TW202116875A - Liquid crystal alignment agent, liquid crystal alignment film and manufacturing method thereof, liquid crystal display device, compound, and polymer including a polymer formed by reacting tetracarboxylic dianhydrides and diamines - Google Patents

Abstract

The present invention is to provide a liquid crystal alignment agent, a liquid crystal alignment film and a manufacturing method thereof, a liquid crystal display device, a compound, and a polymer that can form a liquid crystal display element with good afterimage characteristics and contrast, and a high light resistance. A liquid crystal alignment agent comprises at least one polymer. The at least one polymer is a polymer formed by reacting tetracarboxylic dianhydrides and diamines. At least one of the diamines is a compound represented by formula (1). In the formula (1), X is an alkylene group having 1 to 12 carbon atoms where each of a to c is independently as an integer of 0 to 2, each of Ra and Rb is independently a hydrogen atom, -F, formula (P1 -1) or formula (P1-2), etc., each of Rc is independently a hydrogen atom, etc. In formulas (P1-1) and (P1-2), each of R6a to R8a is independently a hydrogen atom, etc. and * indicates a bonding position on the benzene ring in formula (1).

Description

Liquid crystal alignment agent, liquid crystal alignment film and manufacturing method thereof, liquid crystal display element, compound and polymer

The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element using the liquid crystal alignment film. In detail, it relates to a liquid crystal alignment agent used to form a liquid crystal alignment film of a photo-alignment method (hereinafter sometimes referred to as a photo-alignment film), and a photo-alignment liquid crystal alignment film formed using the liquid crystal alignment agent And a liquid crystal display element having the liquid crystal alignment film. Furthermore, it relates to a polymer such as polyamide used in the liquid crystal alignment agent and a diamine used as a raw material thereof.

As liquid crystal display elements, known are twisted nematic (TN) mode, super twisted nematic (STN) mode, in-plane switching (IPS) mode, fringe field switching (Fringe Field Switching (FFS) mode, vertical alignment-type vertical alignment (Vertical Alignment, VA) (Multi-domain Vertical Alignment (Multi-domain Vertical Alignment)) mode and other driving modes of liquid crystal display elements. These liquid crystal display elements are used in image display devices of various electronic devices such as televisions and mobile phones, and are being developed with the goal of further improving the display quality. Specifically, the improvement of the performance of the liquid crystal display element can be achieved not only by the improvement of the driving method and the element structure, but also by the constituent members used in the element. Moreover, among the constituent members used in the liquid crystal display element, in particular, the liquid crystal alignment film is one of the important materials related to the display quality. In order to meet the high quality requirements of the liquid crystal display element, the liquid crystal alignment film is also being used Actively conduct research.

Here, the liquid crystal alignment film is provided in contact with the liquid crystal layer on a pair of substrates provided on both sides of the liquid crystal layer of the liquid crystal display element, and is provided to align the liquid crystal molecules constituting the liquid crystal layer with a certain regularity with respect to the substrate. Function. By using a liquid crystal alignment film with high liquid crystal alignment, a liquid crystal display element with high contrast and improved afterimage characteristics can be realized (for example, refer to Patent Document 1 and Patent Document 2). In the formation of such a liquid crystal alignment film, a solution (varnish) obtained by dissolving polyamide acid, soluble polyimide, or polyamide ester in an organic solvent is currently mainly used. When using these varnishes to form a liquid crystal alignment film, the varnish is coated on a substrate, and then the coating film is cured by heating or the like to form a polyimide-based liquid crystal alignment film, and an alignment treatment suitable for the display mode is performed as necessary . As the alignment treatment method, known are: a rubbing method in which the surface of the alignment film is rubbed with cloth or the like to adjust the direction of polymer molecules; and the alignment film is irradiated with linearly polarized ultraviolet rays to cause photoisomerization or photoisomerization in the polymer molecules. A photo-alignment method that imparts anisotropy to the film by photochemical changes such as dimerization. Among them, compared with the rubbing method, the photo-alignment method has higher alignment uniformity and is a non-contact alignment treatment method, so it has no damage to the film , It can reduce the advantages of dust or static electricity that cause poor display of the liquid crystal display element.

As such a liquid crystal alignment film using a photo-alignment method, for example, Patent Document 1 to Patent Document 6 describe: using diaminoazobenzene as a raw material and applying a photoisomerization technology to obtain an anchor A photo-alignment film with large energy and good liquid crystal alignment. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-197999 [Patent Document 2] International Publication 2013/157463 [Patent Document 3] Japanese Patent Laid-Open No. 2005-275364 [Patent Document 4] Japanese Patent Laid-Open No. 2007-248637 [Patent Document 5] Japanese Patent Laid-Open No. 2009-069493 [Patent Document 6] International Publication 2015/016118

[The problem to be solved by the invention] As described above, there is known a liquid crystal alignment film formed by performing alignment treatment on a polyimide-based liquid crystal alignment film using a photo-alignment method. However, compared with the polyimide-based liquid crystal alignment film using the rubbing treatment, the polyimide-based liquid crystal alignment film using the photo-alignment method generally has inferior electrical properties, and thus the display quality of the liquid crystal display element tends to be impaired. It is thought that this is because of the photoreactive groups introduced to produce photochemical reactions. Among them, the azo group absorbs light and easily generates free radicals. Therefore, the voltage retention rate of the liquid crystal display element (hereinafter, sometimes abbreviated as VHR (Voltage Holding Ratio)) decrease.

Therefore, the inventors of the present invention provide an alignment film that can form a liquid crystal display element that has good afterimage characteristics and contrast, maintains a high voltage retention rate and does not deteriorate display quality even if exposed to strong light for a long time, and provides A liquid crystal alignment agent capable of forming such a liquid crystal alignment film has been studied diligently for the purpose. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the inventors have conducted diligent studies. As a result, the present inventors have discovered that by using the diamine represented by the formula (1) as a raw material monomer that causes the photochemical change of the liquid crystal alignment agent (sometimes also described as photosensitive) Monomer), an alignment film with high anisotropy can be obtained, and by using the alignment film, a good afterimage characteristic and contrast can be formed, and a high voltage retention rate can be maintained even if exposed to strong light for a long time Furthermore, a liquid crystal display element with no degradation in display quality has completed the present invention. The present invention includes the following structures.

式（1）中，X為碳數1～12的伸烷基，所述伸烷基的-(CH₂ )₂ -的不相鄰的一個以上可經-O-及-NH-的任一者取代， a～c分別獨立地為0～2的整數， R^a 及R^b 分別獨立地為氫原子、式（P1-1）、式（P1-2）、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ， R^c 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F，

式（P1-1）及式（P1-2）中，R^6a ～R^8a 分別獨立地為氫原子、經取代或未經取代的烷基、經取代或未經取代的烷醯基、經取代或未經取代的烷氧基羰基、或者經取代或未經取代的芳基羰基，R^6a ～R^8a 可相互相同，也可不同，*表示在式（1）中的苯環上的鍵結位置， 式（1）中，鍵結位置未固定於構成環的任一個碳原子上的基表示在所述環上的鍵結位置為任意。[1] A liquid crystal alignment agent comprising at least one polymer, and in the liquid crystal alignment agent, at least one of the polymers is a polymer formed by reacting tetracarboxylic dianhydrides and diamines, the At least one of the diamines is a compound represented by formula (1).

In the formula (1), X is an alkylene group having 1 to 12 carbon atoms, _{and one or more non-adjacent -(CH 2} ) ₂ -of the alkylene group may pass through any of -O- and -NH- Substitution, a to c are each independently an integer of 0 to 2, R ^a and R ^b are each independently a hydrogen atom, formula (P1-1), formula (P1-2), -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , R ^{c is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F,

In formula (P1-1) and formula (P1-2), R ^6a to R ^8a are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane group, a substituted Or an unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl group, R ^6a to R ^8a may be the same as or different from each other, and * represents the bond on the benzene ring in formula (1) Position, in formula (1), a group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary.

式（1-1）中，X為碳數1～12的伸烷基，所述伸烷基的-(CH₂ )₂ -的不相鄰的一個以上可經-O-及-NH-的任一者取代， R¹ 及R² 分別獨立地為氫原子、式（P1-1）或式（P1-2），R¹ 及R² 的至少一個為式（P1-1）或式（P1-2）， c為0～2的整數，R⁴ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 或-F， 式（1-2）中，X為碳數1～12的伸烷基，所述伸烷基的-(CH₂ )₂ -的不相鄰的一個以上可經-O-及-NH-的任一者取代， a為0～2的整數，R³ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ， b為0～2的整數，R⁵ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ， c為0～2的整數，R⁴ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 或-F，

式（P1-1）及式（P1-2）中，R^6a ～R^8a 分別獨立地為氫原子、經取代或未經取代的烷基、經取代或未經取代的烷醯基、經取代或未經取代的烷氧基羰基、或者經取代或未經取代的芳基羰基，R^6a ～R^8a 可相互相同，也可不同，*表示在式（1-1）中的苯環上的鍵結位置， 式（1-1）及式（1-2）中，鍵結位置未固定於構成環的任一個碳原子上的基表示在所述環上的鍵結位置為任意。[2] The liquid crystal alignment agent according to [1], wherein at least one of the compounds represented by formula (1) is a compound represented by formula (1-1) or formula (1-2).

In the formula (1-1), X is an alkylene group having 1 to 12 carbon atoms, and one or more non-adjacent _{-(CH 2} ) _{2-of the alkylene group may pass through -O- and -NH-} Either one is substituted, R ¹ and R ² are each independently a hydrogen atom, formula (P1-1) or formula (P1-2), ^{at least one of R 1} and R ² is formula (P1-1) or formula (P1) -2), c is an integer of 0-2, R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F, in formula (1-2), X is carbon number 1 to The alkylene group of 12, the _{non-adjacent one or more of -(CH 2} ) ₂ -of the alkylene group may be substituted by any one of -O- and -NH-, a is an integer of 0-2, R ^{3 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , b is an integer from 0 to 2, and R ^{5 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , c is an integer from 0 to 2, and R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F,

In formula (P1-1) and formula (P1-2), R ^6a to R ^8a are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane group, a substituted Or an unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl group, R ^6a to R ^8a may be the same as or different from each other, and * means that on the benzene ring in formula (1-1) Bonding position: In formula (1-1) and formula (1-2), the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary.

式（1-1-1）～式（1-1-12）中，R⁶ 為碳數1～4的烷基， l為1～10的整數，m為1～11的整數，n為1～12的整數。[3] The liquid crystal alignment agent according to [2], wherein the compound represented by formula (1-1) is selected from the group consisting of formula (1-1-1) to formula (1-1-12) A compound represented by at least one formula in the group.

In formulas (1-1-1) to (1-1-12), R ⁶ is an alkyl group having 1 to 4 carbons, l is an integer of 1 to 10, m is an integer of 1 to 11, and n is 1 An integer of ～12.

式（1-2-1）～式（1-2-9）中，l為1～10的整數，m為1～11的整數，n為1～12的整數。[4] The liquid crystal alignment agent according to [2], wherein the compound represented by formula (1-2) is selected from the group consisting of formula (1-2-1) to formula (1-2-9) A compound represented by at least one formula in the group.

In formula (1-2-1) to formula (1-2-9), l is an integer of 1-10, m is an integer of 1-11, and n is an integer of 1-12.

[5] The liquid crystal alignment agent according to any one of [1] to [4], wherein all the polymers include at least one compound represented by formula (1) as a raw material.

[6] The liquid crystal alignment agent according to any one of [1] to [4], wherein at least one polymer does not contain the compound represented by formula (1) as a raw material.

[7] A liquid crystal alignment film formed of the liquid crystal alignment agent according to any one of [1] 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: applying the liquid crystal alignment agent according to any one of [1] to [6] on a substrate; and irradiating the obtained coating film with polarized ultraviolet rays step.

式（1）中，X為碳數1～12的伸烷基，所述伸烷基的-(CH₂ )₂ -的不相鄰的一個以上可經-O-及-NH-的任一者取代， a～c分別獨立地為0～2的整數， R^a 及R^b 分別獨立地為氫原子、式（P1-1）、式（P1-2）、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ， R^c 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 或-F，

式（P1-1）及式（P1-2）中，R^6a ～R^8a 分別獨立地為氫原子、經取代或未經取代的烷基、經取代或未經取代的烷醯基、經取代或未經取代的烷氧基羰基、或者經取代或未經取代的芳基羰基，R^6a ～R^8a 可相互相同，也可不同，*表示在式（1）中的苯環上的鍵結位置， 式（1）中，鍵結位置未固定於構成環的任一個碳原子上的基表示在所述環上的鍵結位置為任意。[10] A compound represented by formula (1).

In the formula (1), X is an alkylene group having 1 to 12 carbon atoms, _{and one or more non-adjacent -(CH 2} ) ₂ -of the alkylene group may pass through any of -O- and -NH- Substitution, a to c are each independently an integer of 0 to 2, R ^a and R ^b are each independently a hydrogen atom, formula (P1-1), formula (P1-2), -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , R ^{c is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F,

In formula (P1-1) and formula (P1-2), R ^6a to R ^8a are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane group, a substituted Or an unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl group, R ^6a to R ^8a may be the same as or different from each other, and * represents the bond on the benzene ring in formula (1) Position, in formula (1), a group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary.

式（1-1）中，X為碳數1～12的伸烷基，所述伸烷基的-(CH₂ )₂ -的不相鄰的一個以上可經-O-及-NH-的任一者取代， R¹ 及R² 分別獨立地為氫原子、式（P1-1）或式（P1-2），R¹ 及R² 的至少一個為式（P1-1）或式（P1-2）， c為0～2的整數，R⁴ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 或-F， 式（1-2）中，X為碳數1～12的伸烷基，所述伸烷基的-(CH₂ )₂ -的不相鄰的一個以上可經-O-及-NH-的任一者取代， a為0～2的整數，R³ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ， b為0～2的整數，R⁵ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ， c為0～2的整數，R⁴ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 或-F，

式（P1-1）及式（P1-2）中，R^6a ～R^8a 分別獨立地為氫原子、經取代或未經取代的烷基、經取代或未經取代的烷醯基、經取代或未經取代的烷氧基羰基、或者經取代或未經取代的芳基羰基，R^6a ～R^8a 可相互相同，也可不同，*表示在式（1-1）中的苯環上的鍵結位置， 式（1-1）及式（1-2）中，鍵結位置未固定於構成環的任一個碳原子上的基表示在所述環上的鍵結位置為任意。[11] The compound according to the item [10], which is represented by formula (1-1) or formula (1-2).

In the formula (1-1), X is an alkylene group having 1 to 12 carbon atoms, and one or more non-adjacent _{-(CH 2} ) _{2-of the alkylene group may pass through -O- and -NH-} Either one is substituted, R ¹ and R ² are each independently a hydrogen atom, formula (P1-1) or formula (P1-2), ^{at least one of R 1} and R ² is formula (P1-1) or formula (P1) -2), c is an integer of 0-2, R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F, in formula (1-2), X is carbon number 1 to The alkylene group of 12, the _{non-adjacent one or more of -(CH 2} ) ₂ -of the alkylene group may be substituted by any one of -O- and -NH-, a is an integer of 0-2, R ^{3 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , b is an integer from 0 to 2, and R ^{5 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , c is an integer from 0 to 2, and R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F,

In formula (P1-1) and formula (P1-2), R ^6a to R ^8a are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane group, a substituted Or an unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl group, R ^6a to R ^8a may be the same as or different from each other, and * means that on the benzene ring in formula (1-1) Bonding position: In formula (1-1) and formula (1-2), the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary.

式（1-1-1）～式（1-1-12）中，R⁶ 為碳數1～4的烷基， l為1～10的整數，m為1～11的整數，n為1～12的整數。[12] The compound according to the item [11], wherein the compound represented by formula (1-1) is selected from the group consisting of formula (1-1-1) to formula (1-1-12) At least one of the formulas.

In formulas (1-1-1) to (1-1-12), R ⁶ is an alkyl group having 1 to 4 carbons, l is an integer of 1 to 10, m is an integer of 1 to 11, and n is 1 An integer of ～12.

式（1-2-1）～式（1-2-9）中，l為1～10的整數，m為1～11的整數，n為1～12的整數。[13] The compound according to [11], wherein the compound represented by formula (1-2) is selected from the group consisting of formula (1-2-1) to formula (1-2-9) At least one of the formulas.

In formula (1-2-1) to formula (1-2-9), l is an integer of 1-10, m is an integer of 1-11, and n is an integer of 1-12.

[14] A polymer that is formed by reacting tetracarboxylic dianhydrides and diamines, and in the polymer, the diamines are according to any one of [10] to [13] At least one of the aforementioned compounds. [Effects of the invention]

By using the liquid crystal alignment agent for optical alignment of the present invention, a liquid crystal alignment film with high anisotropy can be obtained. In addition, by using the liquid crystal alignment film, it is possible to realize a liquid crystal display element that has excellent afterimage characteristics and contrast, maintains a high voltage retention rate and does not degrade display quality even when exposed to strong light for a long time.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. The "liquid crystal alignment agent" in the present invention is a liquid crystal alignment agent that can impart anisotropy by irradiating polarized ultraviolet rays when the film is formed on a substrate. In this specification, if sometimes it is also simply referred to as "liquid crystal alignment agent" , It is sometimes called "liquid crystal alignment agent for optical alignment." In addition, in the present invention, the "tetracarboxylic dianhydrides" refer to tetracarboxylic dianhydrides, tetracarboxylic acid diesters, or tetracarboxylic acid diester dihalides. In addition, in the present invention, diamine and dihydrazine may also be referred to as "diamines".

式（1）中，X為碳數1～12的伸烷基，所述伸烷基的-(CH₂ )₂ -的不相鄰的一個以上可經-O-及-NH-的任一者取代， a～c分別獨立地為0～2的整數， R^a 及R^b 分別獨立地為氫原子、式（P1-1）、式（P1-2）、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ， R^c 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 或-F，

式（P1-1）及式（P1-2）中，R^6a ～R^8a 分別獨立地為氫原子、經取代或未經取代的烷基、經取代或未經取代的烷醯基、經取代或未經取代的烷氧基羰基、或者經取代或未經取代的芳基羰基，R^6a ～R^8a 可相互相同，也可不同，*表示在式（1）中的苯環上的鍵結位置， 式（1）中，鍵結位置未固定於構成環的任一個碳原子上的基表示在所述環上的鍵結位置為任意。<Compound represented by formula (1)> The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent containing a polymer formed by reacting tetracarboxylic dianhydrides and diamines, and the diamines include those selected from the group consisting of At least one of the group consisting of the compound represented by formula (1).

In the formula (1), X is an alkylene group having 1 to 12 carbon atoms, _{and one or more non-adjacent -(CH 2} ) ₂ -of the alkylene group may pass through any of -O- and -NH- Substitution, a to c are each independently an integer of 0 to 2, R ^a and R ^b are each independently a hydrogen atom, formula (P1-1), formula (P1-2), -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , R ^{c is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F,

In formula (P1-1) and formula (P1-2), R ^6a to R ^8a are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane group, a substituted Or an unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl group, R ^6a to R ^8a may be the same as or different from each other, and * represents the bond on the benzene ring in formula (1) Position, in formula (1), a group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary.

The compound represented by the formula (1) of the present invention has a structure in which a benzene ring is bonded to one side of the azobenzene structure via an alkylene group or the like.

When the compound represented by the formula (1) is used as a raw material for a polymer, it will have an azobenzene structure, but a monomer that is not bonded to an alkylene ring or the like via an alkylene ring on one side (For example, diamino azobenzene) When used as a raw material of a polymer, the ratio of the azobenzene structure in the whole polymer is relatively lowered. Therefore, it is considered that when a liquid crystal alignment agent containing a polymer using a compound represented by formula (1) as a raw material is used to form a liquid crystal alignment film, and the film is used to form a liquid crystal display element, it is possible to suppress The VHR of the liquid crystal display element is reduced due to light irradiation during the formation process.

However, by simply reducing the use ratio of monomers having an azobenzene structure (for example, diaminoazobenzene) in the raw material of the liquid crystal alignment agent, although the reduction in VHR is suppressed, the residual image characteristics of the liquid crystal display element are obtained. Or worry about the deterioration of contrast.

In contrast, the present inventors found that by using at least one of the compounds represented by formula (1) as a raw material, the ratio of the azobenzene structure is reduced to suppress the reduction in VHR, and it is possible to achieve good afterimage characteristics and contrast. The reason is not necessarily clear, but it is considered as follows.

In the liquid crystal alignment agent for optical alignment using photoisomerization of the azobenzene structure, when polarized ultraviolet rays are irradiated during the process of forming the liquid crystal alignment film using the liquid crystal alignment agent for optical alignment, the azobenzene structure causes photoisomerization After the reaction, the final azobenzene structure is aligned in one direction (the direction perpendicular to the deflection direction). In the polyamide acid using the compound represented by formula (1), for example, compared with the case of using diaminoazobenzene, a benzene ring is bonded to one side of the azobenzene structure via an alkylene group or the like, Since there are few steric obstacles and the photoisomerization reaction is likely to occur, it is estimated that even if the proportion of the azobenzene structure is small, good afterimage characteristics and contrast can be obtained. Furthermore, in the polymer, the ratio of the alkylene group to the imine bond or the ring structure is relatively high. Therefore, it is speculated that the polymer as a whole is also easy to move and exhibits high anisotropy, which is also the reason for obtaining good afterimage characteristics and contrast. One.

式（A）中，*為鍵結鍵，鍵結鍵相對於苯環的鍵結位置分別獨立地為任意，苯環的能夠進行取代的氫也可具有取代基。In this specification, the azobenzene structure means a structure represented by the following formula (A).

In formula (A), * is a bonding bond, and the bonding position of the bonding bond with respect to the benzene ring is independently arbitrary, and the substitutable hydrogen of the benzene ring may have a substituent.

式（1-1）中，X為碳數1～12的伸烷基，所述伸烷基的-(CH₂ )₂ -的不相鄰的一個以上可經-O-及-NH-的任一者取代， R¹ 及R² 分別獨立地為氫原子、式（P1-1）或式（P1-2），R¹ 及R² 的至少一個為式（P1-1）或式（P1-2）， c為0～2的整數，R⁴ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 或-F， 式（1-2）中，X為碳數1～12的伸烷基，所述伸烷基的-(CH₂ )₂ -的不相鄰的一個以上可經-O-及-NH-的任一者取代， a為0～2的整數，R³ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ， b為0～2的整數，R⁵ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ， c為0～2的整數，R⁴ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 或-F，

式（P1-1）及式（P1-2）中，R^6a ～R^8a 分別獨立地為氫原子、經取代或未經取代的烷基、經取代或未經取代的烷醯基、經取代或未經取代的烷氧基羰基、或者經取代或未經取代的芳基羰基，R^6a ～R^8a 可相互相同，也可不同，*表示在式（1-1）中的苯環上的鍵結位置， 式（1-1）及式（1-2）中，鍵結位置未固定於構成環的任一個碳原子上的基表示在所述環上的鍵結位置為任意。<Compound represented by formula (1)> As the compound represented by formula (1), a compound represented by the following formula (1-1) or formula (1-2) can be mentioned.

