligning agent" in the present invention is a liquid crystal aligning agent which can impart anisotropy by irradiation with polarized ultraviolet rays when the above-mentioned film is formed on a substrate, and may be referred to as a "liquid crystal aligning agent" in the present specification. In the present invention, the term "tetracarboxylic dianhydrides" refers to tetracarboxylic dianhydrides, tetracarboxylic diesters, or tetracarboxylic diester dihalides. In the present invention, the diamine and the dihydrazide may be referred to as "diamine".

In the following description, the diamine compound represented by the general formula (1), the dinitro compound represented by the general formula (2), the cyclopropane derivative represented by the general formula (3), the nitro compound represented by the general formula (4), the protected aminophenol compound represented by the general formula (6-1), and the protected diamino compound represented by the general formula (7-1) may be referred to as the diamine compound (1), the dinitro compound (2), the cyclopropane derivative (3), the nitro compound (4), the protected aminophenol compound (6-1), and the protected diamino compound (7-1), respectively.

< diamine Compound >

The diamine compound of the present invention is a compound represented by the general formula (1).

[ solution 19]

In the general formula (1), R¹And R²Each independently represents a hydrogen atom or a halogenAn atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R¹And R²May be the same or different from each other. In addition, R¹And R²Can be integrated to form methylene which can be substituted. Examples of the methylene group substituent include: examples of the alkyl group include a halogen atom such as a fluorine atom or a chlorine atom, an alkyl group which may be substituted with a halogen atom such as a fluorine atom or a chlorine atom or an alkoxy group having 1 to 4 carbon atoms, and an aryl group which may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. X each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4. When the total of two n is 2 or more, a plurality of X's may be the same or different from each other. X and amino (-NH)₂) The bonding position of (b) is any position of the benzene ring bonded by the bonding bond, which can be substituted.

When a coating film is formed from a polymer synthesized using a diamine compound represented by the general formula (1) (diamine compound (1)) as a monomer and is irradiated with a bias light, high liquid crystal alignment properties can be imparted to the coating film. This is presumably due to the following mechanism.

That is, the diamine compound (1) of the present invention is considered to have a structure in which phenyl ester is bonded to the adjacent carbon of cyclopropane, and thus a photo fries rearrangement reaction occurs by light irradiation. Therefore, when a coating film of a polymer synthesized using the diamine compound (1) is irradiated with light polarization for orientation, a photochemical reaction (photo fries rearrangement reaction) selectively occurs in a randomly oriented polymer chain on a diamine-derived structural unit of a polymer main chain substantially parallel to the polarization direction. As a result, the orientation component derived from the polymer chain substantially perpendicular to the polarization direction is dominant, and the polymer chain is highly oriented in a specific direction.

Further, when the oriented film is used as a liquid crystal alignment film of a liquid crystal display element, the interaction between the surface of the liquid crystal alignment film and liquid crystal molecules results in: the liquid crystal molecules are aligned with their long axes in a direction substantially perpendicular to the polarization direction of the irradiated polarized light and are uniformly aligned, thereby imparting high anisotropy to the liquid crystal layer.

According to the above, the diamine compound (1) is effectively used as a raw material monomer (diamine monomer) of a polymer used in the liquid crystal aligning agent. Further, a liquid crystal alignment film having high liquid crystal alignment properties can be formed by using a polymer synthesized using the diamine compound as a liquid crystal aligning agent. Further, by applying the liquid crystal alignment film to a liquid crystal display element, a liquid crystal layer thereof can be provided with high alignment properties, and display can be performed with high contrast.

In the present specification, a state in which a component oriented in a specific direction in a polymer chain is dominant may be expressed as a state in which the polymer chain is oriented, and a state in which the polymer chain forming an alignment film is oriented in the specific direction may be expressed as a state in which anisotropy occurs. In addition, further aligning the polymer chains in a particular direction sometimes appears to have high anisotropy.

Hereinafter, preferred examples of the diamine compound represented by the general formula (1) will be described.

[ diamine Compound represented by the general formula (1-1) ]

Preferable examples of the diamine compound represented by the general formula (1) include diamine compounds represented by the following general formula (1-1).

[ solution 20]

In the general formula (1-1), R¹、R²X and n are independently from R in the formula (1)¹、R²X and n are the same. The bonding position of X is any position of the benzene ring to which the bonding bond is bonded, which can be substituted. Since the amino group of the polymer synthesized using the diamine compound represented by the general formula (1-1) is positioned at the para-position with respect to the ester, the linearity is high, and a liquid crystal alignment film using the polymer can exhibit high anisotropy.

[ diamine Compound represented by the general formula (1-2) ]

Preferable examples of the diamine compound represented by the general formula (1-1) include diamine compounds represented by the following general formula (1-2).

[ solution 21]

In the general formula (1-2), R¹And R²Are respectively connected with R in the general formula (1)¹And R²Are the same meaning. The diamine compound represented by the general formula (1-2) is useful in terms of ease of acquisition of raw materials in the production thereof.

In the compound represented by the general formula (1), the general formula (1-1) or the general formula (1-2), it is preferable that two esters on the cyclopropane ring are in a trans configuration.

[ Compounds represented by the general formulae (1-3) ]

Preferable examples of the diamine compound represented by the general formula (1-1) include a diamine compound represented by the following general formula (1-3) and an enantiomer (mirror image isomer) thereof. The compounds represented by the general formulae (1-3) and their enantiomers can be used as a raw material for a polymer by mixing them, or can be used as a raw material for a polymer by mixing them in an equivalent amount as a racemate.

[ solution 22]

In the general formula (1-3), R¹、R²X and n are independently from R in the formula (1)¹、R²X and n are the same. The diamine compound represented by the formula (1-3) and the enantiomer thereof have high linearity because the two esters on the cyclopropane ring are in the trans-configuration, and a liquid crystal alignment film using the diamine compound as a polymer of a raw material can exhibit high anisotropy.

In terms of preferable characteristics, R¹And R²Preferably a hydrogen atom, or R¹And R²And become a whole to form methylene.

Specific examples of the diamine compound represented by the general formula (1) include diamine compounds represented by the following formulae (1-2-1), formulae (1-3-1) to (1-3-13), and formulae (1-4-1) to (1-4-13). In the following formula, Me represents a methyl group.

[ solution 23]

The formula (1-3-1) and the formula (1-4-1), the formula (1-3-2) and the formula (1-4-2), the formula (1-3-3) and the formula (1-4-3), the formula (1-3-4) and the formula (1-4-4), the formula (1-3-5) and the formula (1-4-5), the formula (1-3-6) and the formula (1-4-6), the formula (1-3-7) and the formula (1-4-7), the formula (1-3-8) and the formula (1-4-8), the formula (1-3-9) and the formula (1-4-9), the formula (1-3-10) and the formula (1-4-10), The formula (1-3-11) and the formula (1-4-11), the formula (1-3-12) and the formula (1-4-12), and the formula (1-3-13) and the formula (1-4-13) are in enantiomeric relationship, respectively. A mixture of the diamine compound represented by the formula (1-3-1) and the diamine compound represented by the formula (1-4-1), a mixture of the diamine compound represented by the formula (1-3-2) and the diamine compound represented by the formula (1-4-2), a mixture of the diamine compound represented by the formula (1-3-3) and the diamine compound represented by the formula (1-4-3), a mixture of the diamine compound represented by the formula (1-3-4) and the diamine compound represented by the formula (1-4-4), a mixture of the diamine compound represented by the formula (1-3-5) and the diamine compound represented by the formula (1-4-5), a mixture of the diamine compound represented by the formula (1-3-6) and the diamine compound represented by the formula (1-4-6) may be used A mixture of the diamine compound represented by the formula (1-3-7) and the diamine compound represented by the formula (1-4-7), a mixture of the diamine compound represented by the formula (1-3-8) and the diamine compound represented by the formula (1-4-8), a mixture of the diamine compound represented by the formula (1-3-9) and the diamine compound represented by the formula (1-4-9), a mixture of the diamine compound represented by the formula (1-3-10) and the diamine compound represented by the formula (1-4-10), a mixture of the diamine compound represented by the formula (1-3-11) and the diamine compound represented by the formula (1-4-11), a mixture of the diamine compound represented by the formula (1-3-12) and the diamine compound represented by the formula (1-4-12), And a mixture of the diamine compound represented by the formula (1-3-13) and the diamine compound represented by the formula (1-4-13) are used as the diamine compound (1) for the raw material composition, respectively.

In the present specification, a mixture of the diamine compound represented by the formula (1-3-1) and the diamine compound represented by the formula (1-4-1) is sometimes referred to as "diamine isomer mixture 1", a mixture of the diamine compound represented by the formula (1-3-2) and the diamine compound represented by the formula (1-4-2) is sometimes referred to as "diamine isomer mixture 2", a mixture of the diamine compound represented by the formula (1-3-3) and the diamine compound represented by the formula (1-4-3) is sometimes referred to as "diamine isomer mixture 3", a mixture of the diamine compound represented by the formula (1-3-4) and the diamine compound represented by the formula (1-4-4) is sometimes referred to as "diamine isomer mixture 4", and a mixture of the diamine compound represented by the formula (1-3-5) and the diamine compound represented by the formula (1-4-5) The mixture of the diamine compound represented by the formula (1-3-6) is referred to as "diamine isomer mixture 5", the mixture of the diamine compound represented by the formula (1-3-6) and the diamine compound represented by the formula (1-4-6) is referred to as "diamine isomer mixture 6", the mixture of the diamine compound represented by the formula (1-3-7) and the diamine compound represented by the formula (1-4-7) is referred to as "diamine isomer mixture 7", the mixture of the diamine compound represented by the formula (1-3-8) and the diamine compound represented by the formula (1-4-8) is referred to as "diamine isomer mixture 8", the mixture of the diamine compound represented by the formula (1-3-9) and the diamine compound represented by the formula (1-4-9) is referred to as "diamine isomer mixture 9", the mixture of the diamine compound represented by the formula (1-3-10) and the diamine compound represented by the formula (1-4-10) is referred to as "diamine isomer mixture 10", the mixture of the diamine compound represented by the formula (1-3-11) and the diamine compound represented by the formula (1-4-11) is referred to as "diamine isomer mixture 11", the mixture of the diamine compound represented by the formula (1-3-12) and the diamine compound represented by the formula (1-4-12) is referred to as "diamine isomer mixture 12", and the mixture of the diamine compound represented by the formula (1-3-13) and the diamine compound represented by the formula (1-4-13) is referred to as "diamine isomer mixture 13".

< Polymer >

Next, the polymer of the present invention will be explained.

The polymers of the invention are characterized in that: the polymer is a polymer or a derivative thereof obtained by polymerizing a raw material composition containing diamines and tetracarboxylic dianhydrides, and at least one of the diamines is a diamine compound represented by the general formula (1) of the present invention.

In the polymer or derivative thereof obtained by polymerizing the raw material composition containing diamine and tetracarboxylic dianhydride, the polymer of diamine and tetracarboxylic dianhydride is polyamic acid, and the other polymer is a derivative of polyamic acid. Therefore, the polymer of the present invention may be referred to as a polyamic acid or a derivative thereof, and at least one of the diamine monomers of the polyamic acid is a diamine compound represented by the general formula (1) of the present invention. The polymer of the present invention comprises at least one polymer selected from the group of polyamic acids or derivatives thereof. The polymer of the present invention may include any one of polyamic acids or derivatives thereof, and may also include a mixture of two or more selected from the group of polyamic acids or derivatives thereof. In addition, the polymer of the present invention may also constitute a mixture of one or more selected from the group of polyamic acids and one or more selected from the group of derivatives of polyamic acids. As the derivative of polyamic acid, there can be mentioned: polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide. In the present specification, these are also sometimes referred to as polyamic acid derivatives.

The polyamic acid or a derivative thereof will be described in detail below.

The polyamic acid is a polymer synthesized by a polymerization reaction of a diamine represented by the formula (DI) and a tetracarboxylic dianhydride represented by the formula (AN), and has a structural unit represented by the formula (PAA), as shown in the following reaction formula. The diamine and tetracarboxylic dianhydride used for the synthesis of the polyamic acid may be one or two or more, respectively. The liquid crystal alignment agent containing polyamic acid can form a polyimide liquid crystal alignment film having a structural unit represented by formula (PI) by imidizing the polyamic acid when heated and calcined in the step of forming the liquid crystal alignment film.

[ solution 24]

(in the formula, X¹Represents a tetravalent organic group. X²Represents a divalent organic group)

With respect to X¹The preferable range and specific examples of the tetravalent organic group in (b) can be referred to structures corresponding to tetracarboxylic dianhydrides described in the following tetracarboxylic dianhydride group. With respect to X²The preferable range and specific examples of the divalent organic group in (2) can be referred to the description of the structure corresponding to the diamine or dihydrazide described in the formula (1) or the column of the diamine group described below.

The polyamic acid derivative is a compound having characteristics changed by substituting a part of the polyamic acid with another atom or atomic group, and is particularly preferably a polyamic acid derivative having improved solubility in a solvent used for a liquid crystal aligning agent. Specific examples of such a polyamic acid derivative include: 1) a polyimide obtained by subjecting all amino groups of a polyamic acid and a carboxyl group to a dehydration ring-closure reaction, 2) a partial polyimide obtained by partially subjecting the amino groups of the polyamic acid and the carboxyl group to a dehydration ring-closure reaction, 3) a polyamic acid ester obtained by converting the carboxyl group of the polyamic acid into an ester, 4) a polyamic acid-polyamide copolymer obtained by reacting a tetracarboxylic dianhydride compound in which a part of the acid dianhydride is substituted with an organic dicarboxylic acid, and 5) a polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closure reaction. Among these derivatives, for example, polyimide having a structural unit represented by the formula (PI) is exemplified as polyimide, and polyamic acid ester having a structural unit represented by the following formula (PAE) is exemplified as polyamic acid ester.

[ solution 25]

(in the formula, X¹Denotes a tetravalent organic radical, X²Represents a divalent organic group, Z independently represents an alkyl group)

With respect to X¹And X²With reference to preferred ranges and specific examples of (A) in the formula (PAA), X in the formula¹And X²The description of (1). Z is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a tert-butyl group.

The polyamic acid or the derivative thereof of the present invention may be a block polymer comprising a first polymer chain and a second polymer chain having a structure different from that of the first polymer chain. In addition, the block polymer may further include another polymer chain having a structure different from the first polymer chain and the second polymer chain. For example, the block polymer of polyamic acid can be obtained by reacting a solution of a specific polyamic acid (PAA1) represented by the formula (PAA) with X¹And X²And a solution of a different polyamic acid (PAA2) that the polyamic acid (PAA1) is mixed and heated to form. The block polymer of polyamic acid thus formed comprises (PAA1)_n1The block represented by (PAA2)_n2The block represented. (PAA1)_n1And (PAA2)_n2N1 and n2 in (a) are each independently an integer of 1 or more, preferably 2 or more. In the block polymer, the diamine compound (1) may be used in any one of the polymer chains of the raw material composition, two or more of the polymer chains, or all of the polymer chains.

Here, the polyamic acid block polymer may be synthesized by separately producing two or more kinds of polyamic acids, and then mixing and heating the polyamic acids, or may be synthesized by synthesizing two or more kinds of polyamic acids in the same reaction vessel and then heating the polyamic acids.

When the polyamic acid of the present invention is a polyimide as a derivative of the polyamic acid, the obtained polyamic acid solution is imidized at a temperature of 20 to 150 ℃ together with an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride as a dehydrating agent and a tertiary amine such as triethylamine, pyridine, or collidine as a dehydration ring-closure catalyst to obtain the polyimide. Alternatively, the polyimide may be obtained by precipitating a polyamic acid from the obtained polyamic acid solution using a large amount of a poor solvent (an alcohol solvent such as methanol, ethanol, or isopropanol, or a glycol solvent such as ethylene glycol), and subjecting the precipitated polyamic acid to imidization reaction in a solvent such as toluene or xylene at a temperature of 20 to 150 ℃ together with the dehydrating agent and the dehydration ring-closure catalyst.

In the imidization reaction, the ratio of the dehydrating agent to the dehydration ring-closing catalyst is preferably 0.1 to 10 (molar ratio). The total amount of the dehydrating agent and the dehydration ring-closing catalyst used is preferably 1.5 to 10 times by mole based on the total molar amount of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid. The degree of imidization can be controlled by adjusting the amount of the dehydrating agent, the amount of the catalyst, the reaction temperature, and the reaction time used in the imidization reaction, whereby a partial polyimide in which only a part of the polyamic acid is imidized can be obtained. The obtained polyimide may be used as a liquid crystal aligning agent by being separated from the solvent used in the reaction and redissolved in another solvent, or may be used as a liquid crystal aligning agent without being separated from the solvent.

The polyamic acid ester can be obtained by the following method: a method of synthesizing by reacting a polyamic acid with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like, or a method of synthesizing by reacting a tetracarboxylic acid diester derived from a tetracarboxylic dianhydride or a tetracarboxylic acid diester dichloride with a diamine. The tetracarboxylic acid diester derived from the tetracarboxylic acid dianhydride can be obtained by, for example, reacting the tetracarboxylic acid dianhydride with 2 equivalents of an alcohol and opening the ring, and the tetracarboxylic acid diester dichloride can be obtained by reacting the tetracarboxylic acid diester with 2 equivalents or more of a chlorinating agent (for example, thionyl chloride or the like). The polyamic acid ester may have only the amic acid ester structure or may be a partially esterified product in which the amic acid structure and the amic acid ester structure coexist. The polyamic acid ester of the present invention can be obtained by using a diamine compound represented by the general formula (1) as at least one of diamines.

The polyamic acid or the derivative thereof using the diamine compound represented by the general formula (1) as a raw material can be produced in the same manner as a conventional polyamic acid or a derivative thereof used for forming a polyimide film.

The total amount of the tetracarboxylic dianhydrides to be charged is preferably 0.9 to 1.1 mol based on 1 mol of the diamine in total.

The liquid crystal aligning agent of the present invention may contain only one of these polyamic acids, polyamic acid esters, and polyimides obtained by imidizing these, or may contain two or more kinds.

The molecular weight of the polyamic acid or derivative thereof as a polymer of the present invention is preferably 5,000 to 500,000, more preferably 5,000 to 50,000, in terms of a weight average molecular weight (Mw) in terms of polystyrene. The molecular weight of the polyamic acid or its derivative can be determined by measurement using a Gel Permeation Chromatography (GPC) method.

The polyamic acid or its derivative as the polymer of the present invention can be confirmed for its presence by: the solid component obtained by precipitation in a large amount of a poor solvent was analyzed by Infrared spectroscopy (IR) and Nuclear Magnetic Resonance analysis (NMR). In addition, the monomers used can be confirmed by: the extract extracted from the decomposition product of the polyamic acid or the derivative thereof by decomposing the polyamic acid or the derivative thereof with an aqueous solution of a strong base such as potassium hydroxide or sodium hydroxide and then using an organic solvent is analyzed by Gas Chromatography (GC), High Performance Liquid Chromatography (HPLC), or Gas Chromatography-Mass Spectrometry (GC-MS).

Tetracarboxylic dianhydrides

The tetracarboxylic dianhydrides used in the raw material composition of the polymer of the present invention can be selected from the existing tetracarboxylic dianhydrides without limitation.

Examples of tetracarboxylic dianhydrides are listed below. These tetracarboxylic dianhydrides can also be derivatized to tetracarboxylic diesters or tetracarboxylic diester dichlorides for use as starting materials for the polymers. That is, the "tetracarboxylic dianhydrides" of the present invention include derivatives of tetracarboxylic dianhydrides, such as tetracarboxylic diesters or tetracarboxylic diester dihalides, in addition to tetracarboxylic dianhydrides. Any of these may be used for the polymerization, or two or more of these may be used in combination for the polymerization.

The tetracarboxylic dianhydride may be an aromatic system (including a heteroaromatic ring system) in which the dicarboxylic anhydride is directly bonded to the aromatic ring, or an aliphatic system (including a heteroaromatic ring system) in which the dicarboxylic anhydride is not directly bonded to the aromatic ring.

Examples of such tetracarboxylic dianhydrides include those represented by the following formulae (AN-1) to (AN-9), formula (AN-11), formula (AN-12), formula (AN-15), formula (AN-10-1), formula (AN-10-2), and formulae (AN-16-1) to (AN-16-17).

[ tetracarboxylic dianhydride represented by the formula (AN-1) ]

[ solution 26]

In the formula (AN-1), R¹¹Each independently represents a hydrogen atom or a methyl group. G¹¹Represents a single bond, an alkylene group having 1 to 12 carbon atoms, a1, 4-phenylene group or a1, 4-cyclohexylene group. X¹¹Each independently represents a single bond or-CH₂-。G¹²Each independently represents any one of the following trivalent groups.

[ solution 27]

At G¹²For > CH-, the hydrogen atoms > CH-may be substituted by methyl groups. At G¹²When is > N-, G¹¹Not being a single bond and-CH₂-，X¹¹Not a single bond. R¹¹Each independently represents a hydrogen atom or a methyl group.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formulae (AN-1-1) to (AN-1-15).

[ solution 28]

In the formulas (AN-1-2) and (AN-1-14), m is AN integer of 1 to 12 independently.

[ tetracarboxylic dianhydride represented by the formula (AN-2) ]

[ solution 29]

In the formula (AN-2), R⁶¹Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formulae (AN-2-1) to (AN-2-3).

[ solution 30]

[ tetracarboxylic dianhydride represented by the formula (AN-3) ]

[ solution 31]

In the formula (AN-3), ring A¹¹Represents a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formulae (AN-3-1) and (AN-3-2).

