CN114702393A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The invention relates to a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display element. According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for an in-plane-switching-type liquid crystal display element, which is provided with an alignment control ability with high efficiency and has excellent afterimage characteristics, an in-plane-switching-type liquid crystal display element having the substrate, and a compound for providing the same, and more specifically, a novel diamine which can improve reliability without affecting alignment properties by adding a small amount.

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element

This application is a divisional application of a Chinese patent application with an application date of December 20, 2017, an application number of 201780086602.5, and an invention name of "liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element".

technical field

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element for producing a liquid crystal display element having excellent afterimage characteristics.

Background technique

Liquid crystal display elements are known as display devices that are lightweight, thin, and low in power consumption, and in recent years, they have been used for large-scale television applications and the like, and have achieved remarkable development. The liquid crystal display element is configured by sandwiching a liquid crystal layer between, for example, a pair of transparent substrates provided with electrodes. Also, in the liquid crystal display element, an organic film formed of an organic material is used as a liquid crystal aligning film so that the liquid crystal exhibits a desired alignment state between substrates.

That is, the liquid crystal aligning film is a constituent member of the liquid crystal display element, is formed on the surface in contact with the liquid crystal of the substrates sandwiching the liquid crystal, and plays a role of aligning the liquid crystal in a specific direction between the substrates. In addition, the liquid crystal aligning film may be required to control the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a specific direction such as a direction parallel to the substrate. The ability to control the liquid crystal orientation of such a liquid crystal aligning film (hereinafter referred to as orientation control ability) is imparted by subjecting the organic film constituting the liquid crystal aligning film to an orientation treatment.

As an alignment treatment method for a liquid crystal aligning film for imparting alignment control ability, a brushing method is conventionally known. The brushing method refers to the following method: for the organic film of polyvinyl alcohol, polyamide, polyimide, etc. on the substrate, the surface is rubbed (brushed) in a certain direction with a cloth such as cotton, nylon, polyester, etc., Thereby, the liquid crystal is oriented in the rubbing direction (brushing direction). Since this brushing method can easily realize a relatively stable liquid crystal alignment state, it is used in the manufacturing process of a conventional liquid crystal display element. In addition, as the organic film used for the liquid crystal aligning film, a polyimide-based organic film excellent in reliability such as heat resistance and electrical properties was mainly selected.

However, the brushing method of rubbing the surface of a liquid crystal aligning film formed of polyimide or the like has problems of dust generation and static electricity generation. In addition, due to the recent high-definition liquid crystal display elements and unevenness caused by electrodes on the corresponding substrates or switching active elements for liquid crystal driving, the surface of the liquid crystal aligning film cannot be uniformly rubbed with a cloth, and uniform liquid crystal alignment cannot be achieved. .

Therefore, the photo-alignment method has been actively studied as another method of aligning the liquid crystal aligning film without brushing.

There are various methods for the photo-alignment method, and anisotropy is formed in the organic film constituting the liquid crystal aligning film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.

As a main photo-alignment method, a decomposition-type photo-alignment method is known. For example, when a polyimide film is irradiated with polarized ultraviolet rays, anisotropic decomposition is caused by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure. And a liquid crystal is orientated by the polyimide which does not decompose and remains (for example, refer patent document 1).

In addition, photo-crosslinking type and photo-isomerization type photo-alignment methods are also known. For example, by using polyvinyl cinnamate, polarized ultraviolet rays are irradiated to cause a dimerization reaction (crosslinking reaction) of the double bond moieties of the two side chains parallel to the polarized light. Then, the liquid crystal is aligned in the direction perpendicular to the polarization direction (for example, refer to Non-Patent Document 1). In addition, in the case of using a side chain type polymer having an azobenzene in the side chain, polarized ultraviolet rays are irradiated to cause an isomerization reaction of the azobenzene moiety of the side chain parallel to the polarized light, so that the liquid crystal is aligned in the polarization direction. Orientation is performed in the vertical direction (for example, refer to Non-Patent Document 2).

As in the above-mentioned example, in the method of aligning a liquid crystal aligning film by the photo-alignment method, there is no need to perform brushing, and there is no need to worry about the generation of dust and static electricity. Moreover, even if it is a board|substrate of the liquid crystal display element which has unevenness|corrugation on the surface, an orientation process can be performed, and it becomes the orientation process method of the liquid crystal aligning film suitable for an industrial production process.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent No. 3893659

Non-patent literature

Non-Patent Document 1: M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992).

Non-patent document 2: K.Ichimura et al., Chem. Rev. 100, 1847 (2000).

SUMMARY OF THE INVENTION

Invention to solve problem

As described above, compared with the brushing method which has been conventionally used in the industrial field as an alignment treatment method of a liquid crystal display element, the photo-alignment method does not require a step such as a brushing step, and therefore has a significant advantage. Moreover, compared with the brushing method in which the orientation control ability is substantially fixed by brushing, the photo-alignment method can control the orientation control ability by changing the irradiation amount of polarized light. However, in the photo-alignment method, in order to achieve the same level of alignment control ability as in the case of using the brushing method, a large amount of polarized light irradiation may be required, or stable liquid crystal alignment may not be achieved.

For example, in the decomposition-type photo-alignment method described in the aforementioned Patent Document 1, it is necessary to irradiate the polyimide film for 60 minutes with ultraviolet light emitted from a high-pressure mercury lamp with a power of 500 W, etc., and a large amount of ultraviolet irradiation is required for a long time. In addition, in the case of a dimerization type and a photoisomerization type photoalignment method, a large amount of ultraviolet irradiation of about several J (joules) to several tens of J may be required in the same manner. Furthermore, in the case of the photo-crosslinking type and photo-isomerization type photo-alignment method, the thermal stability and photostability of liquid crystal alignment are poor, and therefore, when a liquid crystal display element is produced, there are problems of poor alignment and display afterimage. In particular, in a lateral electric field driven liquid crystal display element, liquid crystal molecules are switched in-plane, so that the liquid crystal orientation shift after liquid crystal driving is likely to occur, and display afterimages caused by AC driving have become a major problem.

Therefore, the photo-alignment method is required to realize efficient alignment treatment and stable liquid crystal alignment, and a liquid crystal aligning film, a liquid crystal aligning agent, and a compound providing the same that can efficiently impart high alignment control ability to the liquid crystal aligning film are sought.

An object of the present invention is to provide a substrate having a liquid crystal aligning film for a transverse electric field driven liquid crystal display element which is efficiently imparted with alignment control ability and excellent in afterimage characteristics, a transverse electric field driven liquid crystal display element having the substrate, and The compound providing it, more specifically, is a novel diamine which can improve reliability without affecting the orientation by adding a small amount.

solution to the problem

The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found the following technical solutions.

1. A liquid crystal aligning agent containing a polymer obtained from a diamine component containing a diamine having a structure represented by the following formula (1), and an organic solvent.

(In formula (1), X is a single bond or a divalent organic group, Y and Z are each independently a divalent organic group containing an alkylene group, and R ¹ and R ² are each independently a monovalent organic group , R ³ is an alkyl group having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4.)

2. The liquid crystal aligning agent according to the above 1, which contains at least one polymer selected from the group consisting of a polyimide precursor and an imide thereof, that is, a polyimide, and an organic solvent, wherein the The polyimide precursor is a polymer containing the diamine component of the above-mentioned diamine and tetracarboxylic dianhydride.

3. The liquid crystal aligning agent of said 1 or 2 whose said diamine is represented by following formula (2).

(In the formula (2), the definitions of X, Y, Z, R ¹ to R ³ , m and n are the same as those of the above formula (1).)

4. The liquid crystal aligning agent in any one of said 1-3 whose said polyimide precursor is represented by following formula (3).

(In formula (3), X ¹ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ¹ is a divalent organic group derived from a diamine including the structure of formula (1), and R ¹¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms.)

5. The liquid crystal aligning agent according to 4 above, wherein, in the formula (3), the structure of X ¹ is at least 1 selected from the group consisting of the following structural formulae (A-1) to (A-21). kind.