In the formula (1-1), X is an alkylene group having 1 to 12 carbon atoms, and one or more non-adjacent _{-(CH 2} ) _{2-of the alkylene group may pass through -O- and -NH-} Either one is substituted, R ¹ and R ² are each independently a hydrogen atom, formula (P1-1) or formula (P1-2), ^{at least one of R 1} and R ² is formula (P1-1) or formula (P1) -2), c is an integer of 0-2, R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F, in formula (1-2), X is carbon number 1 to The alkylene group of 12, the _{non-adjacent one or more of -(CH 2} ) ₂ -of the alkylene group may be substituted by any one of -O- and -NH-, a is an integer of 0-2, R ^{3 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , b is an integer from 0 to 2, and R ^{5 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , c is an integer from 0 to 2, and R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F,

In formula (P1-1) and formula (P1-2), R ^6a to R ^8a are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane group, a substituted Or an unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl group, R ^6a to R ^8a may be the same as or different from each other, and * means that on the benzene ring in formula (1-1) Bonding position: In formula (1-1) and formula (1-2), the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary.

Regarding the compound represented by the formula (1-1), in the case of reacting a raw material composition containing the compound to form a polymer, firing when forming a liquid crystal alignment film from a liquid crystal alignment agent containing the polymer In the step, the cyclization reaction is caused by heat. As a result, the disappearance or reduction of the azobenzene structure can suppress the absorption of light in the vicinity of 400 nm derived from the azobenzene structure. Therefore, the compound represented by the formula (1-1) makes the obtained alignment film more transparent.

For example, in the formula (1-1), in a compound in which R ¹ is a hydrogen atom and R ² has the structure represented by the formula (P1-1) or the formula (P1-2), as shown in the following scheme ( Scheme) Generally, the cyclization reaction is caused by heat.

In terms of ease of synthesis and the height of anisotropy of the obtained liquid crystal alignment film, the compound represented by formula (1-2) is useful.

式（1-1-1）～式（1-1-12）中，R⁶ 為碳數1～4的烷基， l為1～10的整數，m為1～11的整數，n為1～12的整數。 R⁶ 的碳數1～4的烷基的優選具體例為甲基、乙基、丙基、異丙基、丁基、異丁基、叔丁基。Specifically, the compound represented by the formula (1-1) is a compound represented by the following formulas (1-1-1) to (1-1-12).

In formulas (1-1-1) to (1-1-12), R ⁶ is an alkyl group having 1 to 4 carbons, l is an integer of 1 to 10, m is an integer of 1 to 11, and n is 1 An integer of ～12. Preferable specific examples of the alkyl group having 1 to 4 carbon atoms for R ⁶ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl.

Specifically, the compound represented by the formula (1-2) is a compound represented by the following formulas (1-2-1) to (1-2-9).

In formula (1-2-1) to formula (1-2-9), l is an integer of 1-10, m is an integer of 1-11, and n is an integer of 1-12.

In the case of attaching importance to the transparency of the formed liquid crystal alignment film, it is more preferable to use any one or more compounds selected from the group consisting of formula (1-1-1) to formula (1-1-12) . In the case of attaching importance to the height of the contrast of the formed liquid crystal display element, it is more preferable to use any one of the compounds selected from the group consisting of formula (1-2-1) to formula (1-2-9) the above. In the case of attaching importance to obtaining a liquid crystal alignment film with higher anisotropy, it is more preferable to use any one of the compounds selected from the group consisting of formula (1-2-1) to formula (1-2-9) the above. In the case of attaching importance to obtaining a liquid crystal alignment film (ie, a liquid crystal alignment agent with high sensitivity) that can form an element with good afterimage characteristics even with low energy during alignment processing, it is more preferable to use a liquid crystal alignment film selected from the formula (1- 2-4) Any one or more of compounds in the group consisting of formula (1-2-9).

A preferable specific example of formula (1-1) is a compound represented by formula (1-1-9) or formula (1-1-4). Among these compounds, a compound in which n=2 to 6 in formula (1-1-9) and R ⁶ is a methyl or ethyl group or a compound in which l=2 to 6 in formula (1-1-4) is more preferable, More preferably, it is a compound in which n=2-6 in formula (1-1-9) and R ⁶ is an ethyl group or a compound in which l=2-4 in formula (1-1-4).

Preferred specific examples of formula (1-2) are compounds represented by formula (1-2-1), formula (1-2-4) or formula (1-2-7), and more preferably l=2-6 , More preferably l=4, and particularly preferably l=4 in formula (1-2-1) or formula (1-2-4).

<Method for producing compound represented by formula (1)> The method for producing the compound represented by formula (1) of the present invention will be described.

[Method for producing compound represented by formula (1-1)] The compound represented by formula (1-1) is produced through step 1-1 to step 1-3. Here, the case where R ² is a hydrogen atom and R ³ is a formula (P1-1) in the formula (1-1) is illustrated, but other compounds represented by the formula (1-1) can also refer to the following exemplification and use well-known Reaction to manufacture.

The azobenzene represented by the formula (1c) is produced by step 1-1 (Scheme 1-1) of reacting the aniline derivative represented by the formula (1a) with the phenol derivative represented by the formula (1b) derivative.

In formula (1a) and formula (1c), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group, or an optionally substituted alkoxycarbonylamino group. In formula (1b) and formula (1c), R ^6a is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, Or substituted or unsubstituted arylcarbonyl. In formula (1a) and formula (1c), the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary.

The reaction between the aniline derivative represented by the formula (1a) and the phenol derivative represented by the formula (1b) (the reaction of step 1-1) is a diazo coupling reaction, which can be carried out using the usual reaction conditions in a diazo coupling reaction . For example, a benzene diazonium salt is prepared from an aniline derivative represented by the formula (1a), and a reaction is carried out with the phenol derivative represented by the formula (1b) in the presence of a carboxylate such as sodium acetate or potassium acetate, As a result, the target azobenzene derivative represented by formula (1c) can be obtained in a high yield.

By reacting the azobenzene derivative represented by the formula (1c) with the halogenated alkylbenzene derivative represented by the formula (1d) in step 1-2 (Scheme 1-2) to produce the formula (1e) Represents the azobenzene derivative.

In formula (1c) and formula (1e), R ^6a is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane group, a substituted or unsubstituted alkoxycarbonyl group, Or substituted or unsubstituted arylcarbonyl. In formula (1c), formula (1d) and formula (1e), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group or an optionally substituted alkoxy group Carbonyl amino group. Y in the formula (1d) and X in the formula (1e) are an alkylene group having 1 to 12 carbons, and one or more non-adjacent _{-(CH 2} ) _{2-of the alkylene group may be controlled by -O} -And -NH-. In formula (1d), L is a halogen atom such as a bromine atom or an iodine atom, or a sulfonyl group such as a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a benzenesulfonyloxy group, or a p-toluenesulfonyloxy group. In the acyloxy group, in formula (1d) and formula (1e), c is an integer of 0 to 2, and R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F. In formula (1c), formula (1d), and formula (1e), a group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary.

The reaction between the azobenzene derivative represented by the formula (1c) and the halogenated alkylbenzene derivative represented by the formula (1d) (the reaction of step 1-2) is an etherification reaction, and the usual etherification reaction can be used The reaction conditions are carried out. For example, in the presence of a base such as sodium hydroxide or potassium carbonate, the reaction of the azobenzene derivative represented by the formula (1c) with the halogenated alkylbenzene derivative represented by the formula (1d) can be carried out. The target azobenzene derivative represented by formula (1e) is obtained in a high yield.

式（1e）及式（1-1a）中，R^6a 為氫原子、經取代或未經取代的烷基、經取代或未經取代的烷醯基、經取代或未經取代的烷氧基羰基、或者經取代或未經取代的芳基羰基。 式（1e）中，R⁹ 為硝基、可經取代的芳基甲基胺基、可經取代的烷基羰基胺基或可經取代的烷氧基羰基胺基。 式（1e）及式（1-1a）中，X為碳數1～12的伸烷基，所述伸烷基的-(CH₂ )₂ -的不相鄰的一個以上可經-O-及-NH-的任一個取代，c為0～2的整數，R⁴ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 或-F。 式（1e）及式（1-1a）中，鍵結位置未固定於構成環的任一個碳原子上的基表示在所述環上的鍵結位置為任意。By the reaction of step 1-3 (Scheme 1-3), R ⁹ of the azobenzene derivative represented by formula (1e) is converted into an amino group, thereby producing a compound represented by formula (1).

In formula (1e) and formula (1-1a), R ^6a is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxy group A carbonyl group, or a substituted or unsubstituted arylcarbonyl group. In formula (1e), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group, or an optionally substituted alkoxycarbonylamino group. In formula (1e) and formula (1-1a), X is an alkylene group having 1 to 12 carbon atoms, and one or more non-adjacent ones _{of -(CH 2} ) _{2-of the alkylene group may be through -O-} And any one of -NH- is substituted, c is an integer of 0-2, and R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F. In formula (1e) and formula (1-1a), the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary.

In the reaction of step 1-3, by using a method suitable for R ⁹ in formula (1e), the azobenzene derivative represented by formula (1-1a) can be produced in a high yield.

^{In the case where R 9} is a nitro group in formula (1e), the reaction in steps 1-3 is a reduction reaction, and various reduction methods can be used as follows: sodium sulfide and other sulfides, sodium bisulfite and other inorganic salts are used as reduction The use of reagents for the reduction of reagents; or in a hydrogen environment, the use of Pd/C catalysts, Reye's nickel, etc. for reduction contact reduction; in the presence of acid such as hydrochloric acid, acetic acid, etc., the use of iron, zinc or tin chloride for reduction Metal reduction, etc.; however, in terms of suppressing the reduction of the azo bond while reducing the nitro group, reduction with a reagent using a reducing agent such as a sulfide is preferred.

^{When R 9} in formula (1e) is a substituted arylmethylamino group, examples include: _{deprotection by hydrogenolysis (for example, H 2} , Pd/C), deprotection under oxidative conditions, Deprotection under strong acid conditions, etc. Among them, deprotection under oxidizing conditions is preferred. In terms of suppressing the reduction of the azo bond and simultaneously deprotecting the arylmethylamino group, it is more preferred to use 2,3-dichloro-5,6 -Dicyano-p-benzoquinone (2,3-dichloro-5,6-dicyano-p-benzoquinone, DDQ), quinone-based oxidizing reagents such as p-chloroquinone and o-chloroquinone, or oxidizing agents such as diammonium cerium (IV) nitrate Deprotection under mild oxidizing conditions. In addition, in the deprotection under strong acid conditions, Trifluoroacetic Acid (TFA) or hydrochloric acid can be used.

^{When R 9} in the formula (1e) is an optionally substituted alkylcarbonylamino group or an optionally substituted alkoxycarbonylamino group, the protecting group R ⁹ can be easily deprotected by acid treatment. As the acid used in the deprotection, TFA or hydrochloric acid can be exemplified.

式（1f）中，R⁹ 為硝基、可經取代的芳基甲基胺基、可經取代的烷基羰基胺基或可經取代的烷氧基羰基胺基，R^6a 為氫原子、經取代或未經取代的烷基、經取代或未經取代的烷醯基、經取代或未經取代的烷氧基羰基、或者經取代或未經取代的芳基羰基。In the above, the method for producing a compound in formula (1-1) where R ¹ is a hydrogen atom and R ² is a formula (P1-1) is shown. Other compounds represented by formula (1-1) can also be synthesized by similar production methods. For example, by substituting step 1-1 into a reaction between a compound represented by formula (1f) and a phenol derivative, it is possible to obtain formula (1-1) where R ¹ is formula (P1-1) and R ² is a hydrogen atom Compound. In addition, for example, by substituting step 1-1 into a reaction of a compound represented by formula (1f) with formula (1b), a compound in which R ¹ and R ² in formula (1) are formula (P1-1) can be obtained.

In formula (1f), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group or an optionally substituted alkoxycarbonylamino group, and R ^6a is a hydrogen atom, A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkanoyl group, a substituted or unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl group.

[Method for producing compound represented by formula (1-2)] Through step 2-1 to step 2-3, the compound represented by formula (1-2) is produced.

式（2a）及式（2c）中，R⁹ 為硝基、可經取代的芳基甲基胺基、可經取代的烷基羰基胺基或可經取代的烷氧基羰基胺基。 式（2a）、式（2b）及式（2c）中，R³ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ，R⁵ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ，a為0～2的整數，b為0～2的整數。 式（2a）、式（2b）及式（2c）中，鍵結位置未固定於構成環的任一個碳原子上的基表示在所述環上的鍵結位置為任意。The azobenzene represented by the formula (2c) is produced by step 2-1 (Scheme 2-1) of reacting the aniline derivative represented by the formula (2a) with the phenol derivative represented by the formula (2b) derivative.

In formula (2a) and formula (2c), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group or an optionally substituted alkoxycarbonylamino group. In formula (2a), formula (2b) and formula (2c), R ^{3 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , and R ^{5 is} each independently For a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , a is an integer of 0-2, and b is an integer of 0-2. In Formula (2a), Formula (2b), and Formula (2c), the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary.

The reaction between the aniline derivative represented by the formula (2a) and the phenol derivative represented by the formula (2b) (reaction of step 2-1) is a diazo coupling reaction, for example, refer to the aforementioned step 1-1.

式（2c）、式（2d）及式（2e）中，R⁹ 為硝基、可經取代的芳基甲基胺基、可經取代的烷基羰基胺基或可經取代的烷氧基羰基胺基。 式（2c）及式（2e）中，R³ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ，R⁵ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ，a為0～2的整數，b為0～2的整數。 式（2d）中的Y及式（2e）中的X為碳數1～12的伸烷基，所述伸烷基的-(CH₂ )₂ -的不相鄰的一個以上可經-O-或-NH-的任一個取代。 式（2d）中，L為溴原子或碘原子等鹵素原子、或甲磺醯基氧基、三氟甲磺醯基氧基、苯磺醯基氧基或對甲苯磺醯基氧基等磺醯基氧基，c為0～2的整數，R⁴ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 或-F。 式（2c）、式（2d）及式（2e）中，鍵結位置未固定於構成環的任一個碳原子上的基表示在所述環上的鍵結位置為任意。By reacting the azobenzene derivative represented by the formula (2c) with the halogenated alkylbenzene derivative represented by the formula (2d) in step 2-2 (Scheme 2-2) to produce the formula (2e) Represents the azobenzene derivative.

In formula (2c), formula (2d) and formula (2e), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group or an optionally substituted alkoxy group Carbonyl amino group. In formula (2c) and formula (2e), R ^{3 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , and R ^{5 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , a is an integer of 0-2, and b is an integer of 0-2. Y in the formula (2d) and X in the formula (2e) are an alkylene group having 1 to 12 carbons, and one or more non-adjacent _{-(CH 2} ) _{2-of the alkylene group may be controlled by -O} -Or any one of -NH- substitution. In the formula (2d), L is a halogen atom such as a bromine atom or an iodine atom, or a sulfonyl group such as a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a benzenesulfonyloxy group or a p-toluenesulfonyloxy group. In the acyloxy group, c is an integer of 0 to 2, and R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F. In formula (2c), formula (2d), and formula (2e), a group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary.

The reaction between the azobenzene derivative represented by the formula (2c) and the halogenated alkylbenzene derivative represented by the formula (2d) (reaction in step 2-2) is an etherification reaction, for example, refer to the step 1-2 .

式（2e）中，R⁹ 為硝基、可經取代的芳基甲基胺基、可經取代的烷基羰基胺基或可經取代的烷氧基羰基胺基。 式（2e）及式（1-2）中，R³ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ，R⁵ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 、-F或-COOCH₃ ，a為0～2的整數，b為0～2的整數。 式（2e）及式（1-2）中，X為碳數1～12的伸烷基，所述伸烷基的-(CH₂ )₂ -的不相鄰的一個以上可經-O-及-NH-的任一個取代，c為0～2的整數，R⁴ 分別獨立地為氫原子、-CH₃ 、-OCH₃ 、-CF₃ 或-F。 式（2e）及式（1-2）中，鍵結位置未固定於構成環的任一個碳原子上的基表示在所述環上的鍵結位置為任意。 步驟2-3的反應中，通過利用適合於式（2e）中的R⁹ 的方法，可高產率地製造式（1-2）所表示的偶氮苯衍生物。詳細而言，可參照所述步驟1-3。 ^{The R 9} of the azobenzene derivative represented by the formula (2e) is converted into an amino group by the reaction of step 2-3 (Scheme 2-3) to produce the formula (1-2) Compound.

In the formula (2e), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group, or an optionally substituted alkoxycarbonylamino group. In formula (2e) and formula (1-2), R ^{3 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , and R ^{5 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , a is an integer of 0-2, and b is an integer of 0-2. In formula (2e) and formula (1-2), X is an alkylene group having 1 to 12 carbons, and one or more non-adjacent _{-(CH 2} ) _{2-of the alkylene group may be controlled by -O-} And any one of -NH- is substituted, c is an integer of 0-2, and R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F. In formula (2e) and formula (1-2), the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary. In the reaction of step 2-3, by using a method suitable for R ⁹ in formula (2e), the azobenzene derivative represented by formula (1-2) can be produced in a high yield. For details, please refer to the steps 1-3.

＜Type of polymer＞ The polymer used in the liquid crystal alignment agent in the present invention is selected from polyamide acids, polyimines, partial polyimines, and polyamides containing at least one compound represented by formula (1) as a raw material. At least one of the group consisting of acid ester, polyamide acid-polyamide copolymer, and polyamide imide. In this specification, polyimide, partial polyimide, polyamide, polyamide acid-polyamide copolymer, and polyamide imine are sometimes referred to as polyamide acid derivatives. .

Hereinafter, the polyamide acid and the polyamide acid derivative will be described in detail.

Here, polyamide acid is a polymer synthesized by the polymerization reaction of diamines represented by formula (DI) and tetracarboxylic dianhydride represented by formula (AN), and has a formula (PAA) represented by Constitutional unit. When the liquid crystal alignment agent containing polyamide acid is heated and fired in the step of forming a liquid crystal alignment film, the polyamide acid is imidized to form a polyamide having a structural unit represented by the formula (PI) Amine liquid crystal alignment film.

In formula (AN), formula (PAA) and formula (PI), X ¹ is a tetravalent organic group. In formula (DI), formula (PAA) and formula (PI), X ² is a divalent organic group. Specific examples of the preferred range of about X ¹ is a tetravalent organic group, may be known in reference to the following tetracarboxylic dianhydride of the tetracarboxylic dianhydride described configuration corresponding to a column. Regarding ^{the preferred range and specific examples of the divalent organic group in X 2} , refer to the description related to the structure corresponding to the diamine or dihydrazine described in the column of formula (1) or the following known diamines .

式（PAE）中，X¹ 為四價有機基，X² 為二價有機基，Y為烷基。關於X¹ 、X² 的優選範圍與具體例，可參照與式（PAA）中的X¹ 、X² 相關的記載。Y中，優選為碳數1～6的直鏈狀或分支狀的烷基，更優選為甲基、乙基、丙基、異丙基、丁基、異丁基或叔丁基。Polyamide acid derivatives are compounds whose properties are changed by substituting a part of polyamide acid with other atoms or atomic groups, and are particularly preferably polyamide acid whose solubility in the solvent used in the liquid crystal alignment agent is improved. derivative. Specific examples of such polyamide acid derivatives include: 1) polyimide in which all amine groups of polyamide and carboxyl groups undergo a dehydration ring-closing reaction; 2) a partial dehydration ring-closing reaction is carried out. Part of the polyimide, 3) Polyurethane obtained by converting the carboxyl group of polyamide into an ester, 4) Substituting part of the acid dianhydride contained in the tetracarboxylic dianhydride compound with organic Polyamide acid-polyamide copolymer obtained by reacting dicarboxylic acid and 5) polyamide obtained by dehydrating and ring-closing a part or all of said polyamide acid-polyamide copolymer Imine. Among these derivatives, for example, as polyimines, polyimines having a structural unit represented by the formula (PI) can be cited, and as polyamide esters, those having the following formula (PAE) can be cited: Polyurethane of the structural unit shown.

In the formula (PAE), X ¹ is a tetravalent organic group, X ² is a divalent organic group, and Y is an alkyl group. For the preferred ranges and specific examples of X ¹ and X ² , refer to the descriptions related to ^{X 1} and X ^{2 in formula (PAA).} Among Y, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or a tert-butyl group is more preferable.

Polyamide acid can be obtained in the form of a reaction product obtained by the polymerization reaction of tetracarboxylic dianhydrides and diamines. For the description, preferred range, and specific examples of tetracarboxylic dianhydrides, refer to the description in the column of tetracarboxylic dianhydrides below. For the description of diamines, preferred ranges, and specific examples, refer to the description in the column of diamines below. The tetracarboxylic dianhydrides and diamines used in the synthesis of the polyamide acid may each be one type or two or more types. By using the compound represented by the formula (1) as at least one of the diamines, the polyamide acid of the present invention can be obtained.

When the polyimide of the present invention is used as a polyimide as a polyimide acid derivative, the obtained polyimide solution is combined with acetic anhydride, propionic anhydride, and a dehydrating agent. Anhydrides such as trifluoroacetic anhydride and tertiary amines such as triethylamine, pyridine, and collidine as a dehydration ring-closing catalyst are carried out together at a temperature of 20°C to 150°C to obtain polyimide. Alternatively, a large amount of poor solvents (alcohol-based solvents such as methanol, ethanol, isopropanol, or glycol-based solvents) may be used to precipitate polyamide acid from the obtained polyamide acid solution, and the precipitated polyamide The amide acid undergoes an imidization reaction in a solvent such as toluene, xylene, etc. together with the dehydrating agent and the dehydration ring-closing catalyst at a temperature of 20°C to 150°C, thereby obtaining a polyimide.

In the imidization reaction, the ratio of the dehydrating agent to the dehydration ring-closing catalyst is preferably 0.1-10 (molar ratio). The total usage amount of the dehydrating agent and the dehydration ring-closing catalyst is preferably 1.5 times mol to 10 times mol relative to the total molar amount of the tetracarboxylic dianhydride used in the synthesis of the polyamide acid. By adjusting the dehydrating agent, the amount of catalyst, the reaction temperature, and the reaction time used in the imidization reaction, the degree of imidization can be controlled, so that only a part of the imidization of polyamide can be obtained. Part of the polyimide. The obtained polyimide can also be separated from the solvent used in the reaction and re-dissolved in other solvents to be used as a liquid crystal alignment agent, or can be used as a liquid crystal alignment agent without being separated from the solvent.