[ solution 32]

[ tetracarboxylic dianhydride represented by the formula (AN-4) ]

[ solution 33]

In the formula (AN-4), G¹³Represents a single bond, -C.ident.C-, - (CH)₂)_m-、-O-、-S-、-C(CH₃)₂-、-SO₂-、-CO-、-C(CF₃)₂A divalent group represented by the formula (G13-1) or the formula (G13-2), and m is an integer of 1 to 12. Ring A¹¹Each independently represents a cyclohexane ring or a benzene ring. G¹³May be bonded to ring A¹¹At any arbitrary position of the substrate. Here, "arbitrary position" refers to a position of a skeleton structure to which a bond is bonded, which can be substituted. The "arbitrary position" in the following description is also synonymous.

[ chemical 34]

In the formulae (G13-1) and (G13-2), G^13aAnd G^13bEach independently represents a divalent group represented by a single bond, -O-, -COO-, -OCO-, -CONH-, or-NHCO-. The phenylene group represented by each formula is preferably a1, 4-phenylene group or a1, 3-phenylene group. In the formula (G13-2), G^13cIs C1-4 alkylene or cycloalkylene, G^13dIs methyl, and n is an integer of 0 to 2.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formulae (AN-4-1) to (AN-4-37).

[ solution 35]

[ solution 36]

In the formula (AN-4-17), m is AN integer of 1-12.

[ solution 37]

[ solution 38]

[ solution 39]

[ tetracarboxylic dianhydride represented by the formula (AN-5) ]

[ solution 40]

In the formula (AN-5), R¹¹Each independently represents a hydrogen atom or a methyl group. Two R¹¹R on the middle benzene ring¹¹Bonded to any position of the benzene ring where substitution can be performed.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-5) include compounds represented by the following formulae (AN-5-1) to (AN-5-3).

[ solution 41]

[ tetracarboxylic dianhydride represented by the formula (AN-6) ]

[ solution 42]

In the formula (AN-6), X¹¹Each independently represents a single bond or-CH₂-。X¹²represents-CH₂-、-CH₂CH₂-or-CH ═ CH-. n is 1 or 2. When n is 2, two X¹²May be the same or different from each other。

Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formulae (AN-6-1) to (AN-6-12).

[ solution 43]

[ tetracarboxylic dianhydride represented by the formula (AN-7) ]

[ solution 44]

In the formula (AN-7), X¹¹Represents a single bond or-CH₂-。

Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formulae (AN-7-1) and (AN-7-2).

[ solution 45]

[ tetracarboxylic dianhydride represented by the formula (AN-8) ]

[ solution 46]

In the formula (AN-8), X¹¹Represents a single bond or-CH₂-。R¹²Represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group. Ring A¹²Represents a cyclohexane ring or a cyclohexene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formulae (AN-8-1) and (AN-8-2).

[ solution 47]

[ tetracarboxylic dianhydride represented by the formula (AN-9) ]

[ solution 48]

In the formula (AN-9), r is each independently 0 or 1.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formulae (AN-9-1) to (AN-9-3).

[ solution 49]

[ tetracarboxylic dianhydrides represented by the formulae (AN-10-1) and (AN-10-2) ]

[ solution 50]

[ tetracarboxylic dianhydride represented by the formula (AN-11) ]

[ solution 51]

In the formula (AN-11), ring A¹¹Each independently represents a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formulae (AN-11-1) to (AN-11-3).

[ solution 52]

[ tetracarboxylic dianhydride represented by the formula (AN-12) ]

[ Hua 53]

In the formula (AN-12), ring A¹¹Each independently represents a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-12) include compounds represented by the following formulae (AN-12-1) to (AN-12-3).

[ solution 54]

[ tetracarboxylic dianhydride represented by the formula (AN-15) ]

[ solution 55]

In the formula (AN-15), w is AN integer of 1 to 10.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formulae (AN-15-1) to (AN-15-3).

[ solution 56]

Examples of the tetracarboxylic dianhydrides other than those mentioned above include compounds represented by the following formulae (AN-16-1) to (AN-16-17).

[ solution 57]

[ more preferable examples of tetracarboxylic dianhydrides ]

Suitable materials for improving various properties of the liquid crystal alignment film described later among the tetracarboxylic dianhydrides will be described. When importance is attached to further improvement of the anisotropy or liquid crystal alignment property in forming the liquid crystal alignment film, the compound represented by the formula (AN-3-2), the formula (AN-4-5), the formula (AN-4-29) or the formula (AN-4-37) is more preferable.

When importance is attached to increase in transmittance of a liquid crystal display element, a compound represented by formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-16-3), or formula (AN-16-4) is preferable, where m is preferably 4 to 8 in formula (AN-1-2) and m is preferably 4 to 8 in formula (AN-4-17).

When emphasis is placed on improving the Voltage Holding Ratio (VHR) of the liquid crystal display device, the compound represented by formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-7-2), formula (AN-10-1), formula (AN-16-3), formula (AN-16-4), or formula (AN-16-17) is preferable, and m is preferably 4 to 8 in formula (AN-1-2) and m is preferably 4 to 8 in formula (AN-4-17).

As one of the methods for preventing the burn-in, it is effective to increase the relaxation speed of the residual charge (direct current (DC)) in the liquid crystal alignment film by lowering the volume resistance value of the liquid crystal alignment film. In the case where importance is attached to the object, preferred is a compound represented by the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), the formula (AN-4-29) or the formula (AN-11-3).

The compounds represented by the formulae (AN-4-32), (AN-4-33), (AN-4-34), (AN-4-35) and (AN-4-36) are compounds which are likely to undergo a photoFries rearrangement reaction. Since the diamine compound (1) of the present invention has photoreactivity, the tetracarboxylic dianhydride to be combined therewith does not necessarily have photoreactivity, but may be used in combination with the diamine compound (1) of the present invention.

Diamines

The diamine used in the raw material composition of the polymer in the present invention includes a diamine compound represented by the general formula (1) in the present invention (diamine compound (1)). For the description of the diamine compound (1), < diamine compound > column. The diamine compound (1) included in the diamine may be one kind or two or more kinds. The diamine may contain only the diamine compound (1) or may contain other diamines.

Diamines (other diamines) other than the diamine compound (1) which can be used in the diamines will be described below.

The other diamines may be selected from conventional diamines without limitation. Here, the "other diamines" include dihydrazides in addition to diamines.

In addition, diamines can be classified into two types according to their structures. That is, a diamine having a side chain group branched from the main chain when the skeleton connecting two amino groups is regarded as the main chain, and a diamine having no side chain group are used. In the following description, such a diamine having a side chain group may be referred to as a side chain type diamine. Such a diamine having no side chain group is sometimes referred to as a non-side chain type diamine. The side chain group is a group having an effect of increasing the pretilt angle.

The diamine of the other diamines used in the raw material composition may be a side chain diamine or a non-side chain diamine, or both of them may be combined. By appropriately separating the non-side chain type diamine from the side chain type diamine, a pretilt angle corresponding to each is required.

The side chain type diamine is preferably used in combination to such an extent that the characteristics of the present invention are not impaired. The side chain type diamine and the non-side chain type diamine are preferably used in a selective manner for the purpose of improving properties such as vertical alignment properties, VHR, and image sticking properties of the liquid crystal.

[ non-side-chain type diamine ]

Known diamines having no side chain are shown in the following formulae (DI-1) to (DI-16).

[ solution 58]

[ chemical 59]

[ solution 60]

The group whose bonding position is not fixed to a carbon atom constituting a ring means that the bonding position on the ring is arbitrary. Or the bonding position of the amino group on the cyclohexane ring or the benzene ring is other than G²¹、G²²、G³³Or G³⁴Any position other than the bonding position(s).

In the formula (DI-1), G²⁰represents-CH₂Or a group represented by the formula (DI-1-a). At G²⁰is-CH₂When is, m-CH₂At least one of-may be substituted by-NH-, -O-, m-CH₂At least one hydrogen atom of (A) may be substituted by a hydroxyl group or a methyl group. m is an integer of 1 to 12. When m in DI-1 is 2 or more, a plurality of G²⁰May be the same or different from each other. Wherein, in G²⁰In the case of a group represented by the following formula (DI-1-a), m is 1.

[ solution 61]

In the formula (DI-1-a), v is an integer of 1 to 6 independently.

In the formulae (DI-3), (DI-6) and (DI-7), G²¹Each independently represents a single bond, -NH-, -NCH₃-、-O-、-S-、-S-S-、-SO₂-、-CO-、-COO-、-OCO-、-CONCH₃-、-CONH-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m-、-O-(CH₂)_m-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、-(O-C₂H₄)_m-O-、-O-CH₂-C(CF₃)₂-CH₂-O-、-O-CO-(CH₂)_m-CO-O-、-CO-O-(CH₂)_m-O-CO-、-(CH₂)_m-NH-(CH₂)_m-、-CO-(CH₂)_k-NH-(CH₂)_k-、-(NH-(CH₂)_m)_k-NH-、-CO-C₃H₆-(NH-C₃H₆)_n-CO-or-S- (CH)₂)_m-S-, m is each independently an integer of 1 to 12, k is each independently an integer of 1 to 5, and n is 1 or 2.

In the formula (DI-4), s is an integer of 0 to 2 independently.

In the formula (DI-4), at least one hydrogen atom of the benzene ring may be substituted by one selected from the group of groups represented by any one of the following formulae (DI-4-a) to (DI-4-i).

[ solution 62]

[ solution 63]

In the formulae (DI-4-a) and (DI-4-b), R²⁰Each independently represents a hydrogen atom or a methyl group. In the formulae (DI-4-f) and (DI-4-g), m is independently an integer of 0 to 12, and Boc is a tert-butoxycarbonyl group.

In the formula (DI-5), G³³Is a single bond, -NH-, -NCH₃-、-O-、-S-、-S-S-、-SO₂-、-CO-、-COO-、-CONCH₃-、-CONH-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m-、-O-(CH₂)_m-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、-(O-C₂H₄)_m-O-、-O-CH₂-C(CF₃)₂-CH₂-O-、-O-CO-(CH₂)_m-CO-O-、-CO-O-(CH₂)_m-O-CO-、-(CH₂)_m-NH-(CH₂)_m-、-CO-(CH₂)_k-NH-(CH₂)_k-、-(NH-(CH₂)_m)_k-NH-、-CO-C₃H₆-(NH-C₃H₆)_n-CO-、-S-(CH₂)_m-S-、-N(Boc)-(CH₂)_e-N(Boc)-、-NH-(CH₂)_e-N(Boc)-、-N(Boc)-(CH₂)_e-、-N(Boc)-(CH₂)_e-N(CH₃)-、-(CH₂)_m-N(Boc)-CONH-(CH₂)_m-、-(CH₂)_m-N(Boc)-(CH₂)_m-, a group represented by the following formula (DI-5-a), the following formula (DI-5-b) or the following formula (DI-5-c), m is independently an integer of 1 to 12, k is an integer of 1 to 5, e is an integer of 2 to 10, and n is 1 or 2. Boc is tert-butoxycarbonyl.

[ solution 64]

In the formulae (DI-5-a) and (DI-5-c), q is an integer of 0 to 6 independently. R⁴⁴Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.

In the formula (DI-6), G³⁴Each independently represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -C (CH)₃)₂-、-C(CF₃)₂Or C1-10 alkylene, ring A¹²Represents a cyclohexane ring or a benzene ring.

In the formula (DI-7), G²²Each independently represents a single bond, -O-, -S-, -CO-, -C (CH)₃)₂-、-C(CF₃)₂Or an alkylene group having 1 to 10 carbon atoms.

At least one hydrogen atom of the cyclohexane ring and the benzene ring in the formulae (DI-2) to (DI-7) may be substituted with a fluorine atom, a chlorine atom, an alkyl group having 1 to 3 carbon atoms, a methoxy group, a hydroxyl group, a trifluoromethyl group, a carboxyl group, a carbamoyl group, a phenylamino group, a phenyl group or a benzyl group. In the formula (DI-5), G³³When it is a single bond, at least one hydrogen atom of the benzene ring may be replaced by N- (tert-butoxycarbonyl) amino or N, N-bis (tert-butoxycarbonyl)Group) amino substitution.

In the formula (DI-11), r is 0 or 1. In the formulae (DI-8) to (DI-11), the bonding position of the amino group bonded to the ring is arbitrary.

In the formula (DI-12), R²¹And R²²Each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, G²³Each independently represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, or an alkyl-substituted phenylene group, and w is an integer of 1 to 10.

In the formula (DI-13), R²³Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a chlorine atom, p is each independently an integer of 0 to 3, and q is an integer of 0 to 4.

In the formula (DI-14), ring B represents a monocyclic heterocyclic aromatic group, and R²⁴Represents a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, an alkenyl group or an alkynyl group, and q is each independently an integer of 0 to 4. When q is 2 or more, plural R²⁴May be the same or different from each other. In the formula (DI-15), ring C represents a heterocyclic aromatic group or a heterocyclic aliphatic group. In the formula (DI-16), G²⁴Represents a single bond, an alkylene group having 2 to 6 carbon atoms or a1, 4-phenylene group, and r is 0 or 1. The term "group whose bonding position is not fixed to a carbon atom constituting a ring" means that the bonding position on the ring is arbitrary. In the formulae (DI-13) to (DI-16), the bonding position of the amino group bonded to the ring is arbitrary.

Next, the known diamines having no side chain will be described in more detail with reference to specific examples. Examples of the diamine represented by the formula (DI-1) are shown in the following formulae (DI-1-1) to (DI-1-9).

[ solution 65]

In the formulae (DI-1-7) and (DI-1-8), k is independently an integer of 1 to 3. In the formula (DI-1-9), v is an integer of 1 to 6 independently.

Examples of the diamines represented by the formulae (DI-2) to (DI-3) are shown in the formulae (DI-2-1), (DI-2-2), and (DI-3-1) to (DI-3-3) below.

[ solution 66]

Examples of the diamine represented by the formula (DI-4) are shown in the following formulae (DI-4-1) to (DI-4-29).

[ solution 67]

[ solution 68]

[ solution 69]

[ solution 70]

[ solution 71]

[ chemical formula 72]

In the formulae (DI-4-20) and (DI-4-21), m is an integer of 1 to 12. In these formulae, Boc is tert-butoxycarbonyl.

[ solution 73]

Examples of the diamine represented by the formula (DI-5) are shown in the following formulae (DI-5-1) to (DI-5-50).

[ chemical formula 74]

In the formula (DI-5-1), m is an integer of 1 to 12.

[ solution 75]

In the formulas (DI-5-12) and (DI-5-13), m is an integer of 1 to 12 independently.

[ 76]

In the formula (DI-5-16), v is an integer of 1 to 6.

[ solution 77]

In the formula (DI-5-30), k is an integer of 1 to 5.

[ solution 78]

In the formulas (DI-5-35) to (DI-5-37) and (DI-5-39), m is an integer of 1 to 12, k is an integer of 1 to 5, and n is an integer of 1 or 2 in the formulas (DI-5-40).

[ solution 79]

In the formulae (DI-5-42) to (DI-5-44), e is an integer of 2 to 10, and in the formula (DI-5-45), R⁴³Each independently a hydrogen atom, an N- (tert-butoxycarbonyl) amino group or an N, N-bis (tert-butoxycarbonyl) amino group. In the formulae (DI-5-42) to (DI-5-44), Boc is a tert-butoxycarbonyl group.

[ solution 80]

[ solution 81]

Examples of the diamines represented by the formula (DI-6) are shown in the following formulae (DI-6-1) to (DI-6-10).

[ solution 82]

Examples of the diamines represented by the formula (DI-7) are shown in the following formulae (DI-7-1) to (DI-7-11).

[ solution 83]

In the formulas (DI-7-3) and (DI-7-4), m is an integer of 1 to 12, and n is 1 or 2 independently.

[ solution 84]

[ solution 85]

Examples of the diamine represented by the formula (DI-8) are shown in the following formulae (DI-8-1) to (DI-8-4).

[ solution 86]

Examples of the diamine represented by the formula (DI-9) are shown in the following formulae (DI-9-1) to (DI-9-3).

[ solution 87]

Examples of the diamines represented by the formula (DI-10) are shown in the following formulae (DI-10-1) and (DI-10-2).

[ solution 88]

Examples of the diamine represented by the formula (DI-11) are shown in the following formulae (DI-11-1) to (DI-11-3).

[ solution 89]

Examples of the diamines represented by formula (DI-12) are shown in the following formula (DI-12-1).

[ solution 90]

Examples of the diamine represented by the formula (DI-13) are shown in the following formulae (DI-13-1) to (DI-13-13).

[ solution 91]

[ solution 92]

[ solution 93]

Examples of the diamines represented by the formula (DI-14) are shown in the following formulae (DI-14-1) to (DI-14-9).

[ solution 94]

Examples of the diamine represented by the formula (DI-15) are shown in the following formulae (DI-15-1) to (DI-15-12).

[ solution 95]

[ solution 96]

Examples of the diamines represented by the formula (DI-16) are shown in the following formula (DI-16-1).

[ solution 97]

[ non-side-chain type dihydrazides ]

Next, dihydrazides that can be used in the raw material composition of the polymer of the present invention will be described. The known dihydrazides having no side chain include compounds represented by any one of the following formulae (DIH-1) to (DIH-3).

[ solution 98]

In the formula (DIH-1), G²⁵A single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-or-C (CF)₃)₂-。

In the formula (DIH-2), ring D represents a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen atom of the group may be substituted with a methyl group, an ethyl group or a phenyl group. In formula (DIH-3), rings E each independently represent a cyclohexane ring or a benzene ring, and at least one hydrogen atom of the group may be substituted with a methyl group, an ethyl group or a phenyl group. The rings E may be the same or different from each other. In the formula (DIH-3), Y represents a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO₂-、-C(CH₃)₂-or-C (CF)₃)₂-. In the formulae (DIH-2) and (DIH-3), the bonding position of the hydrazide group bonded to the ring is arbitrary.

Examples of the compounds represented by any of the formulae (DIH-1) to (DIH-3) are shown in the following formulae (DIH-1-1), (DIH-1-2), the formulae (DIH-2-1) to (DIH-2-3), and the formulae (DIH-3-1) to (DIH-3-6).

[ solution 99]

In the formula (DIH-1-2), m is an integer of 1-12.

[ solution 100]

[ solution 101]

[ side-chain type diamine ]

Diamines suitable for the purpose of increasing the pretilt angle are illustrated. The diamine having a side chain group suitable for the purpose of increasing the pretilt angle includes diamines represented by any of formulae (DI-31) to (DI-35) and formulae (DI-36-1) to (DI-36-8).

[ solution 102]

In the formula (DI-31), G²⁶Represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-or- (CH)₂)_maAnd ma is an integer of 1 to 12. G²⁶Preferred examples of (B) are a single bond, -O-, -COO-, -OCO-, -CH₂O-and C1-3 alkylene, particularly preferred examples being single bonds, -O-, -COO-, -OCO-, -CH₂O-、-CH₂-and-CH₂CH₂-。R²⁵Represents an alkyl group having 3 to 30 carbon atoms, a phenyl group, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In the alkyl group, at least one hydrogen atom may be substituted with a fluorine atom, and at least one-CH₂-O-, -CH ═ CH-or-C ≡ C-may be substituted. The hydrogen atom of the phenyl group may be substituted with a fluorine atom, a methyl group, a methoxy group, a fluoromethyloxy group, a difluoromethyloxy group, a trifluoromethyloxy group, an alkyl group having 3 to 30 carbon atoms, or an alkoxy group having 3 to 30 carbon atoms. The bonding position of the amino group bonded to the benzene ring represents an arbitrary position on the ring, and the bonding positions are preferably in a meta-or para-relationship with each other. I.e. in the reaction of the radical "R²⁵-G²⁶When the bonding position of the two amino groups is 1-position, the bonding positions of the two amino groups are preferably 3-and 5-positions or 2-and 5-positions.

[ solution 103]

In the formula (DI-31-a), G²⁷、G²⁸And G²⁹Are bonding groups, each independently is a single bond or an alkylene group having 1 to 12 carbon atoms, one or more-CH groups of the alkylene group₂-may be substituted by-O-, -COO-, -OCO-, -CONH-or-CH ═ CH-. Ring B²¹Ring B²²Ring B²³And ring B²⁴Each independently represents 1, 4-phenylene, 1, 4-cyclohexylene, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, naphthalene-1, 5-diyl, naphthalene-2, 7-diyl or anthracene-9, 10-diyl, ring B²¹Ring B²²Ring B²³And ring B²⁴Wherein at least one hydrogen atom may be substituted with a fluorine atom or a methyl group, s, t and u are each independently an integer of 0 to 2, the total of these is 1 to 5, and when s, t or u is 2, the two bonding groups in each parenthesis may be the same or different, and the two rings may be the same or different. R²⁶Represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a cyano group, a fluoromethyloxy group, a difluoromethyloxy group or a trifluoromethyloxy group, at least one-CH of the alkyl group having 1 to 30 carbon atoms or the alkoxy group having 1 to 30 carbon atoms₂May be substituted with a divalent group represented by the following formula (DI-31-b).

[ solution 104]

In the formula (DI-31-b), R²⁷And R²⁸Each independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6.