6. The liquid crystal aligning agent of said 4 or 5 which contains the polymer which has a structural unit represented by the said formula (3) in 10 mol% or more with respect to the whole polymer contained in a liquid crystal aligning agent.

7. The liquid crystal aligning agent according to any one of 4 to 6 above, wherein the organic solvent contains a compound selected from the group consisting of 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether. At least 1 of the group.

8. A method for producing a substrate having a liquid crystal aligning film for a transverse electric field-driven liquid crystal display element, comprising the steps of:

Step [I], applying the composition according to any one of the above 1 to 7 on a substrate having a conductive film for driving a transverse electric field to form a coating film;

Step [II], irradiating polarized ultraviolet rays to the coating film obtained in [I]; and

In step [III], the coating film obtained in [II] is heated.

9. A board|substrate which has a liquid crystal aligning film for transverse electric field drive type liquid crystal display elements manufactured by the method as described in said 8.

10. A lateral electric field driven liquid crystal display element comprising the substrate according to 9 above.

11. A method for producing a transverse electric field driven liquid crystal display element, comprising the following steps to obtain the liquid crystal display element:

The process of preparing the substrate described in 9 above, that is, the first substrate;

The process of obtaining the 2nd board|substrate which has a liquid crystal aligning film by including the following process [I'], process [II'], and process [III'] to obtain the said liquid crystal aligning film provided with the orientation control ability; and

In step [IV], a liquid crystal display element is obtained by arranging the first substrate and the second substrate to face each other so that the liquid crystal aligning films of the first substrate and the second substrate are opposed to each other with the liquid crystal interposed therebetween,

The step [I'], step [II'], and step [III'] are:

Step [I'], coating the composition according to claims 1 to 7 on the second substrate to form a coating film;

Step [II'], irradiating polarized ultraviolet rays to the coating film obtained in [I'];

In step [III'], the coating film obtained in [II'] is heated.

12. A lateral electric field driven liquid crystal display element manufactured by the method described in 11 above.

13. A polymer, which is at least one polymer selected from the group consisting of a polyimide precursor and an imide thereof, that is, a polyimide, the polyimide precursor containing A polymer of a diamine component of a diamine having a structure represented by the following formula (1) and a tetracarboxylic dianhydride,

(In formula (1), X is a single bond or a divalent organic group, Y and Z are each independently a divalent organic group containing an alkylene group, and R ¹ and R ² are each independently a monovalent organic group , R ³ is an alkyl group having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4.)

14. The polymer according to 13 above, wherein the diamine is represented by the following formula (2).

(In the formula (2), the definitions of X, Y, Z, R ¹ to R ³ , m and n are the same as those of the above formula (1).)

15. The polymer according to 13 or 14 above, wherein the polyimide precursor is represented by the following formula (3).

(In formula (3), X ¹ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ¹ is a divalent organic group derived from a diamine including the structure of formula (1), and R ¹¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms.)

16. The polymer according to 15 above, wherein, in the formula (3), the structure of X ¹ is at least one selected from the group consisting of the following structural formulae (A-1) to (A-21). .

17. A diamine represented by the above formula (2).

effect of invention

According to the present invention, it is possible to provide a substrate having a liquid crystal aligning film for a transverse electric field driven liquid crystal display element which is efficiently imparted with alignment control ability and excellent in afterimage characteristics, and a transverse electric field driven liquid crystal display element including the substrate.

The lateral electric field-driven liquid crystal display element manufactured by the method of the present invention is efficiently provided with orientation control capability, and therefore, display characteristics are not impaired even when continuously driven for a long time.

The polymer composition used in the production method of the present invention has a photosensitive main chain type polymer (hereinafter also referred to as a main chain type polymer) capable of exhibiting self-assembly ability, and the coating film obtained using the polymer composition has A film of a photosensitive main-chain polymer capable of exhibiting self-assembly ability. The coating film was not subjected to a brushing treatment, but was subjected to an orientation treatment by irradiation with polarized light. And it becomes a coating film (henceforth a liquid crystal aligning film) provided with the orientation control ability after the process of heating this main chain type polymer film after polarized light irradiation. At this time, the minute anisotropy expressed by polarized light irradiation becomes a driving force, and the main chain polymer itself is effectively reoriented by self-assembly. As a result, as a liquid crystal aligning film, the liquid crystal aligning film which implement|achieves efficient orientation process, and is provided with the high orientation control ability can be obtained.

Detailed ways

Hereinafter, embodiments of the present invention will be described in detail.

The liquid crystal aligning agent of this invention is a liquid crystal aligning agent containing the polymer (henceforth a specific polymer, main chain type polymer) obtained from the diamine component containing the diamine which has a structure represented by following formula (1) . Hereinafter, each condition will be described in detail.

<Diamine with specific structure>

The liquid crystal aligning agent of this invention is a liquid crystal aligning agent containing the polymer obtained from the diamine (this invention also calls specific diamine) which has a structure of following formula (1), and an organic solvent.

(In formula (1), X is a single bond or a divalent organic group, Y and Z are each independently a divalent organic group containing an alkylene group, and R ¹ and R ² are each independently a monovalent organic group , R ³ is an alkyl group having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4.)

Examples of the monovalent organic group here include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, or a fluoroalkane group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. Oxygen. Among them, as the monovalent organic group, a methyl group is preferable.

Examples of the divalent organic group include benzene, naphthalene, cyclohexyl, and groups in which hydrogen atoms of these groups are substituted with a monovalent organic group. Among them, as the divalent organic group, benzene is preferable.

Examples of the divalent organic group containing an alkylene group include an alkylene group, a group composed of an alkylene group and an ether bond, a group composed of an alkylene group and an ester bond, a group composed of part or all of hydrogen atoms A group composed of a halogen-substituted alkylene group and an ether bond, a group composed of an alkylene group in which some or all of the hydrogen atoms are substituted with a halogen, and an ester bond. Among them, as the divalent organic group containing an alkylene group, an alkylene group and a group composed of an alkylene group and an ether bond are preferable. The number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 10 or less.

In addition, when the total number of carbon atoms and the number of oxygen atoms related to the length of the main chain is an even number in the total number of atoms of Y and Z, the linearity of the obtained polymer is increased, and as a result, the linearity of the obtained polymer is increased in the heating step after polarized light irradiation. It is preferable that a liquid crystal aligning film to which a high orientation control ability is provided can be obtained by reorienting in an orderly manner.

As R ³ , a methyl group and an ethyl group are preferable, and a methyl group is more preferable from the viewpoint of the easiness of the reaction during polymerization.

As m and n, 0 is preferable from the viewpoint that the steric hindrance is small, the phenyl groups are easily overlapped with each other, and the reorientation proceeds in a more orderly manner.

As said diamine, the diamine represented by following formula (2) is preferable.

(In the formula (2), the definitions of X, Y, Z, R ¹ to R ³ , m and n are the same as those of the above formula (1).)

As a specific example of the diamine which has the structure of the said formula (2), the following examples are given, but it is not limited to these.

<Synthesis method of specific diamine>

The method of synthesizing the above-mentioned specific diamine is not particularly limited. For example, the method of converting the nitro group which it has into an amino group by a reduction reaction using a nitro compound represented by following formula (5) is mentioned.

The catalyst used in the above-mentioned reduction reaction is preferably a commercially available activated carbon-supported metal, and examples thereof include palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon, and the like. In addition, palladium hydroxide, platinum oxide, Raney nickel, iron, zinc, tin, etc. may be used, and it is not necessary to be an activated carbon-supported metal catalyst. Iron, zinc, and tin, which are generally widely used, are preferred because good results are obtained.

In order to advance the reduction reaction more efficiently, the reaction may be carried out in the coexistence of activated carbon. In this case, the amount of activated carbon to be used is not particularly limited, but is preferably in the range of 1 to 30 mass %, more preferably 10 to 20 mass %, relative to the dinitro compound X1. For the same reason, the reaction may also be carried out under pressure. At this time, in order to avoid reduction of the benzene nucleus, it is carried out in a pressurized range of at most 20 atmospheres. The reaction is preferably carried out in the range of up to 10 atmospheres. If necessary, an acid catalyst may be added in order to shorten the time.