Polyurethane can be obtained by a method of synthesis by reacting polyamide acid with hydroxyl-containing compounds, halides, epoxy-containing compounds, etc., or by deriving from tetracarboxylic dianhydride The tetracarboxylic acid diester or tetracarboxylic acid diester dichloride reacts with diamines to synthesize. The tetracarboxylic acid diester derived from tetracarboxylic dianhydride can be obtained, for example, by reacting tetracarboxylic dianhydride with 2 equivalents of alcohol and opening the ring. The tetracarboxylic acid diester dichloride can be obtained by making the tetracarboxylic acid diester and 2 Equivalent chlorinating agent (for example, sulfite chloride, etc.) is obtained by reaction. Furthermore, the polyamide ester may have only an amide acid ester structure, or may be a partial ester product in which an amide acid structure and an amide acid ester structure coexist. By using the compound represented by formula (1) as at least one of the diamines, the polyamide ester of the present invention can be obtained.

The polyamide acid or its derivative which uses the compound represented by formula (1) as a raw material can be manufactured similarly to the well-known polyamide acid or its derivative(s) used for formation of a polyimide film. The total input amount of tetracarboxylic dianhydrides is preferably 0.9 mol to 1.1 mol relative to 1 mol in total of the diamines.

The liquid crystal alignment agent of the present invention may contain only one of these polyamide acids, polyamide esters, and polyimines obtained by imidizing them, or two or more types.

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

The presence of the polyamide acid or its derivatives of the present invention can be confirmed by the following methods: using infrared spectroscopy (IR), nuclear magnetic resonance analysis (Nuclear Magnetic Resonance, NMR) to make the polyamide of the present invention The solid content obtained by precipitating the acid or its derivatives in a large amount of poor solvents is analyzed. In addition, the monomers used can be confirmed by the following methods: using gas chromatography (Gas Chromatography, GC), high performance liquid chromatography (High Performance Liquid Chromatography, HPLC), or gas chromatography mass spectrometry (Gas Chromatography-Mass Spectrometry, GC-MS) After decomposing the polyamide acid or its derivatives using an aqueous solution of a strong base such as KOH or NaOH, the extract extracted from the decomposed product using an organic solvent is analyzed.

Tetracarboxylic dianhydrides The tetracarboxylic dianhydrides used as the raw material of the polymer of the present invention can be selected from known tetracarboxylic dianhydrides without limitation.

Hereinafter, examples of tetracarboxylic dianhydride are given. These tetracarboxylic dianhydrides can also be derivatized into tetracarboxylic acid diesters or tetracarboxylic acid diester dichlorides and used as raw materials for polymers.

Such tetracarboxylic dianhydrides can be aromatic systems in which dicarboxylic anhydrides are directly bonded to aromatic rings (including heteroaromatic ring systems) and aliphatic systems in which dicarboxylic anhydrides are not directly bonded to aromatic rings (including heteroaromatic rings). Ring system) tetracarboxylic dianhydride in any one of the group.

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

式（AN-1）中，G¹¹ 為單鍵、碳數1～12的伸烷基、1,4-伸苯基或1,4-伸環己基。X¹¹ 獨立地為單鍵或-CH₂ -。G¹² 獨立地為下述三價基的任一種。

在G¹² 為＞CH-時，＞CH-的氫原子可經甲基取代。在G¹² 為＞N-時，G¹¹ 不為單鍵及-CH₂ -，X¹¹ 不為單鍵。R¹¹ 為氫原子或甲基。[Tetracarboxylic dianhydride represented by formula (AN-1)]

In the formula (AN-1), G ¹¹ is a single bond, an alkylene group having 1 to 12 carbon atoms, a 1,4-phenylene group, or a 1,4-cyclohexylene group. X ^{11 is} independently a single bond or -CH ₂ -. G ^{12 is} independently any one of the following trivalent groups.

When G ¹² is >CH-, the hydrogen atom >CH- may be substituted by a methyl group. When G ¹² is >N-, G ^{11 is} not a single bond and -CH ₂ -, and X ^{11 is} not a single bond. R ¹¹ is a hydrogen atom or a methyl group.

式（AN-1-2）及式（AN-1-14）中，m分別獨立地為1～12的整數。As an example of the tetracarboxylic dianhydride represented by Formula (AN-1), the compound represented by following formula (AN-1-1)-Formula (AN-1-15) is mentioned.

In formula (AN-1-2) and formula (AN-1-14), m is an integer of 1-12 each independently.

式（AN-2）中，R⁶¹ 獨立地為氫原子、碳數1～5的烷基或苯基。[Tetracarboxylic dianhydride represented by formula (AN-2)]

In the formula (AN-2), R ^{61 is} independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

As an example of the tetracarboxylic dianhydride represented by Formula (AN-2), the compound represented by following formula (AN-2-1)-Formula (AN-2-3) is mentioned.

式（AN-3）中，環A¹¹ 為環己烷環或苯環。[Tetracarboxylic dianhydride represented by formula (AN-3)]

In the formula (AN-3), the ring A ¹¹ is a cyclohexane ring or a benzene ring.

As an example of the tetracarboxylic dianhydride represented by formula (AN-3), the compound represented by following formula (AN-3-1) and formula (AN-3-2) can be mentioned.

式（AN-4）中，G¹³ 為單鍵、-(CH₂ )_m -、-O-、-S-、-C(CH₃ )₂ -、-SO₂ -、-CO-、-C(CF₃ )₂ -或下述式（G13-1）所表示的二價基，m為1～12的整數。環A¹¹ 分別獨立地為環己烷環或苯環。G¹³ 可鍵結於環A¹¹ 的任意的位置。

式（G13-1）中，G^13a 及G^13b 分別獨立地為單鍵、-O-、-CONH-或-NHCO-所表示的二價基。伸苯基優選為1,4-伸苯基或1,3-伸苯基。[Tetracarboxylic dianhydride represented by formula (AN-4)]

In the formula (AN-4), G ¹³ is a single bond, -(CH ₂ ) _m -, -O-, -S-, -C(CH ₃ ) ₂ -, -SO ₂ -, -CO-, -C (CF ₃ ) ₂ -or a divalent group represented by the following formula (G13-1), where m is an integer of 1-12. Ring A ^{11 is} each independently a cyclohexane ring or a benzene ring. G ¹³ can be bonded to any position of ^{ring A 11.}

In formula (G13-1), G ^13a and G ^13b are each independently a single bond, a divalent group represented by -O-, -CONH-, or -NHCO-. The phenylene is preferably 1,4-phenylene or 1,3-phenylene.

式（AN-4-17）中，m為1～12的整數。Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formulas (AN-4-1) to (AN-4-31).

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

式（AN-5）中，R¹¹ 獨立地為氫原子或甲基。兩個R¹¹ 中的苯環上的R¹¹ 鍵結於苯環的能夠進行取代的位置的任一者上。[Tetracarboxylic dianhydride represented by formula (AN-5)]

In formula (AN-5), R ^{11 is} independently a hydrogen atom or a methyl group. Any one of the two R ¹¹ R ¹¹ is a benzene ring bonded to the benzene ring can be substituted on position.

As an example of the tetracarboxylic dianhydride represented by formula (AN-5), the compound represented by following formula (AN-5-1)-formula (AN-5-3) is mentioned.

式（AN-6）中，X¹¹ 獨立地為單鍵或-CH₂ -。X¹² 為-CH₂ -、-CH₂ CH₂ -或-CH=CH-。n為1或2。在n為2時，兩個X¹² 可相互相同，也可不同。[Tetracarboxylic dianhydride represented by formula (AN-6)]

In formula (AN-6), X ^{11 is} independently a single bond or -CH ₂ -. X ¹² is -CH ₂ -, -CH ₂ CH ₂ -or -CH=CH-. n is 1 or 2. When n is 2, two X ¹² may be the same as or different from each other.

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

式（AN-7）中，X¹¹ 為單鍵或-CH₂ -。[Tetracarboxylic dianhydride represented by formula (AN-7)]

In formula (AN-7), X ¹¹ is a single bond or -CH ₂ -.

As an example of the tetracarboxylic dianhydride represented by formula (AN-7), the compound represented by following formula (AN-7-1) and formula (AN-7-2) can be mentioned.

式（AN-8）中，X¹¹ 為單鍵或-CH₂ -。R¹² 為氫原子、甲基、乙基或苯基。環A¹² 為環己烷環或環己烯環。[Tetracarboxylic dianhydride represented by formula (AN-8)]

In the formula (AN-8), X ¹¹ is a single bond or -CH ₂ -. R ¹² is a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. Ring A ¹² is a cyclohexane ring or a cyclohexene ring.

As an example of the tetracarboxylic dianhydride represented by formula (AN-8), the compound represented by following formula (AN-8-1) and formula (AN-8-2) can be mentioned.

式（AN-9）中，r分別獨立地為0或1。[Tetracarboxylic dianhydride represented by formula (AN-9)]

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

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

[Tetracarboxylic dianhydride represented by formula (AN-10-1) and formula (AN-10-2)]

式（AN-11）中，環A¹¹ 獨立地為環己烷環或苯環。[Tetracarboxylic dianhydride represented by formula (AN-11)]

In formula (AN-11), ring A ^{11 is} independently a cyclohexane ring or a benzene ring.

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

式（AN-12）中，環A¹¹ 分別獨立地為環己烷環或苯環。[Tetracarboxylic dianhydride represented by formula (AN-12)]

In formula (AN-12), ring A ^{11 is} each independently a cyclohexane ring or a benzene ring.

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

式（AN-15）中，w為1～10的整數。[Tetracarboxylic dianhydride represented by formula (AN-15)]

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

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

Examples of tetracarboxylic dianhydrides other than the above include compounds represented by the following formulas (AN-16-1) to (AN-16-15).

Among the above-mentioned tetracarboxylic dianhydrides, suitable materials that improve the characteristics of the liquid crystal alignment film described later will be described. In the case of focusing on further improving the orientation of liquid crystals, it is more preferable to use the formula (AN-1-2), the formula (AN-4-17), the formula (AN-4-21) or the formula (AN-4-29). The compound represented is preferably m=4-8 in formula (AN-1-2), and preferably m=4-8 in formula (AN-4-17).

In the case of attaching importance to improving the transmittance of the liquid crystal display element, the formula (AN-1-1), the formula (AN-1-2), the formula (AN-3-1), and the formula (AN-4-17) are preferred , Formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-16-3), formula (AN- 16-4) or a compound represented by formula (AN-2-1), wherein m=4 or 8 is preferred in formula (AN-1-2), and m=4 or 8 is preferred in formula (AN-4-17). m=4-8, more preferably m=8.

In the case of focusing on improving the VHR of the liquid crystal display element, the formula (AN-1-1), formula (AN-1-2), 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-2 -1) The compound represented by the formula (AN-1-2), preferably m=4 or 8, and in the formula (AN-4-17), preferably m=4 or 8, more preferably m=8 .

As one of the methods for preventing burn marks, it is effective to increase the relaxation speed of residual charges (residual direct current (DC)) in the liquid crystal alignment film by reducing the volume resistance value of the liquid crystal alignment film. In the case of attaching importance to the purpose, 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 compound represented.

Diamines The diamines other than the compound represented by formula (1) used as the raw material of the polymer of the present invention can be selected from known diamines without limitation.

Diamines can be divided into two types according to their structure. That is, a diamine having a side chain group and a diamine having no side chain group are groups that branch from the main chain when the skeleton connecting two amine groups is regarded as the main chain. In the following description, such a diamine having a side chain group may be referred to as a side chain diamine. Moreover, such a diamine which does not have a side chain group may be called a non-side chain type diamine. The side chain group is a group having the effect of increasing the pretilt angle. By appropriately separating the non-side-chain type diamine and the side-chain type diamine, it is possible to correspond to the pretilt angle required for each.

The side chain diamine is preferably used in combination to an extent that does not impair the characteristics of the present invention. In addition, as for the side-chain type diamine and the non-side-chain type diamine, it is preferable to select and use them for the purpose of improving characteristics such as vertical alignment to the liquid crystal, VHR, and residual image characteristics.

所述式（DI-1）中，G²⁰ 為-CH₂ -或式（DI-1-a）所表示的基。在G²⁰ 為-CH₂ -時，m個-CH₂ -的至少一個可被取代為-NH-、-O-，m個-CH₂ -的至少一個氫原子可經羥基或甲基取代。m為1～12的整數。在DI-1中的m為2以上時，多個G²⁰ 可相互相同，也可不同。其中，在G²⁰ 為式（DI-1-a）時，m為1。

式（DI-1-a）中，v分別獨立地為1～6的整數。The following formulas (DI-1) to (DI-16) show known diamines that do not have a side chain.

In the formula (DI-1), G ²⁰ is -CH ₂ -or a group represented by the formula (DI-1-a). In G ²⁰ is -CH ₂ -, m is a -CH ₂ - of which may be substituted with at least one -NH -, - O-, m -CH ₂ - in at least one hydrogen atom may be substituted with hydroxy or methyl. m is an integer of 1-12. When m in DI-1 is 2 or more, the plurality of G ²⁰ may be the same as or different from each other. Among them, when G ²⁰ is the formula (DI-1-a), m is 1.

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

In formula (DI-3), formula (DI-6) and formula (DI-7), G ^{21 is} independently a single bond, -NH-, -NCH ₃ -, -O-, -S-, -SS- , -SO ₂ -, -CO-, -COO-, -CONCH ₃ -, -CONH-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -,- O-(CH ₂ ) _m -O-, -N(CH ₃ )-(CH ₂ ) _k -N(CH ₃ )-, -(OC ₂ H ₄ ) _m -O-, -O-CH ₂ -C (CF ₃ ) ₂ -CH ₂ -O-, -O-CO-(CH ₂ ) _m -CO-O-, -CO-O-(CH ₂ ) _m -O-CO-, -(CH ₂ ) _m -NH-(CH ₂ ) _m -, -CO-(CH ₂ ) _k -NH-(CH ₂ ) _k -, -(NH-(CH ₂ ) _m ) _k -NH-, -CO-C ₃ H ₆ -(NH-C ₃ H ₆ ) _n -CO- or -S-(CH ₂ ) _m -S-, m is independently an integer of 1-12, k is an integer of 1-5, and n is 1 or 2. In formula (DI-4), s is independently an integer of 0-2.

In the formula (DI-5), G ³³ is a single bond, -NH-, -NCH ₃ -, -O-, -S-, -SS-, -SO ₂ -, -CO-, -COO-, -CONCH ₃ -, -CONH-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, -N(CH ₃ )-(CH ₂ ) _k -N(CH ₃ )-, -(OC ₂ H ₄ ) _m -O-, -O-CH ₂ -C(CF ₃ ) ₂ -CH ₂ -O-, -O-CO -(CH ₂ ) _m -CO-O-, -CO-O-(CH ₂ ) _m -O-CO-, -(CH ₂ ) _m -NH-(CH ₂ ) _m -, -CO-(CH ₂ ) _k -NH-(CH ₂ ) _k -, -(NH-(CH ₂ ) _m ) _k -NH-, -CO-C ₃ H ₆ -(NH-C ₃ H ₆ ) _n -CO- or -S -(CH ₂ ) _m -S-, -N(Boc)-(CH ₂ ) _e -N(Boc)-, -NH-(CH ₂ ) _e -N(Boc)-, -N(Boc)-( CH ₂ ) _e -, -(CH ₂ ) _m -N(Boc)-CONH-(CH ₂ ) _m -, -(CH ₂ ) _m -N(Boc)-(CH ₂ ) _m -, the following formula ( In the group represented by DI-5-a) or the following formula (DI-5-b), m is independently an integer from 1 to 12, k is an integer from 1 to 5, e is an integer from 2 to 10, and n is 1 or 2. Boc is tert-butoxycarbonyl.

In formula (DI-6) and formula (DI-7), G ^{22 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -or alkylene having 1 to 10 carbon atoms.

At least one hydrogen atom of the cyclohexane ring and the benzene ring in formula (DI-2)～(DI-7) can be through -F, -Cl, alkylene with carbon number of 1 to 3, -OCH ₃ ,- OH, -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl substituted, in addition, in formula (DI-4), at least one hydrogen atom of the cyclohexane ring and the benzene ring It may be substituted by one selected from the group of groups represented by any one of the following formula (DI-4-a) to formula (DI-4-i). In formula (DI-5), in G ³³ When it is a single bond, at least one hydrogen atom of the cyclohexane ring and the benzene ring may be substituted _{with NHBoc or N(Boc) 2.}

式（DI-4-a）及式（DI-4-b）中，R²⁰ 獨立地為氫原子或-CH₃ 。式（DI-4-f）及式（DI-4-g）中，m分別獨立地為0～12的整數，Boc為叔丁氧基羰基。A 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 addition, the bonding position of -NH ₂ on the cyclohexane ring or the benzene ring is any position other than the ^{bonding position of G 21} , G ²² or G ^33.

In formula (DI-4-a) and formula (DI-4-b), R ^{20 is} independently a hydrogen atom or -CH ₃ . In formula (DI-4-f) and formula (DI-4-g), m is each independently an integer of 0-12, and Boc is a tert-butoxycarbonyl group.

式（DI-5-a）中，q分別獨立地為0～6的整數。R⁴⁴ 為氫原子、-OH、碳數1～6的烷基或碳數1～6的烷氧基。

In formula (DI-5-a), q is an integer of 0-6 each independently. R ⁴⁴ is a hydrogen atom, -OH, an alkyl group having 1 to 6 carbons, or an alkoxy group having 1 to 6 carbons.

式（DI-11）中，r為0或1。式（DI-8）～式（DI-11）中，鍵結於環上的-NH₂ 的鍵結位置為任意的位置。

In the formula (DI-11), r is 0 or 1. In formulas (DI-8) to (DI-11), the bonding _{position of -NH 2} bonded to the ring is an arbitrary position.

式（DI-12）中，R²¹ 及R²² 分別獨立地為碳數1～3的烷基或苯基，G²³ 獨立地為碳數1～6的伸烷基、伸苯基或經烷基取代的伸苯基，w為1～10的整數。 式（DI-13）中，R²³ 獨立地為碳數1～5的烷基、碳數1～5的烷氧基或-Cl，p獨立地為0～3的整數，q為0～4的整數。 式（DI-14）中，環B為單環的雜環式芳香族基，R²⁴ 為氫原子、-F、-Cl、碳數1～6的烷基、烷氧基、烯基、炔基，q獨立地為0～4的整數。在q為2以上時，多個R²⁴ 可相互相同，也可不同。式（DI-15）中，環C為雜環式芳香族基或雜環式脂肪族基。式（DI-16）中，G²⁴ 為單鍵、碳數2～6的伸烷基或1,4-伸苯基，r為0或1。而且，鍵結位置未固定於構成環的碳原子上的基表示在所述環上的鍵結位置為任意。式（DI-13）～式（DI-16）中，鍵結於環上的-NH₂ 的鍵結位置為任意的位置。

In the formula (DI-12), R ²¹ and R ²² are each independently an alkyl group having 1 to 3 carbons or a phenyl group, and G ^{23 is} independently an alkylene group having 1 to 6 carbon atoms, a phenyl group or an alkylene group. In the group-substituted phenylene, w is an integer of 1-10. In the formula (DI-13), R ^{23 is} independently an alkyl group having 1 to 5 carbons, an alkoxy group having 1 to 5 carbons or -Cl, p is independently an integer of 0 to 3, and q is 0 to 4 Integer. In the formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, R ²⁴ is a hydrogen atom, -F, -Cl, alkyl with 1 to 6 carbons, alkoxy, alkenyl, alkyne Base, q is independently an integer of 0-4. When q is 2 or more, a plurality of R ²⁴ may be the same as or different from each other. In formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In the formula (DI-16), G ²⁴ is a single bond, a C 2-6 alkylene group or 1,4-phenylene group, and r is 0 or 1. In addition, a 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 formulas (DI-13) to (DI-16), the bonding _{position of -NH 2} bonded to the ring is an arbitrary position.

式（DI-1-7）及式（DI-1-8）中，k分別獨立地為1～3的整數。式（DI-1-9）中，v分別獨立地為1～6的整數。Examples of the diamine represented by the formula (DI-1) are shown in the following formulas (DI-1-1) to (DI-1-9).

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

The following formula (DI-2-1), formula (DI-2-2), formula (DI-3-1) ~ formula (DI-3-3) show formula (DI-2) ~ formula (DI -3) Examples of diamines shown.

式（DI-4-20）及式（DI-4-21）中，m分別獨立地為1～12的整數。

Examples of the diamine represented by the formula (DI-4) are shown in the following formulas (DI-4-1) to (DI-4-27).

In formula (DI-4-20) and formula (DI-4-21), m is an integer of 1-12 each independently.

式（DI-5-1）中，m為1～12的整數。Examples of the diamine represented by the formula (DI-5) are shown in the following formulas (DI-5-1) to (DI-5-50).

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

式（DI-5-12）及式（DI-5-13）中，m分別獨立地為1～12的整數。

In formula (DI-5-12) and formula (DI-5-13), m is each independently an integer of 1-12.

式（DI-5-16）中，v為1～6的整數。

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

式（DI-5-30）中，k為1～5的整數。

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

式（DI-5-35）～式（DI-5-37）及式（DI-5-39）中，m分別獨立地為1～12的整數，式（DI-5-38）及式（DI-5-39）中，k分別獨立地為1～5的整數，式（DI-5-40）中，n為1或2的整數。

In formula (DI-5-35) to formula (DI-5-37) and formula (DI-5-39), m is an integer from 1 to 12, respectively, and formula (DI-5-38) and formula ( In DI-5-39), k is each independently an integer of 1 to 5, and in formula (DI-5-40), n is an integer of 1 or 2.

式（DI-5-42）～式（DI-5-44）中，e分別獨立地為2～10的整數，式（DI-5-45）中，R⁴³ 為氫原子、-NHBoc或-N(Boc)₂ 。式（DI-5-42）～式（DI-5-44）中，Boc為叔丁氧基羰基。

In formulas (DI-5-42) to (DI-5-44), e is each independently an integer from 2 to 10, and in formula (DI-5-45), R ⁴³ is a hydrogen atom, -NHBoc or- N(Boc) ₂ . In formulas (DI-5-42) to (DI-5-44), Boc is tert-butoxycarbonyl.

Examples of the diamine represented by the formula (DI-6) are shown in the following formulas (DI-6-1) to (DI-6-7).