[ solution 105]

In formulae (DI-32) and (DI-33), G³⁰Each independently represents a single bond, -CO-or-CH₂-，R²⁹Each independently represents a hydrogen atom or a methyl group, R³⁰Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. At least one hydrogen atom of the benzene ring in the formula (DI-33) may be substituted with an alkyl group having 1 to 20 carbon atoms or a phenyl group. Further, a group whose bonding position is not fixed to any carbon atom constituting a ring means that the bonding position on the ring is arbitrary. Preferred are the two radicals "aminophenyl-G" in formula (DI-32)³⁰One of the-O- "bonds to the 3-position of the steroid nucleus and the other bonds to the 6-position of the steroid nucleus. Two radicals "aminophenyl-G" in the formula (DI-33)³⁰The bonding position of-O- "on the phenyl ring is preferably meta or para, respectively, with respect to the bonding position of the steroid nucleus. In the formulae (DI-32) and (DI-33), the amino group bonded to the benzene ring represents an arbitrary bonding position on the ring.

[ solution 106]

In formulae (DI-34) and (DI-35), G³¹Each independently represents-O-or C1-6 alkylene, G³²Represents a single bond or an alkylene group having 1 to 3 carbon atoms. R³¹Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, at least one-CH of the alkyl group₂-may be substituted by-O-, -CH ═ CH-, or-C ≡ C-. R³²Represents an alkyl group having 6 to 22 carbon atoms, R³³Represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. Ring B²⁵Is 1, 4-phenylene or 1, 4-cyclohexylene, r is 0 or 1. The amino group bonded to the benzene ring represents any bonding position on the ring, and is preferably independent of each other with respect to G³¹The bonding position of (A) is meta or para.

More specifically, examples of the compounds represented by formula (DI-31) are shown in the following formulae (DI-31-1) to (DI-31-55).

[ solution 107]

In the formulae (DI-31-1) to (DI-31-11), R³⁴Each independently represents an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 5 to 25 carbon atoms or an alkoxy group having 5 to 25 carbon atoms. R³⁵Each independently represents an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

[ solution 108]

In the formulae (DI-31-12) to (DI-31-17), R³⁶Each independently represents an alkyl group having 4 to 30 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms. R³⁷Each independently represents an alkyl group having 6 to 30 carbon atoms, preferably an alkyl group having 8 to 25 carbon atoms.

[ solution 109]

[ solution 111]

[ solution 112]

[ solution 113]

In the formulae (DI-31-18) to (DI-31-43), R³⁸Each independently represents carbonAlkyl group having 1 to 20 carbon atoms or alkoxy group having 1 to 20 carbon atoms, preferably alkyl group having 3 to 20 carbon atoms or alkoxy group having 3 to 20 carbon atoms. R³⁹Each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a cyano group, a fluoromethyloxy group, a difluoromethyloxy group or a trifluoromethyloxy group, preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. And G³³Represents an alkylene group having 1 to 20 carbon atoms.

[ chemical formula 114]

[ solution 115]

[ solution 116]

[ solution 117]

Examples of the compounds represented by formula (DI-32) are shown in the following formulae (DI-32-1) to (DI-32-4).

[ chemical formula 118]

Examples of the compounds represented by formula (DI-33) are shown in the following formulae (DI-33-1) to (DI-33-8).

[ solution 119]

[ chemical formula 120]

Examples of the compounds represented by formula (DI-34) are shown in the following formulae (DI-34-1) to (DI-34-12).

[ solution 121]

[ chemical formula 122]

[ solution 123]

[ solution 124]

In the formulae (DI-34-1) to (DI-34-12), R⁴⁰Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R⁴¹Each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

Examples of the compounds represented by formula (DI-35) are shown below in formulas (DI-35-1) to (DI-35-3).

[ solution 125]

In the formulae (DI-35-1) to (DI-35-3), R³⁷Each independentlyRepresents an alkyl group having 6 to 30 carbon atoms, R⁴¹Each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

The compounds represented by the formulae (DI-36-1) to (DI-36-8) are shown below.

[ solution 126]

In the formulae (DI-36-1) to (DI-36-8), R⁴²Each independently represents an alkyl group having 3 to 30 carbon atoms.

[ more preferable examples of other diamines ]

Suitable materials for improving the properties of the liquid crystal alignment film described later in the above diamines are described. In the case where importance is attached to improvement of anisotropy or liquid crystal alignment properties in forming a photo-alignment film, it is preferable to use a compound represented by formula (DI-1-3), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-29), formula (DI-6-7), formula (DI-7-3), or formula (DI-11-2). In the formula (DI-5-1), m is preferably 2 to 8, and more preferably 2 to 4. In the formula (DI-5-12), m is preferably 2 to 6, and more preferably 2 to 4. In formula (DI-5-13), m is preferably 1 or 2, and more preferably m is 1.

When importance is attached to the improvement of the transmittance, it is preferable to use a diamine represented by the formula (DI-1-3), the formula (DI-2-1), the formula (DI-5-5), the formula (DI-5-24) or the formula (DI-7-3), and more preferable is a compound represented by the formula (DI-2-1). In the formula (DI-5-1), m is preferably 2 to 8, and more preferably 8. In formula (DI-7-3), m is preferably 2 or 3 and n is 1 or 2, more preferably m is 3 and n is 1.

In the case where importance is attached to increase of VHR of a liquid crystal display element, a compound represented by formula (DI-2-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-4-22), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30) or formula (DI-13-1) is preferably used, and a diamine represented by formula (DI-2-1), formula (DI-5-1) or formula (DI-13-1) is more preferably used. In formula (DI-5-1), m is preferably 1. In the formula (DI-5-30), k is preferably 2.

As one of the methods for preventing burn marks, it is effective to increase the relaxation rate of residual charges (residual DC) in the liquid crystal alignment film by decreasing the volume resistance value of the liquid crystal alignment film. In the case where the object is important, it is preferable to use a compound represented by formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-4-20), formula (DI-4-21), or formula (DI-16-1), and more preferably a compound represented by formula (DI-4-1), formula (DI-5-1), or formula (DI-5-13). In the formula (DI-5-1), m is preferably 2 to 8, and more preferably 4 to 8. In the formula (DI-5-12), m is preferably 2 to 6, and more preferably 5. In formula (DI-5-13), m is preferably 1 or 2, and more preferably m is 1.

[ other photoreactive diamines ]

As described above, the diamine compound (1) of the present invention shows photoreactivity, and therefore, other diamines used in combination therewith do not necessarily have photoreactivity, but diamines showing photoreactivity may be used in combination with the diamine compound (1). Examples of the other photoreactive diamine compound that may undergo a photo-Fries rearrangement reaction include compounds represented by the following formulae (DI-5-32), (DI-5-33), (DI-5-35), (DI-5-36), (DI-6-8), (DI-6-9) and (DI-6-10).

[ solution 127]

In the formulas (DI-5-35) and (DI-5-36), m is an integer of 1 to 12.

[ blending amount of diamine Compound represented by the general formula (1) in the raw Material composition ]

In the raw material composition of the polymer used in the present invention, the amount of the diamine compound (1) to be used as the polymer in the raw material composition is preferably 40 to 100 mol%, more preferably 50 to 100 mol%, based on the total amount of diamines used as the raw material. The blending amount of the diamine compound (1) in the case where the polymer used in the present invention is a block polymer is preferably 10 to 100 mol%, more preferably 20 to 70 mol%, based on the total amount of diamines used as raw materials.

In the raw material composition of the polymer used in the present invention, a part of the diamine may be substituted with at least one selected from the group consisting of a monoamine and a monohydrazide. The ratio of substitution is preferably in a range of 40 mol% or less of at least one member selected from the group consisting of monoamines and monohydrazides with respect to diamines. Such substitution can cause termination of the polymerization reaction when the polyamic acid is produced, and can inhibit further progress of the polymerization reaction. Therefore, by such substitution, the molecular weight of the obtained polymer (polyamic acid or derivative thereof) can be easily controlled, and for example, the coating property of the liquid crystal aligning agent can be improved without impairing the effect of the present invention. The diamine which may be substituted with a monoamine or a monohydrazide may be one or two or more species as long as the effect of the present invention is not impaired. Examples of the monoamine include: aniline, 4-hydroxyaniline, cyclohexylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, eicosylamine, p-aminophenyltrimethoxysilane, and 3-aminopropyltriethoxysilane.

The raw material composition of the polymer used in the present invention may further contain a monoisocyanate compound as a monomer. By including a monoisocyanate compound in the monomer, the end of the obtained polyamic acid or a derivative thereof is modified, and the molecular weight is adjusted. By using the end-modified polyamic acid or the derivative thereof, for example, the application characteristics of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. From the above viewpoint, the content of the monoisocyanate compound in the monomer is preferably 1 to 10 mol% based on the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The polymer of the present invention is useful as a material for liquid crystal alignment films, optically anisotropic bodies, retardation films, optical compensation films, antireflection films, various films, optical members, or the like. When the polymer of the present invention is used for a liquid crystal alignment film, an optically anisotropic body, a retardation film, an optical compensation film, an antireflection film, various films, an optical member, or the like, these polymers may include one kind of the polymer of the present invention, or two or more kinds of the polymers of the present invention may be mixed. Among these applications, the polymer of the present invention is preferably included in an application where more importance is placed on orientation, for example, a retardation film.

< liquid Crystal Aligning agent >

Hereinafter, the liquid crystal aligning agent obtained from the polymer of the present invention will be described in detail.

The liquid crystal aligning agent of the present invention is characterized by comprising the polymer of the present invention. For the description of the polymer of the present invention, reference is made to the description in the column < polymer >.

The liquid crystal aligning agent of the present invention may contain one or two or more kinds of the polymers of the present invention. The polymer contained in the liquid crystal aligning agent of the present invention may be only the polymer of the present invention, or may be a mixture of the polymer of the present invention and a polymer (other polymer) other than the polymer of the present invention. In the present specification, a liquid crystal aligning agent containing only one kind of polymer is sometimes referred to as a monolayer type liquid crystal aligning agent. A liquid crystal aligning agent containing two or more polymers is sometimes referred to as a blend liquid crystal aligning agent. The blended liquid crystal aligning agents are particularly useful in cases where VHR reliability or other electrical properties are important.

The other polymer used in the blend-type liquid crystal aligning agent is preferably at least one of polyamic acid or a derivative thereof. As the polyamic acid or the derivative thereof as another polymer, a polymer obtained by polymerizing a raw material composition containing a diamine (another diamine) other than the diamine compound represented by the general formula (1) and a tetracarboxylic acid dianhydride can be used. For the description of tetracarboxylic dianhydrides and other diamines, reference is made to the corresponding statements in the column < polymer >.

In the case of using a two-component polymer, for example, the following forms are mentioned: one of them is a polymer having excellent properties in terms of liquid crystal aligning ability, and the other is a polymer having excellent properties for improving the electrical characteristics of the liquid crystal display element, and it is desirable to obtain a liquid crystal aligning agent having a good balance between liquid crystal aligning properties and electrical characteristics.

In this case, by controlling the structure or molecular weight of each polymer, one polymer can be segregated in the upper layer of the film and the other polymer can be segregated in the lower layer of the film. That is, by controlling the structure or molecular weight of the polymer, in the process of forming a film by pre-drying a coating film of a liquid crystal aligning agent prepared by dissolving two kinds of polymers in a solvent, a polymer having excellent liquid crystal aligning ability is segregated in an upper layer of the film, and a polymer having excellent electrical property improving ability of a liquid crystal display element is segregated in a lower layer of the film. Among them, in the mixed polymers, a phenomenon that a polymer having a small surface energy is separated from an upper layer and a polymer having a large surface energy is separated from a lower layer can be applied. Confirmation of such phase separation can be confirmed by: the surface energy of the formed liquid crystal alignment film is the same as or similar to that of a film formed from a liquid crystal aligning agent containing only a polymer intended to segregate in the upper layer.

Examples of the method of developing the layer separation include a method of making the molecular weight of the polymer segregated in the upper layer smaller than the molecular weight of the polymer segregated in the lower layer, and a method of using polyimide as the polymer segregated in the upper layer.

Here, the diamine compound represented by the general formula (1) can be used as a raw material monomer for a polymer segregated in an upper layer of a thin film, can also be used as a raw material monomer for a polymer segregated in a lower layer of a thin film, and can also be used as a raw material monomer for two polymers.

The tetracarboxylic acid dianhydride used in the raw material composition of the polyamic acid or the derivative thereof that segregates in the upper layer of the thin film can be selected from the conventional tetracarboxylic acid dianhydrides exemplified above without limitation.

The tetracarboxylic dianhydride used in the raw material composition of the polyamic acid or derivative thereof segregated in the upper layer of the thin film is preferably a compound represented by formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-5), formula (AN-4-17) or formula (AN-4-21), and more preferably formula (AN-4-17) or formula (AN-4-21). In the formula (AN-4-17), m is preferably 4-8.

The diamines other than the diamine compound represented by the formula (1) used in the raw material composition of the polyamic acid or derivative thereof segregated in the upper layer of the thin film can be selected from the conventional diamines exemplified above without limitation.

As the diamine other than the diamine compound represented by the formula (1) used in the raw material composition of the polyamic acid or the derivative thereof segregated in the upper layer of the thin film, a compound represented by the formula (DI-4-1), the formula (DI-4-13), the formula (DI-4-15), the formula (DI-5-1), the formula (DI-7-3), or the formula (DI-13-1) is preferably used. Among them, compounds represented by the formula (DI-4-13), the formula (DI-4-15), the formula (DI-5-1) or the formula (DI-13-1) are more preferably used. In the formula (DI-5-1), m is preferably 4 to 8. In formula (DI-7-3), m is preferably 3 and n is preferably 1.

The tetracarboxylic acid dianhydride used in the raw material composition of the polyamic acid or derivative thereof that segregates in the lower layer of the thin film can be selected from the conventional tetracarboxylic acid dianhydrides exemplified above without limitation.

The tetracarboxylic dianhydride used in the raw material composition of the polyamic acid or derivative thereof segregated in the lower layer of the thin film is preferably a compound represented by formula (AN-1-1), formula (AN-1-13), formula (AN-2-1), formula (AN-3-2) or formula (AN-4-21), and more preferably a compound represented by formula (AN-1-1), formula (AN-2-1) or formula (AN-3-2).

The tetracarboxylic dianhydride used in the raw material composition of the polyamic acid or derivative thereof that segregates in the lower layer of the thin film is preferably an aromatic tetracarboxylic dianhydride contained in an amount of 10 mol% or more, more preferably 30 mol% or more, based on the total amount of the tetracarboxylic dianhydride.

The diamines other than the diamine compound represented by the formula (1) used in the raw material composition of the polyamic acid or derivative thereof segregated in the lower layer of the thin film can be selected from the above-mentioned exemplified conventional diamines without limitation.

As the diamine other than the diamine compound represented by the formula (1) used in the raw material composition of the polyamic acid or the derivative thereof segregated in the lower layer of the thin film, preferred is a compound represented by the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), the formula (DI-4-18), the formula (DI-4-19), the formula (DI-5-1), the formula (DI-5-9), the formula (DI-5-28), the formula (DI-5-30), the formula (DI-13-1) or the formula (DIH-1-2). In the formula (DI-5-1), a compound in which m is 1 or 2 is preferable, and in the formula (DI-5-30), a compound in which k is 2 is preferable. Among them, more preferred are compounds represented by the formula (DI-4-1), the formula (DI-4-18), the formula (DI-4-19), the formula (DI-5-9), the formula (DI-13-1) or the formula (DIH-1-2).

The diamine used in the raw material composition of the polyamic acid or the derivative thereof segregated in the lower layer of the thin film preferably contains at least one selected from the group consisting of an aromatic diamine and an aromatic dihydrazide in an amount of 30 mol% or more, more preferably 50 mol% or more, based on all diamines.

The ratio of the polyamic acid or the derivative thereof segregated in the upper layer of the film to the total amount of the polyamic acid or the derivative thereof segregated in the upper layer of the film and the polyamic acid or the derivative thereof segregated in the lower layer of the film is preferably 5 to 50% by weight, more preferably 10 to 40% by weight.

The liquid crystal aligning agent of the present invention may further contain a solvent from the viewpoint of coatability of the liquid crystal aligning agent or adjustment of the concentration of the polyamic acid or the derivative thereof. The solvent is not particularly limited as long as it has an ability to dissolve the polymer component, and may be suitably selected from, for example, a solvent generally used in a production process of a polymer component such as polyamic acid or soluble polyimide, a solvent for polyamic acid or a derivative thereof, and other solvents for the purpose of improving coatability, depending on the purpose of use. The solvent may be one or a mixture of two or more.

Examples of the aprotic polar organic solvent which is a solvent-philic solvent for the polyamic acid or a derivative thereof include: n-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropanamide, N-dimethylacetamide, dimethyl sulfoxide, N-dimethylformamide, N-diethylformamide, diethylacetamide, N-dimethylisobutylamide, γ -butyrolactone, γ -valerolactone, and the like. Among these solvents, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ -butyrolactone, or γ -valerolactone are preferable.

Examples of other solvents for the purpose of improving coatability and the like include: ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether and ethylene glycol monobutyl ether, diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, and diethylene glycol dialkyl ethers such as diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and diethylene glycol butyl methyl ether. Further, there may be mentioned: propylene glycol monoalkyl ether such as propylene glycol monomethyl ether and 1-butoxy-2-propanol, dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether, triethylene glycol monoalkyl ether, phenyl acetate, and ester compounds such as these acetates. Further, there may be mentioned: dialkyl malonate such as diethyl malonate, alkyl lactate, diisobutyl ketone, diacetone alcohol, 3-methyl-3-methoxybutyl alcohol, 4-methyl-2-pentanol, 2, 6-dimethyl-4-heptanol, tetrahydronaphthalene, and isophorone.

Among these solvents, diisobutyl ketone, 4-methyl-2-pentanol, 2, 6-dimethyl-4-heptanol, ethylene glycol monobutyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, 1-butoxy-2-propanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, or butyl cellosolve acetate are preferable.

The concentration of the polymer in the liquid crystal aligning agent of the present invention is not particularly limited, and an optimum value may be selected in combination with the following various coating methods. In general, in order to suppress unevenness, pinholes, and the like during coating, the amount is preferably 0.1 to 30 wt%, more preferably 1 to 10 wt%, based on the weight of the liquid crystal aligning agent.

The viscosity of the liquid crystal aligning agent of the present invention varies in a preferable range according to the method of application, the concentration of the polyamic acid or the derivative thereof, the type of the polyamic acid or the derivative thereof used, and the type and ratio of the solvent. For example, the viscosity is 5 to 100 mPas (more preferably 10 to 80 mPas) when the coating is performed by a printer. When the viscosity is 5mPa · s or more, a sufficient film thickness is easily obtained, and when the viscosity is 100mPa · s or less, uneven printing is easily suppressed. When the coating is performed by spin coating, it is preferably 5 to 200 mPas (more preferably 10 to 100 mPas). When the coating is performed using an inkjet coating apparatus, it is preferably 5 to 50mPa · s (more preferably 5 to 20mPa · s). The viscosity of the liquid crystal aligning agent can be measured by a rotational viscosity measuring method, for example, a rotational viscometer (TVE-20L manufactured by Toyobo industries, Ltd.) (measurement temperature: 25 ℃ C.).

The liquid crystal aligning agent of the present invention may include only a polymer component, and may further include various additives. In order to improve various properties of the alignment film, various additives may be selected and used according to the respective purposes. Examples of additives that can be used in the liquid crystal aligning agent are shown below.

(alkenyl-substituted nadimide Compound)

For example, the liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadimide compound for the purpose of stabilizing the electrical characteristics of a liquid crystal display element for a long period of time. One kind of the alkenyl-substituted nadimide compound may be used, and two or more kinds thereof may be used in combination. For the purpose, the content of the alkenyl-substituted nadimide compound is preferably 1 to 50 wt%, more preferably 1 to 30 wt%, and still more preferably 1 to 20 wt% with respect to the polyamic acid or the derivative thereof. The alkenyl-substituted nadimide compound is preferably a compound that can be dissolved in a solvent in which the polyamic acid or the derivative thereof used in the present invention is dissolved. Preferred examples of the alkenyl-substituted nadimide compound include alkenyl-substituted nadimide compounds disclosed in Japanese patent laid-open Nos. 2008-096979, 2009-109987, and 2013-242526. Particularly preferred alkenyl-substituted nadimide compounds include: bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) phenyl } methane, N '-isophthaloyl-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide) or N, N' -hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide).

(Compound having a radically polymerizable unsaturated double bond)

For example, the liquid crystal aligning agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond for the purpose 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 one kind of compound, or two or more kinds of compounds. Further, the compound having a radical polymerizable unsaturated double bond does not contain an alkenyl-substituted nadimide compound. Among the compounds having a radical polymerizable unsaturated double bond, preferable compounds include: n, N ' -methylenebisacrylamide, N ' -dihydroxyethylene-bisacrylamide, ethylene bisacrylate, 4' -methylenebis (N, N-dihydroxyethylene acrylate aniline), triallyl cyanurate, and compounds having a radical polymerizable unsaturated double bond disclosed in Japanese patent laid-open Nos. 2009-109987, 2013-242526, International publication No. 2014/119682, and 2015/152014. For the above purpose, the content of the compound having a radical polymerizable unsaturated double bond is preferably 1 to 50% by weight, more preferably 1 to 30% by weight, based on the polyamic acid or its derivative.

(oxazine compound)

For example, the liquid crystal aligning agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics of a liquid crystal display element for a long period of time. The oxazine compound may be one compound or two or more compounds. For the purpose, the content of the oxazine compound is preferably 0.1 to 50 wt%, more preferably 1 to 40 wt%, and still more preferably 1 to 20 wt% with respect to the polyamic acid or derivative thereof.