The solvent can be used without limitation as long as it does not react with each raw material. For example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxane, etc.); aliphatic hydrocarbons can be used (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); halogens Hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.); lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, etc.); protic solvent polar organic solvent (methanol, ethanol, H ₂ O, etc.), etc. These solvents can be appropriately selected in consideration of the ease of occurrence of the reaction and the like, and may be used alone or in combination of two or more. If necessary, the solvent may be dried using an appropriate dehydrating agent or desiccant to be used as a non-aqueous solvent.

The amount of the solvent to be used (reaction concentration) is not particularly limited, but is 0.1 to 100 times by mass relative to the nitro compound. Preferably it is 0.5-30 mass times, More preferably, it is 1-10 mass times.

The reaction temperature is not particularly limited, but is in the range from -100°C to the boiling point of the solvent to be used, and preferably -50 to 150°C. The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.

[Manufacturing method of formula (5)]

The method for synthesizing the compound of formula (5) is not particularly limited, and for example, a method of synthesizing by reacting a nitrobenzene derivative having a leaving group X represented by the following formula (7) with a commercially available methylamine solution can be mentioned. . As a preferable leaving group X, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonate group (-OTs), a mesylate group (-OMs), etc. are mentioned.

Regarding the amount of the reaction substrate, 1 to 20 equivalents of methylamine can be used relative to 1 equivalent of the compound represented by the general formula (7).

When a solvent is used, the solvent to be used is not particularly limited as long as it does not inhibit the progress of the reaction. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; and cyclohexane. Alicyclic hydrocarbons such as alkane; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloromethane Aliphatic halogenated hydrocarbons such as ethane, trichloroethylene and tetrachloroethylene; ethers such as diethyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, etc.; Ethyl acetate, ethyl propionate and other esters; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amides; triethylamine, tributyl Amines such as amine and N,N-dimethylaniline; pyridines such as pyridine and picoline; acetonitrile and dimethyl sulfoxide, etc. These solvents may be used alone, or two or more of them may be used in combination.

It is not necessary to necessarily add a base, but when a base is used, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkalis such as sodium carbonate and potassium carbonate can be used in an amount of 1 to 4 equivalents relative to the compound represented by the general formula (7). Metal carbonate, alkali metal bicarbonate such as sodium bicarbonate, potassium bicarbonate, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, 4-(dimethylamino)pyridine, imidazole, 1 , 8-diazabicyclo[5,4,0]-7-undecene and other organic bases, etc.

The reaction temperature can be set to any temperature from -60°C to the reflux temperature of the reaction mixture, and the reaction time can be set arbitrarily within the range of 5 minutes to 100 hours, although it varies depending on the concentration of the reaction substrate and the reaction temperature.

Generally, it is preferable to use, for example, 1 to 20 equivalents of methylamine, 1 to 4 equivalents of potassium carbonate, triethylamine, pyridine, 4- In the presence of a base such as (dimethylamino)pyridine, without using a solvent or using a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, etc., in the range of 0°C to the reflux temperature of these solvents The reaction is carried out for 10 minutes to 24 hours.

[Manufacturing method of formula (7)]

The method for synthesizing the compound of the formula (7) is not particularly limited, and for example, a method of synthesizing by reacting a nitrobenzene derivative having a hydroxyl group represented by the following formula (8) with commercially available methanesulfonyl chloride is exemplified. From the viewpoint of ease of synthesis, the leaving group X is preferably a mesylate group (-OMs), and other preferable leaving groups X include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, p-toluenesulfonate groups (-OTs), etc.

Regarding the amount of the reaction substrate, 1 to 4 equivalents of methanesulfonyl chloride can be used relative to 1 equivalent of the compound represented by the formula (8).

When a solvent is used, the solvent to be used is not particularly limited as long as it does not inhibit the progress of the reaction. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; and cyclohexane. Alicyclic hydrocarbons such as alkane; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloromethane Aliphatic halogenated hydrocarbons such as ethane, trichloroethylene and tetrachloroethylene; ethers such as diethyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, etc.; Ethyl acetate, ethyl propionate and other esters; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amides; triethylamine, tributyl Amines such as amine and N,N-dimethylaniline; pyridines such as pyridine and picoline; acetonitrile and dimethyl sulfoxide, etc. These solvents may be used alone, or two or more of them may be used in combination.

It is not necessary to necessarily add a base, but when a base is used, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and bases such as sodium carbonate and potassium carbonate can be used in an amount of 1 to 4 equivalents relative to the compound represented by the general formula (8). Metal carbonate, alkali metal bicarbonate such as sodium bicarbonate, potassium bicarbonate, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, 4-(dimethylamino)pyridine, imidazole, 1 , 8-diazabicyclo[5,4,0]-7-undecene and other organic bases, etc.

The reaction temperature can be set arbitrarily within the range of -60°C to 25°C, and the reaction time can be arbitrarily set within the range of 5 minutes to 100 hours, although it varies depending on the concentration of the reaction substrate and the reaction temperature.

Generally, it is preferable to use, for example, 1 to 4 equivalents of methanesulfonyl chloride, 1 to 4 equivalents of potassium carbonate, triethylamine, pyridine, 4- In the presence of a base such as (dimethylamino)pyridine, without using a solvent or using a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, and 1,4-dioxane, 10 was carried out in the range of 0°C to 10°C for 10 minutes to 24 hours.

[Manufacturing method of formula (8)]

The method for synthesizing the compound of the formula (8) is not particularly limited. For example, a commercially available phenol derivative (9) can be reacted with a nitrobenzene derivative having a leaving group represented by the following formula (10). synthetic method. As a preferable leaving group X, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonate group (-OTs), a mesylate group (-OMs), etc. are mentioned.

Regarding the amount of the reaction substrate, 1 to 4 equivalents of the compound represented by the formula (10) can be used relative to 1 equivalent of the compound represented by the formula (9).

When a solvent is used, the solvent to be used is not particularly limited as long as it does not inhibit the progress of the reaction. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; and cyclohexane. Alicyclic hydrocarbons such as alkane; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloromethane Aliphatic halogenated hydrocarbons such as ethane, trichloroethylene and tetrachloroethylene; ethers such as diethyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, etc.; Ethyl acetate, ethyl propionate and other esters; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amides; triethylamine, tributyl Amines such as amine and N,N-dimethylaniline; pyridines such as pyridine and picoline; acetonitrile and dimethyl sulfoxide, etc. These solvents may be used alone, or two or more of them may be used in combination.

It is not necessary to add a base, but when a base is used, for example, 1 to 4 equivalents of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and bases such as sodium carbonate and potassium carbonate can be used relative to the compound represented by the general formula (10). Metal carbonate, alkali metal bicarbonate such as sodium bicarbonate, potassium bicarbonate, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, 4-(dimethylamino)pyridine, imidazole, 1 , 8-diazabicyclo[5,4,0]-7-undecene and other organic bases, etc.

The reaction temperature can be set to any temperature from -60°C to the reflux temperature of the reaction mixture, and the reaction time can be set arbitrarily within the range of 5 minutes to 100 hours, although it varies depending on the concentration of the reaction substrate and the reaction temperature.

Generally, it is preferable to use, for example, 1 to 4 equivalents of the compound represented by the formula (9) and, if necessary, 1 to 4 equivalents of potassium carbonate, triethylamine, In the presence of a base such as pyridine, 4-(dimethylamino)pyridine, or a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, or the like, refluxing of these solvents at 0°C to The reaction is carried out for 10 minutes to 24 hours within the temperature range.

＜Polymer＞

The polymer of the present invention is a polymer obtained by using the above-mentioned diamine. Specific examples include polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide, and the like, and from the viewpoint of use as a liquid crystal aligning agent, it is more preferable to be selected from the group consisting of the following formula (3) The polyimide precursor of the shown structural unit, and its imide compound are at least 1 type of polyimide.

In the above formula (3), X ¹ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ¹ is a divalent organic group derived from a diamine including the structure of the formula (1), and R ¹¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms. From the viewpoint of ease of imidization by heating, R ¹¹ is preferably a hydrogen atom, a methyl group, or an ethyl group. As R ³ , a methyl group is preferable from the viewpoint of the easiness of the reaction during polymerization.