式（DI-7-3）及式（DI-7-4）中，m分別獨立地為1～12的整數，n獨立地為1或2。Examples of the diamine represented by the formula (DI-7) are shown in the following formulas (DI-7-1) to (DI-7-11).

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

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

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

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

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

An example of the diamine represented by the formula (DI-12) is shown in the following formula (DI-12-1).

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

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

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

An example of the diamine represented by the formula (DI-16) is shown in the following formula (DI-16-1).

式（DIH-1）中，G²⁵ 為單鍵、碳數1～20的伸烷基、-CO-、-O-、-S-、-SO₂ -、-C(CH₃ )₂ -或-C(CF₃ )₂ -。 式（DIH-2）中，環D為環己烷環、苯環或萘環，所述基的至少一個氫原子可經甲基、乙基或苯基取代。式（DIH-3）中，環E分別獨立地為環己烷環或苯環，所述基的至少一個氫原子可經甲基、乙基或苯基取代。多個環E可相互相同，也可不同。Y為單鍵、碳數1～20的伸烷基、-CO-、-O-、-S-、-SO₂ -、-C(CH₃ )₂ -或-C(CF₃ )₂ -。式（DIH-2）及式（DIH-3）中，鍵結於環上的-CONHNH₂ 的鍵結位置為任意的位置。Next, the dihydrazine used in the raw material of the polymer of the present invention will be described. As known dihydrazine having no side chain, a compound represented by any one of the following formulas (DIH-1) to (DIH-3) can be cited.

In the formula (DIH-1), G ²⁵ is a single bond, an alkylene group with 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -. In the formula (DIH-2), the ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen atom of the group may be substituted by a methyl group, an ethyl group or a phenyl group. In the formula (DIH-3), the ring E is each independently a cyclohexane ring or a benzene ring, and at least one hydrogen atom of the group may be substituted by a methyl group, an ethyl group or a phenyl group. The plurality of rings E may be the same as or different from each other. Y is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -. In formula (DIH-2) and formula (DIH-3), the bonding _{position of -CONHNH 2} bonded to the ring is an arbitrary position.

式（DIH-1-2）中，m為1～12的整數。In the following formula (DIH-1-1), formula (DIH-1-2), formula (DIH-2-1) ~ formula (DIH-2-3), formula (DIH-3-1) ~ formula ( DIH-3-6) shows examples of compounds represented by any of formula (DIH-1) to formula (DIH-3).

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

The diamine suitable for the purpose of increasing the pretilt angle will be described. The compound of the present invention can be suitably used in a liquid crystal alignment agent used in a lateral electric field type liquid crystal display element, but can also be used in combination with a diamine as described below to increase the pretilt angle. As a diamine suitable for the purpose of increasing the pretilt angle and having a side chain group, formulas (DI-31) to (DI-35) and formulas (DI-36-1) to (DI-36-8) ) Is a diamine represented by any one of them.

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O- , -OCF ₂ -or -(CH ₂ ) _ma -, where ma is an integer of 1-12. Preferred examples of G ²⁶ are single bonds, -O-, -COO-, -OCO-, -CH ₂ O- and alkylene groups having 1 to 3 carbon atoms. Particularly preferred examples are single bonds, -O-,- COO-, -OCO-, -CH ₂ O-, -CH ₂ -and -CH ₂ CH ₂ -. R ²⁵ is 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 by -F, and at least one -CH ₂ -may be substituted by -O-, -CH=CH- or -C≡C-. The hydrogen atom of the phenyl group can be passed through -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , an alkyl group having 3 to 30 carbons, or an alkoxy group having 3 to 30 carbons. Substitution. _{The bonding position of -NH 2} to the benzene ring means any position on the ring, and the bonding position is preferably a meta position or a para position. That is, when ^{the bonding position of the group "R 25} -G ²⁶ -" is set to 1 position, the two bonding positions are preferably 3 and 5 positions or 2 and 5 positions.

式（DI-31-a）中，G²⁷ 、G²⁸ 及G²⁹ 為鍵結基，它們分別獨立地為單鍵或碳數1～12的伸烷基，所述伸烷基的一個以上的-CH₂ -可經-O-、-COO-、-OCO-、-CONH-、-CH=CH-取代。環B²¹ 、環B²² 、環B²³ 及環B²⁴ 分別獨立地為1,4-伸苯基、1,4-伸環己基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基、萘-1,5-二基、萘-2,7-二基或蒽-9,10-二基，環B²¹ 、環B²² 、環B²³ 及環B²⁴ 中，至少一個氫原子可經-F或-CH₃ 取代，s、t及u分別獨立地為0～2的整數，它們的合計為1～5，在s、t或u為2時，各個括號內的兩個鍵結基可相同，也可不同，而且，兩個環可相同，也可不同。R²⁶ 為氫原子、-F、-OH、碳數1～30的烷基、碳數1～30的氟取代烷基、碳數1～30的烷氧基、-CN、-OCH₂ F、-OCHF₂ 或-OCF₃ ，所述碳數1～30的烷基的至少一個-CH₂ -可經下述式（DI-31-b）所表示的二價基取代。

式（DI-31-b）中，R²⁷ 及R²⁸ 分別獨立地為碳數1～3的烷基，v為1～6的整數。R²⁶ 的優選例為碳數1～30的烷基及碳數1～30的烷氧基。

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are bonding groups, and they are each independently a single bond or an alkylene group having 1 to 12 carbon atoms, and one or more of the alkylene groups -CH ₂ -can be substituted by -O-, -COO-, -OCO-, -CONH-, -CH=CH-. Ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are each independently 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 B ²¹ , ring In B ²² , ring B ²³ and ring B ²⁴ , at least one hydrogen atom may be _{substituted by -F or -CH 3} , s, t and u are each independently an integer of 0-2, and their total is 1-5, in When s, t or u is 2, the two bonding groups in each bracket may be the same or different, and the two rings may be the same or different. R ²⁶ is a hydrogen atom, -F, -OH, a C1-C30 alkyl group, a C1-C30 fluorine-substituted alkyl group, a C1-C30 alkoxy group, -CN, -OCH ₂ F, -OCHF ₂ or -OCF _{3 , at least one -CH 2} -of the alkyl group having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-31-b).

In formula (DI-31-b), R ²⁷ and R ²⁸ are each independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6. Preferable examples of R ²⁶ are an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms.

式（DI-32）及式（DI-33）中，G³⁰ 獨立地為單鍵、-CO-或-CH₂ -，R²⁹ 獨立地為氫原子或-CH₃ ，R³⁰ 獨立地為氫原子、碳數1～20的烷基或碳數2～20的烯基。式（DI-33）中的苯環的至少一個氫原子可經碳數1～20的烷基或苯基取代。而且，鍵結位置未固定於構成環的任一個碳原子上的基表示在所述環上的鍵結位置為任意。優選為式（DI-32）中的兩個基「-伸苯基-G³⁰ -O-」的其中一個鍵結於類固醇核的3位，另一個鍵結於類固醇核的6位。式（DI-33）中的兩個基「-伸苯基-G³⁰ -O-」在苯環上的鍵結位置優選為相對於類固醇核的鍵結位置，分別為間位或對位。式（DI-32）及式（DI-33）中，鍵結於苯環上的-NH₂ 表示在所述環上的鍵結位置為任意。

In formula (DI-32) and formula (DI-33), G ^{30 is} independently a single bond, -CO- or -CH ₂ -, R ^{29 is} independently a hydrogen atom or -CH ₃ , and R ^{30 is} independently hydrogen Atom, a C 1-20 alkyl group or a C 2-20 alkenyl group. At least one hydrogen atom of the benzene ring in formula (DI-33) may be substituted by an alkyl group or phenyl group having 1 to 20 carbon atoms. In addition, a group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary. Preferably, one of the two groups "-phenylene-G ³⁰ -O-" in the formula (DI-32) is bonded to the 3-position of the steroid core, and the other is bonded to the 6-position of the steroid core. The bonding position of the two groups "-phenylene-G ³⁰ -O-" in the formula (DI-33) on the benzene ring is preferably relative to the bonding position of the steroid core, which is a meta position or a para position, respectively. In formula (DI-32) and formula (DI-33), -NH ₂ bonded to the benzene ring means that the bonding position on the ring is arbitrary.

式（DI-34）及式（DI-35）中，G³¹ 獨立地為-O-或碳數1～6的伸烷基，G³² 為單鍵或碳數1～3的伸烷基。R³¹ 為氫原子或碳數1～20的烷基，所述烷基的至少一個-CH₂ -可經-O-、-CH=CH-或-C≡C-取代。R³² 為碳數6～22的烷基，R³³ 為氫原子或碳數1～22的烷基。環B²⁵ 為1,4-伸苯基或1,4-伸環己基，r為0或1。而且，鍵結於苯環上的-NH₂ 表示在所述環上的鍵結位置為任意，優選為獨立地相對於G³¹ 的鍵結位置而為間位或對位。

In formula (DI-34) and formula (DI-35), G ^{31 is} independently -O- or an alkylene group having 1 to 6 carbons, and G ³² is a single bond or an alkylene group having 1 to 3 carbons. R ³¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and at least one -CH ₂ -of the alkyl group may be substituted with -O-, -CH=CH- or -C≡C-. R ³² is an alkyl group having 6 to 22 carbons, and R ³³ is a hydrogen atom or an alkyl group having 1 to 22 carbons. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. _{Furthermore, -NH 2} bonded to the benzene ring means that the bonding position on the ring is arbitrary, and it is preferably a meta or para position ^{independently of the bonding position of G 31.}

Examples of the compound represented by the formula (DI-31) are shown in the following formulas (DI-31-1) to (DI-31-55).

In formulas (DI-31-1) to (DI-31-11), R ^{34 is} each independently an alkyl group having 1 to 30 carbons or an alkoxy group having 1 to 30 carbons, preferably 5 to 25 alkyl group or C 5-25 alkoxy group. R ^{35 is} each independently an alkyl group having 1 to 30 carbons or an alkoxy group having 1 to 30 carbons, and preferably an alkyl group having 3 to 25 carbons or an alkoxy group having 3 to 25 carbons.

In formulas (DI-31-12) to (DI-31-17), R ^{36 is} each independently an alkyl group having 4 to 30 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms. R ^{37 is} each independently an alkyl group having 6 to 30 carbons, and preferably an alkyl group having 8 to 25 carbons.

In the formulas (DI-31-18) to (DI-31-43), R ^{38 is} each independently an alkyl group having 1 to 20 carbons or an alkoxy group having 1 to 20 carbons, preferably 3 to 20 carbons. 20 alkyl group or alkoxy group having 3 to 20 carbon atoms. R ^{39 is} each independently a hydrogen atom, -F, an alkyl group having 1 to 30 carbons, an alkoxy group having 1 to 30 carbons, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , preferably carbon An alkyl group having 3 to 25 or an alkoxy group having 3 to 25 carbons. Furthermore, G ³³ is an alkylene group having 1 to 20 carbon atoms.

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

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

式（DI-34-1）～式（DI-34-12）中，R⁴⁰ 分別獨立地為氫原子或碳數1～20的烷基，優選為氫原子或碳數1～10的烷基，而且，R⁴¹ 分別獨立地為氫或碳數1～12的烷基。Examples of the compound represented by the formula (DI-34) are shown in the following formulas (DI-34-1) to (DI-34-12).

In formulas (DI-34-1) to (DI-34-12), R ^{40 is} each independently a hydrogen atom or an alkyl group having 1 to 20 carbons, preferably a hydrogen atom or an alkyl group having 1 to 10 carbons And, R ^{41 is} each independently hydrogen or an alkyl group having 1 to 12 carbons.

式（DI-35-1）～式（DI-35-3）中，R³⁷ 分別獨立地為碳數6～30的烷基，R⁴¹ 分別獨立地為氫原子或碳數1～12的烷基。Examples of the compound represented by the formula (DI-35) are shown in the following formulas (DI-35-1) to (DI-35-3).

In formulas (DI-35-1) to (DI-35-3), R ^{37 is} each independently an alkyl group having 6 to 30 carbons, and R ^{41 is} each independently a hydrogen atom or an alkyl group having 1 to 12 carbons. base.

式（DI-36-1）～式（DI-36-8）中，R⁴² 分別獨立地表示碳數3～30的烷基。The compounds represented by formula (DI-36-1) to formula (DI-36-8) are shown below.

In formulas (DI-36-1) to (DI-36-8), R ⁴² each independently represents an alkyl group having 3 to 30 carbon atoms.

Among the above-mentioned diamines, suitable materials that improve the characteristics of the liquid crystal alignment film described later will be described. In the case of focusing on improving the orientation of liquid crystals, it is preferable to use formula (DI-1-3), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), and formula (DI-5-9). (DI-5-12), formula (DI-5-13), formula (DI-5-29), formula (DI-6-7), formula (DI-7-3) or formula (DI-11- 2) The compound represented. In formula (DI-5-1), m=2-8 is preferable, and m=4-8 is more preferable. In formula (DI-5-12), m=2-6 is preferable, and m=5 is more preferable. In formula (DI-5-13), m=1 or 2 is preferable, and m=1 is more preferable.

When emphasis is placed on increasing the transmittance, it is preferable to use the formula (DI-1-3), the formula (DI-2-1), the formula (DI-5-1), the formula (DI-5-5), and the formula ( The diamine represented by DI-5-24) or formula (DI-7-3) is more preferably a compound represented by formula (DI-2-1). In formula (DI-5-1), m=2-8 is preferable, and m=8 is more preferable. In formula (DI-7-3), m=2 or 3 and n=1 or 2 are preferable, and m=3 and n=1 are more preferable.

In the case of focusing on improving the VHR of the liquid crystal display element, it is preferable to use the formula (DI-2-1), the formula (DI-4-1), the formula (DI-4-2), and the 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- The compound represented by 13-1) is more preferably a diamine represented by formula (DI-2-1), formula (DI-5-1), or formula (DI-13-1). In formula (DI-5-1), m=1 is preferable. In formula (DI-5-30), k=2 is preferred.

As one of the methods for preventing burn marks, it is effective to increase the relaxation speed of the residual charge (residual DC) in the liquid crystal alignment film by reducing the volume resistance value of the liquid crystal alignment film. In the case of attaching importance to the purpose, it is preferable to use the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), the formula (DI-4-15), and the formula ( DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-4-20), formula (DI-4-21 ), the compound represented by the formula (DI-7-12) or the formula (DI-16-1), more preferably the formula (DI-4-1), the formula (DI-5-1) or the formula (DI-5 -13) The compound represented. In formula (DI-5-1), m=2-8 is preferable, and m=4-8 is more preferable. In formula (DI-5-12), m=2-6 is preferable, and m=5 is more preferable. In formula (DI-5-13), m=1 or 2 is preferable, and m=1 is more preferable. In formula (DI-7-12), m=3 or 4 is preferable, and m=4 is more preferable.

[The compounding amount of the compound represented by formula (1) in the raw material] In the raw material composition used as the raw material of the polymer of the present invention, the compound represented by formula (1) is preferably 40 mol% to 100 mol% relative to the total amount of diamines used as the raw material, and more preferably It is 50 mol% to 100 mol%.

In the raw material composition used as the raw material of the polymer of the present invention, a part of the diamines may be substituted with at least one selected from the group consisting of monoamines and monohydrazine. Regarding the ratio of substitution, it is preferable that the ratio of at least one selected from the group consisting of monoamines and monohydrazine with respect to diamines is in the range of 40 mol% or less. Such substitution can cause the termination of the polymerization reaction when the polyamide acid is produced, and can inhibit the further progress of the polymerization reaction. Therefore, by such substitution, the molecular weight of the obtained polymer (polyamide acid or its derivative) can be easily controlled, for example, the coating characteristics of the liquid crystal alignment agent can be improved without impairing the effect of the present invention. As long as the effect of the present invention is not impaired, the diamine substituted with monoamine or monohydrazine may be one type or two or more types. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-decylamine Monoamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecamine, n-octadecylamine, n-ecosamine, p-aminophenyl trimethoxy Silane and 3-aminopropyl triethoxysilane.

When the polymer of the present invention is polyamide acid or a derivative thereof, the raw material may further include a monoisocyanate compound as a monomer. By including a monoisocyanate compound as a monomer, the terminal of the obtained polyamide acid or its derivative is modified, and the molecular weight is adjusted. By using the terminal modified polyamide acid or its derivative, for example, the coating characteristics of the liquid crystal alignment agent can be improved without impairing the effect of the present invention. From this viewpoint, the content of the monoisocyanate compound in the monomer is preferably 1 mol% to 10 mol% relative to the total amount of the diamine and tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

在所述各式中，鍵結位置未固定於構成環的任一個碳原子上的基表示在所述環上的鍵結位置為任意。式（V-2）中，R⁶ 分別獨立地為-CH₃ 、-OCH₃ 、-CF₃ 、-COOCH₃ ，a分別獨立地為0～2的整數。式（V-4）中，R¹ 及R² 分別獨立地為氫、式（P1-1）或式（P1-2）所表示的基，R¹ 及R² 的至少一個為式（P1-1）或式（P1-2）所表示的基。式（VII-1）中，R⁴ 及R⁶ 分別獨立地為碳數1～20的直鏈伸烷基、-COO-、-OCO-、-NHCO-、-CONH-、-N(CH₃ )CO-、-CON(CH₃ )-或單鍵，R⁴ 及R⁶ 中，直鏈伸烷基的-CH₂ -的一個或不鄰接的兩個可經-O-取代，R⁵ 及R⁷ 獨立地為單環式烴環、縮合多環式烴環、雜環或單鍵。

式（P1-1）及式（P1-2）中，R^6a ～R^8a 分別獨立地為氫原子、經取代或未經取代的烷基、經取代或未經取代的烷醯基、經取代或未經取代的烷氧基羰基、或者經取代或未經取代的芳基羰基。R^6a ～R^8a 可相互相同，也可不同。*表示在式（V-4）中的苯環上的鍵結位置。A photosensitive monomer other than the photosensitive monomer of the present invention may be used in combination within a range that does not impair the effect of the present invention. Although the example of the photosensitive monomer which can be used together is shown below, it is not limited to this.

In the above formulas, the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary. In formula (V-2), R ^{6 is} each independently -CH ₃ , -OCH ₃ , -CF ₃ , and -COOCH ₃ , and a is each independently an integer of 0-2. In formula (V-4), R ¹ and R ² are each independently hydrogen, a group represented by formula (P1-1) or formula (P1-2), and at least one of ^{R 1} and R ^{2 is formula (P1-} 1) Or the group represented by formula (P1-2). In the formula (VII-1), R ⁴ and R ⁶ are each independently a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N(CH ₃ ) CO-, -CON(CH ₃ )- or a single bond, in R ⁴ and R ⁶ , one or two non-adjacent ones _{of -CH 2} -of the straight-chain alkyl extension ^{may be substituted by -O-, R 5} and R ^{7 is} independently a monocyclic hydrocarbon ring, a condensed polycyclic hydrocarbon ring, a heterocyclic ring, or a single bond.

In formula (P1-1) and formula (P1-2), R ^6a to R ^8a are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane group, a substituted Or unsubstituted alkoxycarbonyl, or substituted or unsubstituted arylcarbonyl. R ^6a to R ^8a may be the same as or different from each other. * Indicates the bonding position on the benzene ring in formula (V-4).

When attaching importance to the transparency of the alignment film of the present invention, it is preferably used in combination with the photosensitive monomer represented by formula (V-4). As a more preferable example of the photosensitive monomer represented by Formula (V-4), Formula (V-4-1) and Formula (V-4-2) are mentioned.

＜Liquid crystal alignment agent＞ Hereinafter, the liquid crystal alignment agent obtained from the polymer of the present invention will be described in detail. The liquid crystal alignment agent of the present invention may include a polymer of the present invention, or a polymer of the present invention and a polymer other than the present invention may be mixed. Furthermore, in this specification, a liquid crystal alignment agent containing one of the polymers is sometimes referred to as a single-layer liquid crystal alignment agent. Sometimes a liquid crystal alignment agent in which two or more of the polymers are mixed is referred to as a blended liquid crystal alignment agent. The blended liquid crystal alignment agent is especially used in situations where VHR reliability or other electrical characteristics are important.

The polymer other than the present invention used in the blend type liquid crystal alignment agent is preferably any one or more of polyamide acid and polyamide acid derivatives. As for polymers other than the present invention, regarding polyamide acid and polyamide acid derivatives, except that the compound represented by formula (1) as a raw material is not included, reference may be made to the description of the polymer of the present invention.

In the case of using a two-component polymer, for example, there are the following forms: one of them selects a polymer having excellent performance in terms of liquid crystal alignment ability, and the other selects a polymer having excellent properties for improving the electrical characteristics of liquid crystal display elements. High-performance polymers are suitable for obtaining an alignment agent with a good balance of liquid crystal alignment and electrical characteristics.

In this case, by controlling the structure or molecular weight of each polymer, a liquid crystal alignment agent prepared by dissolving these polymers in a solvent can be coated on a substrate and pre-dried to form a thin film as described later. , The polymer with excellent performance in liquid crystal alignment ability is segregated on the upper layer of the film, and the polymer with excellent performance for improving the electrical characteristics of the liquid crystal display element is segregated on the lower layer of the film. Among them, among the mixed polymers, a phenomenon in which a polymer with a small surface energy separates in the upper layer and a polymer with a large surface energy separates in the lower layer can be applied. The confirmation of such layer separation can be confirmed by the following method: the surface energy of the formed liquid crystal alignment film is the same as or close to the surface energy of the film formed by the liquid crystal alignment agent containing only the polymer intended to segregate in the upper layer .

As a method of developing layer separation, reducing the molecular weight of the polymer to be segregated in the upper layer can also be cited.

In the liquid crystal alignment agent containing a mixture of polymers, layer separation can also be manifested by setting the polymer to be segregated in the upper layer as polyimide.

The compound represented by formula (1) can be used as a raw material monomer for the polymer segregated in the upper layer of the film, can also be used as a raw material monomer for the polymer segregated in the lower layer of the film, and can also be used as two The raw material monomer for this type of polymer is more preferably a raw material monomer for the polymer segregated on the upper layer of the film.

The tetracarboxylic dianhydride used for synthesizing the polyamide acid or its derivative segregated in the upper layer of the film can be selected without limitation from the well-known tetracarboxylic dianhydrides exemplified above.

The tetracarboxylic dianhydride used to synthesize polyamide acid or its derivatives segregated on the upper layer of the film is preferably of formula (AN-1-1), formula (AN-1-2), and formula (AN-2-1 ), the compound represented by the formula (AN-3-1), the formula (AN-4-5), the formula (AN-4-17) or the formula (AN-4-21), more preferably the formula (AN-4 -17) or formula (AN-4-21). In formula (AN-4-17), m=4-8 is preferable.