The oxazine compound is preferably an oxazine compound that is soluble in a solvent in which the polyamic acid or derivative thereof is soluble and has ring-opening polymerizability. As preferable oxazine compounds, oxazine compounds represented by the formula (OX-3-1), the formula (OX-3-9) and the formula (OX-3-10) and oxazine compounds disclosed in Japanese patent laid-open Nos. 2007-286597 and 2013-242526 are mentioned.

[ solution 128]

(oxazoline compound)

For example, the liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. For the above purpose, the content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably 1 to 20% by weight, based on the polyamic acid or a derivative thereof. As the oxazoline compound, those disclosed in Japanese patent laid-open publication No. 2010-054872 and Japanese patent laid-open publication No. 2013-242526 are preferable. More preferably, 1, 3-bis (4, 5-dihydro-2-oxazolyl) benzene is cited.

(epoxy compound)

For example, the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time, for the purpose of increasing the hardness of the film, or for the purpose of improving the adhesion to the sealant. The epoxy compound may be one compound or two or more compounds. For the above purpose, the content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 20% by weight, and still more preferably 1 to 10% by weight, based on the polyamic acid or a derivative thereof.

As the epoxy compound, various compounds having one or more epoxy rings in the molecule can be used.

For the purpose of increasing the hardness of the film or improving the adhesion to the sealing agent, a compound having two or more epoxy rings in the molecule is preferable, and a compound having three or four epoxy rings in the molecule is more preferable.

Examples of the epoxy compound include those disclosed in Japanese patent laid-open Nos. 2009-175715, 2013-242526, 2016-170409 and 2017/217413. Preferred epoxy compounds include: n, N, N ', N' -tetraglycidyl-4, 4 '-diaminodiphenylmethane, 3-glycidoxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, (3,3',4,4 '-diepoxy) bicyclohexyl, 1' -bis-7-oxabicyclo [4.1.0] heptane, 1, 4-butanediol glycidyl ether, tris (2, 3-epoxypropyl) isocyanurate, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane or N, N, N ', N' -tetraglycidyl-m-xylylenediamine.

In addition to the above, an oligomer or polymer having an epoxy ring may be added. As the oligomer or polymer having an epoxy ring, those disclosed in Japanese patent laid-open publication No. 2013-242526 can be used.

(silane Compound)

For example, the liquid crystal aligning agent of the present invention may further contain a silane compound for the purpose of improving adhesion to a substrate and a sealant. For the above purpose, the content of the silane compound is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and still more preferably 0.5 to 10% by weight, based on the polyamic acid or derivative thereof.

As the silane coupling agent, there can be used those disclosed in Japanese patent laid-open Nos. 2013-242526, 2015-212807, 2018-173545 and International publication No. 2018/181566.

Preferred silane coupling agents include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, p-aminophenyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-isocyanatopropyltriethoxysilane or 3-ureidopropyltriethoxysilane.

In addition to the above-described additives, a compound having a cyclocarbonate group, a compound having a hydroxyalkylamide moiety or a hydroxyl group may be added for the purpose of enhancing the strength of an alignment film or for the purpose of stabilizing the electrical characteristics of a liquid crystal display element for a long period of time. Specific examples of the compound include those disclosed in Japanese patent laid-open publication No. 2016-118753 and International publication No. 2017/110976. Preferred compounds include the following formulae (HD-1) to (HD-4). These compounds are preferably 0.5 to 50 wt%, more preferably 1 to 30 wt%, and still more preferably 1 to 10 wt% with respect to the polyamic acid or a derivative thereof.

[ solution 129]

In addition, an antistatic agent may be used when it is necessary to improve the antistatic property, and an imidization catalyst may be used when imidization is performed at a low temperature. As the imidization catalyst, an imidization catalyst disclosed in Japanese patent laid-open publication No. 2013-242526 can be mentioned.

< liquid Crystal alignment film >

Next, the liquid crystal alignment film of the present invention will be described.

The liquid crystal alignment film of the present invention is formed by using the liquid crystal aligning agent of the present invention. For the description of the liquid crystal aligning agent of the present invention, reference is made to the description in the column of < liquid crystal aligning agent >.

In the case where the liquid crystal alignment agent of the present invention comprises polyamic acid, when a coating film of the liquid crystal alignment agent is heated and calcined in the process of forming a liquid crystal alignment film, the polyamic acid may cause imidization reaction to form a polyimide-based liquid crystal alignment film. The liquid crystal aligning agent of the present invention is suitable for a liquid crystal aligning agent for photo-alignment, and can be applied to a photo-alignment method in alignment treatment in a process of forming a liquid crystal alignment film.

< method for producing liquid crystal alignment film >

The following describes a method for producing a liquid crystal alignment film of the present invention.

The liquid crystal alignment film of the present invention can be obtained by a general method for producing a liquid crystal alignment film from a liquid crystal aligning agent for photo-alignment. Specifically, the liquid crystal alignment film of the present invention can be formed by the following steps: a step of forming a coating film by applying the liquid crystal aligning agent of the present invention to a substrate, and a step of irradiating the coating film with light. Further, the liquid crystal alignment film of the present invention is preferably produced, for example, by performing the following steps: the method for producing a liquid crystal alignment material comprises a step of applying the liquid crystal alignment material of the present invention to a substrate to form a coating film, a step of heating and drying the coating film to form a film of the liquid crystal alignment material, a step of irradiating the film of the liquid crystal alignment material with light to impart anisotropy, and a step of heating and calcining the film of the liquid crystal alignment material to which anisotropy is imparted. That is, the liquid crystal alignment film of the present invention is preferably subjected to a coating step, a heat drying step, a subsequent heat baking step, and then light irradiation to impart anisotropy. The light irradiated to impart anisotropy is preferably polarized ultraviolet light.

The coating film can be formed by applying the liquid crystal aligning agent of the present invention to a substrate in a liquid crystal display device, in the same manner as in the production of a general liquid crystal alignment film. Examples of the substrate include an Indium Tin Oxide (ITO) substrate and an Indium zinc Oxide (In) substrate₂O₃-ZnO, IZO), indium gallium zinc oxide (In-Ga-ZnO)₄IGZO) electrodes, glass substrates such as color filters, silicon nitride substrates, acrylic substrates, polycarbonate substrates, and polyimide substrates.

As a method of applying the liquid crystal aligning agent to the substrate, 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 equally applicable to the present invention.

In the heat drying step, a method of performing heat treatment in an oven or an infrared oven, a method of performing heat treatment on a hot plate, and the like are generally known. The heat drying step is preferably performed at a temperature within a range in which the solvent is evaporable, and more preferably at a temperature relatively lower than the temperature in the heat calcining step. Specifically, the heating and drying temperature is preferably in the range of 30 to 150 ℃, and more preferably in the range of 50 to 120 ℃.

The heating and calcining step may be carried out under conditions necessary for the polyamic acid or a derivative thereof to exhibit imidization. As a method for baking a coating film, a method of performing a heat treatment in an oven or an infrared oven, a method of performing a heat treatment on a hot plate, and the like are generally known. These methods are equally applicable to the present invention. It is generally preferably carried out at a temperature of about 90 to 300 ℃ for 1 minute to 3 hours, more preferably 120 to 280 ℃, and still more preferably 150 to 250 ℃.

In the case where importance is attached to improvement of the anisotropy of the film or improvement of the afterimage characteristics in the production of the liquid crystal display element, it is preferable to gradually increase the temperature in the heating step, and for example, heating may be performed while raising the temperature stepwise and performing heating and baking at different temperatures for a plurality of times or while changing the temperature from a low temperature to a high temperature. Alternatively, two heating methods may be combined.

When the heating and calcination are performed a plurality of times at different temperatures, a plurality of heating devices set to different temperatures may be used, or heating and calcination may be performed while sequentially changing to different temperatures using one heating device.

When the calcination is carried out at different temperatures, the calcination is preferably carried out at a first calcination temperature of 90 to 180 ℃ and preferably at a last calcination temperature of 185 to 300 ℃. For example, it is preferable that the calcination is carried out by heating at 110 ℃ and then at 220 ℃, the calcination is carried out by heating at 110 ℃ and then at 230 ℃, the calcination is carried out by heating at 130 ℃ and then at 220 ℃, the calcination is carried out by heating at 150 ℃ and then at 200 ℃, the calcination is carried out by heating at 150 ℃ and then at 220 ℃, the calcination is carried out by heating at 150 ℃ and then at 230 ℃, or the calcination is carried out by heating at 170 ℃ and then at 200 ℃. Further, it is also preferable to perform heating and calcination while gradually raising the temperature in increasing stages. When the heating temperature is changed to perform the heating and calcination in two or more stages, the heating time in each heating step is preferably 5 to 30 minutes.

When the calcination is performed while changing the temperature from a low temperature to a high temperature, the initial temperature is preferably 90 to 180 ℃. The final temperature is preferably from 185 ℃ to 300 ℃ and more preferably from 190 ℃ to 230 ℃. The heating time is preferably 5 minutes to 60 minutes, more preferably 20 minutes to 60 minutes. The temperature increase rate may be set to 0.5 ℃/min to 40 ℃/min, for example. The rate of temperature rise during temperature rise may not be fixed.

In the method for forming a liquid crystal alignment film of the present invention, a conventional photo-alignment method can be suitably used as a method for imparting anisotropy to a thin film in order to align a liquid crystal in one direction with respect to a horizontal direction and/or a vertical direction.

The method for forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described in detail. The liquid crystal alignment film of the present invention using the photo-alignment method can be formed by: the film obtained by heating and drying the coating film is irradiated with linearly polarized light or unpolarized light to impart anisotropy to the film, and the film is heated and calcined. Alternatively, the film can be formed by heating and drying the coating film, heating and calcining the coating film, and then irradiating the film with linearly polarized light or unpolarized light. In terms of the liquid crystal alignment properties, the light irradiation step is preferably performed before the heating and calcining step.

Further, in order to improve the liquid crystal alignment ability of the liquid crystal alignment film, linearly polarized light or unpolarized light may be irradiated to the coating film while heating the coating film. The irradiation with light may be performed in the step of heating and drying the coating film or in the step of heating and calcining, or may be performed between the heating and drying step and the heating and calcining step.

The heating temperature when light is irradiated in the step of heating and drying or the step of heating and calcining the coating film can be referred to the description of the heating and drying step or the heating and calcining step. The heating temperature when light is irradiated between the heat drying step and the heat calcining step is preferably in the range of 30 to 150 ℃, and more preferably in the range of 50 to 110 ℃.

As the light, for example, ultraviolet rays or visible light rays including light having a wavelength of 150nm to 800nm, preferably ultraviolet rays including light having a wavelength of 200nm to 400nm, can be used. In addition, linearly polarized light or unpolarized light may be used. The light is not particularly limited as long as it can impart liquid crystal alignment ability to the film, and when it is desired to exhibit strong alignment regulating force to the liquid crystal, linear polarization is preferable.

The liquid crystal alignment film of the present invention can exhibit high anisotropy even under light irradiation of low energy. The irradiation amount of linearly polarized light in the light irradiation step is preferably 0.05J/cm²～10J/cm²More preferably 0.1J/cm²～5J/cm². The irradiation angle of the linearly polarized light to the film surface is not particularly limited, and when strong orientation restriction force for the liquid crystal is to be exerted, it is preferable to be as perpendicular as possible to the film surface from the viewpoint of shortening the orientation treatment time. In addition, the liquid crystal alignment film of the present invention can align liquid crystals in a direction perpendicular to the polarization direction of linearly polarized light by irradiating the linearly polarized light.

As a light source used in the step of linearly polarizing or unpolarizing light to be irradiated, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a Deep ultraviolet (Deep UV) lamp, a halogen lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, a mercury xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, a Light Emitting Diode (LED) lamp, a sodium lamp, a microwave excited electrodeless lamp, or the like can be used without limitation.

The liquid crystal alignment film of the present invention can be suitably obtained by a method further including a step other than the above-described steps.

The liquid crystal alignment film of the present invention does not require a step of cleaning the film after firing or light irradiation with a cleaning liquid, but a cleaning step may be provided according to the case of other steps. Examples of the cleaning method using the cleaning liquid include: brushing (brushing), spraying (jet spray), steam cleaning, ultrasonic cleaning, or the like. These methods may be carried out alone or in combination. As the cleaning liquid, there can be used: pure water, alcohols such as methanol, ethanol, and isopropanol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as methylene chloride, and ketones such as acetone and methyl ethyl ketone, but the present invention is not limited thereto. Of course, these cleaning solutions may be sufficiently purified and contain less impurities. Such a cleaning method can be applied to the cleaning step in the formation of the liquid crystal alignment film of the present invention.

In order to improve the liquid crystal alignment ability of the liquid crystal alignment film of the present invention, annealing treatment by heat or light may be used before and after the heating and baking step or before and after irradiation with polarized or unpolarized light. In the annealing treatment, the annealing temperature is 30-180 ℃, preferably 50-150 ℃, and the time is preferably 1 minute-2 hours. Examples of the annealing light used for the annealing treatment include UV lamps, fluorescent lamps, and LED lamps. The irradiation amount of light is preferably 0.3J/cm²～10J/cm²。

The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10nm to 300nm, more preferably 30nm to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a conventional film thickness measuring apparatus such as a profilometer or an ellipsometer.

The liquid crystal alignment film of the present invention is characterized by having particularly large anisotropy of alignment. The magnitude of such anisotropy can be evaluated by the method using polarized IR described in JP-A-2005-275364 and the like. In addition, evaluation can also be performed by a method using ellipsometry (ellipsometry). In detail, the retardation value of the liquid crystal alignment film can be measured by a spectroscopic ellipsometer. The retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, it is considered that a film of a polymer having a large retardation value has a large degree of alignment, and in the case of being used as a liquid crystal alignment film, the liquid crystal alignment film having a larger anisotropy has a larger alignment restriction force with respect to a liquid crystal composition.

The liquid crystal alignment film of the present invention is useful for alignment control of a liquid crystal composition for liquid crystal displays such as smart phones, input panels, vehicle monitors, and televisions. In addition to the alignment use of the liquid crystal composition for liquid crystal displays, the composition can be used for alignment control of all other liquid crystal materials such as optical compensation materials and broadband variable phase shifters using microwaves/millimeter wave bands of liquid crystals. In addition, the liquid crystal alignment film of the present invention has large anisotropy, and thus can be used alone for optical compensation material applications.

< liquid crystal display element >

Next, the liquid crystal display device of the present invention will be described.

The liquid crystal display element of the present invention is characterized by having the liquid crystal alignment film of the present invention, and can realize high display quality due to its high contrast.

The liquid crystal display device of the present invention will be described in detail. In the present invention, a liquid crystal alignment film includes a liquid crystal alignment film of the present invention, and the liquid crystal display element includes a pair of substrates disposed to face each other, an electrode formed on one or both of facing surfaces of the pair of substrates, the liquid crystal alignment film formed on the facing surface of each of the pair of substrates, a liquid crystal layer formed between the pair of substrates, a pair of polarizing films provided so as to sandwich the facing substrates, a backlight, and a driving device.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such an electrode include ITO and a metal vapor deposited film. The electrode may be formed over the entire surface of one surface of the substrate, or may be formed in a desired shape by patterning, for example. Examples of the desired shape of the electrode include a comb-like or zigzag structure. The electrode may be formed on one of the pair of substrates or on both of the substrates. The form of the electrode varies depending on the type of the liquid crystal display element, and for example, in the case of an IPS type liquid crystal display element (lateral electric field type liquid crystal display element), the electrode is disposed on one of the pair of substrates, and in the case of the other liquid crystal display element, the electrode is disposed on both of the pair of substrates. Forming the liquid crystal alignment film on the substrate or the electrode.

In the case of a liquid crystal display element (for example, IPS, FFS, or the like) that is aligned in parallel, as a configuration, at least a backlight, a first polarizing film, a first substrate, a first liquid crystal alignment film, a liquid crystal layer, a second substrate, and a second polarizing film are provided from the backlight side, and the polarizing axis of the polarizing film is provided so that the polarizing axis (the direction of polarization absorption) of the first polarizing film intersects with (preferably intersects with) the polarizing axis of the second polarizing film. In this case, the polarizing axis of the first polarizing film may be parallel to the liquid crystal alignment direction or may be orthogonal to the liquid crystal alignment direction. A liquid crystal display element provided such that the polarizing axis of the first polarizing film is parallel to the liquid crystal alignment direction is referred to as an O-mode, and a liquid crystal display element provided so as to be orthogonal thereto is referred to as an E-mode. The liquid crystal alignment film of the present invention can be applied to either of the O-mode and the E-mode, and can be selected according to the purpose.

When the polarization axis of the polarized light irradiated for imparting anisotropy to the liquid crystal alignment agent is made parallel to and coincident with the polarization axis of the polarized light originating from the polarizing film disposed on the backlight side (in the case of using the liquid crystal alignment agent of the present invention, the O-mode arrangement is adopted), the transmittance of the liquid crystal alignment film in the light absorption wavelength region increases. Therefore, the transmittance of the liquid crystal display element can be further improved.

The liquid crystal layer is formed by sandwiching the liquid crystal composition between the pair of substrates facing each other, the pair of substrates having the liquid crystal alignment films formed thereon. In the formation of the liquid crystal layer, a spacer which is present between the pair of substrates with an appropriate interval interposed therebetween, such as fine particles or a resin sheet, may be used as necessary.

As a method for forming a liquid crystal layer, a vacuum injection method and a One Drop Fill (ODF) method are known.

In the vacuum injection method, a gap (cell gap) is provided so that the liquid crystal alignment films face each other, and a sealant is printed to adhere the substrates while leaving the injection port of the liquid crystal. Liquid crystal is injected and filled into a cell gap defined by the substrate surface and the sealant by using a vacuum differential pressure, and then the injection port is closed, thereby manufacturing a liquid crystal display element.

In the ODF method, a sealant is printed on the outer periphery of the liquid crystal alignment film surface of one of the pair of substrates, liquid crystal is dropped on the region inside the sealant, and then the other substrate is bonded so that the liquid crystal alignment film surfaces face each other. Then, the liquid crystal is spread over the entire surface of the substrate by pressing, and then ultraviolet light is irradiated to the entire surface of the substrate to cure the sealant, thereby manufacturing a liquid crystal display element.

As the sealant used for bonding the substrates, a thermosetting type is also known in addition to a UV curing type. The sealant can be printed by, for example, screen printing.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions (positive liquid crystal compositions) having 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. 8-231960, Japanese patent laid-open No. 9-241644 (European patent application laid-open No. 885272), Japanese patent laid-open No. 9-302346 (European patent application laid-open No. 806466), Japanese patent laid-open No. 8-199168 (European patent application laid-open No. 722998), Japanese patent laid-open No. 9-235552, Japanese patent laid-open No. 9-255956, Japanese patent laid-open No. 9-241643 (European patent application laid-open No. 885271), Japanese patent laid-open No. 10-204016 (European patent application laid-open No. 844229), Liquid crystal compositions disclosed in Japanese patent laid-open Nos. Hei 10-204436, Hei 10-231482, 2000-087040, 2001-48822, and the like.

Preferred examples of the liquid crystal composition having negative dielectric anisotropy (negative liquid crystal composition) include: japanese patent laid-open publication No. 57-114532, Japanese patent laid-open publication No. 2-4725, Japanese patent laid-open publication No. 4-224885, Japanese patent laid-open publication No. 8-40953, Japanese patent laid-open publication No. 8-104869, Japanese patent laid-open publication No. 10-168076, Japanese patent laid-open publication No. 10-168453, Japanese patent laid-open publication No. 10-236989, Japanese patent laid-open publication No. 10-236990, Japanese patent laid-open publication No. 10-236992, Japanese patent laid-open publication No. 10-236993, Japanese patent laid-open publication No. 10-236994, Japanese patent laid-open publication No. 10-237000, Japanese patent laid-open publication No. 10-237004, Japanese patent laid-open publication No. 10-237024, Japanese patent laid-open publication No. 10-237035, Japanese patent laid-open publication No. 10-237075, Japanese patent laid-open No. Hei 10-237076, Japanese patent laid-open No. Hei 10-237448 (European patent application publication No. 967261), Japanese patent laid-open No. Hei 10-287874, Japanese patent laid-open No. Hei 10-287875, Japanese patent laid-open No. Hei 10-291945, Japanese patent laid-open No. Hei 11-029581, Japanese patent laid-open No. Hei 11-080049, Japanese patent laid-open No. 2000 and 256307, Japanese patent laid-open No. 2001 and 019965, liquid crystal compositions disclosed in Japanese patent laid-open Nos. 2001-072626, 2001-192657, 2010-037428, 2011/024666, 2010/072370, 2010-537010, 2012-077201, 2009-084362 and the like.

The liquid crystal composition having positive or negative dielectric anisotropy may be used without any influence by adding at least one optically active compound.

In addition, for example, from the viewpoint of improving the alignment properties, an additive may be further added to the liquid crystal composition used in the liquid crystal display element of the present invention. Such additives include photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like. Preferable examples of the photopolymerizable monomer, optically active compound, antioxidant, ultraviolet absorber, dye, antifoaming agent, polymerization initiator, and polymerization inhibitor include those disclosed in international publication No. 2015/146330.

In order to be suitable for a liquid crystal display element of a Polymer Stabilized Alignment (PSA) mode, a polymerizable compound may be mixed in the liquid crystal composition. Preferable examples of the polymerizable compound are compounds having a polymerizable group such as acrylic acid esters, methacrylic acid esters, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxetane ) and vinyl ketones. Preferred examples of the compound include those disclosed in International publication No. 2015/146330 and the like.

< dinitro Compound >

Next, the dinitro compound of the present invention will be explained.

The dinitro compound of the present invention is a compound represented by the following general formula (2).