<Tetracarboxylic dianhydride>

X ¹ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. In addition, X ¹ in the polyimide precursor can be determined by the solubility of the polymer in the solvent, the applicability of the liquid crystal aligning agent, the orientation of the liquid crystal when the liquid crystal aligning film is formed, the voltage retention rate, the accumulated charge, etc. The degree of desired properties may be appropriately selected, and one type may be used in the same polymer, or two or more types may be mixed.

Unless specific examples of X ¹ are shown, the structures of formulae (X-1) to (X-46) described in International Publication No. 2015/119168, pages 13 to 14, and the like can be mentioned.

Preferred structures of X ¹ are shown below, but the present invention is not limited to these structures.

Among the above-mentioned structures, (A-1), (A-2), and (A-4) are preferable, and (A-1) is particularly preferable from the viewpoint of photo-alignment properties.

＜Diamine＞

In formula (3), as a specific example of ^Y1 , the structure obtained by removing an amino group and an alkylamino group from the diamine which has the structure of the said formula (1) is mentioned. Among them, Y ¹ is particularly preferably a structure obtained by removing an amino group and an alkylamino group from the structure of the above formula (2).

<Polymer (other structural unit)>

The polyimide precursor containing the structural unit represented by the formula (3) may contain a structural unit selected from the group consisting of the structural unit represented by the following formula (4) and an imide thereof, that is, a polyimide, within a range that does not impair the effects of the present invention. At least one of imides.

In formula (4), X ² is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ² is a divalent organic group derived from a diamine that does not contain the structure of formula (1) in the main chain direction, R ¹² is the same as that of R ¹¹ in the formula (3).

Specific examples of X ² include the same structures as those listed for X ¹ in formula (6) including preferred examples. Moreover, ^Y2 in a polyimide precursor is a divalent organic group derived from the diamine which does not contain the structure of formula (1) in the main chain direction. Its structure is not particularly limited. In addition, Y ² can be appropriately selected according to the solubility of the polymer in the solvent, the applicability of the liquid crystal aligning agent, the orientation of the liquid crystal when the liquid crystal aligning film is formed, the voltage retention rate, the degree of the accumulated charge and other desired properties. , may be one kind in the same polymer, or two or more kinds may be mixed.

Unless specific examples of Y ² are shown, the structure of formula (2) described on page 4 of International Publication No. 2015/119168 and the formula (Y-1)-( Structures of Y-97), (Y-101) to (Y-118); a divalent organic group obtained by removing two amino groups from the formula (2) described in International Publication No. 2013/008906 on page 6; from A divalent organic group obtained by removing two amino groups from the formula (1) described in International Publication No. 2015/122413 on page 8; the structure of formula (3) described in International Publication No. 2015/060360 on page 8; from Japan A divalent organic group obtained by removing two amino groups from the formula (1) described in the Laid-Open Patent Publication No. 2012-173514 on page 8; formulas (A) to (F) described on the page 9 of the International Publication No. 2010-050523 A divalent organic group obtained by removing two amino groups from

As a preferable structure of ^Y2 , the structure of following formula (11) is mentioned.

In formula (11), R ³² is a single bond or a divalent organic group, preferably a single bond.

R ³³ is a structure represented by -(CH ₂ ) _r -. r is an integer of 2-10, Preferably it is 3-7. In addition, any _-CH2- is optionally replaced by ether, ester, amide, urea, urethane linkages under the condition that they are not adjacent to each other.

R ³⁴ is a single bond or a divalent organic group.

Any hydrogen atom on the benzene ring is optionally substituted with a monovalent organic group, preferably a fluorine atom or a methyl group.

Specific examples of the structure represented by the formula (11) include, but are not limited to, the following structures.

Among them, from the viewpoint of not inhibiting the reorientation of at least one selected from the group consisting of a polyimide precursor including a structural unit represented by formula (3) and an imide thereof, that is, a polyimide, it is preferable to include a specific The benzene ring-Y-benzene ring moiety of the diamine (2) has the same partial structure.

When the polyimide precursor containing the structural unit represented by the formula (3) also contains the structural unit represented by the formula (4), the liquid crystal alignment may be further improved when the structural unit represented by the formula (3) is small. The reason is that since R ₂₁ in the formula (3) is an alkyl group, imidization does not occur during heating, and the alignment ability of liquid crystal molecules decreases. Therefore, the structural unit represented by the formula (3) is preferably 1 to 70 mol %, more preferably 5 to 50 mol %, and particularly preferably 10 to 30 mol % relative to the sum of the formula (3) and the formula (4).

The molecular weight of the polyimide precursor used in the present invention is preferably 2,000 to 500,000 in terms of weight average molecular weight, more preferably 5,000 to 300,000, and even more preferably 10,000 to 100,000.

As a polyimide which has a divalent group represented by Formula (1) in a main chain, the polyimide obtained by ring-closing the above-mentioned polyimide precursor is mentioned. In this polyimide, the ring closure rate (also referred to as imidization rate) of the amic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted according to the use and purpose.

As a method of imidizing the polyimide precursor, thermal imidization in which the solution of the polyimide precursor is directly heated, or adding to the solution of the polyimide precursor can be mentioned. Catalytic imidization of catalysts.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention contains the polymer (specific polymer) obtained from the diamine component containing the diamine which has a structure represented by Formula (1), but may contain it in the limit which the effect as described in this invention is exhibited. Two or more specific polymers with different structures. In addition to the specific polymer, another polymer, that is, a polymer not having a divalent group represented by formula (1) may be contained. Examples of other polymer types include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal, and polyphenylene. Ethylene or its derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like. When the liquid crystal aligning agent of this invention contains another polymer, it is preferable that the ratio of a specific polymer with respect to all polymer components is 5 mass % or more, and 5-95 mass % is mentioned as an example.

A liquid crystal aligning agent is used for preparing a liquid crystal aligning film, and the form of a coating liquid is generally employ|adopted from a viewpoint of forming a uniform thin film. It is also preferable that the liquid crystal aligning agent of this invention is a coating liquid containing the above-mentioned polymer component and the organic solvent which can melt|dissolve this polymer component. At this time, the concentration of the polymer in the liquid crystal aligning agent can be appropriately changed according to the setting of the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by mass or more, and from the viewpoint of the storage stability of the solution, it is preferably 10% by mass or less. A particularly preferable concentration of the polymer is 2 to 8 mass %.

The organic solvent contained in a liquid crystal aligning agent will not be specifically limited if it is an organic solvent in which a polymer component can be melt|dissolved uniformly. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, Methyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, etc. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferably used.

Moreover, as for the organic solvent contained in a liquid crystal aligning agent, the mixed solvent which used together the solvent which can improve the coating property at the time of coating a liquid crystal aligning agent, and the surface smoothness of a coating film is usually used in addition to the said solvent, this invention It is also preferable to use such a mixed solvent in the liquid crystal aligning agent of . Specific examples of the organic solvent used in combination are listed below, but are not limited to these examples.

For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1- Butanol, isoamyl alcohol, tert-amyl alcohol, 3-methyl-2-butanol, neopentanol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1 -Methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol , 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl -1,3-Hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether , 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, Diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl Acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2 -(Methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, furfuryl alcohol, diethylene glycol, Propylene Glycol, Propylene Glycol Monobutyl Ether, 1-(Butoxyethoxy) Propanol, Propylene Glycol Monomethyl Ether Acetate, Dipropylene Glycol, Dipropylene Glycol Monomethyl Ether, Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Di Methyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetic acid ester, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, Diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol Monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethyl Oxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionate propyl, 3-methoxypropionate, 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate , isoamyl lactate, solvents represented by the following formulae [D-1] to [D-3], and the like.

In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms.

Among them, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propanediol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl- 2-pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether. The kind and content of such a solvent can be appropriately selected according to the coating apparatus of the liquid crystal aligning agent, coating conditions, coating environment, and the like.