Diamines other than the compound represented by formula (1) used to synthesize polyamic acid or its derivatives segregated on the upper layer of the film can be selected from the well-known diamines exemplified above without limitation .

As diamines for synthesizing polyamide acid or its derivatives segregated on the upper layer of the film, it is preferable to use the formula (DI-4-1), the formula (DI-4-13), and the formula (DI-4- 15) Compounds represented by formula (DI-5-1), formula (DI-7-3) or formula (DI-13-1). Among them, it is more preferable to use a compound represented by formula (DI-4-13), formula (DI-4-15), formula (DI-5-1), or formula (DI-13-1). In formula (DI-5-1), m=4-8 is preferable. In formula (DI-7-3), m=3 and n=1 are preferable.

The tetracarboxylic dianhydride used for synthesizing the polyamide acid or its derivative segregated in the lower layer of the film can be selected without limitation from the well-known tetracarboxylic dianhydrides exemplified above.

As the tetracarboxylic dianhydride used to synthesize polyamide acid or its derivatives segregated in the lower layer of the film, the formula (AN-1-1), the formula (AN-1-13), and the formula (AN-2 -1), the compound represented by formula (AN-3-2) or formula (AN-4-21), more preferably formula (AN-1-1), formula (AN-2-1) or formula (AN -3-2).

The tetracarboxylic dianhydride used to synthesize the polyamide acid or its derivatives segregated in the lower layer of the film preferably contains 10 mol% or more of the aromatic tetracarboxylic dianhydride in the total amount of the tetracarboxylic dianhydride, More preferably, it contains 30 mol% or more.

Diamines other than the compound represented by formula (1) used to synthesize polyamic acid or its derivatives segregated in the lower layer of the film can be selected without limitation from the well-known diamines exemplified above .

As diamines used to synthesize polyamide acid or its derivatives segregated in the lower layer of the film, the formula (DI-4-1), the formula (DI-4-2), and the formula (DI-4-10 ), formula (DI-4-18), formula (DI-4-19), formula (DI-5-1), formula (DI-5-9), formula (DI-5-28), formula (DI -5-30), a compound represented by formula (DI-13-1) or formula (DIH-1-2). In formula (DI-5-1), m=1 or 2 is preferred, and in formula (DI-5-30), k=2 is preferred. Among them, formula (DI-4-1), formula (DI-4-18), formula (DI-4-19), formula (DI-5-9), formula (DI-13-1) or The compound represented by formula (DIH-1-2).

Relative to all diamines, the diamines used to synthesize polyamide acid or its derivatives segregated in the lower layer of the film preferably contain at least 30 mol% selected from aromatic diamines and aromatic dihydrazine. At least one of the constituent groups is more preferably 50 mol% or more.

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

The polyamide acid or its derivative of the present invention may be a block polymer including a first polymer chain and a second polymer chain having a structure different from the first polymer chain. In addition, the block polymer may also include other polymer chains whose structures are different from those of the first polymer chain and the second polymer chain. For example, a block polymer of polyamide acid can be obtained by combining a solution of a specific polyamide acid (PAA1) represented by the formula (PAA) ^{and a combination of X 1} and X ² and a polyamide acid (PAA1) different from polyamide acid (PAA1). A solution of PAA2 is mixed and heated to form. The block polymer of polyamide acid formed in this way contains _{a block represented by (PAA1) n1} and a block represented by (PAA2) _n2 . (PAA1) _n1 and (PAA2) n1 _n2 and n2 are each independently an integer of 1 or more, preferably are each independently an integer of 2 or more. In the block polymer, the polymer chains in which the compound represented by formula (1) is used as the raw material composition may be any one type, two or more types, or all polymer chains.

Here, the polyamide block polymer can be synthesized by separately producing two or more polyamides and then mixing them and heating them, or synthesizing two or more polyamides in the same reaction vessel, Then it is heated to synthesize.

In addition, from the viewpoint of coating properties of the liquid crystal alignment agent or adjustment of the concentration of the polyamide acid or its derivative, the liquid crystal alignment agent of the present invention may further contain a solvent. The solvent can be used without particular limitation as long as it has the ability to dissolve polymer components. The solvent includes a wide range of solvents generally used in the production steps or applications of polymer components such as polyamide acid and soluble polyimide, and can be appropriately selected according to the purpose of use. The solvent may be one type or a mixed solvent of two or more types.

As a solvent, the hydrophilic solvent of the said polyamic acid or its derivative(s), or other solvents for the purpose of improving coatability can be mentioned.

Examples of aprotic polar organic solvents that are solvent-philic to polyamide acid or its derivatives include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and dimethylimidazolidinone , N-methylcaprolactam, N-methylpropanamide, N,N-dimethylacetamide, dimethylsulfide, N,N-dimethylformamide, N,N- Diethylformamide, diethylacetamide, N,N-dimethylisobutylamide, γ-butyrolactone and γ-valerolactone, etc. Among these solvents, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone or γ-valerolactone is preferable.

Examples of other solvents for the purpose of improving coating properties include: ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether and ethylene glycol mono-tert-butyl ether, and diethylene glycol such as diethylene glycol monoethyl ether. Diethylene glycol dialkyl ethers such as glycol monoalkyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, and diethylene glycol butyl methyl ether. In addition, examples include: propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, 1-butoxy-2-propanol, dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, triethylene glycol monoalkyl ether, butyl soluble Cellulose acetate, phenyl acetate, and ester compounds such as these acetates. Furthermore, examples include dialkyl malonates such as diethyl malonate, alkyl lactate, diisobutyl ketone, diacetone alcohol, 3-methyl-3-methoxybutanol, 4- Methyl-2-pentanol, diisobutyl methanol, tetralin and isophorone.

Among these solvents, diisobutyl ketone, 4-methyl-2-pentanol, diisobutyl methanol, ethylene glycol monobutyl ether, ethylene glycol mono-tert-butyl ether, and diethylene glycol monoethyl ether are preferred. , 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剂Acetate.

The solid content concentration in the liquid crystal alignment agent of the present invention is not particularly limited, as long as the most suitable value is selected in combination with the following various coating methods. Generally, in order to suppress unevenness or pinholes during coating, it is preferably 0.1% by weight to 30% by weight, and more preferably 1% by weight to 10% by weight relative to the weight of the varnish.

The viscosity of the liquid crystal alignment agent of the present invention differs in its preferred range depending on the coating method, the concentration of the polyamide acid or its derivative, the type of polyamide acid or its derivative used, and the type and ratio of the solvent. For example, in the case of coating with a printer, it is 5 mPa·s to 100 mPa·s (more preferably 10 mPa·s to 80 mPa·s). If it is 5 mPa·s or more, it is easy to obtain a sufficient film thickness, and if it is 100 mPa·s or less, it is easy to suppress printing unevenness. In the case of coating by spin coating, 5 mPa·s to 200 mPa·s (more preferably 10 mPa·s to 100 mPa·s) is suitable. In the case of coating using an inkjet coating device, 5 mPa·s to 50 mPa·s (more preferably 5 mPa·s to 20 mPa·s) are suitable. The viscosity of the liquid crystal alignment agent can be measured by a rotational viscosity measuring method, for example, it can be measured using a rotational viscometer (TVE-20L type manufactured by Toki Sangyo) (measurement temperature: 25°C).

The liquid crystal alignment agent of the present invention may also contain various additives. In order to improve various characteristics of the alignment film, various additives can be selected and used according to each purpose. Examples are shown below.

＜Alkenyl Substituted Nadicimidin Compounds＞ For example, for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time, the liquid crystal alignment agent of the present invention may further contain an alkenyl substituted nadicimidin compound. Alkenyl-substituted nadicimidin compounds may be used singly, or two or more of them may be used in combination. For the purpose, the content of the alkenyl-substituted nadicimide compound is preferably 1% by weight to 50% by weight, and more preferably 1% by weight to 30% by weight, relative to the polyamide acid or its derivatives. More preferably, it is 1 weight%-20 weight%. The alkenyl-substituted nadicimidin compound is preferably a compound that is soluble in a solvent that dissolves the polyamide acid or its derivative used in the present invention. Preferable alkenyl-substituted nadic imine compounds include the alkenyl-substituted sodium compounds disclosed in Japanese Patent Laid-Open No. 2008-096979, Japanese Patent Laid-Open No. 2009-109987, and Japanese Patent Laid-Open No. 2013-242526. Dick's imine compound. Particularly preferred alkenyl substituted nadicimidin compounds include: bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimidin)phenyl} Methane, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimidine) or N,N'-hexamethylene -Bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimidine).

<Compounds with radically polymerizable unsaturated double bonds> For example, for the purpose of stabilizing the electrical characteristics of the liquid crystal display element over a long period of time, the liquid crystal alignment agent of the present invention may further contain a compound having a radically polymerizable unsaturated double bond. The compound having a radically polymerizable unsaturated double bond may be one compound or two or more compounds. In addition, the compound having a radically polymerizable unsaturated double bond does not include an alkenyl substituted nadicimidin compound. Among the compounds having radically polymerizable unsaturated double bonds, preferred compounds include N,N'-methylenebisacrylamide and N,N'-dihydroxyethylene-bisacrylamide , Ethylene diacrylate, 4,4'-methylene bis (N,N-dihydroxy ethylene acrylate aniline), triallyl cyanurate; and Japanese Patent Laid-Open No. 2009-109987 , Japanese Patent Laid-Open No. 2013-242526, International Publication 2014/119682, International Publication 2015/152014, disclosed compounds having radically polymerizable unsaturated double bonds. For the purpose, the content of the compound having a radically polymerizable unsaturated double bond is preferably 1% by weight to 50% by weight, and more preferably 1% by weight to 30% by weight, relative to polyamide acid or its derivatives. %.

＜Oxazine compound＞ For example, for the purpose of stabilizing the electrical characteristics of the liquid crystal display element over a long period of time, the liquid crystal alignment agent of the present invention may further contain an oxazine compound. 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% by weight to 50% by weight, more preferably 1% by weight to 40% by weight, and still more preferably 1% by weight relative to polyamide acid or its derivatives. ~20% by weight.

The oxazine compound is preferably an oxazine compound that is soluble in a solvent in which polyamide acid or a derivative thereof is dissolved and has ring-opening polymerizability. As for preferred oxazine compounds, oxazine compounds represented by formula (OX-3-1), formula (OX-3-9), and formula (OX-3-10) can be cited; and Japanese Patent Laid-Open No. 2007-286597 An oxazine compound disclosed in Japanese Patent Publication No. 2013-242526 and Japanese Patent Application Publication No. 2013-242526.

＜Oxazoline compound＞ For example, for the purpose of stabilizing the electrical characteristics of the liquid crystal display element over a long period of time, the liquid crystal alignment agent of the present invention may further contain an oxazoline compound. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. For the purpose, the content of the oxazoline compound is preferably 0.1% by weight to 50% by weight, more preferably 1% by weight to 40% by weight, and still more preferably 1% by weight relative to polyamide acid or its derivatives. %～20% by weight. Preferred oxazoline compounds include oxazoline compounds disclosed in JP 2010-054872 A and JP 2013-242526 A. More preferably, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene can be mentioned.

＜Epoxy compound＞ For example, for the purpose of stabilizing the electrical characteristics of the liquid crystal display element over a long period of time, the purpose of improving the hardness of the film, or the purpose of improving the adhesion to a sealing compound, the liquid crystal alignment agent of the present invention may further contain an epoxy compound. The epoxy compound may be one compound or two or more compounds. For the purpose, the content of the epoxy compound is preferably 0.1% by weight to 50% by weight, more preferably 1% by weight to 20% by weight, and still more preferably 1% by weight relative to polyamide acid or its derivatives. ~10% by weight.

As the epoxy compound, various compounds having one or two or more epoxy rings in the molecule can be used. In order to achieve the purpose of increasing the hardness of the film or the purpose of improving the adhesion to the sealant, a compound having two or more epoxy rings in the molecule is preferable, and a compound having three or four epoxy rings is more preferable .

As the epoxy compound, the epoxy compounds disclosed in Japanese Patent Application Publication No. 2009-175715, Japanese Patent Application Publication No. 2013-242526, Japanese Patent Application Publication No. 2016-170409, and International Publication No. 2017/217413 can be cited. As a preferred epoxy compound, 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) dicyclohexyl, 1,4-butanediol glycidyl ether, tris(2,3-epoxypropyl) isocyanurate, 1,3-bis(N,N-diglycidyl) (Aminomethyl) cyclohexane or N,N,N',N'-tetraglycidyl-m-xylene diamine. In addition to this, an oligomer or polymer having an epoxy ring may be added. As the oligomer or polymer having an epoxy ring, the oligomer or polymer disclosed in JP 2013-242526 A can be used.

＜Silane compound＞ For example, for the purpose of improving the adhesion to the substrate and the sealant, the liquid crystal alignment agent of the present invention may further contain a silane compound. For the purpose, the content of the silane compound is preferably 0.1% by weight to 30% by weight, more preferably 0.5% by weight to 20% by weight, and still more preferably 0.5% by weight to polyamide acid or its derivatives. 10% by weight.

As the silane coupling agent, the silane coupling agent disclosed in Japanese Patent Laid-Open No. 2013-242526, Japanese Patent Laid-Open No. 2015-212807, Japanese Patent Laid-Open No. 2018-173545, and International Publication No. 2018/181566 can be used. Examples of preferred silane coupling agents include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, p-aminophenyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropylmethyl diethoxysilane, 3-isocyanatopropyl Triethoxysilane or 3-ureidopropyltriethoxysilane.

In addition to the additives described above, for the purpose of increasing the strength of the alignment film or for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long time, a compound having a cyclic carbonate group or a hydroxyalkylamide moiety can also be added. Or hydroxyl compounds. As a specific compound, the compound disclosed in Unexamined-Japanese-Patent No. 2016-118753 and International Gazette 2017/110976 can be mentioned. As a preferable compound, the following formula (HD-1)-formula (HD-4) are mentioned. These compounds are preferably 0.5% by weight to 50% by weight, more preferably 1% by weight to 30% by weight, and still more preferably 1% by weight to 10% by weight, relative to polyamide acid or its derivatives.

In addition, when it is necessary to improve antistatic properties, an antistatic agent can also be used, and when the imidization is carried out at a low temperature, an imidization catalyst can also be used. As the imidization catalyst, the imidization catalyst disclosed in JP 2013-242526 A can be cited.

＜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 using the liquid crystal alignment agent of the present invention. When the liquid crystal alignment agent of the present invention is used to form a liquid crystal alignment film, heating and sintering can cause an imidization reaction to form a polyimide-based liquid crystal alignment film. The liquid crystal alignment agent of the present invention is suitable for the liquid crystal alignment agent for optical alignment, and the optical alignment method can be applied in the alignment treatment in the process of forming the liquid crystal alignment film.

Hereinafter, a method for forming a liquid crystal alignment film using the liquid crystal alignment agent for optical alignment of the present invention will be described.

The liquid crystal alignment film of the present invention can be obtained by a usual method of producing a liquid crystal alignment film from a liquid crystal alignment agent for optical alignment. For example, the liquid crystal alignment film of the present invention can be obtained by going through the following steps: the step of forming a coating film of the liquid crystal alignment agent for optical alignment of the present invention, the step of heating and drying the coating film to form a film of the liquid crystal alignment agent, and the step of forming a film of the liquid crystal alignment agent. The step of irradiating the film of the alignment agent with light to impart anisotropy and the step of heating and baking the film of the anisotropic liquid crystal alignment agent. Regarding the liquid crystal alignment film of the present invention, it is preferable to irradiate light to impart anisotropy after the coating step and the heating and drying step, and then undergo a heating and sintering step.

The coating film can be formed by applying the liquid crystal alignment agent of the present invention on a substrate in a liquid crystal display element in the same manner as the production of a general liquid crystal alignment film. The substrate may be provided with electrodes such as indium tin oxide (ITO), indium zinc oxide (In ₂ O ₃ -ZnO, IZO), indium gallium zinc oxide (In-Ga-ZnO ₄ , IGZO) electrodes, or colored Substrates made of glass, silicon nitride, acrylic, polycarbonate, polyimide, etc., such as filters.

As a method of applying a liquid crystal alignment agent on a substrate, a spinner method, a printing method, a dipping method, a dropping method, an inkjet method, etc. are generally known. These methods can be similarly applied to the present invention.

In the heating and drying step, a method of heating in an oven or an infrared oven, a method of heating on a hot plate, and the like are generally known. The heating and drying step is preferably carried out at a temperature within the range in which the solvent can evaporate, and more preferably carried out at a relatively low temperature relative to the temperature in the heating and sintering step. Specifically, the heating and drying temperature is preferably in the range of 30°C to 150°C, and more preferably in the range of 50°C to 120°C.

The heating and sintering step can be carried out under the conditions required for the polyamide acid or its derivative to exhibit an imidization reaction. For the baking of the coating film, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods can be similarly applied to the present invention. Usually, it is preferably performed at a temperature of about 90°C to 300°C for 1 minute to 3 hours, more preferably 120°C to 280°C, and still more preferably 150°C to 250°C.

When emphasis is placed on improving the anisotropy of the film or the residual image characteristics during the production of the liquid crystal display element, it is preferable to slowly increase the temperature of the heating step. For example, the temperature can be increased stepwise while performing more at different temperatures. The secondary heating is simmered, or the temperature is changed from a low temperature to a high temperature for heating. In addition, it is also possible to combine two heating methods.

When heating and sintering are performed multiple times at different temperatures, multiple heating devices set to different temperatures can be used, or one heating device can be used to sequentially change to different temperatures.

When heating and sintering are performed multiple times at different temperatures, it is preferably performed at the initial sintering temperature of 90°C to 180°C, and preferably at the final temperature of 185°C to 300°C. For example, it is preferable to heat and burn at 110°C and then heat and burn at 220°C; heat and burn at 110°C and then heat and burn at 230°C; heat and burn at 130°C and then burn at 220°C After heating and simmering at 150℃, heating and simmering at 200℃; after heating and sintering at 150℃, heating and simmering at 220℃; heating and simmering at 150℃, after heating and simmering at 230 Heating and simmering at ℃; or heating and simmering at 170℃, then heating and simmering at 200℃. Furthermore, it is also preferable to perform heating and sintering while increasing the stage and gradually raising the temperature. When heating and sintering are performed in two or more stages by changing the heating temperature, the heating time in each heating step is preferably 5 minutes to 30 minutes.

When sintering is performed by changing the temperature from a low temperature to a high temperature, the initial temperature is preferably 90°C to 180°C. The final temperature is preferably 185°C to 300°C, more preferably 190°C to 230°C. The heating time is preferably 5 minutes to 60 minutes, more preferably 20 minutes to 60 minutes. The temperature increase rate can be set to 0.5°C/min to 40°C/min, for example. The rate of temperature increase in the temperature increase may not be fixed.

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

The method for forming the liquid crystal alignment film of the present invention using 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 irradiating a film after heating and drying the coating film with linearly polarized or unpolarized light to impart anisotropy to the film, and to The film is heated and simmered. Alternatively, it can be formed by heating and drying the coating film, heating and sintering, and then irradiating the film with linearly polarized or unpolarized light. In terms of liquid crystal orientation, the light irradiation step is preferably performed before the heating and burning step.

Furthermore, in order to improve the liquid crystal alignment ability of the liquid crystal alignment film, it is also possible to irradiate the coating film with linearly polarized or unpolarized light while heating the coating film. The light irradiation may be performed in the step of heating and drying the coating film or the step of heating and burning, or may be performed between the heating and drying step and the heating and burning step. For the heating temperature when irradiating light in the step of heating and drying the coating film or the step of heating and baking, refer to the description of the step of heating and drying or the step of heating and baking. The heating temperature when irradiating light between the heating and drying step and the heating and sintering step is preferably in the range of 30°C to 150°C, and more preferably in the range of 50°C to 110°C.

As the light, for example, ultraviolet rays or visible light including light having a wavelength of 150 nm to 800 nm can be used, and ultraviolet rays including light of 300 nm to 400 nm are preferable. In addition, linearly polarized light or unpolarized light can be used. These lights are not particularly limited as long as they can provide the liquid crystal alignment ability to the film. In the case where a strong alignment restriction force is desired to be expressed on the liquid crystal, linearly polarized lights are preferred.

The irradiation amount of linearly polarized light in the light irradiation step is preferably 0.05 J/cm ² to 10 J/cm ² , and more preferably 0.1 J/cm ² to 5 J/cm ² . In addition, the wavelength of linearly polarized light is preferably 200 nm to 400 nm, and more preferably 300 nm to 400 nm. The irradiation angle of the linear polarized light on the film surface is not particularly limited. In the case where a strong alignment restriction force for the liquid crystal is desired to be exhibited, from the viewpoint of shortening the alignment treatment time, it is preferably as perpendicular to the film surface as possible. In addition, the liquid crystal alignment film of the present invention can align the liquid crystal in a direction at a right angle to the polarization direction of the linear polarization by irradiating linearly polarized light.

Among the light sources used in the step of irradiating light with linear polarization or non-polarization, ultra-high-pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, deep ultraviolet (Deep UV) lamps, halogen lamps, metal halide lamps, and large lamps can be used without limitation. Power metal halide lamp, xenon lamp, mercury xenon lamp, excimer lamp, KrF excimer laser, fluorescent lamp, light emitting diode (LED) lamp, sodium lamp, microwave discharged electrodeless lamp, etc.

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

Although the liquid crystal alignment film of the present invention does not require the step of cleaning the burned or light-irradiated film with a cleaning solution, a cleaning step may be provided according to the conditions of other steps. Examples of the cleaning method using the cleaning liquid include brushing, jet spray, steam cleaning, ultrasonic cleaning, and the like. These methods can be performed individually or in combination. As the cleaning liquid, you can use: pure water; or various alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene, toluene, and xylene; halogen-based solvents such as dichloromethane; acetone, methyl ethyl ketone Such as ketones, but it is not limited to these. Of course, these cleaning solutions can be sufficiently purified cleaning solutions with few impurities. This cleaning method can also 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, an annealing treatment using heat or light may be used before and after the heating and burning step or before and after the irradiation of polarized or unpolarized light. In the annealing treatment, the annealing temperature is 30°C to 180°C, preferably 50°C to 150°C, and the time is preferably 1 minute to 2 hours. In addition, the annealing light used in the annealing treatment includes UV lamps, fluorescent lamps, LED lamps, and the like. The irradiation amount of light is preferably 0.3 J/cm ² to 10 J/cm ² .

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

The liquid crystal alignment film of the present invention is characterized by having particularly large alignment anisotropy. The magnitude of such anisotropy can be evaluated by the method using polarized IR described in Japanese Patent Laid-Open No. 2005-275364 and the like. In addition, it can also be evaluated by using an ellipsometry method. 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 alignment of the polymer main chain.