[ solution 130]

In the general formula (2), R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R¹And R²May be the same or different from each other. In addition, R¹And R²Can be integrated to form methylene which can be substituted. With respect to the description of the substituent and the preferable ranges and specific examples, the description of the substituent which can substitute the methylene group of the general formula (1) and the preferable ranges and specific examples can be referred to. X each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4. When the total of two n is 2 or more, a plurality of X's may be the same or different from each other. X and nitro (-NO)₂) The bonding position of (b) is any position of the benzene ring bonded by the bonding bond, which can be substituted.

The dinitro compound represented by the general formula (2) (dinitro compound (2)) can be easily converted to the diamine compound represented by the general formula (1) (diamine compound (1)) by reduction. Therefore, the dinitro compound (2) is effectively used as a synthesis intermediate of the diamine compound (1). As for the method for producing the diamine compound (1) using the dinitro compound (2) as a synthesis intermediate, the following description of < method for producing a diamine compound > is referred to.

As a preferred example of the dinitro compound (2), a dinitro compound represented by the general formula (2-1) is mentioned, and as a more preferred example, a dinitro compound represented by the general formula (2-2) is mentioned. In the dinitro compound (2), the dinitro compound (2-1) and the dinitro compound (2-2), it is preferable that the two esters on the cyclopropane ring are in the trans-form.

[ solution 131]

X and n of the general formula (2-1), and R of the general formula (2-1) and the general formula (2-2)¹And R²Are each independently of R of the formula (2)¹、R²X and n are the same. In the general formula (2-1), the bonding position of X is any position of the benzene ring bonded by the bonding bond, which can be substituted.

With respect to the preferable ranges and specific examples of the dinitro compound (2), two amino groups are substituted with nitro groups with reference to the preferable ranges and specific examples of the diamine compound (1) in the column of the above-mentioned < diamine compound >.

< protection of diamino Compounds >

Next, the protected diamino compound of the present invention will be described.

The protected diamino compound of the present invention is a compound represented by the following general formula (7-1).

[ solution 132]

In the general formula (7-1), R¹And R²Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R¹And R²Can mutually communicateThe same or different. In addition, R¹And R²Can be integrated to form methylene which can be substituted. With respect to the description of the substituent and the preferable ranges and specific examples, the description of the substituent which can substitute the methylene group of the general formula (1) and the preferable ranges and specific examples can be referred to. X each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4. When the total of two n is 2 or more, a plurality of X's may be the same or different from each other. The bonding position of X is any position of the benzene ring to which the bonding bond is bonded, which can be substituted. Boc represents tert-butoxycarbonyl.

The protected diamino compound represented by the general formula (7-1) (protected diamino compound (7-1)) can be easily converted to a diamine compound represented by the general formula (1-1) (diamine compound (1-1)) by deprotecting an amino group protected with a Boc group. Therefore, the protected diamino compound (7-1) is useful as a synthesis intermediate of the diamine compound (1-1). As for the method for producing the diamine compound (1-1) using the protected diamino compound (7-1) as a synthesis intermediate, the following description in the section of < method for producing diamine compound > can be referred to.

In the protected diamino compound (7-1), it is preferable that the two esters on the cyclopropane ring are in the trans configuration.

With respect to the preferable ranges and specific examples of the protected diamino compound (7-1), the two amino groups are replaced with the amino group protected with the Boc group with reference to the preferable ranges and specific examples of the diamine compound (1) in the column of < diamine compound > mentioned above.

< Process for producing diamine compound >

Next, a method for producing the diamine compound of the present invention will be described.

[ Process for producing diamine Compound Via dinitro Compound (2) ]

As shown in the following reaction scheme, the diamine compound represented by the general formula (1) (diamine compound (1)) of the present invention can be produced by reducing the nitro group of the dinitro compound represented by the general formula (2) (dinitro compound (2)). For the description and preferred ranges of the dinitro compound (2), reference is made to the description in the section "dinitro compound".

[ solution 133]

In the formula, R¹、R²X and n are respectively related to R of general formula (1) and general formula (2)¹、R²X and n are the same.

The dinitro compound (2) can be produced by a condensation reaction of a cyclopropane derivative represented by the general formula (3) and a nitro compound represented by the general formula (4).

[ solution 134]

In the general formula (3), R¹And R²Are each independently of R of the formula (2)¹And R²Are the same meaning. Y represents a leaving group.

[ solution 135]

In the general formula (4), X and n are the same as those in the general formula (2), respectively. When n is 2 or more, plural xs may be the same or different from each other.

Preferred examples of the method for producing the diamine compound of the present invention include the following methods: as shown in the following reaction scheme, the diamine compound (1) was synthesized by the following steps: a step (first step) for obtaining a dicarboxylic acid compound (3-1) obtained by hydrolyzing and synthesizing a1, 2-cyclopropane dicarboxylic acid diester (3-0) prepared from an acrylate and a halogenated acetate; a step (second step) for producing a carboxylic acid chloride compound (3-2); a step (third step) of reacting a nitro compound (4) with the dicarboxylic acid chloride compound (3-2) to obtain a dinitro compound (2) as an intermediate; and a step (fourth step) of reducing the nitro group of the intermediate.

[ solution 136]

In the formula, R¹、R²X and n are respectively related to R of general formula (1) and general formula (2)¹、R²X and n are the same. Et represents an ethyl group.

In the reaction in the first step, as a method for synthesizing the dicarboxylic acid compound (3-1), conventional methods described in journal of the American chemical society (J.Am.chem.Soc.), 114(24), 9401-9408(1992) and the like can be used, and examples thereof include the following methods: after the acrylic ester compound (5-1) is reacted with a haloacetic acid ester (5-2) in the presence of sodium hydride or sodium tert-butoxide to obtain a dicarboxylic ester compound (3-0), the ester moiety is hydrolyzed in the presence of an aqueous sodium hydroxide solution to obtain a dicarboxylic acid compound (3-1). Further, an organic solvent may be used in the reaction. Examples of the organic solvent used include dimethyl sulfoxide and dimethylformamide, and dimethylformamide is preferably used in terms of good yield. In addition, in R¹And R²In the case where the dicarboxylic acid compound (3-1) is a methylene group as a whole, conventional methods described in Helvetica Chimica Acta, 95(2), 268-277(2012), and the like can be used as the step (first step) for obtaining the dicarboxylic acid compound (3-1).

In the reaction in the second step, as a method for synthesizing the dicarboxylic acid chloride compound (3-2), any conventional method described in International publication No. 2008/112251 or Tetrahedron (Tetrahedron), 56(29), 5225 (5239) (2000) and the like can be used, and there is no particular limitation, and examples thereof include a method in which the dicarboxylic acid compound (3-1) is stirred in the presence of excess thionyl chloride under reflux conditions. In the above reaction, the organic solvent may be present or absent, and when the organic solvent is used, the organic solvent may be removed together with the removal of thionyl chloride by distillation after the reaction. Further, the dicarboxylic acid chloride compound (3-2) can also be obtained by stirring the dicarboxylic acid compound (3-1) in the presence of oxalyl chloride. In this case, a catalyst may be added for the purpose of promoting the reaction.

The organic solvent used in the reaction in the second step is not particularly limited as long as it does not affect the reaction, and it is possible to use: aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane and cyclohexane; amides such as N, N-dimethylformamide (hereinafter referred to as DMF (N, N-dimethyl formamide)), N-dimethylacetamide (hereinafter referred to as DMAc (N, N-dimethyl acetate)), and N-methyl-2-pyrrolidone (hereinafter referred to as NMP (N-methyl-2-pyrrolidone)); ethers such as diethyl ether, tetrahydrofuran (hereinafter, referred to as thf), 1, 4-dioxane, 1, 2-dimethoxyethane (hereinafter, referred to as DME (1, 2-dimethyl ethane)), and cyclopentyl methyl ether; ketones such as 2-butanone and 4-methyl-2-pentanone; nitriles such as acetonitrile and propionitrile; dimethyl sulfoxide (hereinafter referred to as dmso (dimethyl sulfoxide)); halogenated hydrocarbons such as chloroform, dichloromethane, and dichloroethane. These solvents may be used singly or in combination of two or more kinds.

The reaction temperature may be about 0 ℃ to 200 ℃, preferably 0 ℃ to 150 ℃, and more preferably 0 ℃ to 80 ℃ as long as the boiling point of the solvent used is not higher.

The catalyst used when thionyl chloride or oxalyl chloride is used is not particularly limited as long as it promotes the reaction, and examples thereof include DMF. The amount of the compound to be used is not particularly limited, and is usually 0.01 to 50 mol%, preferably 0.1 to 20 mol%, based on the dicarboxylic acid compound (3-1).

After the reaction, the solvent and the like are distilled off, and the reaction mixture is used in the next step in a crude state or purified. The purification method is arbitrary, and may be appropriately selected from conventional methods such as recrystallization, distillation, and silica gel chromatography.

In the reaction in the third step, the method for synthesizing the dinitro compound (2) from the dicarboxylic acid chloride compound (3-2) is not particularly limited, and examples thereof include a method in which the nitro compound (4) and the dicarboxylic acid chloride compound (3-2) are reacted in an organic solvent in the presence of a base.

The organic solvent used in the reaction in the third step is not particularly limited as long as it does not affect the reaction, and it is possible to use: aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane and cyclohexane; amides such as DMF, DMAc, NMP, etc.; ethers such as diethyl ether, THF, 1, 4-dioxane, DME, and cyclopentyl methyl ether; ketones such as 2-butanone and 4-methyl-2-pentanone; nitriles such as acetonitrile and propionitrile; DMSO; halogenated hydrocarbons such as chloroform, dichloromethane, and dichloroethane. These solvents may be used singly or in combination of two or more kinds. Further, in the case where the nitro compound (4) and the dicarboxylic acid chloride compound (3-2) are rapidly reacted to be condensed, the Schotten-Baumann (Schotten-Baumann) condition in which the organic solvent is combined with water may be used.

The reaction temperature may be about 0 ℃ to 200 ℃, preferably 0 ℃ to 100 ℃, and more preferably 0 ℃ to 50 ℃, as long as the boiling point of the solvent used is not higher.

The base to be used is not particularly limited as long as it can trap the acid produced as a by-product, and examples thereof include: organic bases such as pyridine, dimethylaminopyridine (hereinafter, dmap (dimethyl amino pyridine)), triethylamine, and tributylamine; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, and potassium carbonate.

After the reaction, the solvent is distilled off and used in the next step in a crude state or purified. The purification method is arbitrary, and may be selected as appropriate from conventional methods such as recrystallization, distillation, extraction, washing with an acidic or basic aqueous solution, silica gel column chromatography, and the like.

In the reaction in the fourth step, a conventional method may be employed as a method for reducing the nitro group of the dinitro compound (2) to an amino group.

As the hydrogen source for reduction, there may be mentioned: hydrogen, hydrazine, hydrogen chloride, ammonium formate, and the like.

As the catalyst for contact hydrogenation, there may be mentioned: the catalyst may be a catalyst in which metal powder such as platinum, palladium, ruthenium, rhodium, nickel, iron, zinc, tin, or the like is supported on an active body. The type of catalyst is not particularly limited as long as it is a catalyst capable of reducing only a nitro group, and preferably includes: palladium-carbon, platinum oxide, raney nickel, platinum-carbon, rhodium-alumina, platinum sulfide carbon, and the like.

For example, palladium-carbon, platinum oxide, raney nickel, platinum-carbon, rhodium-alumina, platinum sulfide-carbon, reduced iron, iron chloride, tin chloride, zinc, or the like may be used as a catalyst, and hydrogen gas, hydrazine, hydrogen chloride, ammonium chloride, or the like may be used as a hydrogen source. In particular, the target compound is preferably obtained by a catalytic hydrogenation or a beraprost (Bechamp) reduction reaction using tin chloride or a hydrate thereof, because the side reaction due to the ester site of the dinitro compound (2) is not easily caused.

The amount of the catalyst is not particularly limited, and is usually 0.01 to 50 mol%, preferably 0.1 to 20 mol%, in terms of metal, relative to the dinitro compound (2) as a raw material. For example, the amount of tin chloride to be used is not particularly limited, and is usually 1 to 50 molar equivalents, preferably 5 to 20 molar equivalents, relative to the dinitro compound as the raw material, because it can be suitably determined according to the reaction conditions. In addition, instead of tin chloride, tin chloride dihydrate may also be used.

As the reaction solvent, a solvent which does not affect the reaction can be used. For example, the following may be used: esters such as methyl acetate, ethyl acetate, and propyl acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane and cyclohexane; amides such as DMF, DMAc, NMP, etc.; ethers such as THF, 1, 4-dioxane, DME, cyclopentyl methyl ether, and the like; ketones such as 2-butanone and 4-methyl-2-pentanone; alcohols such as methanol, ethanol, propanol, etc.; DMSO; water, and the like. These solvents may be used singly or in combination of two or more kinds.

The reaction temperature may be a temperature at which the starting material or product is not decomposed and the boiling point of the solvent used is not higher than the boiling point, and the reaction can be carried out at a temperature selected from such a temperature range that the reaction proceeds efficiently. Specifically, the reaction temperature is preferably from-78 ℃ to the boiling point of the solvent or lower, and more preferably from 0 ℃ to the boiling point of the solvent or lower, from the viewpoint of ease of synthesis.

The contact hydrogenation may be carried out under a pressurized condition using an autoclave or the like, from the viewpoints of increasing the reaction rate and enabling the reaction at a low temperature.

Then, the solvent is distilled off from the obtained reaction mixture, and then, the reaction mixture is purified by a conventional method such as recrystallization, distillation, or silica gel chromatography, whereby the diamine compound (1) of the present invention can be obtained.

Further, as a preferable example of the method for producing the diamine compound of the present invention, the following method can be mentioned: as shown in the following reaction scheme, the diamine compound (1) was synthesized by the following steps: a step (fifth step) of reacting the dicarboxylic acid compound (3-1) with the nitro compound (4) to obtain a dinitro compound (2) as an intermediate; and a step of reducing the nitro group of the dinitro compound (2).

[ solution 137]

In the formula, R¹、R²X and n are each independently of R of the formula (2)¹、R²X and n are the same. As for the description and specific conditions of the method for synthesizing the dicarboxylic acid compound (3-1) and the method for reducing the dinitro compound (2) to the diamine compound (1), reference is made to the descriptions of the first step and the fourth step.

In the fifth step, for example, the dicarboxylic acid compound (3-1) synthesized by the method described in Helvetica Chimica Acta, 95(2), 268-277(2012) is reacted with the nitro compound (4) in an organic solvent in the presence of a condensing agent to obtain the dinitro compound (2) (intermediate). The dicarboxylic acid compound (3-1) can be synthesized by other synthesis methods listed in the description of the first step.

In the reaction in the fifth step, the method for condensing the dicarboxylic acid compound (3-1) and the nitro compound (4) is not particularly limited as long as a conventional method (such as a sterling esterification reaction) is employed, and for example, a method of carrying out the reaction in the presence of a condensing agent may be mentioned.

The organic solvent used in the reaction is not particularly limited as long as it does not affect the reaction, and it is possible to use: aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane and cyclohexane; amides such as DMF, DMAc, NMP, etc.; ethers such as diethyl ether, THF, 1, 4-dioxane, DME, and cyclopentyl methyl ether; ketones such as 2-butanone and 4-methyl-2-pentanone; nitriles such as acetonitrile and propionitrile; DMSO; halogenated hydrocarbons such as chloroform, dichloromethane, and dichloroethane. These solvents may be used singly or in combination of two or more kinds.

The reaction temperature may be about 0 ℃ to 200 ℃, preferably-10 ℃ to 100 ℃, and more preferably 0 ℃ to 50 ℃, as long as the boiling point of the solvent used is not higher.

After the reaction, the reaction mixture is used in the next step in a crude state or after purification. The purification method is arbitrary, and may be selected as appropriate from conventional methods such as recrystallization, distillation, and silica gel column chromatography.

The condensing agent to be used is not particularly limited as long as it can promote esterification, and examples thereof include: dicyclohexylcarbodiimide (hereinafter, referred to as dcc (dicyclohexylcarbodiimide)), diisopropylcarbodiimide (hereinafter, referred to as dic (diisopropyl carbodiimide)), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (hereinafter, referred to as EDC (1-ethyl-3- (3-dimethylamino-propyl) carbodiimide) or WSCI (1-ethyl-3- (3-dimethylamino-propyl) carbodiimide)), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter, referred to as EDC-HCl (1-ethyl-3- (3-dimethylamino-propyl) carbodiimide), and the like.

The catalyst to be used is not particularly limited as long as it promotes the reaction, and examples thereof include DMAP, pyridine, and the like. The amount of the dicarboxylic acid compound (3-1) used is not particularly limited, and is usually 1 to 100 mol%, preferably 10 to 50 mol%.

[ Process for producing diamine Compound having diamino Compound (7) protected therewith ]

Further, as a preferable example of the method for producing the diamine compound of the present invention, the following method can be mentioned: as shown in the following reaction scheme, the diamine compound (1) was synthesized by the following steps: a step (sixth step) of reacting the cyclopropane derivative (3) with a phenol compound (6) having an amino group protected with Boc to obtain a protected diamino compound (7) as an intermediate; and a step (seventh step) of deprotecting the protecting group of the intermediate.

[ 138]

In the formula, R¹、R²X, n and Y are independently related to R of formula (1) and formula (2)¹、R²X and n are the same as those of Y in the general formula (3). Boc represents tert-butoxycarbonyl. The dicarboxylic acid compound (3-1) can be preferably used in the cyclopropane derivative (3). For the description of the method for synthesizing the dicarboxylic acid compound (3-1) and the specific conditions, reference may be made to the description of the first step.

The sixth step is, for example, a step of obtaining a protected diamino compound (7) by condensation reaction of a dicarboxylic acid compound (3-1) and a phenol compound (6) having an amino group protected with Boc, and can be performed in the same manner as the fifth step except that the nitro compound (4) is replaced with the phenol compound (6) having an amino group protected with Boc. That is, the sixth step is not particularly limited as long as it is carried out by a conventional condensation method (e.g., a sterculia esterification reaction).

Here, as a preferred example of the phenol compound (6) having an amino group protected with Boc, a protected aminophenol compound (6-1)) represented by the following general formula (6-1) can be mentioned. By using the protected aminophenol compound (6-1), the protected diamino compound (7-1) having a protected amino group at the para-position with respect to the ester group can be synthesized, and by deprotecting the same, the diamine compound (1-1) can be produced. For the description and preferred ranges of the protected diamino compound (7-1), the description in the column of the < protected diamino compound > can be referred to, and for the description and preferred ranges and specific examples of the diamino compound (1-1), the description in the column of the < diamine compound > can be referred to.

[ solution 139]

In the general formula (6-1), X, n and Boc have the same meanings as X, n and Boc in the general formula (6), respectively.

The phenol compound (6) having an amino group protected with Boc used in the sixth step can be prepared, for example, by the method described in Japanese patent laid-open No. 2015-176110.

The seventh step is a step of deprotecting the Boc group of the protected diamino compound (7) obtained in the sixth step to obtain a diamine compound (1). Deprotection of the Boc group can be performed by a conventional deprotection method using an acid, and for example, trifluoroacetic acid or the like can be used as an acid for deprotection.

[ examples ]

The features of the present invention will be described in more detail below with reference to examples and comparative examples. The materials, amounts used, ratios, processing contents, processing procedures and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited to the specific examples shown below.

Synthesis of dinitro compound, diamine compound and diamine isomer mixture

In the reaction formulae shown in the respective synthesis examples, Me represents a methyl group and Et represents an ethyl group. In the reaction formulae, when the compound is a trans-form, only one enantiomer is shown, but the other enantiomer is also included in the starting material and the product.

Synthesis example 1 Synthesis of dinitro Compound 1

[ solution 140]

After a solution of diethyl trans-1, 2-cyclopropanedicarboxylate (10.0g, 53.7mmol) in ethanol (100mL) was cooled in an ice bath, a solution of sodium hydroxide (8.60g, 215mmol) in water (100mL) was added. After slowly warming the mixture to room temperature over 1 hour, it was stirred for 15 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and ethanol was distilled off. The residue was cooled again in an ice bath, concentrated hydrochloric acid (20mL) was added, and an excess of common salt was added, followed by extraction with ethyl acetate (100 mL. times.8 times). The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure, whereby a white solid of trans-1, 2-cyclopropanedicarboxylic acid was obtained (yield 6.44g, yield 92%).

¹H-NMR(400MHz,DMSO-d₆)：δ1.89-1.77(m,2H),1.26-1.14(m,2H).

[ solution 141]

Thionyl chloride (30mL) was added to trans-1, 2-cyclopropanedicarboxylic acid (6.00g, 46.1mmol), and after stirring at 70 ℃ for 4 hours, the mixture was concentrated under reduced pressure and distilled off to remove thionyl chloride, whereby crude trans-1, 2-cyclopropanedicarboxylic acid chloride was obtained. The carboxylic acid chloride was used as a THF (90mL) solution, and all were used in the following reaction.

To a solution of 4-nitrophenol (13.5g, 96.8mmol) in THF (100mL) under argon was added triethylamine (16.3g, 161mmol) and cooled in an ice bath. The mixture was stirred vigorously, and the prepared carboxylic acid chloride in THF was added over 5 minutes, then warmed to room temperature, and stirred at room temperature for two and a half hours. To the reaction mixture was added saturated aqueous ammonium chloride (100mL), and concentrated under reduced pressure. The residue was extracted with ethyl acetate (300 mL. times.3 times), and then washed with saturated sodium bicarbonate (300 mL). The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure, whereby bis (4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate (7.36g) was obtained as a pale yellow solid. Further, the solid remaining in the aqueous layer was separated by filtration and washed with water to recover a pale yellow solid (6.72g) of bis (4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate, which was combined with the above 7.36g, to obtain the dinitro compound 1 (bis (4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate) (total yield 14.1g, yield 82%).