The liquid crystal aligning agent of this invention may additionally contain components other than a polymer component and an organic solvent in the range which does not impair the effect of this invention. As such an additional component, the adhesive agent for improving the adhesiveness of a liquid crystal aligning film and a board|substrate, the adhesiveness of a liquid crystal aligning film and a sealing material, and the crosslinking for improving the intensity|strength of a liquid crystal aligning film are mentioned. agent; used to adjust the dielectric constant and resistance of the liquid crystal aligning film, dielectric or conductive substances, etc. Specific examples of these additional components include various components disclosed in known documents about liquid crystal aligning agents, and if an example of these is not necessarily shown, pages 53 [0105] to 53 of Pamphlet No. 2015/060357 can be cited. The ingredients disclosed in [0116] on page 55, etc.

<The manufacturing method of the board|substrate which has a liquid crystal aligning film> and the <the manufacturing method of the liquid crystal display element>

The manufacturing method of the board|substrate with a liquid crystal aligning film of this invention is equipped with the following process:

In step [I], a polymer containing (A) a diamine component containing a diamine having a structure represented by formula (1) and (B) an organic solvent are coated on a substrate having a conductive film for lateral electric field driving the polymer composition to form a coating film;

Step [II], irradiating polarized ultraviolet rays to the coating film obtained in [I]; and

In step [III], the coating film obtained in [II] is heated.

By the said process, the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements provided with the orientation control ability can be obtained, and the board|substrate which has this liquid crystal aligning film can be obtained.

In addition to the above-obtained substrate (first substrate), a second substrate is prepared, whereby a lateral electric field-driven liquid crystal display element can be obtained.

The second substrate uses the above-mentioned steps [I] to [III] (due to the use of the conductive film without the transverse electric field driving) by using the substrate without the transverse electric field driving conductive film instead of the substrate with the transverse electric field driving conductive film. Therefore, in this application, it may be abbreviated as process [I'] - [III']) for convenience, and the 2nd board|substrate which has the liquid crystal aligning film provided with the orientation control ability can be obtained.

A method for manufacturing a lateral electric field driven liquid crystal display element includes:

In step [IV], a liquid crystal display element is obtained by arranging the first substrate and the second substrate obtained above so that the liquid crystal aligning films of the first substrate and the second substrate face each other with the liquid crystal interposed therebetween. In this way, a lateral electric field-driven liquid crystal display element can be obtained.

Hereinafter, each step of [I] to [III] and [IV] included in the production method of the present invention will be described.

<Process [I]>

In step [I], a polymer composition containing a photosensitive main chain type polymer and an organic solvent is applied on the substrate having the conductive film for lateral electric field driving to form a coating film.

＜Substrate＞

The substrate is not particularly limited, but when the liquid crystal display element to be manufactured is a transmissive type, it is preferable to use a substrate with high transparency. In this case, it does not specifically limit, A glass substrate, or a plastic substrate, such as an acrylic substrate, a polycarbonate substrate, etc. can be used.

In addition, in consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used.

<Conductive film for transverse electric field drive>

The substrate has a conductive film for lateral electric field driving.

Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide: Indium Tin Oxide), IZO (Indium Zinc Oxide: Indium Zinc Oxide), etc. when the liquid crystal display element is a transmission type.

Moreover, in the case of a reflection type liquid crystal display element, although the material etc. which reflect light, such as aluminum, are mentioned as a conductive film, it is not limited to these.

A conventionally known method can be used for the method of forming the conductive film on the substrate.

The method of applying the above-mentioned polymer composition to the substrate having the conductive film for lateral electric field driving is not particularly limited.

The coating method is generally carried out by screen printing, offset printing, flexographic printing, or inkjet method in industry. As another coating method, there are a dip method, a roll coating method, a slit coating method, a spin coating method (spin coating method), a spray coating method, and the like, and these methods can be used according to the purpose.

After coating the polymer composition on the substrate having the conductive film for lateral electric field driving, it can be heated at 50 to 300° C., preferably 50 to 180° C., by heating means such as a hot plate, a thermal cycle type oven, or an IR (infrared) type oven. The solvent was evaporated to obtain a coating film. From the viewpoint of the stability of liquid crystal alignment, the drying temperature at this time is preferably lower than that in step [III].

When the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when it is too thin, the reliability of the liquid crystal display element may decrease, so it is preferably 5 nm to 300 nm, and more preferably 10 nm to 150 nm.

In addition, after the process [I] and before the next process [II], you may provide the process of cooling the board|substrate on which the coating film was formed to room temperature.

<Process [II]>

In step [II], polarized ultraviolet rays are irradiated to the coating film obtained in step [I]. When irradiating polarized ultraviolet rays to the film surface of the coating film, polarized ultraviolet rays are irradiated to the substrate through a polarizing plate from a specific direction. As the ultraviolet ray to be used, an ultraviolet ray having a wavelength in the range of 100 nm to 400 nm can be used. It is preferable to select the optimum wavelength by a filter etc. according to the kind of coating film used. In addition, for example, in order to selectively induce a photolysis reaction, ultraviolet rays within a wavelength range of 240 nm to 400 nm can be selected and used. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp or a metal halide lamp can be used.

The irradiation amount of polarized ultraviolet rays depends on the coating film used. The irradiation dose is preferably within a range of 1% to 70% of the amount of polarized ultraviolet rays that achieves the maximum value of ΔA (hereinafter also referred to as ΔAmax), and more preferably within a range of 1% to 50%. A is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays of the coating film.

<Process [III]>

In the step [III], the coating film irradiated with the polarized ultraviolet rays in the step [II] is heated. By heating, the orientation control ability can be imparted to the coating film.

For the heating, heating means such as a hot plate, a thermal cycle type oven, or an IR (infrared) type oven can be used. The heating temperature can be determined in consideration of the temperature at which the coating film to be used exhibits favorable liquid crystal alignment stability and electrical properties.

The heating temperature is preferably within a temperature range in which the main chain type polymer exhibits favorable liquid crystal alignment stability. When the heating temperature is too low, the effect of amplifying the anisotropy by heat and thermal imidization tend to be insufficient, and when the heating temperature is too high above the temperature range, the anisotropy imparted by polarized light exposure may disappear. , and in this case, it may be difficult to re-orientate in one direction by self-assembly.

For the same reason as described in the step [I], the thickness of the coating film formed after heating is preferably 5 nm to 300 nm, and more preferably 50 nm to 150 nm.

By having the above-mentioned steps, the production method of the present invention can efficiently introduce anisotropy into the coating film. And the board|substrate with a liquid crystal aligning film can be manufactured efficiently.

<Process [IV]>

Step [IV] is a step of obtaining the substrate (first substrate) having a liquid crystal aligning film on the conductive film for lateral electric field drive obtained in [III] in the same manner as the above [I'] to [III'] The substrate (second substrate) with a liquid crystal aligning film that does not have a conductive film is arranged to face each other so that both liquid crystal aligning films are opposed to each other with the liquid crystal interposed therebetween, a liquid crystal cell is produced by a known method, and a transverse electric field driven liquid crystal display element is produced. . It should be noted that, in the steps [I′] to [III′], in the step [I], a substrate without the conductive film for lateral electric field driving is used in place of the substrate having the conductive film for lateral electric field driving. It carries out similarly to process [I] - [III]. The steps [I] to [III] are different from the steps [I'] to [III'] only in the presence or absence of the above-mentioned conductive film, so the description of the steps [I'] to [III'] is omitted.

One example of production of a liquid crystal cell or a liquid crystal display element can be exemplified by a method in which the first and second substrates described above are prepared, spacers are scattered on the liquid crystal aligning film of one substrate, and the liquid crystal aligning film surface is inside. A method of bonding another substrate by means of a method, injecting a liquid crystal under reduced pressure, and sealing; or a method of bonding a substrate and sealing after dropping a liquid crystal on the surface of the liquid crystal aligning film where the spacers are scattered. In this case, it is preferable to use a substrate having electrodes having a structure such as comb teeth for transverse electric field driving as the substrate on one side. The diameter of the spacer at this time is preferably 1 μm to 30 μm, and more preferably 2 μm to 10 μm. The spacer diameter will determine the distance between a pair of substrates for sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the manufacturing method of the board|substrate with a coating film of this invention, after apply|coating a polymer composition on a board|substrate and forming a coating film, polarized ultraviolet rays are irradiated. Next, by heating, anisotropy can be efficiently introduced into the main chain type polymer film, and a substrate with a liquid crystal aligning film having a liquid crystal orientation control ability is produced.