The liquid crystal alignment film of the present invention can be used for alignment control of liquid crystal compositions for liquid crystal displays such as smart phones, input boards, car monitors, televisions, and the like. In addition to the alignment use of liquid crystal compositions for liquid crystal displays, it can also be used for alignment control of all other liquid crystal materials, such as optical compensation materials or broadband variable phase shifters in the microwave/millimeter wave band using liquid crystals. In addition, the liquid crystal alignment film of the present invention has a large anisotropy, so it can be used alone as an optical compensation material.

＜Liquid crystal display element＞ Next, the liquid crystal display element 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 achieve high display quality due to its good after-image characteristics and contrast.

The liquid crystal display element of the present invention will be described in detail. In the present invention, in the following liquid crystal display element, the liquid crystal alignment film includes the liquid crystal alignment film of the present invention, and the liquid crystal display element includes a pair of substrates arranged facing each other, and formed in each of the facing surfaces of the pair of substrates One or both of the electrodes, the liquid crystal alignment film formed on the opposing surfaces of the pair of substrates, the liquid crystal layer formed between the pair of substrates, one disposed in such a way as to sandwich the opposing substrates For polarizing film, backlight and 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 electrodes include ITO or metal vapor-deposited films. In addition, the electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired shape that is patterned, for example. The desired shape of the electrode includes, for example, a comb shape or a zigzag structure. The electrode may be formed on one of a pair of substrates, or may be formed on two substrates. The form of electrode formation differs according to the type of liquid crystal display element. For example, in the case of an IPS type liquid crystal display element (lateral electric field type liquid crystal display element), the electrode is arranged on one of the pair of substrates, and the other liquid crystal display element In the case of a display element, electrodes are arranged on both of the pair of substrates. The liquid crystal alignment film is formed on the substrate or the electrode.

In the case of a parallel-aligned liquid crystal display element (for example, IPS, FFS, etc.), as a structure, it has at least a backlight, a first polarizing film, a first substrate, a first liquid crystal alignment film, a liquid crystal layer, and a second The substrate and the second polarizing film, the polarizing axis of the polarizing film is set in such a way that the polarizing axis (direction of polarized light absorption) of the first polarizing film and the polarizing axis of the second polarizing film cross (preferably orthogonal). At this time, the polarization axis of the first polarizing film may be arranged in a manner parallel or orthogonal to the alignment direction of the liquid crystal. The liquid crystal display element arranged in such a manner that the polarization axis of the first polarizing film is parallel to the liquid crystal alignment direction is referred to as O-mode, and the liquid crystal display element arranged in an orthogonal manner is referred to as E-mode. The liquid crystal alignment film of the present invention can also be applied to any of O-mode and E-mode, and can be selected according to the purpose.

Compounds with dichroism can be used in a large number of photoisomerization-type materials. Therefore, when the polarization axis of the polarized light irradiated to add anisotropy to the liquid crystal alignment agent is parallel and consistent with the polarization axis of the polarized light originating from the polarizing film arranged on the backlight side (in the case of using the liquid crystal alignment agent of the present invention) , Set to O-mode configuration), the transmittance of the light absorption wavelength region of the liquid crystal alignment film increases. Therefore, the transmittance of the liquid crystal display element can be further improved.

The liquid crystal layer is formed in a form in which a liquid crystal composition is sandwiched by the pair of substrates on which the liquid crystal alignment film is formed facing each other. In the formation of the liquid crystal layer, if necessary, spacers which are interposed between the pair of substrates such as fine particles or resin sheets to form an appropriate interval may be used.

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

In the vacuum injection method, a gap (cell gap) is provided so that the liquid crystal alignment film faces face each other, and the injection port of the liquid crystal is left, the sealant is printed and the substrate is bonded. A vacuum differential pressure is used to inject and fill liquid crystal into the cell gap partitioned by the substrate surface and the sealant, 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 a pair of substrates, and liquid crystal is dropped on the area inside the sealant, and then the other substrate is bonded so that the liquid crystal alignment film faces face each other. Then, the liquid crystal is pressed and spread on the entire surface of the substrate, and then ultraviolet light is irradiated to the entire surface of the substrate to harden the sealant, thereby manufacturing a liquid crystal display element.

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

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 with positive dielectric anisotropy include: Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Publication No. 5-501735, Japanese Patent Publication No. 8-157826, Japanese Patent Application No. 8-231960, and Japan Patent Publication No. 9-241644 (EP885272A1), Japanese Patent Publication No. 9-302346 (EP806466A1), Japanese Patent Publication No. 8-199168 (EP722998A1), Japanese Patent Publication No. 9-235552, Japanese Patent Publication No. 9-255956, Japanese Patent Japanese Patent Publication No. 9-241643 (EP885271A1), Japanese Patent Publication No. 10-204016 (EP844229A1), Japanese Patent Publication No. 10-204436, Japanese Patent Publication No. 10-231482, Japanese Patent Publication No. 2000-087040, Japanese Patent Publication No. 2001- The liquid crystal composition disclosed in 48822 and the like.

Preferable examples of the liquid crystal composition having negative dielectric anisotropy include: Japanese Patent Laid-Open No. 57-114532, Japanese Patent Laid-Open No. 2-4725, Japanese Patent Laid-Open No. 4-224885, and Japanese Patent No. Kaihei 8-40953, Japanese Patent Publication No. 8-104869, Japanese Patent Publication No. 10-168076, Japanese Patent Publication No. 10-168453, Japanese Patent Publication No. 10-236989, Japanese Patent Publication No. 10-236990, Japanese Patent Publication No. -236992, Japanese Patent Publication No. 10-236993, Japanese Patent Publication No. 10-236994, Japanese Patent Publication No. 10-237000, Japanese Patent Publication No. 10-237004, Japanese Patent Publication No. 10-237024, Japanese Patent Publication No. 10-237035 , Japanese Patent Publication No. 10-237075, Japanese Patent Publication No. 10-237076, Japanese Patent Publication No. 10-237448 (EP967261A1), Japanese Patent Publication No. 10-287874, Japanese Patent Publication No. 10-287875, Japanese Patent Publication No. 10- 291945, Japanese Patent Publication No. 11-029581, Japanese Patent Publication No. 11-080049, Japanese Patent Publication No. 2000-256307, Japanese Patent Publication No. 2001-019965, Japanese Patent Publication No. 2001-072626, Japanese Patent Publication No. 2001-192657, The liquid crystal composition disclosed in Japanese Patent Publication No. 2010-037428, International Publication No. 2011/024666, International Publication No. 2010/072370, Japanese Patent Publication No. 2010-537010, Japanese Patent Publication No. 2012-077201, Japanese Patent Publication No. 2009-084362, etc. Things.

Even if one or more optically active compounds are added to a liquid crystal composition with positive or negative dielectric anisotropy and used, there is no effect at all.

In addition, for example, from the viewpoint of improving the orientation, for example, the liquid crystal composition used in the liquid crystal display element of the present invention may further add an additive. Such additives include photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerization initiators, polymerization inhibitors, and the like. Preferred photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerization initiators, and polymerization inhibitors include the compounds disclosed in International Publication 2015/146330.

In order to be suitable for a polymer sustained alignment (PSA) mode liquid crystal display element, a polymerizable compound may be mixed in the liquid crystal composition. Preferable examples of polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxetane, oxetane), vinyl ketones, etc. Polymerizable base compound. Preferred compounds include those disclosed in International Publication 2015/146330 and the like. [Example]

Hereinafter, the present invention will be explained through examples. In addition, the evaluation methods and compounds used in the examples are as follows.

＜Weight average molecular weight (Mw)＞ The weight average molecular weight of polyamic acid is determined by using a 2695 separation module·2414 differential refractometer (manufactured by Waters), measuring it by the GPC method, and converting it into polystyrene. Using a phosphoric acid-dimethylformamide (Dimethylformamide, DMF) mixed solution (phosphoric acid/DMF=0.6/100: weight ratio), the obtained polyamide acid concentration was adjusted to approximately 2% by weight. Dilute. HSPgel RT MB-M (manufactured by Waters) was used for the column, and the mixed solution was used as a developing agent, and the measurement was performed under the conditions of a column temperature of 50° C. and a flow rate of 0.40 mL/min. The standard polystyrene uses TSK standard polystyrene manufactured by Tosoh (stock).

<Alternating Current (AC) residual image measurement/contrast measurement> The AC residual image is measured according to the method described in the pamphlet of International Publication No. 2000/43833. Specifically, the brightness-voltage characteristic (BV characteristic) of the produced liquid crystal cell was measured, and it was set as the brightness-voltage characteristic before stress application: B (before (before)). Next, an alternating current of 4.5 V and 60 Hz was applied to the liquid crystal cell for 20 minutes, followed by a short circuit for 1 second, and the brightness-voltage characteristics (BV characteristics) were measured again. Let this be the brightness-voltage characteristic after stress is applied: B (after). Here, the brightness at a voltage of 1.3 V for each brightness-voltage characteristic measured is used, and the brightness change rate ΔB (%) is obtained by the following equation. The smaller the value of ΔB (%) is, the more the AC residual image can be suppressed, that is, the better the residual image characteristic. If ΔB is 3% or less, it can be said that the after-image characteristics are good, but in recent years, the demand for after-image characteristics has further increased, and it is preferably lower. ΔB(%)={[B(after)-B(before)]/B(before)}×100 In addition, use the minimum brightness and maximum brightness in the BV characteristics before the stress is applied Calculate the contrast ratio (Contrast Ratio, CR). The larger the value of CR, the more vivid the dark display and the better the contrast. When it is 3000 or more, it can be said that it has excellent contrast. CR=B (before) _max /B (before) _{min In the} formula, B (before) _max represents the maximum brightness in the BV characteristics before stress is applied, and B (before) _min Indicates the minimum brightness in the BV characteristics before stress is applied.

＜Evaluation of the reliability of voltage holding ratio (VHR)＞ The voltage holding ratio (VHR) of the liquid crystal display element is measured by applying a rectangular wave with a wave height of ±5 V to the cell at 60°C according to the method described in "Mizushima et al., 14th Liquid Crystal Symposium Draft Collection p78 (1988)" . Set the VHR at this time to VHR (before). The voltage retention rate is an index indicating how much the applied voltage is maintained after the frame period. If the value is 100%, it means that all electric charges are maintained. The unit was exposed to the LED backlight for 300 hours, and the VHR was measured again. Set the VHR at this time to VHR (after). The VHR reliability is evaluated using the VHR reduction rate calculated using the following formula. It can be said that the smaller the VHR reduction rate, the higher the VHR reliability and the higher the stability to light. VHR reduction rate (%)={[VHR(after)-VHR(before)]/VHR(before)}×100

＜Delay (retardation, Re) measurement＞ A spectroscopic ellipsometer was used to determine the retardation (Re) at 589 nm. It can be said that the larger the Re, the more uniform the orientation of the polymer chains forming the alignment film, and the higher the anisotropy of the film.

＜Tetracarboxylic dianhydride＞

式（1-1-4）、式（1-2-1）、式（1-2-4）、式（DI-5-1）或式（DIH-1-2）中的l、m的值記載於表1或表2中。＜Diamines＞

Formula (1-1-4), formula (1-2-1), formula (1-2-4), formula (DI-5-1) or formula (DIH-1-2) in l, m The values are described in Table 1 or Table 2.

＜Solvent＞ NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve (ethylene glycol monobutyl ether) ＜Additives＞ Ad.1: 1,3-bis(4,5-dihydro-2-oxazolyl)benzene

使4-硝基苯酚（50.0 g、359 mmol）、1,4-二溴丁烷（310.4 g、1438 mmol）及碳酸鉀（74.5 g、539 mmol）的DMF（500 mL）溶液在60度下反應2小時。將反應混合物冷卻至室溫，添加乙酸乙酯（1 L），利用水（1 L）清洗3次，利用硫酸鈉進行乾燥，然後將溶媒減壓餾去而獲得粗體。針對所述粗體，將庚烷：乙酸乙酯=100：1的混合溶媒用作洗脫液，並利用矽膠管柱色譜法進行純化，以產量45.9 g、產率47%獲得1-(4-溴代-丁氧基)-4-硝基苯。[Synthesis Example 1] Synthesis of a compound of formula (1-2-1) and l=4

Make 4-nitrophenol (50.0 g, 359 mmol), 1,4-dibromobutane (310.4 g, 1438 mmol) and potassium carbonate (74.5 g, 539 mmol) in DMF (500 mL) solution at 60 degrees React for 2 hours. The reaction mixture was cooled to room temperature, ethyl acetate (1 L) was added, and it was washed with water (1 L) three times, dried with sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude body. For the bold body, a mixed solvent of heptane: ethyl acetate=100:1 was used as the eluent, and purified by silica gel column chromatography. The yield of 1-(4) was obtained with a yield of 45.9 g and a yield of 47%. -Bromo-butoxy)-4-nitrobenzene.

在4-硝基苯胺（29.4 g、213 mmol）的水（130 mL）溶液中，在冰浴冷卻下（冰浴）添加濃鹽酸（53 mL）。繼而，在所述溶液中，在冰浴冷卻下（冰浴）滴加亞硝酸鈉（14.7 g、213 mmol）的水（45 mL）溶液，然後攪拌30分鐘，製備4-硝基苯重氮鹽酸鹽的水溶液。 一邊對所獲得的4-硝基苯重氮鹽酸鹽的水溶液進行攪拌，一邊緩慢地添加於經冰浴冷卻的苯酚（20.0 g、213 mmol）與乙酸鈉（139.5 g、1700 mmol）的乙醇（10 mL）及水（400 mL）的混合溶液中。將反應溶液在冰浴冷卻下（冰浴）攪拌2小時，然後進行過濾。將所獲得的固體溶解於乙酸乙酯（2 L）中，利用水（1 L）清洗3次，利用硫酸鈉進行乾燥，然後將溶媒減壓餾去，以產量40.1 g、產率78%獲得偶氮苯衍生物1。

To a solution of 4-nitroaniline (29.4 g, 213 mmol) in water (130 mL), add concentrated hydrochloric acid (53 mL) under ice cooling (ice bath). Then, in the solution, a solution of sodium nitrite (14.7 g, 213 mmol) in water (45 mL) was added dropwise under ice cooling (ice bath), and then stirred for 30 minutes to prepare 4-nitrobenzene diazonium Aqueous solution of hydrochloride. While stirring the obtained 4-nitrobenzene diazonium hydrochloride aqueous solution, slowly add ethanol to the ice-cooled phenol (20.0 g, 213 mmol) and sodium acetate (139.5 g, 1700 mmol) (10 mL) and water (400 mL) in a mixed solution. The reaction solution was stirred for 2 hours under cooling in an ice bath (ice bath), and then filtered. The obtained solid was dissolved in ethyl acetate (2 L), washed 3 times with water (1 L), dried with sodium sulfate, and then the solvent was distilled off under reduced pressure. The yield was 40.1 g and the yield was 78%. Azobenzene derivative 1.

使1-(4-溴代-丁氧基)-4-硝基苯（20.0 g、73 mmol）、偶氮苯衍生物1（17.7 g、73 mmol）及碳酸鉀（15.1 g、109 mmol）的DMF（200 mL）溶液在60度下反應6小時。將反應混合物冷卻至室溫，添加二氯甲烷（4 L），利用水（2 L）清洗3次，利用硫酸鈉進行乾燥，然後將溶媒減壓餾去而獲得粗體。針對所述粗體，將二氯甲烷用作洗脫液，並利用矽膠管柱色譜法進行純化，以產量30.5 g、產率96%獲得偶氮苯衍生物2。

Make 1-(4-bromo-butoxy)-4-nitrobenzene (20.0 g, 73 mmol), azobenzene derivative 1 (17.7 g, 73 mmol) and potassium carbonate (15.1 g, 109 mmol) The DMF (200 mL) solution was reacted at 60 degrees for 6 hours. The reaction mixture was cooled to room temperature, dichloromethane (4 L) was added, and it was washed with water (2 L) three times, dried with sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. For the bold body, dichloromethane was used as the eluent, and purified by silica gel column chromatography to obtain the azobenzene derivative 2 with a yield of 30.5 g and a yield of 96%.

在偶氮苯衍生物2（29.4 g、67 mmol）的乙醇（60 mL）溶液中添加水（60 mL）及硫化鈉九水合物（97.2 g、405 mmol），並加熱回流2小時。將反應混合物冷卻至室溫，進行減壓濃縮，然後添加乙酸乙酯（3 L），利用水（1 L）清洗3次，利用硫酸鈉進行乾燥，然後將溶媒減壓餾去而獲得粗體。針對所述粗體，將甲苯：乙酸乙酯=3：1的混合溶媒用作洗脫液，並利用矽膠管柱色譜法進行純化，以產量3.9 g、產率15%獲得式（1-2-1）、l=4的化合物。¹ H-NMR（500 MHz,二甲基亞碸（dimethyl sulfoxide，DMSO）-D₆ ）：δ 7.72 (d, J=8.9 Hz, 2H), 7.61 (d, J=8.7 Hz, 2H), 7.05 (d, J=9.0 Hz, 2H), 6.64-6.66 (m, 4H), 6.49 (d, J=8.8 Hz, 2H), 5.97 (br, 2H), 4.59 (br, 2H), 4.09 (t, J=6.2 Hz, 2H), 3.89 (t, J=6.1 Hz, 2H), 1.80-1.87 (m, 4H).

Water (60 mL) and sodium sulfide nonahydrate (97.2 g, 405 mmol) were added to a solution of azobenzene derivative 2 (29.4 g, 67 mmol) in ethanol (60 mL), and heated to reflux for 2 hours. The reaction mixture was cooled to room temperature, concentrated under reduced pressure, then ethyl acetate (3 L) was added, washed with water (1 L) three times, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product . For the bold body, a mixed solvent of toluene: ethyl acetate=3:1 was used as the eluent, and purified by silica gel column chromatography, with a yield of 3.9 g and a yield of 15% to obtain formula (1-2 -1) Compounds with l=4. ¹ H-NMR (500 MHz, dimethyl sulfoxide (DMSO)-D ₆ ): δ 7.72 (d, J=8.9 Hz, 2H), 7.61 (d, J=8.7 Hz, 2H), 7.05 (d, J=9.0 Hz, 2H), 6.64-6.66 (m, 4H), 6.49 (d, J=8.8 Hz, 2H), 5.97 (br, 2H), 4.59 (br, 2H), 4.09 (t, J=6.2 Hz, 2H), 3.89 (t, J=6.1 Hz, 2H), 1.80-1.87 (m, 4H).

使4'-羥基乙醯苯胺（60.0 g、397 mmol）、1,2-二溴乙烷（298 g、1590 mmol）及碳酸鉀（82.3 g、595 mmol）的DMF（600 mL）溶液在80度下反應8小時。將反應混合物冷卻至室溫，添加乙酸乙酯（1.5 L），利用水（1 L）清洗3次，利用硫酸鈉進行乾燥，然後將溶媒減壓餾去而獲得粗體。針對所述粗體，將庚烷：乙酸乙酯=2：3的混合溶媒用作洗脫液，並利用矽膠管柱色譜法進行純化，以產量5.95 g、產率6%獲得1-(2-溴代-乙氧基)-4-乙醯苯胺。[Synthesis Example 2] Synthesis of a compound of formula (1-2-1) and l=2

Make 4'-hydroxyacetaniline (60.0 g, 397 mmol), 1,2-dibromoethane (298 g, 1590 mmol) and potassium carbonate (82.3 g, 595 mmol) in DMF (600 mL) solution in 80 The reaction temperature is 8 hours. The reaction mixture was cooled to room temperature, ethyl acetate (1.5 L) was added, washed with water (1 L) three times, dried with sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude body. For the bold body, a mixed solvent of heptane: ethyl acetate=2:3 was used as the eluent, and purified by silica gel column chromatography, with a yield of 5.95 g and a yield of 6% to obtain 1-(2 -Bromo-ethoxy)-4-acetaniline.

在4-胺基乙醯苯胺（63.8 g、425 mmol）的水（250 mL）溶液中，在冰浴冷卻下（冰浴）添加濃鹽酸（106 mL）。繼而，在所述溶液中，在冰浴冷卻下（冰浴）滴加亞硝酸鈉（29.3 g、425 mmol）的水（90 mL）溶液，然後攪拌30分鐘，製備重氮鹽的水溶液。 一邊對所獲得的重氮鹽的水溶液進行攪拌一邊緩慢地添加於經冰浴冷卻的苯酚（40.0 g、425 mmol）與乙酸鈉（279 g、3400 mmol）的乙醇（20 mL）及水（800 mL）的混合溶液中。將反應溶液在冰浴冷卻下（冰浴）攪拌2小時，然後進行過濾。將所獲得的固體溶解於乙酸乙酯（4 L）中，利用水（2 L）清洗3次，利用硫酸鈉進行乾燥，然後將溶媒減壓餾去，以產量31.2 g、產率29%獲得偶氮苯衍生物3。

To 4-aminoacetaniline (63.8 g, 425 mmol) in water (250 mL), add concentrated hydrochloric acid (106 mL) under ice cooling (ice bath). Then, in the solution, a water (90 mL) solution of sodium nitrite (29.3 g, 425 mmol) was added dropwise under ice cooling (ice bath), and then stirred for 30 minutes to prepare an aqueous solution of diazonium salt. While stirring the obtained diazonium salt aqueous solution, slowly add ethanol (20 mL) and water (800 mL) to phenol (40.0 g, 425 mmol) and sodium acetate (279 g, 3400 mmol) cooled in an ice bath. mL) in the mixed solution. The reaction solution was stirred for 2 hours under cooling in an ice bath (ice bath), and then filtered. The obtained solid was dissolved in ethyl acetate (4 L), washed 3 times with water (2 L), dried with sodium sulfate, and then the solvent was distilled off under reduced pressure. The yield was 31.2 g and the yield was 29%. Azobenzene derivative 3.

使1-(2-溴代-乙氧基)-4-乙醯苯胺（5.95 g、23.1 mmol）、偶氮苯衍生物3（5.30 g、20.8 mmol）及碳酸鉀（4.78 g、34.6 mmol）的DMF（30 mL）溶液在80度下反應4小時。將反應混合物冷卻至室溫，添加水（50 mL），對所析出的固體物進行過濾，以產量8.66 g、產率87%獲得偶氮苯衍生物4。

Make 1-(2-bromo-ethoxy)-4-acetaniline (5.95 g, 23.1 mmol), azobenzene derivative 3 (5.30 g, 20.8 mmol) and potassium carbonate (4.78 g, 34.6 mmol) The DMF (30 mL) solution was reacted at 80 degrees for 4 hours. The reaction mixture was cooled to room temperature, water (50 mL) was added, the precipitated solid was filtered, and the azobenzene derivative 4 was obtained with a yield of 8.66 g and a yield of 87%.