¹H-NMR(400MHz,CDCl₃)：δ8.31(d,J＝9.2Hz,4H),7.35(d,J＝9.2Hz,4H),2.66-2.59(m,2H),1.86-1.78(m,2H).

Synthesis example 2 Synthesis of diamine isomer mixture 1 (mixture of diamine Compound (1-4-1) and its enantiomer)

[ solution 142]

Tin (II) chloride dihydrate (84.8g, 376mmol) was added to a solution of dinitro compound 1(14.0g, 37.6mmol) in ethyl acetate (370mL) under argon atmosphere, and stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and after adding the reaction mixture to a saturated aqueous sodium bicarbonate solution (1L), extraction was performed with ethyl acetate (300mL × 3 times). The obtained organic layer was washed with saturated aqueous sodium hydrogencarbonate (300mL) and saturated brine (300mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. For the obtained residue, chloroform: a mixed solvent of methanol was used for the eluent so that the ratio thereof was in the range of 100: 0-95: 5, while purifying the mixture by silica gel column chromatography, the objective diamine isomer mixture 1 (a mixture of the diamine compound (1-4-1) and its enantiomer) was obtained as a white solid (yield 8.50g, yield 72%).

¹H-NMR(400MHz,CDCl₃)：δ6.90(d,J＝8.8Hz,4H),6.67(d,J＝8.8Hz,4H),3.64(brs,4H),2.53-2.47(m,2H),1.71-1.65(m,2H).

[ Synthesis example 3] Synthesis of dinitro Compound 2

[ solution 143]

A suspension of 3-oxabicyclo [3.1.0] hexane-2, 4-dione (10.0g, 81.9mmol) in water (160mL) was stirred under reflux for 3 hours. After cooling to room temperature, it was concentrated under reduced pressure, whereby a pale yellow solid of cis-1, 2-cyclopropanedicarboxylic acid was obtained (yield 10.7 g).

¹H-NMR(400MHz,DMSO-d₆)：δ12.26(brs,2H),2.53(dd,J＝8.3,6.6Hz,2H),2.01(td,J＝6.6,4.2Hz,1H),1.64(td,J＝8.3,4.2Hz,1H).

[ solution 144]

To a suspension of cis-1, 2-cyclopropanedicarboxylic acid (8.02g, 61.6mmol) in toluene (40mL) were added thionyl chloride (40mL) and DMF (0.4mL), and after stirring at 100 ℃ for 4 hours, the mixture was concentrated under reduced pressure to obtain crude cis-1, 2-cyclopropanedicarboxylic acid chloride. The carboxylic acid chloride was dissolved in THF (80mL), and all of the solutions were used in the following reaction.

To a solution of 4-nitrophenol (17.9g, 129mmol) in THF (160mL) under argon was added triethylamine (21.9g, 216mmol) and cooled in an ice bath. The mixture was stirred vigorously, and the prepared carboxylic acid chloride in THF was added over 5 minutes, then warmed to room temperature, and stirred at room temperature for two and a half hours. To the reaction mixture was added saturated aqueous ammonium chloride (200mL), and concentrated under reduced pressure. The residue was extracted with ethyl acetate (300 mL. times.3 times), and then washed with saturated sodium bicarbonate (300 mL). The resulting solid was separated by filtration, washed with water (100mL) and a saturated aqueous solution of sodium hydrogencarbonate (100mL), and then washed again with water (100 mL). The obtained solid was dried under reduced pressure, whereby a pale yellow solid of the aimed dinitro compound 2 (cis-1, 2-cyclopropanedicarboxylic acid bis (4-nitrophenyl) ester) was obtained (yield 12.6g, yield 55%).

¹H-NMR(400MHz,CDCl₃)：δ8.26(d,J＝9.2Hz,4H),7.29(d,J＝9.2,4H),2.53(dd,J＝8.5,6.7Hz,2H),2.01(td,J＝6.7,5.4Hz,1H),1.64(td,J＝8.5,5.4Hz,1H).

[ Synthesis example 4] Synthesis of diamine Compound (1-2-1)

[ solution 145]

Tin (II) chloride dihydrate (86.0g, 381mmol) was added to a solution of dinitro compound 2(14.2g, 38.1mmol) in ethyl acetate (380mL) under argon atmosphere, and stirred under reflux for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, added to a saturated aqueous sodium bicarbonate solution (1L), and then filtered with celite. The obtained mixture was extracted with ethyl acetate (300mL × 3 times), and the organic layer was washed with a saturated aqueous sodium bicarbonate solution (300mL) and a saturated saline solution (300 mL). The obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. For the residue, chloroform: a mixed solvent of methanol was used for the eluent so that the ratio thereof was in the range of 100: 0-95: 5, and then the mixture was reprecipitated with ethyl acetate (50mL) and hexane (50mL) while varying the amount of the reaction mixture, whereby a white solid of the intended diamine compound (1-2-1) (cis-1, 2-cyclopropanedicarboxylic acid bis (4-aminophenyl) ester) was obtained (yield 8.52g, yield 72%).

¹H-NMR(400MHz,CDCl₃)：δ6.87(d,J＝8.8Hz,4H),6.62(d,J＝8.8Hz,4H),3.61(brs,4H),2.37(dd,J＝8.4,6.7Hz,2H),1.91(td,J＝6.7,5.2Hz,1H),1.45(td,J＝8.4,5.2Hz,1H).

Synthesis example 5 Synthesis of dinitro Compound 3

[ solution 146]

Ethylacetoacetate (26.6g, 204mmol) was added dropwise to concentrated sulfuric acid (20mL) over 30 minutes while cooling in an ice bath. After the dropwise addition, the mixture was warmed to room temperature and stirred for 22 hours. After completion of the reaction, the reaction solution was poured into ice (60g), and then stirred until all the ice was dissolved. The obtained mixture was extracted with diethyl ether (100 mL. times.3 times), and then washed with a10 wt% aqueous solution of sodium carbonate. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. For the obtained residue, hexane: a mixed solvent of ethyl acetate was used for the eluent, so that the ratio thereof was in the range of 100: 0-80: purification was performed by silica gel column chromatography while varying the concentration of 20, whereby ethyl 4, 6-dimethyl-2-oxo-2H-pyran-5-carboxylate was obtained as a pale yellow oily substance (yield 6.88g, yield 34%).

¹H-NMR(400MHz,CDCl₃)：δ6.01(s,1H),4.35(q,J＝7.1Hz,2H),2.40(s,3H),2.23(s,3H),1.37(t,J＝7.1Hz,3H).

[ solution 147]

A solution of ethyl 4, 6-dimethyl-2-oxo-2H-pyran-5-carboxylate (25.0g, 127mmol) in chloroform (50mL) was cooled in an ice bath under argon, and a solution of bromine (23.3g, 146mmol) in chloroform (50mL) was added dropwise over 30 minutes while stirring. After the mixture was warmed to room temperature, it was stirred for 24 hours. After completion of the reaction, the reaction mixture was poured into ice (300g), and then stirred until the ice was completely dissolved. The mixture was extracted with ethyl acetate (150 mL. times.3 times), and then washed with a10 wt% aqueous solution of sodium carbonate (300mL) and saturated brine (100 mL). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude solid, which was washed with hexane (100mL), to obtain ethyl 3-bromo-4, 6-dimethyl-2-oxo-2H-pyran-5-carboxylate as a pale yellow solid (yield 33.1g, yield 95%).

¹H-NMR(400MHz,CDCl₃)：δ4.37(q,J＝7.1Hz,2H),2.35(s,3H),2.34(s,3H),1.38(q,J＝7.1Hz,3H).

[ solution 148]

After a solution of 3-bromo-4, 6-dimethyl-2-oxo-2H-pyran-5-carboxylic acid ethyl ester (34.0g, 124mmol) in 1, 4-dioxane (70mL) was warmed under an oil bath (110 ℃), 7M aqueous potassium hydroxide solution (171mL) was added dropwise over 20 minutes under heated reflux. After the dropwise addition, the mixture was stirred at the temperature for 1 hour, cooled in an ice bath, and then 50% sulfuric acid (68mL) was slowly added. The reaction mixture was filtered and washed with diethyl ether (150 mL). The mixture was extracted with diethyl ether (150 mL. times.3 times), and washed with saturated brine (100 mL). The organic layer was dried over magnesium sulfate and then concentrated under reduced pressure, whereby a crude product was obtained. It was recrystallized from ethyl acetate (10mL) -hexane (100mL), thereby obtaining brown crystals of trans-3-methylene-1, 2-cyclopropanedicarboxylic acid (yield 5.92g, yield 34%).

¹H-NMR(400MHz,DMSO-d₆)：δ12.8(brs,2H),5.66-5.62(m,2H),2.63-2.59(m,2H).

[ 149]

4-nitrophenol (24.5g, 176mmol) was added to a solution of trans-3-methylene-1, 2-cyclopropanedicarboxylic acid (10.0g, 70.4mmol) in dichloromethane (700mL) under argon, and EDC-HCl (33.7g, 176mmol) and DMAP (1.72g, 14.1mmol) were added while stirring under cooling in an ice bath. The mixture was slowly warmed to room temperature, stirred for 6 hours, and then water (150mL) was added. The reaction mixture was extracted with ethyl acetate (500mL × 3 times), and the organic layer was dried over sodium sulfate and concentrated under reduced pressure. The obtained crude solid was reprecipitated with ethanol (5mL) -ethyl acetate (20mL) -hexane (20mL), and then washed with hot water (500mL) at 80 ℃ to obtain a pale yellow solid (yield 16.7g, yield 62%) of the dinitro compound 3 (bis (4-nitrophenyl) trans-3-methylene-1, 2-cyclopropanedicarboxylate).

¹H-NMR(400MHz,DMSO-d₆)：δ8.31(d,J＝9.2Hz,4H),7.35(d,J＝9.2Hz,4H),5.98-5.94(m,2H),3.32-3.28(m,2H).

Synthesis example 6 Synthesis of diamine isomer mixture 2 (mixture of diamine Compound (1-3-2) and its enantiomer)

[ solution 150]

Tin (II) chloride dihydrate (88.0g, 390mmol) was added to a solution of dinitro compound 3(15.0g, 39.0mmol) in ethyl acetate (300mL) under argon atmosphere, and stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, added to a saturated aqueous sodium hydrogencarbonate solution (1.1L), and then filtered through celite. The filtrate was extracted with ethyl acetate (300 mL. times.3 times), and then washed with saturated brine (300 mL). The obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. For the obtained residue, chloroform: methanol 90: 10 was used for the eluent, and purification was performed by silica gel column chromatography, whereby a white solid (yield 7.05g, yield 56%) of the intended diamine isomer mixture 2 (a mixture of the diamine compound (1-3-2) and its enantiomer) was obtained.

¹H-NMR(400MHz,CDCl₃)：δ6.81(d,J＝8.8Hz,4H),6.54(d,J＝8.8Hz,4H),5.90-5.85(m,2H),5.08(brs,4H),3.12-3.08(m,2H).

[ Synthesis example 7] Synthesis of dinitro Compound 4

[ solution 151]

Trans-1, 2-cyclopropanedicarboxylic acid (2.00g, 15.4mmol) and 4-nitro-o-cresol (4.93g, 31.6mmol) were dissolved in dichloromethane (154mL) and cooled in an ice bath. 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (6.18g, 31.6mmol) and 4-dimethylaminopyridine (0.38g, 3.1mmol) were added thereto, and the mixture was warmed to room temperature and stirred for 24 hours. After completion of the reaction, water (50mL) was added to the reaction mixture, and extraction was performed with ethyl acetate (50 mL. times.3). The combined organic layers were dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained crude product was washed with methanol (40mL), whereby a yellow solid of the dinitro compound 4[ trans-1, 2-cyclopropanedicarboxylic acid bis (2-methyl-4-nitrophenyl) ester ] was obtained (yield 5.03g, yield 82%).

¹H-NMR(400MHz,DMSO-d₆)：δ8.27(dd,J＝2.8,0.6Hz,2H),8.16(ddd,J＝8.8,2.8,0.6Hz,2H),7.51(d,J＝8.8Hz,2H),2.71-2.67(m,2H),2.29(s,6H),1.85-1.81(m,2H).

Synthesis example 8 Synthesis of diamine isomer mixture 3 (mixture of diamine Compound (1-3-3) and its enantiomer)

[ solution 152]

A mixture of bis (2-methyl-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate (5.02g, 12.5mmol), 10% palladium on carbon (0.53g, 0.50mmol), tetrahydrofuran (200mL) was stirred at room temperature under argon for 17 hours. After completion of the reaction, the reaction mixture was washed with tetrahydrofuran (200mL), filtered through celite, and the filtrate was concentrated under reduced pressure. The obtained solid was washed with methanol (30mL), thereby obtaining a pale yellow solid (yield 2.47g, yield 58%) of the aimed diamine isomer mixture 3 (a mixture of the diamine compound (1-3-3) and its enantiomer).

¹H-NMR(400MHz,DMSO-d₆)：δ6.73(d,J＝8.5Hz,2H),6.43(d,J＝2.5Hz,2H),6.38(dd,J＝8.5,2.5Hz,2H),4.98(brs,4H),2.44-2.40(m,2H),1.97(s,6H),1.65-1.61(m,2H).

[ Synthesis example 9] Synthesis of dinitro Compound 5

[ solution 153]

To trans-1, 2-cyclopropanedicarboxylic acid (3.03g, 23.2mmol) was added thionyl chloride (15.4mL), and the mixture was stirred at 70 ℃ for 4 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, whereby thionyl chloride was distilled off to obtain a crude trans-1, 2-cyclopropanedicarboxylic acid chloride. The acid chloride was used as a THF (46mL) solution, and all were used in the following reaction.

To a solution of 4-nitro-m-cresol (7.64g, 48.9mmol) in THF (50mL) under argon was added triethylamine (11.3mL, 81.5mmol) and cooled in an ice bath. After a solution of the acid chloride in THF prepared before was added dropwise to the solution over 5 minutes, it was warmed to room temperature and stirred for 18 hours. After completion of the reaction, water (100mL) was added to the reaction mixture, and concentrated under reduced pressure. The residue was extracted with ethyl acetate (100 mL. times.3), and then washed with a saturated aqueous solution of sodium chloride (100 mL). The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The obtained residue was washed with methanol (50mL), whereby a yellow solid of the dinitro compound 5[ trans-1, 2-cyclopropanedicarboxylic acid bis (3-methyl-4-nitrophenyl) ester ] was obtained (yield 8.09g, yield 87%).

¹H-NMR(400MHz,DMSO-d₆)：δ8.10(d,J＝8.9Hz,2H),7.42(d,J＝2.4Hz,2H),7.35(dd,J＝2.4,8.9Hz,2H),2.62-2.59(m,2H),2.54(s,6H),1.80-1.76(m,2H).

Synthesis example 10 Synthesis of diamine isomer mixture 4 (mixture of diamine Compound (1-3-4) and its enantiomer)

[ solution 154]

Tin (II) chloride dihydrate (17.6g, 75.5mmol) was added to a solution of bis (3-methyl-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate (3.02g, 7.55mmol) in ethyl acetate (76mL) under argon atmosphere, and the mixture was stirred under reflux for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and after adding the reaction mixture to a saturated aqueous sodium bicarbonate solution (300mL), the mixture was filtered through celite, and the filtrate was extracted with ethyl acetate (100 mL. times.3). The combined organic layers were washed with saturated aqueous sodium bicarbonate (200mL) and saturated brine (200mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. For the obtained residue, chloroform: a mixed solvent of methanol was used for the eluent so that the ratio thereof was in the range of 95: 5-85: 15 was purified by silica gel chromatography, whereby a pale yellow solid (yield 2.09g, yield 81%) of the aimed diamine isomer mixture 4 (mixture of the diamine compound (1-3-4) and its enantiomer) was obtained.

¹H-NMR(400MHz,DMSO-d₆)：δ6.74(d,J＝2.4Hz,2H),6.69(dd,J＝2.4,8.5Hz,2H),6.58(d,J＝8.5Hz,2H),4.82(brs,4H),2.38-2.34(m,2H),2.04(s,6H),1.61-1.57(m,2H).

Synthesis example 11 Synthesis of dinitro Compound 6

[ solution 155]

To trans-1, 2-cyclopropanedicarboxylic acid (1.81g, 13.9mmol) was added thionyl chloride (9.2mL), and the mixture was stirred at 70 ℃ for 4 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, whereby thionyl chloride was distilled off to obtain a crude trans-1, 2-cyclopropanedicarboxylic acid chloride. The acid chloride was used as a THF (28mL) solution, and all were used in the following reaction.

To a solution of 2, 6-dimethyl-4-nitrophenol (4.97g, 29.2mmol) in THF (30mL) under argon was added triethylamine (6.7mL, 48.6mmol) and cooled in an ice bath. After a solution of the acid chloride in THF prepared before was added dropwise to the solution over 30 minutes, the temperature was raised to room temperature and stirred for 21 hours. After completion of the reaction, water (150mL) was added to the reaction mixture, and the precipitate was separated by filtration and washed with methanol (30mL) to obtain a light brown solid (yield 5.58g, yield 94%) of the dinitro compound 6[ bis (2, 6-dimethyl-4-nitrophenyl) bis (trans-1, 2-cyclopropanedicarboxylate ].

¹H-NMR(400MHz,DMSO-d₆)：δ8.10(s,4H),2.78-2.75(m,2H),2.26(s,12H),1.89-1.85(m,2H).

Synthesis example 12 Synthesis of diamine isomer mixture 5 (mixture of diamine Compound (1-3-5) and its enantiomer)

[ solution 156]

Tin (II) chloride dihydrate (13.8g, 59.5mmol) was added to a solution of bis (2, 6-dimethyl-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate (2.55g, 6.0mmol) in ethyl acetate (60mL) under an argon atmosphere, and the mixture was stirred under reflux for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, and then added to a saturated aqueous sodium bicarbonate solution (300mL), followed by filtration through celite, and the filtrate was extracted with ethyl acetate (100 mL. times.3). The combined organic layers were washed with saturated aqueous sodium bicarbonate (200mL) and saturated brine (200mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. For the obtained residue, chloroform: a mixed solvent of methanol was used for the eluent so that the ratio thereof was in the range of 95: 5-85: 15, and then washed with methanol (50mL) while purified by silica gel chromatography, thereby obtaining a pale yellow solid (yield 1.41g, yield 64%) of the aimed diamine isomer mixture 5[ a mixture of the diamine compound (1-3-5) and its enantiomer ].

¹H-NMR(400MHz,DMSO-d₆)：δ6.26(s,4H),4.88(brs,4H),2.47-2.44(m,2H),1.94(s,12H),1.69-1.66(m,2H).

Synthesis example 13 Synthesis of dinitro Compound 7

[ chemical formula 157]

Thionyl chloride (9.8mL) was added to trans-1, 2-cyclopropanedicarboxylic acid (1.91g, 14.7mmol), and after stirring at 70 ℃ for 4 hours, the mixture was concentrated under reduced pressure, whereby thionyl chloride was distilled off to obtain crude trans-1, 2-cyclopropanedicarboxylic acid chloride. The acid chloride was used as a THF (30mL) solution, and all were used in the following reaction.

To a solution of 2-fluoro-4-nitrophenol (4.98g, 30.8mmol) in THF (32mL) under argon was added triethylamine (7.10mL, 51.3mmol) and cooled in an ice bath. After a solution of the acid chloride in THF prepared before was added dropwise to the solution over 10 minutes, it was warmed to room temperature and stirred for 16 hours. After completion of the reaction, water (100mL) was added to the reaction mixture, and concentrated under reduced pressure. The residue was extracted with ethyl acetate (100mL × 3), washed with saturated aqueous sodium chloride (100mL), and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was washed with methanol (50mL) to obtain a white solid of the dinitro compound 7[ trans-1, 2-cyclopropanedicarboxylic acid bis (2-fluoro-4-nitrophenyl) ester ] (yield 5.29g, yield 88%).

¹H-NMR(400MHz,DMSO-d₆)：δ8.39(d,J＝2.6Hz,1H),8.37(d,J＝2.6Hz,1H),8.22-8.19(m,2H),7.78(d,J＝7.7Hz,1H),7.75(d,J＝7.7Hz,1H),2.76-2.72(m,2H),1.89-1.85(m,2H).¹⁹F-NMR(376MHz,DMSO-d₆)：δ-124.4(s,2F).

Synthesis example 14 Synthesis of diamine isomer mixture 6 (mixture of diamine Compound (1-3-6) and its enantiomer)

[ solution 158]

Tin (II) chloride dihydrate (18.2g, 78.3mmol) was added to a solution of bis (2-fluoro-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate (3.20g, 7.83mmol) in ethyl acetate (78mL) under an argon atmosphere, and the mixture was stirred under reflux for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, and then added to a saturated aqueous sodium bicarbonate solution (300mL), followed by filtration through celite, and the filtrate was extracted with ethyl acetate (100 mL. times.3). The combined organic layers were washed with saturated aqueous sodium bicarbonate (200mL) and saturated brine (200mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. For the obtained residue, chloroform: a mixed solvent of methanol was used for the eluent so that the ratio thereof was in the range of 95: 5-85: 15 was purified by silica gel chromatography, whereby a pale yellow solid (yield 2.34g, yield 86%) of the aimed diamine isomer mixture 6[ a mixture of the diamine compound (1-3-6) and its enantiomer ] was obtained.