In the coating film used in the present invention, anisotropy can be efficiently introduced into the coating film by utilizing the principle that the self-assembly of the main chain by photoreaction induces molecular reorientation. In the production method of the present invention, when the main chain polymer has a structure in which a photodegradable group is a photoreactive group, after forming a coating film on a substrate using the main chain polymer, polarized ultraviolet rays are irradiated, followed by heating to prepare Liquid crystal display element.

Therefore, the coating film used in the method of the present invention can efficiently introduce anisotropy by irradiating the coating film with polarized ultraviolet rays and heat treatment in this order, and can be used as a liquid crystal aligning film excellent in alignment control ability.

In addition, with respect to the coating film used in the method of the present invention, the irradiation amount of the polarized ultraviolet rays irradiated to the coating film and the heating temperature in the heat treatment are optimized. Thereby, anisotropy can be efficiently introduced into the coating film.

The optimal irradiation amount of polarized ultraviolet rays for efficiently introducing anisotropy into the coating film used in the present invention corresponds to the optimal amount of polarized ultraviolet rays for photolysis reaction of photosensitive groups in the coating film. exposure. As a result of irradiating polarized ultraviolet rays to the coating film used in the present invention, when there are few photosensitive groups that undergo a photolysis reaction, a sufficient photoreaction amount cannot be achieved. At this time, sufficient self-assembly does not proceed even if heating is subsequently performed.

Therefore, in the coating film used in the present invention, the optimum amount of photolysis reaction of the photosensitive group by irradiation of polarized ultraviolet rays is preferably 0.1 mol % to 90 mol % of the polymer film, more preferably 0.1 mol % to 90 mol %. 0.1 mol% to 80 mol%. By making the quantity of the photosensitive group which generate|occur|produce a photoreaction into this range, the self-assembly in subsequent heat processing can be advanced efficiently, and anisotropy can be efficiently formed in a film.

For the coating film used in the method of the present invention, the amount of photolysis reaction of the photosensitive group in the main chain of the polymer film is optimized by optimizing the irradiation amount of polarized ultraviolet rays. In addition, it is possible to efficiently introduce anisotropy into the coating film used in the present invention together with the subsequent heat treatment. At this time, the suitable amount of polarized ultraviolet rays can be performed based on the evaluation of the ultraviolet absorption of the coating film used in the present invention.

That is, for the coating film used in the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorption in the direction perpendicular to the polarization direction of the polarized ultraviolet rays were measured after irradiation of the polarized ultraviolet rays, respectively. ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays in the coating film, was evaluated based on the measurement results of the ultraviolet absorption. Then, the maximum value (ΔAmax) of ΔA that can be realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet rays to realize the value were obtained. In the production method of the present invention, the amount of polarized ultraviolet light to be irradiated in the production of the liquid crystal aligning film can be determined based on the amount of polarized ultraviolet light that achieves this ΔAmax.

As described above, in the production method of the present invention, in order to efficiently introduce anisotropy into the coating film, the above-mentioned suitable heating temperature can be determined on the basis of the temperature range in which the main chain type polymer imparts liquid crystal alignment stability. . Therefore, for example, the temperature range in which the main chain type polymer used in the present invention imparts liquid crystal alignment stability can be determined in consideration of the temperature at which the used coating film exhibits favorable liquid crystal alignment stability and electrical properties, and can be determined according to the The temperature range corresponding to the liquid crystal aligning film formed from polyimide etc. is set. That is, the heating temperature after polarized ultraviolet irradiation is preferably set to 100°C to 300°C, and more preferably 150°C to 250°C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.

By doing so, the liquid crystal display element provided by the present invention exhibits high reliability against external stress such as light and heat.

As described above, the substrate for a lateral electric field driven liquid crystal display element produced using the polymer of the present invention or a lateral electric field driven liquid crystal display element having the substrate is excellent in reliability, and can be suitably used for large-screen and high-definition displays. LCD TV, etc. In addition, the liquid crystal aligning film produced by the method of the present invention has excellent liquid crystal alignment stability and reliability, and thus can also be used in a variable phaser using liquid crystal, which can be suitably used, for example, with a variable resonant frequency. Changed antenna, etc.

Example

Abbreviations used in the examples are as follows.

DMF: N,N-Dimethylformamide

MeOH: methanol

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

DA-1: compound represented by the following structural formula (DA-1)

DA-2: a compound represented by the following structural formula (DA-2)

DA-3: compound represented by the following structural formula (DA-3)

CA-1: compound represented by the following structural formula (CA-1)

< Measurement of ¹ HNMR>

Apparatus: Fourier transform superconducting nuclear magnetic resonance apparatus (FT-NMR) "INOVA-400" (manufactured by Varian) 400 MHz.

Solvent: deuterated N,N-dimethylsulfoxide (DMSO-d ₆ ).

Reference material: Tetramethylsilane (TMS).

<Measurement of viscosity>

In the synthesis example, the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL, a conical rotor TE-1 (1°34', R24), and a temperature of 25°C. measured under the conditions.

<Diamine compound>

DA-1 is a novel compound not disclosed in the literature or the like, and its synthesis method will be described in detail in Synthesis Example 1 below.

<Synthesis example 1>

[DA-1]: Synthesis of 4-(2-(4-(2-(methylamino)ethyl)phenoxy)ethoxy)aniline

The aromatic diamine compound (DA-1) was synthesized according to the 4-step route shown below. In addition, the aromatic diamine compound (DA-1) belongs to the said specific diamine compound.

Step 1: Synthesis of 2-(4-(2-(4-nitrophenoxy)ethoxy)phenyl)ethanol (DA-1-1)

4-(2-Hydroxyethyl)phenol (15.0 g, 108.6 mmol) was dissolved in DMF (22.5 g), potassium carbonate (22.5 g, 162.9 mmol) was added, and β-bromo-4 was added dropwise at 80°C. - A solution obtained by dissolving nitrophenethyl ether (29.4 g, 119.4 mmol) in DMF (22.5 g). The mixture was stirred at 80°C for 5 hours as it was, and the disappearance of the starting material was confirmed by high performance liquid chromatography (hereinafter, abbreviated as HPLC). Then, the reaction liquid was left to cool to room temperature, water (540.0 g) was added, and dichloroethane (270.0 g) was added, followed by a liquid separation operation, and the organic layer was extracted. It extracted again with pure water (540.0 g), dried with magnesium sulfate (5.0 g), and concentrated. To the concentrated crude product, tetrahydrofuran (50.0 g) and heptane (40.0 g) were added, and after dissolving all of them at 60°C, the mixture was cooled to 0°C, and the precipitate was filtered. The filtered precipitate was washed with MeOH (50.0 g) and dried under reduced pressure at 40°C to obtain 2-(4-(2-(4-nitrophenoxy)ethoxy)phenyl) Ethanol (white powder, yield: 14.0 g, yield: 42%).

¹ H NMR (DMSO-d ₆ ): δ 8.22 (d, J=9.2 Hz, 2H, C ₆ H ₄ ), 7.22 (d, J=9.2 Hz, 2H, C ₆ H ₄ ), 7.14 (d, J=8.4Hz, 2H, _C6H4 ), 6.89 (d, J=8.4Hz, 2H, _C6H4 ), _4.47-4.32 (m, _4H , _CH2 ), 3.55 (t, J=7.2Hz , 2H, _CH2 ), 2.66 (t, J=7.2 Hz, 2H, _CH2 ).