在偶氮苯衍生物4（8.66 g、20.0 mmol）的甲醇（90 mL）與四氫呋喃（Tetrahydrofuran，THF）（210 mL）的混合溶液中添加濃鹽酸（41.7 mL），加熱回流30小時。將反應混合物冷卻至室溫，利用1 mol/L氫氧化鈉水溶液進行鹼性化。對所獲得的固體成分進行過濾而獲得粗體。針對所述粗體，將乙酸乙酯用作洗脫液，並利用矽膠管柱色譜法進行純化，以產量5.08 g、產率73%獲得式（1-2-1）、l=2的化合物。¹ H-NMR（500 MHz, DMSO-D₆ ）：δ 7.73 (d, J=8.9 Hz, 2H), 7.61 (d, J=8.7 Hz, 2H), 7.10 (d, J=9.0 Hz, 2H), 6.70 (d, J=8.7 Hz, 2H), 6.65 (d, J=8.7 Hz, 2H), 6.51 (d, J=8.7 Hz, 2H), 5.97 (br, 2H), 4.63 (br, 2H), 4.32 (t, J=4.4 Hz, 2H), 4.18 (t, J=4.4 Hz, 2H).

Concentrated hydrochloric acid (41.7 mL) was added to a mixed solution of azobenzene derivative 4 (8.66 g, 20.0 mmol) in methanol (90 mL) and tetrahydrofuran (Tetrahydrofuran, THF) (210 mL), and heated to reflux for 30 hours. The reaction mixture was cooled to room temperature and alkalized with a 1 mol/L sodium hydroxide aqueous solution. The obtained solid content was filtered to obtain a bold body. For the bold body, ethyl acetate was used as the eluent and purified by silica gel column chromatography. The compound of formula (1-2-1) and l=2 was obtained with a yield of 5.08 g and a yield of 73%. . ¹ H-NMR (500 MHz, DMSO-D ₆ ): δ 7.73 (d, J=8.9 Hz, 2H), 7.61 (d, J=8.7 Hz, 2H), 7.10 (d, J=9.0 Hz, 2H) , 6.70 (d, J=8.7 Hz, 2H), 6.65 (d, J=8.7 Hz, 2H), 6.51 (d, J=8.7 Hz, 2H), 5.97 (br, 2H), 4.63 (br, 2H) , 4.32 (t, J=4.4 Hz, 2H), 4.18 (t, J=4.4 Hz, 2H).

使4'-羥基乙醯苯胺（60.0 g、397 mmol）、1,4-二溴丁烷（343 g、1590 mmol）及碳酸鉀（82.3 g、595 mmol）的DMF（600 mL）溶液在80度下反應8小時。將反應混合物冷卻至室溫，添加乙酸乙酯（1.5 L），利用水（1 L）清洗3次，利用硫酸鈉進行乾燥，然後將溶媒減壓餾去而獲得粗體。針對所述粗體，將庚烷：乙酸乙酯=2：3的混合溶媒用作洗脫液，並利用矽膠管柱色譜法進行純化，以產量31.9 g、產率28%獲得1-(4-溴代-丁氧基)-4-乙醯苯胺。[Synthesis Example 3] Synthesis of a compound of formula (1-2-4) and l=4

Make 4'-hydroxyacetaniline (60.0 g, 397 mmol), 1,4-dibromobutane (343 g, 1590 mmol) and potassium carbonate (82.3 g, 595 mmol) in DMF (600 mL) solution in 80 The reaction temperature is 8 hours. The reaction mixture was cooled to room temperature, ethyl acetate (1.5 L) was added, washed with water (1 L) three times, dried with sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude body. For the bold body, a mixed solvent of heptane: ethyl acetate=2:3 was used as the eluent, and purified by silica gel column chromatography, with a yield of 31.9 g and a yield of 28% to obtain 1-(4 -Bromo-butoxy)-4-acetaniline.

在4-胺基乙醯苯胺（26.8 g、178 mmol）的水（130 mL）溶液中，在冰浴冷卻下（冰浴）添加濃鹽酸（45 mL）。繼而，在所述溶液中，在冰浴冷卻下（冰浴）滴加亞硝酸鈉（12.3 g、178 mmol）的水（40 mL）溶液，然後攪拌30分鐘，製備重氮鹽的水溶液。 一邊對所獲得的重氮鹽的水溶液進行攪拌一邊緩慢地添加於經冰浴冷卻的2-氟苯酚（20.0 g、178 mmol）與乙酸鈉（117 g、1430 mmol）的乙醇（10 mL）及水（400 mL）的混合溶液中。將反應溶液在冰浴冷卻下（冰浴）攪拌3小時，然後進行過濾，以產量27.9 g、產率57%獲得偶氮苯衍生物5。

To a solution of 4-aminoacetaniline (26.8 g, 178 mmol) in water (130 mL), add concentrated hydrochloric acid (45 mL) under ice cooling (ice bath). Then, in the solution, a water (40 mL) solution of sodium nitrite (12.3 g, 178 mmol) was added dropwise under ice cooling (ice bath), and then stirred for 30 minutes to prepare an aqueous solution of diazonium salt. While stirring the obtained diazonium salt aqueous solution, slowly add ethanol (10 mL) and ice-bath cooled 2-fluorophenol (20.0 g, 178 mmol) and sodium acetate (117 g, 1430 mmol) and In a mixed solution of water (400 mL). The reaction solution was stirred under ice cooling (ice bath) for 3 hours, and then filtered to obtain the azobenzene derivative 5 with a yield of 27.9 g and a yield of 57%.

使1-(4-溴代-丁氧基)-4-乙醯苯胺（20.0 g、69.9 mmol）、偶氮苯衍生物5（19.1 g、69.9 mmol）及碳酸鉀（14.5 g、105 mmol）的DMF（100 mL）溶液在80度下反應4小時。將反應混合物冷卻至室溫，添加水（200 mL），對所析出的固體物進行過濾，以產量29.5 g、產率92%獲得偶氮苯衍生物6。

Make 1-(4-bromo-butoxy)-4-acetaniline (20.0 g, 69.9 mmol), azobenzene derivative 5 (19.1 g, 69.9 mmol) and potassium carbonate (14.5 g, 105 mmol) The DMF (100 mL) solution was reacted at 80 degrees for 4 hours. The reaction mixture was cooled to room temperature, water (200 mL) was added, and the precipitated solid was filtered to obtain an azobenzene derivative 6 with a yield of 29.5 g and a yield of 92%.

在偶氮苯衍生物6（29.5 g、61.6 mmol）的甲醇（300 mL）與THF（740 mL）的混合溶液中添加濃鹽酸（128 mL），加熱回流170小時。將反應混合物冷卻至室溫，利用1 mol/L氫氧化鈉水溶液進行鹼性化。對所獲得的固體成分進行過濾而獲得粗體。針對所述粗體，將乙酸乙酯用作洗脫液，並利用矽膠管柱色譜法進行純化，以產量13.0 g、產率54%獲得式（1-2-4）、l=4的化合物。¹ H-NMR（500 MHz, DMSO-D₆ ）：δ 9.78-10.9 (br, 2H), 7.61 (d, J=8.8 Hz, 2H), 7.60 (s, 1H), 7.55 (m, 1H), 7.31 (m, 1H), 7.29 (dd, J=8.9 Hz, 2H), 7.04 (d, J=8.9 Hz, 2H), 6.66 (d, J=8.8 Hz, 2H), 5.95-6.28 (br, 2H), 4.20 (t, J=5.8 Hz, 2H), 4.07 (t, J=5.9 Hz, 2H), 1.91 (m, 4H).

Concentrated hydrochloric acid (128 mL) was added to a mixed solution of azobenzene derivative 6 (29.5 g, 61.6 mmol) in methanol (300 mL) and THF (740 mL), and heated to reflux for 170 hours. The reaction mixture was cooled to room temperature and alkalized with a 1 mol/L sodium hydroxide aqueous solution. The obtained solid content was filtered to obtain a bold body. For the bold body, ethyl acetate was used as the eluent and purified by silica gel column chromatography. The compound of formula (1-2-4) and l=4 was obtained with a yield of 13.0 g and a yield of 54%. . ¹ H-NMR (500 MHz, DMSO-D ₆ ): δ 9.78-10.9 (br, 2H), 7.61 (d, J=8.8 Hz, 2H), 7.60 (s, 1H), 7.55 (m, 1H), 7.31 (m, 1H), 7.29 (dd, J=8.9 Hz, 2H), 7.04 (d, J=8.9 Hz, 2H), 6.66 (d, J=8.8 Hz, 2H), 5.95-6.28 (br, 2H ), 4.20 (t, J=5.8 Hz, 2H), 4.07 (t, J=5.9 Hz, 2H), 1.91 (m, 4H).

在4-硝基苯胺（55.6 g、403 mmol）的水（330 mL）溶液中，在冰浴冷卻下（冰浴）添加濃鹽酸（100 mL）。繼而，在所述溶液中，在冰浴冷卻下（冰浴）滴加亞硝酸鈉（27.8 g、403 mmol）的水（100 mL）溶液，然後攪拌30分鐘，製備4-硝基苯重氮鹽酸鹽的水溶液。 一邊對所獲得的4-硝基苯重氮鹽酸鹽的水溶液進行攪拌，一邊緩慢地添加於經冰浴冷卻的3-羥基苄醇（50.0 g、403 mmol）與乙酸鈉（264 g、3220 mmol）的乙醇（30 mL）及水（1000 mL）的混合溶液中。將反應溶液在冰浴冷卻下（冰浴）攪拌2小時，然後進行過濾。將所獲得的固體溶解於乙酸乙酯（10 L）中，利用水（5 L）清洗3次，利用硫酸鈉進行乾燥，然後將溶媒減壓餾去，以產量103 g、產率94%獲得偶氮苯衍生物7。[Synthesis Example 4] Synthesis of a compound of formula (1-1-4) and l=4

To a solution of 4-nitroaniline (55.6 g, 403 mmol) in water (330 mL), add concentrated hydrochloric acid (100 mL) under ice cooling (ice bath). Then, in the solution, a solution of sodium nitrite (27.8 g, 403 mmol) in water (100 mL) was added dropwise under ice cooling (ice bath), and then stirred for 30 minutes to prepare 4-nitrobenzene diazonium Aqueous solution of hydrochloride. While stirring the obtained aqueous solution of 4-nitrobenzene diazonium hydrochloride, it was slowly added to 3-hydroxybenzyl alcohol (50.0 g, 403 mmol) and sodium acetate (264 g, 3220) cooled in an ice bath. mmol) in a mixed solution of ethanol (30 mL) and water (1000 mL). The reaction solution was stirred for 2 hours under cooling in an ice bath (ice bath), and then filtered. The obtained solid was dissolved in ethyl acetate (10 L), washed 3 times with water (5 L), dried with sodium sulfate, and then the solvent was distilled off under reduced pressure. The yield was 103 g and the yield was 94%. Azobenzene derivative 7.

使1-(4-溴代-丁氧基)-4-硝基苯（50.0 g、182 mmol）、偶氮苯衍生物7（49.8 g、182 mmol）及碳酸鉀（37.8 g、274 mmol）的DMF（500 mL）溶液在60度下反應6小時。將反應混合物冷卻至室溫，添加乙酸乙酯（5 L），利用水（3 L）清洗3次，利用硫酸鈉進行乾燥，然後將溶媒減壓餾去而獲得粗體。針對所述粗體，將乙酸乙酯用作洗脫液，並利用矽膠管柱色譜法進行純化，以產量26.5 g、產率31%獲得偶氮苯衍生物8。

Make 1-(4-bromo-butoxy)-4-nitrobenzene (50.0 g, 182 mmol), azobenzene derivative 7 (49.8 g, 182 mmol) and potassium carbonate (37.8 g, 274 mmol) The DMF (500 mL) solution was reacted at 60 degrees for 6 hours. The reaction mixture was cooled to room temperature, ethyl acetate (5 L) was added, and it was washed with water (3 L) three times, and dried with sodium sulfate. Then, the solvent was distilled off under reduced pressure to obtain a crude body. For the bold body, ethyl acetate was used as the eluent and purified by silica gel column chromatography to obtain the azobenzene derivative 8 with a yield of 26.5 g and a yield of 31%.

在偶氮苯衍生物8（20.0 g、43 mmol）的乙醇（300 mL）溶液中添加水（100 mL）及硫化鈉九水合物（41.2 g、172 mmol），加熱回流2小時。將反應混合物冷卻至室溫，進行過濾而獲得粗體。針對所述粗體，將甲苯：乙酸乙酯=4：1的混合溶媒用作洗脫液，並利用矽膠管柱色譜法進行純化，以產量1.23 g、產率7%獲得式（1-1-4）、l=4的化合物。¹ H-NMR（500 MHz, DMSO-D₆ ）：δ 7.59 (d, J=8.8 Hz, 2H), 7.53 (d, J=8.9 Hz, 1H), 7.17 (d, J=2.8 Hz, 1H), 6.87 (dd, J=2.7, 8.9 Hz, 1H), 6.63-6.66 (m, 4H), 6.49 (d, J=8.8 Hz, 2H), 5.96 (br, 2H), 5.20 (t, J=5.7 Hz, 1H), 4.99 (d, J=5.7 Hz, 2H), 4.59 (br, 2H), 4.09 (t, J=6.0 Hz, 2H), 3.89 (t, J=6.3 Hz, 2H), 1.82-1.88 (m, 4H).

Add water (100 mL) and sodium sulfide nonahydrate (41.2 g, 172 mmol) to a solution of azobenzene derivative 8 (20.0 g, 43 mmol) in ethanol (300 mL), and heat to reflux for 2 hours. The reaction mixture was cooled to room temperature and filtered to obtain a crude body. For the bold body, a mixed solvent of toluene: ethyl acetate=4:1 was used as the eluent, and purified by silica gel column chromatography, with a yield of 1.23 g and a yield of 7% to obtain formula (1-1 -4) Compounds with l=4. ¹ H-NMR (500 MHz, DMSO-D ₆ ): δ 7.59 (d, J=8.8 Hz, 2H), 7.53 (d, J=8.9 Hz, 1H), 7.17 (d, J=2.8 Hz, 1H) , 6.87 (dd, J=2.7, 8.9 Hz, 1H), 6.63-6.66 (m, 4H), 6.49 (d, J=8.8 Hz, 2H), 5.96 (br, 2H), 5.20 (t, J=5.7 Hz, 1H), 4.99 (d, J=5.7 Hz, 2H), 4.59 (br, 2H), 4.09 (t, J=6.0 Hz, 2H), 3.89 (t, J=6.3 Hz, 2H), 1.82- 1.88 (m, 4H).

＜Preparation of varnish＞ The varnish used in this example was prepared according to the following procedure. Here, the varnish A1 to the varnish A11 prepared in Preparation Example 1 to Preparation Example 11 of the varnish are solutions of polyamide acid obtained by reacting at least one compound having photoreactivity as one of the raw materials. Varnish for blending B1 to Varnish for blending B3 prepared in Preparation Example 12 to Preparation Example 14 is a solution of polyamide acid obtained without using a photoreactive compound in the raw material, and is combined with varnish A1 to varnish Use after blending A11.

[Preparation Example 1 of Varnish] Preparation of Varnish A1 Put 1.665 g of the compound represented by the formula (1-2-1-2) in a 100 mL three-necked flask equipped with a stirring blade and a nitrogen introduction tube, add 17.0 g of N-methyl-2-pyrrolidone and stir . Add 0.175 g of the compound represented by formula (AN-2-1), 0.263 g of the compound represented by formula (AN-1-1), and 0.899 g of formula (AN-4-17) ( m=8) The compound represented by stirring at room temperature for 12 hours. Add 15.0 g of N-Methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone, NMP) and 15.0 g of Butyl Cellosolve (BC), and heat the obtained solution at 70°C Stirring is performed until the weight average molecular weight of the polymer as the solute becomes the desired weight average molecular weight, thereby obtaining a varnish A1 having a weight average molecular weight of the solute of approximately 13,000 and a resin component concentration of 6% by weight.

[Preparation Example 2 of Varnish-Preparation Example 17] Preparation of Varnish A2-Varnish A14, Varnish B1-Varnish B3 Except having changed the compound used as a diamine and a tetracarboxylic dianhydride as shown in Table 1, it carried out similarly to the preparation example 1, and prepared varnish A2-varnish A14 with a resin component concentration of 6 weight%. Except having changed the compound used as a diamine and a tetracarboxylic dianhydride as shown in Table 2, it carried out similarly to the preparation example 1, and prepared varnish B1-varnish B3. In varnish B1 to varnish B3, the conditions of heating and stirring are adjusted so that the weight average molecular weight of the polymer becomes about 50,000. The weight average molecular weight of the produced polymer is shown in Tables 1 and 2 together with the results of Preparation Example 1. In addition, in Table 1, about the preparation examples in which two or more compounds are described as diamines, it means that all of the above-mentioned compounds are combined as diamines, and two or more are described as tetracarboxylic dianhydrides. The preparation example of the compound refers to combining all the compounds described above as tetracarboxylic dianhydride. The value in square brackets indicates the compounding ratio (mol%), and the blank column means that the compound corresponding to the column is not used. The same is true in Table 2 and Table 3.

[Table 1] Varnish preparation example Varnish No. Tetracarboxylic dianhydride Diamines Mw Preparation Example 1 A1 AN-4-17 m=8 [50] AN-1-1 [30] AN-2-1 [20] 1-2-1 l=4 [100] 13,000 Preparation Example 2 A2 AN-4-17 m=4 [50] AN-1-1 [30] AN-2-1 [20] 1-2-1 l=4 [100] 13,400 Preparation Example 3 A3 AN-4-5 [50] AN-1-1 [30] AN-2-1 [20] 1-2-1 l=6 [100] 12,800 Preparation Example 4 A4 AN-4-17 m=8 [50] AN-1-1 [30] AN-2-1 [20] 1-2-1 l=4 [90] DI-13-1 [5] DI-4-13 [5] 14,000 Preparation Example 5 A5 AN-4-17 m=8 [50] AN-1-1 [30] AN-2-1 [20] V-2-1 [100] 12,000 Preparation Example 6 A6 AN-4-17 m=8 [50] AN-1-1 [30] AN-2-1 [20] V-2-1 [54] DI-5-1 m=4 [46] 13,100 Preparation Example 7 A7 AN-4-17 m=8 [50] AN-1-1 [30] AN-2-1 [20] V-2-1 [60] DI-5-1 m=8 [40] 12,800 Preparation Example 8 A8 AN-4-17 m=8 [50] AN-1-1 [30] AN-2-1 [20] V-4-2 [100] 13,800 Preparation Example 9 A9 AN-4-17 m=8 [50] AN-1-1 [30] AN-4-21 [20] 1-2-1 l=2 [65] V-2-1 [35] 13,000 Preparation Example 10 A10 AN-4-17 m=8 [50] AN-1-1 [30] AN-2-1 [20] 1-2-4 l=4 [100] 12,800 Preparation Example 11 A11 AN-4-17 m=8 [55] AN-1-1 [15] AN-4-21 [30] 1-2-4 l=4 [90] DI-5-17 [10] 15,000 Preparation Example 12 A12 AN-4-17 m=4 [70] AN-1-1 [30] 1-1-4 l=4 [100] 9,800 Preparation Example 13 A13 AN-4-17 m=8 [40] AN-4-5 [30] AN-2-1 [30] 1-2-1 l=4 [85] V-2-1 [10] DI-13-1 [5] 13,000 Preparation Example 14 A14 AN-4-17 m=8 [40] AN-4-5 [30] AN-1-1 [40] 1-2-1 l=4 [60] V-4-2 [35] DI-5-28 [5] 12,900

[Table 2] Varnish preparation example Varnish No. Tetracarboxylic dianhydride Diamines Weight average molecular weight Preparation Example 15 B1 AN-2-1 [50] AN-3-2 [50] DI-5-1 m=1 [10] DI-4-1 [40] DI-13-1 [50] 53,000 Preparation Example 16 B2 AN-2-1 [30] AN-3-2 [40] AN-1-1 [30] DI-5-9 [10] DI-13-1 [40] DI-4-18 [50] 55,000 Preparation Example 17 B3 AN-2-1 [30] AN-3-2 [40] AN-1-1 [30] DI-4-1 [10] DI-13-1 [10] DI-4-19 [50] DIH-1-2 m=4 [30] 55,000

[Preparation Example 18 of Varnish] Preparation of Varnish C1 In this preparation example, a two-stage polymerization step is performed to synthesize a block polymer of polyamide acid. (1) The first stage of polymerization steps Add the diamine compound (DI-5-9) (0.226 g), the diamine compound (DI-13-1) (0.910 g), and the diamine compound to a 200 mL three-necked flask equipped with a stirring blade and a nitrogen inlet tube (DI-4-19) (0.308 g) and NMP (20.0 g) and stir. Put tetracarboxylic dianhydride (AN-2-1) (0.665 g), tetracarboxylic dianhydride (AN-3-2) (0.740 g) and NMP (10.0 g) in the solution, at room temperature Continue stirring for 6 hours to obtain the first polyamide acid solution.

(2) The second stage of polymerization steps Put the diamine compound (1-2-1, l=4) (1.28 g), the diamine compound (V-2-1) (0.120 g), and the diamine compound in the flask where the first stage of polymerization was carried out. (DI-13-1) (0.152 g), tetracarboxylic dianhydride (AN-4-17, m=8) (1.38 g), tetracarboxylic dianhydride (AN-2-1) (0.111 g), Tetracarboxylic dianhydride (AN-1-1) (0.112 g) and NMP (34.0 g) were continuously stirred at room temperature for 24 hours to obtain a mixed solution of the first polyamide acid and the second polyamide acid. BC (30.0 g) was added to the reaction solution, and stirring was performed for 8 hours while heating to 60°C to obtain a polyamide block polymer solution having a polymer solid content concentration of 6 wt%. The polyamide block polymer solution was used as varnish C1.

[Preparation Example 19-Preparation Example 22 of Varnish] Preparation of Varnish C2-Varnish C5 Except having changed the compound used as a diamine and a tetracarboxylic dianhydride as shown in Table 3, it carried out similarly to Preparation Example 18, and prepared varnish C2-varnish C5 with a resin component concentration of 6 weight%. The compound used and the formulation ratio are shown in Table 3 together with Preparation Example 18.