¹H-NMR(400MHz,DMSO-d₆)：δ6.94(t,J＝8.8Hz,2H),6.43(dd,J＝8.8,2.5Hz,2H),6.34(dd,J＝8.8,2.5Hz,2H),5.39(brs,4H),2.48-2.44(m,2H),1.68-1.64(m,2H).¹⁹F-NMR(376MHz,DMSO-d₆)：δ-130.1(s,2F).

[ Synthesis example 15] Synthesis of dinitro Compound 8

[ chemical formula 159]

Thionyl chloride (9.8mL) was added to trans-1, 2-cyclopropanedicarboxylic acid (1.90g, 14.6mmol), and after stirring at 70 ℃ for 4 hours, the mixture was concentrated under reduced pressure, whereby thionyl chloride was distilled off to obtain crude trans-1, 2-cyclopropanedicarboxylic acid chloride. The acid chloride was used as a THF (30mL) solution, and all were used in the following reaction.

To a solution of 3-fluoro-4-nitrophenol (4.92g, 30.7mmol) in THF (32mL) under argon was added triethylamine (7.10mL, 51.2mmol) and cooled in an ice bath. After a solution of the acid chloride in THF prepared before was added dropwise to the solution over 5 minutes, it was warmed to room temperature and stirred for 16 hours. After completion of the reaction, water (100mL) was added to the reaction mixture, and the precipitate was separated by filtration and dried to obtain a white solid (yield: 2.87g, yield: 48%) of the dinitro compound 8[ bis (3-fluoro-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate ].

¹H-NMR(400MHz,DMSO-d₆)：δ8.28(t,J＝8.9Hz,2H),7.67(dd,J＝12.0,2.4Hz,2H),7.38(ddd,J＝12.0,8.9,2.4Hz,2H),2.66-2.62(m,2H),1.84-1.80(m,2H).¹⁹F-NMR(376MHz,DMSO-d₆)：δ-115.3(s,2F).

Synthesis example 16 Synthesis of diamine isomer mixture 7 (mixture of diamine Compound (1-3-7) and its enantiomer)

[ solution 160]

Tin (II) chloride dihydrate (16.0g, 68.9mmol) was added to a solution of bis (3-fluoro-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate (2.81g, 6.89mmol) in ethyl acetate (70mL) under an argon atmosphere, and the mixture was stirred under reflux for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, and then added to a saturated aqueous sodium hydrogencarbonate solution (200mL), followed by filtration through celite, and the filtrate was extracted with ethyl acetate (100 mL. times.3). The combined organic layers were washed with saturated aqueous sodium bicarbonate (150mL) and saturated brine (150mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. For the obtained residue, chloroform: a mixed solvent of methanol was used for the eluent so that the ratio thereof was in the range of 95: 5-85: 15 was purified by silica gel chromatography, whereby a pale yellow solid (yield 1.08g, yield 45%) of the aimed diamine isomer mixture 7[ a mixture of the diamine compound (1-3-7) and its enantiomer ] was obtained.

¹H-NMR(400MHz,DMSO-d₆)：δ6.97-6.93(m,2H),6.78-6.71(m,4H),2.42-2.39(m,2H),1.65-1.61(m,2H).¹⁹F-NMR(376MHz,DMSO-d₆)：δ-132.8(s,2F).

Synthesis example 17 Synthesis of dinitro Compound 9

[ solution 161]

Thionyl chloride (15.4mL) was added to trans-1, 2-cyclopropanedicarboxylic acid (3.01g, 23.2mmol), and after stirring at 70 ℃ for 4 hours, the mixture was concentrated under reduced pressure, whereby thionyl chloride was distilled off to obtain a crude trans-1, 2-cyclopropanedicarboxylic acid chloride. The acid chloride was used as a THF (46mL) solution, and all were used in the following reaction.

To a solution of 2-chloro-4-nitrophenol (8.61g, 48.6mmol) in THF (50mL) under argon was added triethylamine (11.2mL, 81.0mmol) and cooled in an ice bath. After a solution of the acid chloride in THF prepared before was added dropwise to the solution over 5 minutes, it was warmed to room temperature and stirred for 18 hours. After completion of the reaction, water (150mL) was added to the reaction mixture, and the precipitate was separated by filtration and dried to obtain a white solid of the dinitro compound 9[ bis (2-chloro-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate ] (yield 9.96g, yield 98%).

¹H-NMR(400MHz,DMSO-d₆)：δ8.51(d,J＝2.7Hz,2H),8.32(dd,J＝9.0,2.7Hz,2H),7.77(d,J＝9.0Hz,2H),2.77-2.73(m,2H),1.92-1.88(m,2H).

Synthesis example 18 Synthesis of diamine isomer mixture 8 (mixture of diamine Compound (1-3-8) and its enantiomer)

[ chemical 162]

Tin (II) chloride dihydrate (11.1g, 47.6mmol) was added to a solution of bis (2-chloro-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate (2.10g, 4.76mmol) in ethyl acetate (48mL) under an argon atmosphere, and the mixture was stirred under reflux for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, and then added to a saturated aqueous sodium hydrogencarbonate solution (200mL), followed by filtration through celite, and the filtrate was extracted with ethyl acetate (100 mL. times.3). The combined organic layers were washed with saturated aqueous sodium bicarbonate (200mL) and saturated brine (200mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. For the obtained residue, chloroform: a mixed solvent of methanol was used for the eluent so that the ratio thereof was in the range of 95: 5-85: 15 by silica gel chromatography, the objective diamine isomer mixture 8[ the mixture of the diamine compound (1-3-8) and its enantiomer ] was obtained as a white solid (yield 1.19g, yield 65%).

¹H-NMR(400MHz,DMSO-d₆)：δ6.97(d,J＝8.7Hz,2H),6.67(d,J＝2.6Hz,2H),6.51(dd,J＝8.7,2.6Hz,2H),5.38(brs,4H),2.49-2.45(m,2H),1.71-1.68(m,2H).

[ Synthesis example 19] Synthesis of dinitro Compound 10

[ chemical 163]

Thionyl chloride (9.0mL) was added to trans-1, 2-cyclopropanedicarboxylic acid (1.75g, 13.5mmol), and after stirring at 70 ℃ for 4 hours, the mixture was concentrated under reduced pressure, whereby thionyl chloride was distilled off to obtain a crude trans-1, 2-cyclopropanedicarboxylic acid chloride. The acid chloride was used as a THF (27mL) solution, and all were used in the following reaction.

To a solution of 3-chloro-4-nitrophenol (5.01g, 28.3mmol) in THF (30mL) under argon was added triethylamine (6.50mL, 47.2mmol) and cooled in an ice bath. After a solution of the prepared acid chloride in THF was added dropwise thereto over a period of 5 minutes, it was warmed to room temperature and stirred for 18 hours. After completion of the reaction, water (100mL) was added to the reaction mixture, and the precipitate was separated by filtration to obtain a pale yellow solid (yield: 3.48g, yield: 58%) of the dinitro compound 10[ bis (3-chloro-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate ].

¹H-NMR(400MHz,DMSO-d₆)：δ8.21(d,J＝8.9Hz,2H),7.83(d,J＝2.4Hz,2H),7.52(dd,J＝8.9,2.4Hz,2H),2.66-2.62(m,2H),1.83-1.80(m,2H).

Synthesis example 20 Synthesis of diamine isomer mixture 9 (mixture of diamine Compound (1-3-9) and its enantiomer)

[ 164]

Tin (II) chloride dihydrate (18.1g, 77.7mmol) was added to a solution of bis (3-chloro-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate (3.43g, 7.77mmol) in ethyl acetate (78mL) under an argon atmosphere, and the mixture was stirred under reflux for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, and then added to a saturated aqueous sodium hydrogencarbonate solution (200mL), followed by filtration through celite, and the filtrate was extracted with ethyl acetate (50 mL. times.3). The combined organic layers were washed with saturated aqueous sodium bicarbonate (150mL) and saturated brine (150mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. For the obtained residue, hexane: ethyl acetate 50: a mixed solvent of 50 was used as an eluent, and after purification by silica gel chromatography, the mixture was washed with methanol (30mL), whereby a white solid of the aimed diamine isomer mixture 9[ a mixture of the diamine compound (1-3-9) and its enantiomer ] was obtained (yield 2.09g, yield 70%).

¹H-NMR(400MHz,DMSO-d₆)：δ7.12(d,J＝2.6Hz,2H),6.87(dd,J＝8.7,2.6Hz,2H),6.78(d,J＝8.7Hz,2H),5.34(brs,4H),2.43-2.39(m,2H),1.65-1.61(m,2H).

Synthesis example 21 Synthesis of dinitro Compound 11

[ solution 165]

Thionyl chloride (10.4mL) was added to trans-1, 2-cyclopropanedicarboxylic acid (2.022g, 15.5mmol), and after stirring at 70 ℃ for 4 hours, the mixture was concentrated under reduced pressure, whereby thionyl chloride was distilled off to obtain crude trans-1, 2-cyclopropanedicarboxylic acid chloride. The acid chloride was used as a THF (31mL) solution, and all were used in the following reaction.

To a solution of 2-methoxy-4-nitrophenol (5.63g, 32.6mmol) in THF (31mL) under argon was added triethylamine (7.5mL, 54.4mmol) and cooled in an ice bath. After a solution of the acid chloride in THF prepared before was added dropwise to the solution over 15 minutes, it was warmed to room temperature and stirred for 16 hours. After completion of the reaction, water (80mL) was added to the reaction mixture, and the precipitate was separated by filtration to obtain a white solid (yield: 6.34g, yield: 94%) of the dinitro compound 11[ bis (2-methoxy-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate ].

¹H-NMR(400MHz,DMSO-d₆)：δ7.95(d,J＝2.6Hz,2H),7.92(dd,J＝8.6,2.6Hz,2H),7.54(d,J＝8.6Hz,2H),3.95(s,6H),2.63-2.59(m,2H),1.80-1.76(m,2H).

Synthesis example 22 Synthesis of diamine isomer mixture 10 (mixture of diamine Compound (1-3-10) and its enantiomer)

[ solution 166]

Tin (II) chloride dihydrate (17.0g, 73.0mmol) was added to a solution of bis (2-methoxy-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate (3.16g, 7.30mmol) in ethyl acetate (73mL) under argon atmosphere, and the mixture was stirred under reflux for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and then added to a saturated aqueous sodium bicarbonate solution (300mL), followed by filtration through celite, and the filtrate was extracted with ethyl acetate (100 mL. times.3). The combined organic layers were washed with saturated aqueous sodium bicarbonate (200mL) and saturated brine (200mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. For the obtained residue, chloroform: a mixed solvent of methanol was used for the eluent so that the ratio thereof was in the range of 95: 5-85: 15 by silica gel chromatography, the objective diamine isomer mixture 10[ the mixture of the diamine compound (1-3-10) and its enantiomer ] was obtained as a white solid (yield 1.68g, yield 62%).

¹H-NMR(400MHz,DMSO-d₆)：δ6.74(d,J＝8.5Hz,2H),6.31(d,J＝2.4Hz,2H),6.09(dd,J＝8.5,2.4Hz,2H),5.08(brs,4H),3.67(s,6H),2.35-2.32(m,2H),1.60-1.57(m,2H).

Synthesis example 23 Synthesis of dinitro Compound 12

[ 167]

Thionyl chloride (11.6mL) was added to trans-1, 2-cyclopropanedicarboxylic acid (2.27g, 17.5mmol), and after stirring at 70 ℃ for 4 hours, the mixture was concentrated under reduced pressure, whereby thionyl chloride was distilled off to obtain crude trans-1, 2-cyclopropanedicarboxylic acid chloride. The acid chloride was used as a THF (35mL) solution, and all were used in the following reaction.

To a solution of 3-methoxy-4-nitrophenol (6.20g, 36.7mmol) in THF (35mL) under argon was added triethylamine (8.5mL, 61.1mmol) and cooled in an ice bath. After a THF solution of the acid chloride prepared previously was added dropwise to the solution over 40 minutes, it was warmed to room temperature and stirred for 18 hours. After completion of the reaction, water (100mL) was added to the reaction mixture, and extraction was performed with ethyl acetate (50 mL. times.3). The combined organic layers were washed with saturated brine (50mL × 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. For the obtained residue, chloroform: 99 parts of methanol: 1 was used as an eluent, and purification was performed by silica gel chromatography, whereby a white solid of the dinitro compound 12[ trans-1, 2-cyclopropanedicarboxylic acid bis (3-methoxy-4-nitrophenyl) ester ] was obtained (yield 1.94g, yield 26%).

¹H-NMR(400MHz,DMSO-d₆)：δ8.01(d,J＝8.8Hz,2H),7.33(d,J＝2.3Hz,2H),7.01(dd,J＝8.8,2.3Hz,2H),3.92(s,6H),2.64-2.60(m,2H),1.82-1.78(m,2H).

Synthesis example 24 Synthesis of diamine isomer mixture 11 (mixture of diamine Compound (1-3-11) and its enantiomer)

[ solution 168]

Tin (II) chloride dihydrate (10.2g, 44.0mmol) was added to a solution of bis (3-methoxy-4-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate (1.90g, 4.40mmol) in ethyl acetate (44mL) under an argon atmosphere, and the mixture was stirred under reflux for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, and then added to a saturated aqueous sodium hydrogencarbonate solution (200mL), followed by filtration through celite, and the filtrate was extracted with ethyl acetate (100 mL. times.3). The combined organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate (100mL) and saturated brine (100mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. For the obtained residue, chloroform: methanol 90: the mixed solvent of 10 was used for the eluent, and purification was performed by silica gel chromatography, whereby a pale yellow solid (yield 1.18g, yield 72%) of the aimed diamine isomer mixture 11[ the mixture of the diamine compound (1-3-11) and its enantiomer ] was obtained.

¹H-NMR(400MHz,DMSO-d₆)：δ6.68(d,J＝2.4Hz,2H),6.60(d,J＝8.4Hz,2H),6.49(dd,J＝8.4,2.4Hz,2H),4.68(brs,4H),3.74(s,6H),2.42-2.38(m,2H),1.64-1.61(m,2H).

Synthesis example 25 Synthesis of dinitro Compound 13

[ 169]

Thionyl chloride (10.5mL) was added to trans-1, 2-cyclopropanedicarboxylic acid (2.04g, 15.7mmol), and after stirring at 70 ℃ for 4 hours, the mixture was concentrated under reduced pressure, whereby thionyl chloride was distilled off to obtain a crude trans-1, 2-cyclopropanedicarboxylic acid chloride. The acid chloride was used as a THF (30mL) solution, and all were used in the following reaction.

To a solution of 3-nitrophenol (4.68g, 33.0mmol) in THF (34mL) under argon was added triethylamine (7.6mL, 54.9mmol) and cooled in an ice bath. After a solution of the acid chloride in THF prepared before was added dropwise to the solution over 10 minutes, it was warmed to room temperature and stirred for 25 hours. After completion of the reaction, water (100mL) was added to the reaction mixture, and concentrated under reduced pressure. The residue was extracted with ethyl acetate (100mL × 3), washed with saturated aqueous sodium chloride (100mL), and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. For the obtained residue, chloroform: a mixed solvent of methanol was used for the eluent so that the ratio thereof was in the range of 95: 5-85: 15 was purified by silica gel chromatography to obtain a yellow solid of the dinitro compound 13[ trans-1, 2-cyclopropanedicarboxylic acid bis (3-nitrophenyl) ester ] (yield 4.27g, yield 73%).

¹H-NMR(400MHz,DMSO-d₆)：δ8.21-8.16(m,4H),7.79-7.72(m,4H),2.67-2.63(m,2H),1.83-1.80(m,2H).

Synthesis example 26 Synthesis of diamine isomer mixture 12 (mixture of diamine Compound (1-3-12) and its enantiomer)

[ solution 170]

Tin (II) chloride dihydrate (12.7g, 54.7mmol) was added to a solution of bis (3-nitrophenyl) trans-1, 2-cyclopropanedicarboxylate (2.04g, 5.47mmol) in ethyl acetate (55mL) under an argon atmosphere, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and then added to a saturated aqueous sodium hydrogencarbonate solution (200mL), followed by filtration through celite, and the filtrate was extracted with ethyl acetate (100 mL. times.3). The combined organic layers were washed with saturated aqueous sodium bicarbonate (200mL) and saturated brine (200mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. For the obtained residue, chloroform: a mixed solvent of methanol was used for the eluent so that the ratio thereof was in the range of 95: 5-85: 15 was purified by silica gel chromatography to obtain the objective diamine isomer mixture 12[ a mixture of the diamine compound (1-3-12) and its enantiomer ] as a pale yellow oil (yield 1.34g, yield 79%).

¹H-NMR(400MHz,DMSO-d₆)：δ7.02(t,J＝8.0Hz,2H),6.44(ddd,J＝8.0,2.2,0.8Hz,2H),6.32(t,J＝2.1Hz,2H),6.27(ddd,J＝8.0,2.2,0.8Hz,2H),5.29(brs,4H),2.43-2.39(m,2H),1.64-1.60(m,2H).

Synthesis example 27 Synthesis of diamine isomer mixture 13 (mixture of diamine Compound (1-3-13) and its enantiomer)

[ solution 171]

Concentrated sulfuric acid (0.1mL) was added to a solution of trans-3-methylene-1, 2-cyclopropanedicarboxylic acid (3.20g, 22.5mmol) in methanol (48mL), and the mixture was stirred at 40 ℃ for 4 and a half hours. After the solvent was distilled off by concentration under reduced pressure, water (100mL) was added and extraction was performed with ethyl acetate (30 mL. times.3). The obtained organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate (50mL) and a saturated aqueous solution of sodium chloride (50mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain trans-3-methylene-1, 2-cyclopropane dimethyl ester as a yellow oil (yield 3.74g, yield 98%).

¹H-NMR(400MHz,CDCl₃)：δ5.68(t,J＝2.4Hz,2H),3.72(s,6H),2.89(t,J＝2.4H,2H).

[ solution 172]

To trans-3-methylene-1, 2-cyclopropanedimethyl ester (1.28g, 9.02mmol) were added hydrazine monohydrate (1.1mL, 22.6mmol) and acetonitrile (75 mL). Stirring for 42 hr under oxygen atmosphere while irradiating low pressure mercury lamp (UVL-20 PH-6). After the completion of the reaction, the reaction solution was purified by short column chromatography (ethyl acetate 100mL), whereby trans-3-methyl-1, 2-cyclopropanedimethyl ester was obtained as a brown oil (yield 1.20g, yield 77%).

¹H-NMR(400MHz,CDCl₃)：δ3.71(s,3H),3.69(s,3H),2.29(dd,J＝9.6,4.6Hz,1H),2.11(dd,J＝5.6,4.6Hz,1H),1.88-1.79(m,1H),1.26(d,J＝6.4Hz,3H).

[ chemical formula 173]

To a solution of trans-3-methyl-1, 2-cyclopropanedimethyl ester (1.20g, 6.97mmol) in ethanol (14mL) was added a solution of sodium hydroxide (1.12g, 27.9mmol) in water (14mL) dropwise over 5 minutes under cooling in an ice bath. After the reaction, the reaction mixture was concentrated under reduced pressure, whereby the solvent was distilled off. Concentrated hydrochloric acid (3.0mL) was added to the residue under cooling in an ice bath, and extraction was performed with ethyl acetate (30 mL. times.3). The combined organic layers were dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a pale yellow solid of trans-3-methyl-1, 2-cyclopropanedicarboxylic acid (yield 0.91g, yield 91%).

¹H-NMR(400MHz,DMSO-d₆)：δ12.5(brs,2H),2.01(dd,J＝9.6,4.6Hz,1H),1.78(dd,J＝5.8,4.6Hz,1H),1.73-1.65(m,1H),1.17(d,J＝6.2Hz,3H).

[ solution 174]

Trans-3-methyl-1, 2-cyclopropanedicarboxylic acid (867mg, 6.02mmol) and tert-butyl N- (4-hydroxyphenyl) carbamate (2.64g, 12.6mmol) were dissolved in dichloromethane (60mL) under argon and cooled in an ice bath. To the mixture was added 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (2.47g, 12.6mmol) and 4-dimethylaminopyridine (147mg, 1.20mmol), and the mixture was warmed to room temperature and stirred for 64 hours. After completion of the reaction, water (100mL) was added and extraction was performed with chloroform (30 mL. times.3). The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was washed with methanol (20mL), whereby di-tert-butyl N- (4-hydroxyphenyl) trans-3-methyl-1, 2-cyclopropanedicarboxylate was obtained as a white solid (yield 2.33g, 73%).

¹H-NMR(400MHz,DMSO-d₆)：δ9.41(brs,2H),7.49-7.45(m,4H),7.08-7.05(m,4H),2.57(dd,J＝9.7,4.6Hz,1H),2.27(dd,J＝5.9,4.6Hz,1H),2.09(m,1H),1.48(s,18H),1.31(d,J＝6.3Hz,3H).

[ chemical 175]

Trifluoroacetic acid (8.4mL) was added dropwise to a solution of di-tert-butyl N- (4-hydroxyphenyl) trans-3-methyl-1, 2-cyclopropanedicarboxylate (2.27g, 4.30mmol) in dichloromethane (43mL) over 10 minutes under cooling in an ice bath, and then the temperature was raised to room temperature. After completion of the reaction, a saturated aqueous sodium bicarbonate solution (200mL) was added thereto under cooling in an ice bath, and extraction was performed with chloroform (50 mL. times.3). The combined organic layers were dried over anhydrous magnesium sulfate and concentrated under reduced pressure, whereby di-4-aminophenyl trans-3-methyl-1, 2-cyclopropanedicarboxylate was obtained as a white solid (yield 1.13g, yield 80%).