Step 2: Synthesis of 4-(2-(4-nitrophenoxy)ethoxy)phenethylmethanesulfonate (DA-1-2)

2-(4-(2-(4-nitrophenoxy)ethoxy)phenyl)ethanol (5.0 g, 16.5 mmol) was dissolved in dichloroethane (30.0 g), and triethylamine ( 2.50 g, 24.7 mmol), cooled to 5°C, and a solution obtained by dissolving methanesulfonyl chloride (2.3 g, 19.8 mmol) in dichloroethane (15.0 g) was added dropwise while paying attention to heat generation. The mixture was stirred at 5°C for 1 hour, and the disappearance of the starting material was confirmed by HPLC. Then, water (60.0 g) was added to the reaction liquid, followed by addition of dichloroethane (40.0 g), followed by a liquid separation operation, and the organic layer was extracted. The organic layer was extracted again with water (50.0 g), dried over sodium sulfate (5.0 g) together with the previous organic layer, and concentrated. The concentrate was used as a crude product to obtain 4-(2-(4-nitrophenoxy)ethoxy)phenethylmethanesulfonate (white powder, yield: 6.3 g, yield: 99%).

¹ H NMR (DMSO-d ₆ ): δ 8.22 (d, J=9.2 Hz, 2H, C ₆ H ₄ ), 7.23-7.20 (m, 4H, C ₆ H ₄ ), 7.14 (d, J=8.4 Hz, 2H, _C6H4 ), 6.89 ( _d , J=8.4Hz, 2H, _CH2 ), 4.49-4.47 (m, 2H, _CH2 ), 4.37-4.33 (m, 4H, _CH2 ), 3.10 (s, 3H, _CH3 ), 2.93 (t, J=6.8 Hz, 2H, _CH2 ).

Step 3: Synthesis of N-methyl-2-(4-(2-(4-nitrophenoxy)ethoxy)phenyl)ethaneamine (DA-1-3)

4-(2-(4-Nitrophenoxy)ethoxy)phenethylmethanesulfonate (20.0 g, 52.4 mmol) was dissolved in tetrahydrofuran (200.0 g), and 40% methylamine in MeOH was added (81.4 g, 1048.8 mmol), and heated up to 40 degreeC. The mixture was stirred at 40°C for 24 hours, and the disappearance of the starting material was confirmed by HPLC. Then, the reaction liquid was concentrated, ethyl acetate (400.0 g) was added, and a 2 wt % aqueous sodium hydroxide solution (400.0 g) was added, followed by a liquid separation operation, and the organic layer was extracted. The organic layer was extracted again with water (400.0 g), dried over sodium sulfate (10.0 g) together with the previous organic layer, and concentrated. Heptane (80.0 g) was added to the concentrated crude product, and the precipitate was filtered. The filtered precipitate was dried under reduced pressure at 40°C to obtain N-methyl-2-(4-(2-(4-nitrophenoxy)ethoxy)phenyl)ethaneamine ( Yellow powder, yield: 15.6 g, yield: 94%).

¹ H NMR (DMSO-d ₆ ): δ 8.22 (d, J=9.2 Hz, 2H, C ₆ H ₄ ), 7.21 (d, J=9.2 Hz, 2H, C ₆ H ₄ ), 7.13 (d, J=8.4Hz, 2H, _C6H4 ), 6.89 ( _d , J=8.4Hz, 2H, _CH2 ), 4.48-4.30 (m, 4H, _CH2 ), 2.62 (s, 4H, _CH2 ), 2.27 (s, 3H, _CH3 ), 1.49 (br, 1H, NH).

Step 4: Synthesis of 4-(2-(4-(2-methylamino)ethyl)phenoxy)ethoxy)aniline (DA-1)

Dissolve N-methyl-2-(4-(2-(4-nitrophenoxy)ethoxy)phenyl)ethaneamine (10.0 g, 31.6 mmol) in tetrahydrofuran (100.0 g), add 5% palladium-carbon (0.5 g), stirred at 50°C for 5 hours under a hydrogen atmosphere. The disappearance of the raw material was confirmed by HPLC, the mixture was dissolved in tetrahydrofuran (50.0 g), the catalyst was removed by filtration, and the filtrate was concentrated. This was washed with heptane (50.0 g), the precipitated solid was filtered, and dried under reduced pressure at 50°C to obtain DA-1 (white powder, yield: 9.0 g, yield: 98%).

¹ H NMR (DMSO-d ₆ ): δ 7.11 (d, J=9.2 Hz, 2H, C ₆ H ₄ ), 6.87 (d, J=9.2 Hz, 2H, C ₆ H ₄ ), 6.68 (d, J=6.6Hz, 2H, _C6H4 ), 6.51 ( _d , J=6.6Hz, 2H, _CH2 ), 4.63 (br, 2H, _NH2 ), 4.20-4.12 (m, 4H, _CH2 ), 2.62 (s, 4H, _CH2 ), 2.26 (s, 3H, _CH3 ), 1.48 (br, 1H, NH).

Polymerization example, preparation example of alignment agent

<Synthesis example 2>

1.00 g (3.50 mmol) DA-1 and 2.86 g (10.5 mmol) DA-2 were weighed into a 100 mL four-necked flask with a stirring device and a nitrogen introduction tube, and 37.6 g of NMP was added, and stirring was performed while conveying nitrogen. dissolve. 2.59 g (13.2 mmol) of CA-1 was added while stirring the diamine solution under water cooling, and 9.41 g of NMP was further added, and the solution was stirred at 23° C. for 15 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The solution of this polyamic acid had a viscosity of 270 mPa·s at a temperature of 25°C.

14.5 g of the solution of this polyamic acid was collected and added to a 100 mL conical flask equipped with a stirring bar, 12.6 g of NMP and 11.6 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (A-1).

<Comparative Synthesis Example 1>

4.09 g (15.0 mmol) of DA-2 was weighed into a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 39.3 g of NMP was added, and the mixture was dissolved while stirring while supplying nitrogen gas. 2.77 g (14.1 mmol) of CA-1 was added while stirring the diamine solution under water cooling, and 9.83 g of NMP was further added, and the solution was stirred at 23° C. for 3 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The solution of this polyamic acid had a viscosity of 263 mPa·s at a temperature of 25°C.

14.9 g of the solution of this polyamic acid was separated and added to a 100 mL conical flask equipped with a stirring bar, 12.9 g of NMP and 11.9 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (B-1).

<Comparative Synthesis Example 2>

2.86g (10.5mmol) DA-2 and 0.526g (3.50mmol) DA-3 were weighed into a 100mL four-necked flask with a stirring device and a nitrogen gas introduction tube, and 34.8g of NMP was added, and stirring was carried out while conveying nitrogen. dissolve. 2.62 g (13.4 mmol) of CA-1 was added while stirring the diamine solution under water cooling, and 8.71 g of NMP was further added, and the solution was stirred at 23° C. for 15 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The solution of this polyamic acid had a viscosity of 299 mPa·s at a temperature of 25°C.

14.6 g of the solution of this polyamic acid was collected and added to a 100 mL conical flask equipped with a stirring bar, 12.6 g of NMP and 11.7 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (B-2).

<Preparation of liquid crystal cell for liquid crystal orientation evaluation>

The manufacturing method of the liquid crystal cell for evaluating the liquid crystal alignment property is shown below.

A liquid crystal cell having a liquid crystal display element structure in the FFS mode was produced. First, a substrate with electrodes is prepared. The substrate was a glass substrate with a size of 30 mm×35 mm and a thickness of 0.7 mm. On the substrate, as a first layer, an IZO electrode constituting a counter electrode was formed over the entire surface. On the counter electrode of the first layer, a SiN (silicon nitride) film formed by a CVD method was formed as a second layer. The thickness of the SiN film of the second layer is 500 nm, and it functions as an interlayer insulating film. On the SiN film of the second layer, as a third layer, a comb-shaped pixel electrode formed by patterning an IZO film is arranged, thereby forming two pixels, a first pixel and a second pixel. The size of each pixel is 10 mm in length and 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of the third layer has a comb-like shape formed by arranging a plurality of "<"-shaped electrode elements with curved central portions, as in the figure described in Japanese Patent Laid-Open No. 2014-77845 (Japanese Laid-Open Patent Publication). The width of each electrode element in the width direction was 3 μm, and the interval between the electrode elements was 6 μm. The pixel electrode forming each pixel is formed by arranging a plurality of “<”-shaped electrode elements with a curved center portion. Therefore, the shape of each pixel is not a rectangular shape, but has a similar electrode element that is curved in the center portion. Bold "<" word shape. Further, each pixel is divided up and down with the central curved portion as a boundary, and has a first area on the upper side of the curved portion and a second area on the lower side.