[table 3] Varnish preparation example Varnish No. The first stage of aggregation The second stage of aggregation Tetracarboxylic dianhydride Diamines Tetracarboxylic dianhydride Diamines Preparation Example 18 C1 AN-2-1 [30] AN-3-2 [30] DI-5-9 [10] DI-13-1 [30] DI-4-19 [20] AN-4-17 m=8 [30] AN-2-1 [5] AN-1-1 [5] 1-2-1 l=4 [30] V-2-1 [5] DI-13-1 [5] Preparation Example 19 C2 AN-2-1 [30] AN-3-2 [10] AN-1-1 [10] DI-4-1 [5] DI-13-1 [25] DIH-1-2 m=4 [30] AN-4-17 m=8 [30] AN-2-1 [10] AN-1-1 [10] 1-2-1 l=4 [30] V-4-2 [10] DI-13-1 [10] Preparation Example 20 C3 AN-2-1 [30] AN-3-2 [20] DI-4-1 [10] DI-13-1 [20] DI-4-19 [20] AN-4-17 m=8 [30] AN-2-1 [10] AN-1-1 [10] 1-2-1 l=4 [45] DI-13-1 [5] Preparation Example 21 C4 AN-2-1 [30] AN-3-2 [30] DI-4-1 [10] DI-13-1 [20] DI-4-19 [30] AN-4-17 m=8 [20] AN-2-1 [10] AN-1-1 [10] 1-2-4 l=4 [30] DI-13-1 [5] DI-4-13 [5] Preparation Example 22 C5 AN-2-1 [30] AN-3-2 [20] DI-4-1 [10] DI-13-1 [20] DI-4-19 [20] AN-4-17 m=8 [20] AN-2-1 [20] AN-1-1 [10] V-2-1 [40] DI-13-1 [10]

[Example 1] <Preparation of varnish and measurement of AC residual image> The varnish A1 was diluted and stirred to 4% by weight using a NMP/BC mixed solution (NMP/BC=7/3 weight ratio) to prepare an alignment agent 1. The alignment agent 1 was coated on a glass substrate with FFS electrodes and a glass substrate with column spacers by the spinner method. After coating, the substrate is heated at 60°C for 80 seconds to evaporate the solvent, and then the Multi-Light ML-501C/B manufactured by Oxtail Motor (stock) is used from the vertical direction relative to the substrate The linear polarized light of ultraviolet rays is irradiated through the polarizing plate. The exposure energy at this time is measured by using the UIT-150 (photoreceiver: UVD-S365) ultraviolet cumulative light meter manufactured by Ushio Electric Co., Ltd. to become 2.0±0.1 J/cm ^{2 at a wavelength of 365 nm.} Adjust the exposure time. Thereafter, a firing treatment was performed at 220° C. for 30 minutes, thereby forming an alignment film with a film thickness of about 100 nm. Then, these two substrates on which the alignment film is formed are bonded so that the surfaces on which the liquid crystal alignment film is formed face each other, and a gap for injecting the liquid crystal composition is provided between the opposing liquid crystal alignment films. At this time, the polarization directions of the linearly polarized light irradiated to the respective liquid crystal alignment films are made parallel. The positive liquid crystal composition A was injected into these cells to produce a liquid crystal cell (liquid crystal display element) with a cell thickness of 5 μm.

（物性值） 相轉變溫度NI：100.1℃、介電各向異性Δε：5.1、折射率各向異性Δn：0.093、黏度η：25.6 mPa·s.＜Positive liquid crystal composition A＞

(Physical properties) Phase transition temperature NI: 100.1℃, dielectric anisotropy Δε: 5.1, refractive index anisotropy Δn: 0.093, viscosity η: 25.6 mPa·s.

Using the produced liquid crystal cell, AC residual image measurement and contrast measurement were performed in accordance with the evaluation method "AC residual image measurement/contrast measurement". As a result, ΔB was 1.3%, and CR was 3200.

<VHR reliability evaluation> The aligning agent 1 was applied on a glass substrate with an IPS electrode and a glass substrate with a column spacer (column spacer) by a spinner method. After coating, the substrate is heated at 60°C for 80 seconds to evaporate the solvent, and then the Multi-Light ML-501C/B manufactured by Oxtail Motor (stock) is used from the vertical direction relative to the substrate The linear polarized light of ultraviolet rays is irradiated through the polarizing plate. The exposure energy at this time is measured by using the UIT-150 (photoreceiver: UVD-S365) ultraviolet cumulative light meter manufactured by Ushio Electric Co., Ltd. to become 2.0±0.1 J/cm ^{2 at a wavelength of 365 nm.} Adjust the exposure time. Thereafter, a firing treatment was performed at 220° C. for 30 minutes, thereby forming an alignment film with a film thickness of about 100 nm.

Then, the two substrates on which the liquid crystal alignment film is formed are bonded so that the surfaces on which the liquid crystal alignment film is formed face each other, and a gap for injecting the liquid crystal composition is formed between the facing liquid crystal alignment films. At this time, regarding the orientation of the substrate, the polarization directions of the linearly polarized light irradiated to the respective liquid crystal alignment films during the photo-alignment process were parallel to each other. A negative liquid crystal composition A having the following composition was injected into the gap between the bonded substrates to produce a liquid crystal cell (liquid crystal display element) having a cell thickness of 7 μm.

（物性值） 相轉變溫度NI：75.7℃、介電各向異性Δε：-4.1、折射率各向異性Δn：0.101、黏度η：14.5 mPa·s.＜Negative liquid crystal composition A＞

(Physical properties) Phase transition temperature NI: 75.7℃, dielectric anisotropy Δε: -4.1, refractive index anisotropy Δn: 0.101, viscosity η: 14.5 mPa·s.

Using the produced liquid crystal cell, the VHR reliability evaluation was performed in accordance with the evaluation method "Evaluation of Voltage Holding Ratio (VHR) Reliability". As a result, the VHR reduction rate was -4%.

[Example 2] to [Example 7], [Comparative Example 1] to [Comparative Example 3] Except that the varnish described in Table 4 was used instead of varnish 1, the same operation as in Example 1 was performed to prepare alignment agent 2 to alignment agent 7 and comparative alignment agent 1 to comparison alignment agent 3. Using the prepared alignment agent, the same operations as in Example 1 were performed to perform AC residual image measurement, contrast measurement, and VHR reliability evaluation. The results are shown in Table 4 together with the results of Example 1.

[Table 4] Example No. Alignment agent No. Varnish A No. ΔB (%) CR VHR reduction rate (%) Example 1 Orientation agent 1 A1 1.3 3200 -4 Example 2 Orientation agent 2 A2 1.0 3300 -3 Example 3 Orientation agent 3 A9 1.5 3300 -6 Example 4 Alignment agent 4 A10 1.1 3200 -3 Example 5 Alignment agent 5 A11 1.2 3200 -3 Example 6 Orientation agent 6 A12 1.0 3000 -2 Example 7 Orientation agent 7 A14 1.1 3200 -3 Comparative example 1 Comparison aligner 1 A5 1.0 3300 -20 Comparative example 2 Comparison aligner 2 A6 2.5 2900 -4 Comparative example 3 Comparison Alignment Agent 3 A7 2.8 2700 -4

In Examples 1 to 7 in which the compound of the present invention was used, the value of ΔB was small and showed excellent residual image characteristics. In addition, the contrast is also high, showing excellent contrast. Furthermore, the VHR reduction rate was also small, and a liquid crystal display element with high VHR reliability was obtained. On the other hand, in Comparative Example 1 using diaminoazobenzene, ΔB and contrast were the same as those of Examples 1 to 7, but the VHR reduction rate was large, and high VHR reliability could not be obtained. In Comparative Example 2 and Comparative Example 3 in which diaminoazobenzene and diamine having an alkyl chain structure were used in combination, by reducing the ratio of the azobenzene structure, the VHR reduction rate was the same as that of Examples 1 to 7. And improved the reliability of VHR. However, as compared with Example 1 to Example 7, the value of ΔB is large, the contrast becomes low, and excellent residual image characteristics and contrast cannot be obtained.

[Example 8] The varnish A1 and the varnish B1 are blended so that the weight ratio becomes 3:7, and then, the NMP/BC mixed solution (NMP/BC=7/3 weight ratio) is used to dilute and stir to become 4% by weight, thereby The alignment agent 8 was prepared. Using the alignment agent 8, the same operations as in Example 1 were performed to perform AC residual image measurement, contrast measurement, and VHR reliability evaluation.

[Example 9] to [Example 12], [Comparative Example 4] to [Comparative Example 6] The varnish shown in Table 5 was used instead of varnish A1 and varnish B1, and the blending ratio shown in Table 5 was changed, except that the alignment agent 9 to the alignment agent 12 and the comparison alignment agent 4 were prepared in the same manner as in Example 8. ~Comparative alignment agent 6. 3 parts by weight of 1,3-bis(4,5-dihydro-2-oxazolyl)benzene was added to the aligning agent 10 as an additive with respect to the solid content, and this was used in subsequent evaluations. Using the prepared alignment agent, AC residual image measurement, contrast measurement, and VHR reliability evaluation were performed in the same manner as in Example 8. The varnish used, the blending ratio, and the result are shown in Table 5 together with Example 8.

[table 5] Example No. Alignment agent No. Varnish A No. Varnish B No. Blending ratio A: B ΔB (%) CR VHR reduction rate (%) Example 8 Orientation agent 8 A1 B1 3:7 1.2 3500 -1 Example 9 Orientation agent 9 A2 B2 5:5 2.3 3500 -2 Example 10 Alignment agent 10 A3 B3 4:6 2.5 3100 -2 Example 11 Orientation agent 11 A4 B2 2: 8 1.8 3400 -1 Example 12 Orientation agent 12 A13 B1 2: 8 1.9 3500 -2 Comparative example 4 Comparison Alignment Agent 4 A5 B2 3:7 1.7 3500 -10 Comparative example 5 Comparison Alignment Agent 5 A7 B1 3:7 3.1 2500 -2 Comparative example 6 Comparison Alignment Agent 6 A8 B3 3:7 1.5 2300 -1

Among the blended liquid crystal alignment agents, when the liquid crystal alignment agent of the present invention is used, ΔB is also small, showing excellent residual image characteristics. In addition, the contrast is also high, showing excellent contrast. Furthermore, the VHR reduction rate was also small, and a liquid crystal display element with high VHR reliability was obtained. On the other hand, in Comparative Example 4 in which diaminoazobenzene was used instead of the compound of the present invention, the values of ΔB and contrast were shown to be the same. However, although the VHR reduction rate was lower than that of Comparative Example 1 by using the blended type, there was still a 10% reduction, and high VHR reliability could not be obtained. In Comparative Example 5 in which diaminoazobenzene and a diamine having an alkyl chain structure were used in combination, the VHR reduction rate was about the same as the case of using the compound of the present invention, but the value of ΔB was large, the contrast became low, and an afterimage was formed The result of poor characteristics and contrast. In Comparative Example 6 in which the compound represented by formula (V-4-2) was used instead of the compound of the present invention, the VHR reduction rate and the value of ΔB were the same as those in the case of using the compound of the present invention, but the contrast was low. As described above, in a comparative alignment agent that does not use the compound of the present invention, a liquid crystal display element having excellent residual image characteristics, contrast, and high VHR reliability cannot be obtained.

[Example 13]-[Example 16], [Comparative Example 7] Except that the varnish described in Table 6 was used instead of the varnish 1, the same operation as in Example 1 was performed to prepare the alignment agent 13 to the alignment agent 16 and the comparative alignment agent 7. Using the prepared alignment agent, the same operations as in Example 1 were performed to perform AC residual image measurement, contrast measurement, and VHR reliability evaluation. The results are shown in Table 6.

[Table 6] Example No. Alignment agent No. Varnish A No. ΔB (%) CR VHR reduction rate (%) Example 13 Orientation agent 13 C1 2.1 3300 -2 Example 14 Alignment agent 14 C2 1.0 3100 -1 Example 15 Alignment agent 15 C3 1.6 3200 -2 Example 16 Orientation agent 16 C4 1.5 3200 -2 Comparative example 7 Comparison Alignment Agent 7 C5 1.5 3200 -12

Among the block polymers, when the liquid crystal alignment agent of the present invention is used, ΔB is also small and exhibits excellent residual image characteristics. In addition, the contrast is also high, showing excellent contrast. Furthermore, the VHR reduction rate was also small, and a liquid crystal display element with high VHR reliability was obtained. On the other hand, in Comparative Example 7 in which diamino azobenzene was used instead of the compound of the present invention, the values of ΔB and contrast of the same degree were shown. However, the VHR is reduced by 12%, and high VHR reliability cannot be obtained. As described above, in a comparative alignment agent that does not use the compound of the present invention, a liquid crystal display element having excellent residual image characteristics, contrast, and high VHR reliability cannot be obtained.

[Example 17] The alignment agent 1 was coated on a glass substrate by a spinner method. After coating, the substrate was heated at 60° C. for 80 seconds to evaporate the solvent to form an alignment agent film. The substrate is irradiated with linearly polarized light. During the irradiation, a Multi-Light ML-501C/B manufactured by Oxtail Motor Co., Ltd. was used to irradiate linearly polarized light of ultraviolet rays from a vertical direction with respect to the substrate through a polarizing plate. The exposure energy at this time is measured by using the UIT-150 (photoreceiver: UVD-S365) ultraviolet cumulative light meter manufactured by Ushio Electric Co., Ltd., and it becomes 1.0±0.1 J/cm ^{2 at a wavelength of 365 nm.} Adjust the exposure time to proceed. Thereafter, a firing treatment was performed at 220° C. for 30 minutes, thereby forming an alignment film with a film thickness of about 100 nm. A spectroscopic ellipsometer was used to measure the retardation value (Re value) of the substrate at 589 nm. The result is 34 nm.

[Comparative Example 8] and [Comparative Example 9] Except that the alignment agent described in Table 7 was used instead of the alignment agent 1, the same operation as in Example 17 was performed to measure the Re value. The measured values are shown in Table 7 together with the results of Example 17.

[Table 7] Example No. Alignment agent No. Varnish No. Re value (nm) Example 17 Orientation agent 1 A1 34 Comparative example 8 Comparison aligner 1 A5 25 Comparative example 9 Comparison aligner 2 A6 twenty two

Regarding Example 17 using the compound represented by the formula (1-2-1) of the present invention, and Comparative Example 8 using diaminoazobenzene, or using diaminoazobenzene in combination with an alkyl chain structure Compared with Comparative Example 9 of the diamine, the Re value was significantly higher. It can be seen that when importance is attached to obtaining a liquid crystal alignment film with high anisotropy, it is effective to use a compound selected from the group consisting of formula (1-2-1) to formula (1-2-9).

[Example 18] The alignment agent 4 was used as the liquid crystal alignment agent, and the exposure energy at the time of ultraviolet linearly polarized light irradiation was changed, and a liquid crystal cell was prepared according to Example 1, except that the exposure energy was changed. The exposure time is adjusted so that the exposure energy becomes 0.5±0.1 J/cm ² , 1.0±0.1 J/cm ² , and 2.0±0.1 J/cm ² at a wavelength of 365 nm, respectively, to form three liquid crystal cells. Using the three liquid crystal cells, the AC residual image measurement was performed according to Example 1. As a result, when the exposure energy is 0.5±0.1 J/cm ² , 1.0±0.1 J/cm ² , and 2.0±0.1 J/cm ² , ΔB is 1.4%, 1.5%, and 1.1%, respectively.

[Comparative Example 10] Using the comparative alignment agent 1 as the liquid crystal alignment agent, the AC residual image measurement was performed in the same manner as in Example 14. As a result, ΔB was 4.0%, 1.9%, and 1.0% when the exposure energy was 0.5±0.1 J/cm ² , 1.0±0.1 J/cm ² , and 2.0±0.1 J/cm ^{2, respectively.}

The liquid crystal cell of Example 18 showed a sufficiently low ΔB value compared with the liquid crystal cell of Comparative Example 10 ^{even at relatively low exposure energy of 0.5 J/cm 2} and 1.0 J/cm ^{2 and obtained residual image characteristics.} Good liquid crystal cell. It can be seen that when the sensitivity of the liquid crystal alignment agent is important, it is effective to use a compound selected from the group consisting of formula (1-2-4) to formula (1-2-9). [Industrial availability]

If the liquid crystal alignment film formed by using the liquid crystal alignment agent of the present invention is used, a liquid crystal with good residual image characteristics and contrast can be obtained, and even if exposed to strong light for a long time, a liquid crystal with a high voltage retention rate and no degradation in display quality can be obtained Display components. The liquid crystal alignment agent of the present invention can be suitably applied to a lateral electric field type liquid crystal display element. In addition, by using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film with high anisotropy can be obtained, and it can be used in optical compensation materials and the like.

no.

no.

no.

Claims (14)

A liquid crystal alignment agent, comprising at least one polymer, and in the liquid crystal alignment agent, at least one of the polymers is a polymer formed by reacting tetracarboxylic dianhydrides and diamines, and the diamines At least one of is a compound represented by formula (1);

In the formula (1), X is an alkylene group having 1 to 12 carbon atoms, _{and one or more non-adjacent -(CH 2} ) ₂ -of the alkylene group may pass through any of -O- and -NH- Substitution, a to c are each independently an integer of 0 to 2, R ^a and R ^b are each independently a hydrogen atom, formula (P1-1), formula (P1-2), -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , R ^{c is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F,

In formula (P1-1) and formula (P1-2), R ^6a to R ^8a are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane group, a substituted Or an unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl group, R ^6a to R ^8a may be the same as or different from each other, and * represents the bond on the benzene ring in formula (1) Position, in formula (1), a group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary. The liquid crystal alignment agent according to claim 1, wherein at least one of the compounds represented by formula (1) is a compound represented by formula (1-1) or formula (1-2);

In the formula (1-1), X is an alkylene group having 1 to 12 carbon atoms, and one or more non-adjacent _{-(CH 2} ) _{2-of the alkylene group may pass through -O- and -NH-} Either one is substituted, R ¹ and R ² are each independently a hydrogen atom, formula (P1-1) or formula (P1-2), ^{at least one of R 1} and R ² is formula (P1-1) or formula (P1) -2), c is an integer of 0-2, R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F, in formula (1-2), X is carbon number 1 to The alkylene group of 12, the _{non-adjacent one or more of -(CH 2} ) ₂ -of the alkylene group may be substituted by any one of -O- and -NH-, a is an integer of 0-2, R ^{3 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , b is an integer from 0 to 2, and R ^{5 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , c is an integer from 0 to 2, and R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F,

In formula (P1-1) and formula (P1-2), R ^6a to R ^8a are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane group, a substituted Or an unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl group, R ^6a to R ^8a may be the same as or different from each other, and * means that on the benzene ring in formula (1-1) Bonding position: In formula (1-1) and formula (1-2), the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary. The liquid crystal alignment agent according to claim 2, wherein the compound represented by formula (1-1) is selected from the group consisting of formula (1-1-1) to formula (1-1-12) At least one compound represented by the formula;

In formulas (1-1-1) to (1-1-12), R ⁶ is an alkyl group having 1 to 4 carbons, l is an integer of 1 to 10, m is an integer of 1 to 11, and n is 1 An integer of ～12. The liquid crystal alignment agent according to claim 2, wherein the compound represented by formula (1-2) is selected from the group consisting of formula (1-2-1) to formula (1-2-9) At least one compound represented by the formula;

In formula (1-2-1) to formula (1-2-9), l is an integer of 1-10, m is an integer of 1-11, and n is an integer of 1-12. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein all the polymers include at least one compound represented by formula (1) as a raw material. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein at least one polymer does not contain the compound represented by formula (1) as a raw material. A liquid crystal alignment film, which is formed of the liquid crystal alignment agent according to any one of claims 1 to 6. A liquid crystal display element having the liquid crystal alignment film according to claim 7. A method for manufacturing a liquid crystal alignment film includes: coating the liquid crystal alignment agent according to any one of claims 1 to 6 on a substrate; and irradiating the obtained coating film with polarized ultraviolet rays. A compound represented by formula (1);

In the formula (1), X is an alkylene group having 1 to 12 carbon atoms, _{and one or more non-adjacent -(CH 2} ) ₂ -of the alkylene group may pass through any of -O- and -NH- Substitution, a to c are each independently an integer of 0 to 2, R ^a and R ^b are each independently a hydrogen atom, formula (P1-1), formula (P1-2), -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , R ^{c is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F,

In formula (P1-1) and formula (P1-2), R ^6a to R ^8a are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane group, a substituted Or an unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl group, R ^6a to R ^8a may be the same as or different from each other, and * represents the bond on the benzene ring in formula (1) Position, in formula (1), a group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary. The compound according to claim 10, which is represented by formula (1-1) or formula (1-2);

In the formula (1-1), X is an alkylene group having 1 to 12 carbon atoms, and one or more non-adjacent _{-(CH 2} ) _{2-of the alkylene group may pass through -O- and -NH-} Either one is substituted, R ¹ and R ² are each independently a hydrogen atom, formula (P1-1) or formula (P1-2), ^{at least one of R 1} and R ² is formula (P1-1) or formula (P1) -2), c is an integer of 0-2, R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F, in formula (1-2), X is carbon number 1 to The alkylene group of 12, the _{non-adjacent one or more of -(CH 2} ) ₂ -of the alkylene group may be substituted by any one of -O- and -NH-, a is an integer of 0-2, R ^{3 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , b is an integer from 0 to 2, and R ^{5 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , c is an integer from 0 to 2, and R ^{4 is} each independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ or -F,

In formula (P1-1) and formula (P1-2), R ^6a to R ^8a are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkane group, a substituted Or an unsubstituted alkoxycarbonyl group, or a substituted or unsubstituted arylcarbonyl group, R ^6a to R ^8a may be the same as or different from each other, and * means that on the benzene ring in formula (1-1) Bonding position: In formula (1-1) and formula (1-2), the group whose bonding position is not fixed to any carbon atom constituting the ring means that the bonding position on the ring is arbitrary. The compound according to claim 11, wherein the compound represented by formula (1-1) is at least one selected from the group consisting of formula (1-1-1) to formula (1-1-12) Expression

In formulas (1-1-1) to (1-1-12), R ⁶ is an alkyl group having 1 to 4 carbons, l is an integer of 1 to 10, m is an integer of 1 to 11, and n is 1 An integer of ～12. The compound according to claim 11, wherein the compound represented by formula (1-2) is at least one selected from the group consisting of formula (1-2-1) to formula (1-2-9) Expression

In formula (1-2-1) to formula (1-2-9), l is an integer of 1-10, m is an integer of 1-11, and n is an integer of 1-12. A polymer formed by reacting tetracarboxylic dianhydrides and diamines, and in the polymer, the diamines are the compounds described in any one of claim 10 to claim 13 At least one of.