¹H-NMR(400MHz,CDCl₃)：δ6.92-6.88(m,4H),6.69-6.64(m,4H),2.61(dd,J＝9.7,4.6Hz,1H),2.39(dd,J＝5.9,4.6Hz,1H),2.11-2.03(m,1H),1.40(d,J＝6.4Hz,3H).¹H-NMR(400MHz,DMSO-d₆)：δ6.82-6.77(m,4H),6.57-6.52(m,4H),5.06(brs,4H),2.49-2.47(m,1H),2.20(dd,J＝5.9,4.6Hz,1H),2.06-1.97(m,1H),1.28(d,J＝6.2Hz,3H).

Synthesis of trans-1, 2-cyclopropanedicarboxylic acid

Trans-1, 2-cyclopropane dicarboxylic acid used for the synthesis of dinitro compounds can be synthesized by synthesis examples 28 to 31 described below.

[ Synthesis example 28]

[ solution 176]

After a mixed solution of sodium hydride (5.24g, 120mmol) in DMF (30mL) was cooled to 2 ℃, a solution of ethyl acrylate (10.0g, 99.9mmol) and ethyl chloroacetate (12.2g, 99.9mmol) in DMF (20mL) was added dropwise over 45 minutes. After 2 hours, the temperature was raised to room temperature, and the mixture was stirred in this state for 20 hours. After completion of the reaction, 5M hydrochloric acid (30mL) was slowly added dropwise to the reaction mixture under cooling in an ice bath, and then water (50mL) was added thereto and stirred, followed by extraction with diethyl ether (50 mL. times.3). The combined organic layers were washed with a saturated aqueous solution of sodium hydrogencarbonate (50mL) and saturated brine (50mL × 2), dried over magnesium sulfate, and concentrated under reduced pressure. Trans form of the obtained residue (12.1 g): the cis form is 97: 3. the residue was prepared as an ethanol (200mL) solution, and the total amount was used in the following reaction.

To the ethanol solution obtained by the previous reaction, a solution of sodium hydroxide (16.0g, 400mmol) in water (200mL) was slowly added dropwise with cooling in an ice bath. After the completion of the dropwise addition, the reaction mixture was slowly warmed to room temperature and stirred for 15 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, whereby ethanol was distilled off. The obtained aqueous layer was washed with hexane (150 mL. times.3), and then concentrated hydrochloric acid (40mL) was added dropwise to the aqueous layer under cooling in an ice bath. After stirring for a while, extraction was performed with ethyl acetate (50 mL. times.3). The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The obtained crude product was washed with ethyl acetate (40mL), hexane (200mL), thereby obtaining a white solid of trans-1, 2-cyclopropanedicarboxylic acid (yield 5.88g, yield 45%).

¹H-NMR(400MHz,DMSO-d₆)：δ12.6(brs,2H),1.91-1.87(m,2H),1.29-1.25(m,2H).

[ Synthesis example 29]

A solution of sodium hydride (2.62g, 59.9mmol) in DMF (10mL) was cooled to-10 deg.C and a solution of ethyl acrylate (5.00g, 49.9mmol) and ethyl chloroacetate (6.12g, 49.9mmol) in DMF (15mL) was added dropwise over 20 minutes and stirred for 24 hours. 5M hydrochloric acid (15mL) was slowly added dropwise to the reaction mixture under cooling in an ice bath, and after adding water (30mL) and stirring, extraction was performed with diethyl ether (50 mL. times.3). The combined organic layers were washed with a saturated aqueous solution of sodium hydrogencarbonate (50mL) and saturated brine (50mL × 2), dried over magnesium sulfate, and concentrated under reduced pressure. Trans form of the obtained residue (8.50 g): the cis form is 98: 2. the residue was prepared as an ethanol (100mL) solution, and all of the ethanol solution was used in the following reaction.

To the ethanol solution obtained by the previous reaction, a solution of sodium hydroxide (8.00g, 200mmol) in water (100mL) was slowly added dropwise with cooling in an ice bath. After the completion of the dropwise addition, the reaction mixture was slowly warmed to room temperature and stirred for 15 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, whereby ethanol was distilled off. The obtained aqueous layer was washed with hexane (100 mL. times.3), and then concentrated hydrochloric acid (20mL) was added dropwise to the aqueous layer under cooling in an ice bath. After stirring for a while, extraction was performed with ethyl acetate (50 mL. times.3). The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The obtained crude product was washed with ethyl acetate (18mL), hexane (30mL), thereby obtaining a white solid of trans-1, 2-cyclopropanedicarboxylic acid (yield 3.08g, yield 48%).

¹H-NMR(400MHz,DMSO-d₆)：δ12.6(brs,2H),1.91-1.87(m,2H),1.29-1.25(m,2H).

[ Synthesis example 30]

After a mixed solution of sodium hydride (4.30g, 98.44mmol) in DMF (50mL) was cooled to 2 ℃, ethyl acrylate (10.0g, 99.9mmol) and ethyl chloroacetate (12.2g, 99.9mmol, 1.0eq.) were added dropwise over 40 minutes. After 2 hours, the temperature was raised to room temperature and stirred for 20 hours. After completion of the reaction, 5M-hydrochloric acid (30mL) was slowly added dropwise to the reaction mixture under cooling in an ice bath, and then water (50mL) was added thereto and stirred, followed by extraction with diethyl ether (50 mL. times.3). The combined organic layers were washed with a saturated aqueous solution of sodium hydrogencarbonate (50mL) and saturated brine (50mL × 2), dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue (18.8g) had a trans to cis ratio of trans: cis-85: 15. the residue was prepared as an ethanol (200mL) solution, and all of the ethanol solution was used in the following reaction.

To the ethanol solution obtained by the previous reaction, a solution of sodium hydroxide (16.0g, 400mmol) in water (200mL) was slowly added dropwise with cooling in an ice bath. After the completion of the dropwise addition, the reaction mixture was slowly warmed to room temperature and stirred for 15 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, whereby ethanol was distilled off. The obtained aqueous layer was washed with hexane (150 mL. times.3), and then concentrated hydrochloric acid (40mL) was added dropwise to the aqueous layer under cooling in an ice bath. After stirring for a while, extraction was performed with ethyl acetate (50 mL. times.3). The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The obtained crude product was washed with ethyl acetate (48mL), hexane (40mL), thereby obtaining a white solid of trans-1, 2-cyclopropanedicarboxylic acid (yield 6.46g, yield 50%).

¹H-NMR(400MHz,DMSO-d₆)：δ12.6(brs,2H),1.91-1.87(m,2H),1.29-1.25(m,2H).

[ Synthesis example 31]

After a mixed solution of sodium tert-butoxide (11.8g, 120mmol) in DMF (30mL) was cooled to 2 ℃, a solution of ethyl acrylate (10.0g, 99.9mmol) and ethyl chloroacetate (12.2g, 99.9mmol) in DMF (20mL) was added dropwise over 40 minutes. After 2 hours, the temperature was raised to room temperature, and the mixture was stirred in this state for 20 hours. After completion of the reaction, 5M hydrochloric acid (30mL) was slowly added dropwise to the reaction mixture under cooling in an ice bath, and then water (50mL) was added thereto and stirred, followed by extraction with diethyl ether (50 mL. times.3). The combined organic layers were washed with a saturated aqueous solution of sodium hydrogencarbonate (50mL) and saturated brine (50mL × 2), dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue (17.8g) was prepared as an ethanol (200mL) solution, and all of the solution was used in the following reaction.

To the ethanol solution obtained by the previous reaction, a solution of sodium hydroxide (16.0g, 400mmol) and water (200mL) was slowly added dropwise with cooling in an ice bath. After the completion of the dropwise addition, the reaction mixture was slowly warmed to room temperature and stirred for 15 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, whereby ethanol was distilled off. To the obtained aqueous layer was added dropwise concentrated hydrochloric acid (40mL) under cooling in an ice bath. After stirring for a while, extraction was performed with ethyl acetate (50 mL. times.3). The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The obtained crude product was washed with ethyl acetate (22mL), hexane (20mL), thereby obtaining a white solid of trans-1, 2-cyclopropanedicarboxylic acid (yield 7.50g, yield 58%).

¹H-NMR(400MHz,DMSO-d₆)：δ12.6(brs,2H),1.91-1.87(m,2H),1.29-1.25(m,2H).

Measurement method and evaluation method

The following shows the measurement method and evaluation method used in this example.

[ measurement of weight average molecular weight (Mw) ]

The weight average molecular weight of the polyamic acid is determined by: measured by GPC using a 2695 separation Module 2414 differential refractometer (manufactured by Waters) and converted to polystyrene. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid/DMF in a weight ratio of 0.6/100) so that the polyamic acid concentration became about 2 wt%. The column was measured using HSPgel RT MB-M (manufactured by Waters) at a column temperature of 50 ℃ and a flow rate of 0.40mL/min, using the mixed solution as a developing solvent. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh (Strand) was used.

[ measurement of contrast ]

The luminance-voltage characteristics (B-V characteristics) of the prepared liquid crystal cell were measured, and the Contrast Ratio (CR) was determined using the ratio of the minimum luminance to the maximum luminance. The larger the value of CR, the sharper the bright-dark display and the better the contrast, and when it is 3000 or more, it can be said that the contrast is excellent.

CR＝B_max/B_min

In the formula, B_maxRepresents the maximum luminance in the B-V characteristic, B_minRepresenting the minimum luminance in the B-V characteristic.

[ measurement of Alternating Current (AC) afterimage ]

The AC image sticking was measured according to the method described in the pamphlet of International publication No. 2000/43833. Specifically, the luminance-voltage characteristics (B-V characteristics) of the fabricated liquid crystal cell were measured and were set as the luminance-voltage characteristics before stress application: b (before). Next, an alternating current of 4.5V and 60Hz was applied to the liquid crystal cell for 20 minutes, followed by short-circuiting for 1 second, and the luminance-voltage characteristics (B-V characteristics) were measured again. The luminance-voltage characteristics after stress application were set as: b (after). Here, as the characteristic values of B (before) and B (after), the luminance at a voltage of 1.3V of each measured luminance-voltage characteristic was used, and the luminance change rate Δ B (%) was determined by the following equation. The smaller the value of Δ B (%) is, the more suppressed the generation of AC afterimage, i.e., the better the afterimage characteristics are. When Δ B is less than 3%, it is evaluated as "o", when Δ B is 3% or more, it is evaluated as "x", and when Δ B is "o", it can be said that the afterimage characteristics are good.

Δ B (%) { [ B (after)) -B (before)) ]/B (before)) } × 100

Compounds used in the examples

[ diamine Compound represented by the general formula (1) ]

The diamine compound represented by the general formula (1) used for the preparation of the varnish in this example is shown below.

[ solution 177]

[ other diamine Compound ]

The following are the other diamine compounds used in the preparation of the varnish in the present example and comparative example. Among these, the compound (DI-5-32), the compound (DI-5-35) and the compound (DI-6-8) are photoreactive diamine compounds. The values of m in the following formulae are shown in tables 1 to 5.

[ solution 178]

[ tetracarboxylic dianhydride ]

The tetracarboxylic dianhydrides used for the preparation of the varnishes in the examples and comparative examples are shown below. The values of m in the following formulae are shown in tables 1 to 5.

[ chemical 179]

The following shows solvents used for the preparation of varnishes in the present example and comparative example.

NMP: n-methyl-2-pyrrolidone

BC: butyl Cellosolve (ethylene glycol monobutyl ether)

The following shows additives used for the preparation of varnishes in the present example and comparative example.

Ad.1: 3-aminopropyltriethoxysilane

Ad.2: 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane

And (3) Ad.3: (3,3',4,4' -diepoxy) bicyclohexyl

Ad.4: 1, 3-bis (4, 5-dihydro-2-oxazolyl) benzene

Preparation of the varnish

The varnish used in this example was prepared according to the following procedure. The varnishes varnish a1 to varnish a7 and varnish a21 to varnish a37 prepared in preparation examples 1 to 7 and preparation examples 21 to 37 of the varnishes were solutions of polyamic acid using at least one of the diamine compounds (1) as a diamine monomer, and the varnishes varnish A8 to varnish a10 prepared in preparation examples 8 to 10 of the varnishes were solutions of polyamic acid synthesized using another photoreactive diamine compound (DI-5-32), photoreactive diamine compound (DI-5-35) or photoreactive diamine compound (DI-6-8). Varnishes preparation examples 11 to 13 and preparation examples 41 to 43 were prepared by blending varnishes B1 to B6, which were solutions of polyamic acid synthesized without using a photoreactive diamine compound in the raw materials, with varnishes a1 to a10, varnishes a21 to a37, and varnishes C1 to C6. Varnishes C1 to C6 prepared in preparation examples 14 to 19 were solutions of block polymers of a first polyamic acid synthesized without using a photoreactive diamine compound and a second polyamic acid synthesized using a diamine compound (1).

Preparation example of varnish 1 preparation of varnish A1

A100 mL three-necked flask equipped with a stirring blade and a nitrogen inlet was charged with the diamine isomer mixture 1(0.883g), and NMP (10.0g) was added thereto and stirred. To the solution were added tetracarboxylic dianhydride (AN-3-2) (0.617g) and NMP (2.5g), and the mixture was stirred at room temperature for 12 hours. NMP (6.0g) and BC (5.0g) were added thereto, and the solution was heated and stirred at 80 ℃ until the weight-average molecular weight of the polymer as a solute became the target weight-average molecular weight, thereby obtaining varnish A1 having a weight-average molecular weight of the solute of about 18,000 and a resin component concentration of 6 wt%.

Preparation examples 2 to 13 and 21 to 37 of varnishes varnish A2 to varnish A10, varnish A21 to varnish A37, and varnish B1 to varnish B6

Varnishes a2 to a10 and varnishes a21 to a37 each having a polymer concentration of 6% by weight were prepared in the same manner as in preparation example 1, except that the compounds used as diamines and tetracarboxylic dianhydrides were changed as shown in tables 1 to 3. Varnishes B1 to B6 were prepared in the same manner as in preparation example 1, except that the compounds used as diamines and tetracarboxylic dianhydrides were changed as shown in table 4. In varnishes B1 to B6, the heating and stirring conditions were adjusted so that the weight average molecular weight of the polymer became about 50,000. The weight average molecular weight (Mw) of the resulting polymer is shown in tables 1 to 4. In tables 1 to 4, the production examples in which two or more compounds are described as diamines are used in combination as diamines, and the production examples in which two or more compounds are described as tetracarboxylic dianhydrides are used in combination as tetracarboxylic dianhydrides. The numbers in brackets indicate the formulation ratio (mol%), and the empty column indicates that the compound corresponding to the column is not used. The same applies to table 5 below.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

Preparation example of varnish 14 preparation of varnish C1

In this production example, a two-stage polymerization process was performed to synthesize a block polymer of polyamic acid.

(1) Polymerization step in the first stage

A200 mL three-necked flask equipped with a stirring blade and a nitrogen inlet was charged with and stirred with a diamine compound (DI-4-1) (0.408g), a diamine compound (DI-13-1) (1.011g), and NMP (20.0 g). To the solution were added tetracarboxylic dianhydride (AN-4-21) (1.17g), tetracarboxylic dianhydride (AN-1-1) (0.747g), and NMP (10.0g), and stirring was continued at room temperature for 6 hours to obtain a solution of a first polyamic acid.

(2) Polymerization step in the second stage

In a flask in which the first-stage polymerization was carried out, diamine isomer mixture 1(1.57g), tetracarboxylic dianhydride (AN-3-2) (1.10g), and NMP (34.0g) were placed, and stirring was continued at room temperature for 24 hours to obtain a mixed solution of the first polyamic acid and the second polyamic acid. BC (30.0g) was added to the reaction solution, and the mixture was stirred while being heated to 60 ℃ for 8 hours to obtain a polyamic acid block polymer solution having a polymer solid content of 6 wt%. The polyamic acid block polymer solution was set to varnish C1.

[ preparation examples 15 to 19 of varnishes ] preparation of varnishes C2 to C6

Varnishes C2 to C6 having a resin component concentration of 6% by weight were prepared in the same manner as in preparation example 14, except that the compounds used as diamines and tetracarboxylic dianhydrides were changed as shown in table 5.

[ Table 5]

[ example 1]

< preparation of liquid Crystal alignment agent and measurement of contrast >

Varnish a1 was diluted and stirred with an NMP/BC mixed solution (NMP/BC 7/3 weight ratio) so as to be 4 weight%, thereby preparing liquid crystal alignment agent 1.

The liquid crystal aligning agent 1 was applied to a glass substrate with FFS electrodes and a glass substrate with column spacers (column spacers) by a spinner method. After the coating, the substrate was heated at 60 ℃ for 80 seconds to evaporate the solvent, and then irradiated with ultraviolet linearly polarized Light through a polarizing plate from a direction perpendicular to the substrate using a Multi-Light ML-501C/B manufactured by a bull-tail motor (jet). The exposure energy at this time was measured using an ultraviolet ray integrated light quantity meter UIT-150 (light receiver: UVD-S254) manufactured by a cow tail motor (stock) so as to be 1.0J/cm at a wavelength of 254nm²The exposure time is adjusted. Thereafter, the film was subjected to calcination treatment at 220 ℃ for 30 minutes to form an alignment film having a film thickness of about 100 nm.

Then, the two substrates on which the alignment films are formed are bonded so that the surfaces on which the liquid crystal alignment films are formed face each other and a gap for injecting a liquid crystal composition is provided between the facing liquid crystal alignment films. In this case, the polarization directions of the linearly polarized light irradiated to the respective liquid crystal alignment films are made parallel. These cells were filled with the positive type liquid crystal composition a to prepare liquid crystal cells (liquid crystal display elements) having a cell thickness of 5 μm.

< Positive type liquid Crystal composition A >

[ solution 180]

(physical Property value)

Phase transition temperature NI: 100.1 ℃, dielectric anisotropy Δ ε: 5.1, refractive index anisotropy Δ n: 0.093, viscosity η: 25.6 mPas.

The contrast was measured as described above using the prepared liquid crystal cell. As a result, the contrast was 3800.

Examples 2 to 17, examples 21 to 62, and comparative examples 1 to 3

Liquid crystal aligning agents 2 to 17, 21 to 62, and comparative liquid crystal aligning agents 1 to 3 were prepared in the same manner as in example 1, except that the varnishes shown in tables 6 to 7 were used instead of the varnish a 1. In tables 6 to 7, in the preparation examples in which two or more varnishes were described, all the varnishes were mixed in the blending ratios (weight ratios) shown in tables 6 to 7 to prepare liquid crystal aligning agents. In addition, to the liquid crystal aligning agents 8 to 17, 38 to 40, 50, 51, 54 and 57, the additives shown in tables 6 to 7 were added in the amounts shown in tables 6 to 7 by weight based on the weight of the polymer in the varnish. Using each of the prepared liquid crystal aligning agents, a substrate with a liquid crystal alignment film was produced in the same manner as in example 1, and the contrast of a liquid crystal cell in which the substrate was mounted was measured. The conditions for ultraviolet irradiation during formation of the liquid crystal alignment film were as shown in tables 6 to 7. The evaluation results of the liquid crystal aligning agents and the contrast ratios used in the examples are shown in tables 6 to 7.

[ Table 6]

[ Table 7]

As shown in tables 6 to 7, the liquid crystal cells of examples 1 to 17 and 21 to 62, which used the polymer of diamine compound (1) in the liquid crystal alignment film, had a contrast ratio of 3300 or more, which was higher than that of comparative example 1 which used the polymer of compound (DI-5-32) which is a photoreactive diamine compound other than diamine compound (1), comparative example 2 which used the polymer of compound (DI-5-35), and comparative example 3 which used the polymer of compound (DI-6-8). From this, it is found that the structural unit derived from the diamine compound (1) contributes more effectively to imparting orientation to the film than the structural unit derived from another photoreactive diamine compound.

[ example 80]

< measurement of AC afterimage >

The liquid crystal cell of example 23, which was produced using the liquid crystal aligning agent 23, was evaluated for AC image sticking as described above. As a result, Δ B was 1.8%, and therefore evaluated as "o".

Examples 81 to 87 and comparative example 4

AC image sticking was evaluated in the same manner as in example 80 using the liquid crystal cells in which the liquid crystal aligning agent shown in table 8 was used instead of the liquid crystal aligning agent 23, that is, the liquid crystal cells of examples 24 to 26, example 21, example 29, example 48, example 49, and comparative example 1. The conditions for forming the liquid crystal alignment agent and the liquid crystal alignment film used in each example and the evaluation results of the AC afterimage are shown in table 8.

[ Table 8]

As shown in table 8, the liquid crystal cells of examples 80 to 87, in which the polymer of the diamine compound (1) was used in the liquid crystal alignment film, were all evaluated as "o" for the AC image retention, and the AC image retention was more excellent than that of the liquid crystal cell of comparative example 4, in which the polymer of the compound (DI-5-32) that is a photoreactive diamine compound other than the diamine compound (1) was used. From this, it is understood that the structural unit derived from the diamine compound (1) can produce a liquid crystal cell exhibiting more excellent AC afterimage than the structural unit derived from another photoreactive diamine compound.

[ industrial applicability ]

By using a polymer synthesized using the diamine compound of the present invention as a liquid crystal aligning agent, a liquid crystal alignment film having high liquid crystal alignment properties is realized. Further, by using the liquid crystal alignment film, a liquid crystal display element having high contrast and usable in various modes can be provided. Therefore, the present invention has high industrial applicability.