When the first region and the second region of each pixel are compared, the formation directions of the electrode elements constituting the pixel electrodes thereof are different. That is, the electrode elements of the pixel electrode are formed at an angle of +10° (clockwise) in the first region of the pixel, with reference to the line segment direction when the plane of polarization of the polarized ultraviolet rays described below is projected onto the substrate. In the second region of the pixel, the electrode elements of the pixel electrode are formed at an angle of -10° (clockwise). That is, the first region and the second region of each pixel are configured such that the directions of the rotational motion (in-plane switching) of the liquid crystal in the substrate plane, which are induced by applying a voltage between the pixel electrode and the counter electrode, are opposite to each other. .

Next, the liquid crystal aligning agent obtained by the synthesis example and the comparative synthesis example was filtered with the filter of 1.0 micrometers, and it apply|coated on the prepared said board|substrate with electrodes by the spin coating method. Next, it dried for 90 seconds on a hot plate set at 70°C. Next, using the exposure apparatus APL-L050121S1S-APW01 manufactured by Ushio Electric Co., Ltd., linearly polarized light of ultraviolet rays was irradiated through a wavelength selective filter and a polarizing plate from a direction perpendicular to the substrate. At this time, the polarization plane direction was set so that the line segment direction when the polarization plane of the polarized ultraviolet rays was projected on the substrate was a direction inclined by 10° with respect to the third-layer IZO comb-shaped electrode. Next, it baked for 30 minutes in the IR (infrared) type oven set to 230 degreeC, and obtained the board|substrate with the polyimide liquid crystal aligning film with a film thickness of 100 nm which gave the orientation process. Moreover, as a counter substrate, the ITO electrode was formed in the back surface and the glass substrate which has a columnar spacer with a height of 4 micrometers was given the orientation process similarly to the above, and the board|substrate with a polyimide liquid crystal aligning film was obtained. The two substrates with liquid crystal alignment films are set as one set, and the sealant is printed on one substrate with the liquid crystal injection port left, and the surfaces of the liquid crystal alignment films face each other and the polarized plane of the polarized ultraviolet rays is projected onto the substrate. Another substrate is bonded and crimped with the line segment direction in parallel. Then, the sealant was cured to produce an empty cell with a cell gap of 4 μm. Liquid crystal ML-7026-100 (negative liquid crystal manufactured by Merck) was injected into this empty cell by a reduced pressure injection method, the injection port was sealed, and an FFS mode liquid crystal cell was obtained. Then, the obtained liquid crystal cell was heated at 120 degreeC for 30 minutes, and was used for evaluation of liquid crystal orientation after leaving to stand at 23 degreeC overnight.

<Evaluation of liquid crystal orientation>

Using this liquid crystal cell, an alternating voltage of 16 VPP was applied at a frequency of 30 Hz for 120 hours in a constant temperature environment of 70°C. Then, the liquid crystal cell was left in a short-circuit state between the pixel electrode and the counter electrode, and left at 23° C. overnight in this state.

After standing, the liquid crystal cell was placed between two polarizing plates arranged so that the polarization axes were perpendicular to each other, the backlight was turned on without voltage application, and the arrangement angle of the liquid crystal cell was adjusted to minimize the brightness of transmitted light. Then, the rotation angle when the liquid crystal cell is rotated from the angle at which the second area of the first pixel becomes the darkest to the angle at which the first area becomes the darkest is calculated as the angle Δ. For the second pixel, the second area and the first area are similarly compared, and the same angle Δ is calculated. Then, the average value of the angle Δ values of the first pixel and the second pixel was calculated as the angle Δ of the liquid crystal cell. The case where the angle Δ value of the liquid crystal cell was less than 0.3° was defined and evaluated as "good", and the case where the angle Δ value was 0.3° or more was defined and evaluated as "poor".

<Preparation of liquid crystal cell for evaluation of voltage holding ratio>

It was produced in the same procedure as the production of the liquid crystal cell for liquid crystal alignment evaluation described above, except that a glass substrate with an ITO electrode was used, and spacer microspheres of 4 μm were dispersed on the liquid crystal aligning film surface on one substrate before the sealant was printed. Liquid crystal cell for voltage holding ratio measurement.

<Evaluation of voltage holding ratio>

The evaluation of the voltage holding ratio was performed using this liquid crystal cell. Specifically, a 2VPP AC voltage was applied to the liquid crystal cell obtained by the above method at a temperature of 70° C. for 60 microseconds, the voltage after 1 second was measured, and how much the voltage could be maintained was calculated as the voltage retention ratio (also referred to as the voltage retention ratio). VHR). In addition, using a voltage holding ratio measuring device (VHR-1, manufactured by Toyo Technica), voltage (Voltage): ±1V, pulse width (Pulse Width): 60 microseconds, and frame period (Frame Period): 1000 The millisecond setting is measured. The case where the value of the voltage holding ratio of the liquid crystal cell was 80% or more was defined and evaluated as "good", and the case where the value of the voltage holding ratio was less than 80% was defined and evaluated as "defective".

(Example 1)

Using the liquid crystal aligning agent (A-1) obtained in Synthesis Example 2, two types of liquid crystal cells were produced as described above. Irradiation of polarized ultraviolet rays was performed using a high pressure mercury lamp through a wavelength selective filter: 240LCF and a 254 nm type polarizing plate. The irradiation amount of polarized ultraviolet rays was measured using an illuminometer UVD-S254SB manufactured by Ushio Electric Co., Ltd., and the amount of light was measured at a wavelength of 254 nm in the range of 600 to 1800 mJ/cm ² . Three or more polarized ultraviolet irradiation doses were produced. of the liquid crystal cell.

As a result of evaluating the liquid crystal orientation of these liquid crystal cells, the optimal amount of polarized ultraviolet irradiation at angle Δ was 1800 mJ/cm ² , and the angle Δ was favorable at 0.15°.

Moreover, as a result of evaluating the voltage holding ratio of the liquid crystal cell produced with the same amount of polarized ultraviolet irradiation, the voltage holding ratio was 92.4%, which was favorable.

(Comparative Examples 1 to 2)

Except having used the liquid crystal aligning agent obtained in Comparative Synthesis Examples 1-2, it carried out similarly to Example 1, and evaluated the liquid crystal aligning property and the voltage retention.

Table 1 shows the amount of polarized ultraviolet irradiation at the optimum angle Δ when using the liquid crystal aligning agent obtained in the synthesis example and the comparative synthesis example, the evaluation result of liquid crystal alignment property, and the evaluation result of the voltage holding ratio.

[Table 1]

As shown in Table 1, in Example 1, the difference in the orientation azimuth angle before and after the AC drive, that is, the angle Δ is less than 0.3°, which is good, and the voltage holding ratio is 80% or more, showing good characteristics. Because of good image sticking characteristics, the improvement of the display quality of the liquid crystal display element is excellent. On the other hand, in Comparative Examples 1 and 2, the characteristics of both the angle Δ and the voltage holding ratio were not confirmed.

From this, it was confirmed that the liquid crystal display element produced by the method of the present invention exhibited very excellent image sticking characteristics.

Industrial Availability

The substrate for a lateral electric field driven liquid crystal display element produced using the composition of the present invention or a lateral electric field driven liquid crystal display element having the substrate is excellent in reliability, and can be suitably used for large-screen and high-definition liquid crystal televisions and the like. In addition, the liquid crystal aligning film produced by the method of the present invention has excellent liquid crystal alignment stability and reliability, and thus can also be used in a variable phaser using liquid crystal, which can be suitably used, for example, with a variable resonant frequency. Changed antenna, etc.

Claims (1)

1. A diamine represented by the following formula (2),

in the formula (2), X is a single bond or a 2-valent organic group, Y and Z are each independently a 2-valent organic group containing an alkylene group, R¹And R²Each independently is a 1-valent organic radical, R³Is an alkyl group having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4.