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

Abstract

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. According to the present invention, there can be provided a substrate having a liquid crystal alignment film for a lateral electric field driven liquid crystal display element with an orientation control capability efficiently imparted thereto and excellent afterimage characteristics, a lateral electric field driven liquid crystal display element having the substrate, and a compound providing the same, more specifically, a novel diamine that can improve reliability without affecting orientation properties by adding a small amount thereof.

Description

[0001] This application is a divisional application of a Chinese patent application with an application date of December 20, 2017, application number 201780086602.5, and invention name “LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY ELEMENT”. Technical Field

[0002] 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 Art

[0003] Liquid crystal display elements are known as light, thin, and low-power display devices, and have been used for large-scale television applications in recent years, achieving significant development. Liquid crystal display elements are composed of, for example, a pair of transparent substrates with electrodes sandwiching a liquid crystal layer. In addition, in liquid crystal display elements, an organic film formed of an organic material is used as a liquid crystal alignment film to allow the liquid crystal to present a desired alignment state between the substrates.

[0004] That is, the liquid crystal alignment film is a component of the liquid crystal display element, which is formed on the surface of the substrate that clamps the liquid crystal and contacts the liquid crystal, and plays the role of orienting the liquid crystal along a specific direction between the substrates. In addition, for the liquid crystal alignment film, in addition to the role of orienting the liquid crystal along a specific direction such as a direction parallel to the substrate, it is sometimes required to control the pre-tilt angle of the liquid crystal. The ability of this liquid crystal alignment film to control the orientation of the liquid crystal (hereinafter referred to as the orientation control ability) is given by performing an orientation treatment on the organic film constituting the liquid crystal alignment film.

[0005] As an orientation treatment method for a liquid crystal alignment film that is used to impart orientation control capability, a brushing method has been known in the past. The brushing method refers to the following method: for an organic film of polyvinyl alcohol, polyamide, polyimide, etc. on a substrate, the surface is rubbed (brushed) along a certain direction with a cloth such as cotton, nylon, polyester, etc., so that the liquid crystal is oriented along the rubbing direction (brushing direction). The brushing method can easily achieve a relatively stable liquid crystal orientation state, so it is used in the manufacturing process of liquid crystal display elements in the past. In addition, as an organic film used in a liquid crystal alignment film, a polyimide-based organic film with excellent reliability and electrical properties such as heat resistance is mainly selected.

[0006] However, the brushing method of rubbing the surface of the liquid crystal alignment film formed of polyimide etc. has the problem of dust generation and static electricity generation. In addition, due to the high definition of liquid crystal display elements in recent years, the unevenness caused by the electrodes on the corresponding substrate or the switching active elements for liquid crystal driving, it is sometimes impossible to rub the surface of the liquid crystal alignment film evenly with a cloth, and it is impossible to achieve uniform liquid crystal orientation.

[0007] Therefore, as another alignment treatment method of a liquid crystal alignment film that is not subjected to rubbing, a photo-alignment method has been actively studied.

[0008] There are various photo-alignment methods, and they use linearly polarized light or collimated light to form anisotropy in an organic film constituting a liquid crystal alignment film, and align liquid crystals based on the anisotropy.

[0009] As the main photo-alignment method, a decomposition-type photo-alignment method is known. For example, a polyimide film is irradiated with polarized ultraviolet rays, and the film is anisotropically decomposed by utilizing the polarization direction dependence of ultraviolet absorption of the molecular structure. Then, the liquid crystal is oriented by the polyimide remaining without decomposition (for example, see Patent Document 1).

[0010] In addition, photo-crosslinking type and photo-isomerization type photo-alignment methods are also known. For example, using polyvinyl cinnamate, polarized ultraviolet rays are irradiated to cause a dimerization reaction (crosslinking reaction) in the double bond parts of the two side chains parallel to the polarized light. Then, the liquid crystal is oriented in a direction perpendicular to the polarization direction (for example, refer to non-patent document 1). In addition, when a side chain polymer having azobenzene in the side chain is used, polarized ultraviolet rays are irradiated to cause an isomerization reaction in the azobenzene part of the side chain parallel to the polarized light, thereby aligning the liquid crystal in a direction perpendicular to the polarization direction (for example, refer to non-patent document 2).

[0011] As in the above example, in the method of using the photo-orientation method to orient the liquid crystal alignment film, there is no need to perform brushing, and there is no need to worry about dust generation and static electricity. Moreover, even for a substrate of a liquid crystal display element with a concave-convex surface, the orientation treatment can be performed, thereby becoming an orientation treatment method for a liquid crystal alignment film suitable for industrial production processes.

[0012] Prior art literature

[0013] Patent Literature

[0014] Patent Document 1: Japanese Patent No. 3893659

[0015] Non-patent literature

[0016] Non-patent document 1: M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992).

[0017] Non-patent document 2: K. Ichimura et al., Chem. Rev. 100, 1847 (2000). Summary of the invention

[0018] Problem that the invention aims to solve

[0019] As described above, compared with the brushing method which has been used in industry as an orientation treatment method for liquid crystal display elements, the photo-orientation method does not require the brushing process, so it has obvious advantages. In addition, compared with the brushing method in which the orientation control ability is basically fixed due to brushing, the photo-orientation method can change the irradiation amount of polarized light to control the orientation control ability. However, for the photo-orientation method, when it is desired to achieve the same degree of orientation control ability as when using the brushing method, a large amount of polarized light irradiation is sometimes required, or a stable liquid crystal orientation cannot be achieved.

[0020] For example, in the decomposition type photo-orientation method described in the above-mentioned patent document 1, the polyimide film needs to be irradiated with ultraviolet light emitted by a high-pressure mercury lamp with a power of 500W for 60 minutes, which requires long-term and large-scale ultraviolet irradiation. In addition, in the case of dimerization type and photoisomerization type photo-orientation methods, sometimes a large amount of ultraviolet irradiation of several J (joules) to tens of J is also required. Furthermore, in the case of photo-crosslinking type and photoisomerization type photo-orientation methods, the thermal stability and light stability of the liquid crystal orientation are poor, so when a liquid crystal display element is made, there are problems of poor orientation and display afterimages. In particular, for a lateral electric field driven liquid crystal display element, the liquid crystal molecules switch in the plane, so it is easy for the liquid crystal orientation to shift after liquid crystal driving, and the display afterimage caused by AC driving has become a major issue.

[0021] Therefore, in the photo-alignment method, it is required to realize efficient alignment treatment and stable liquid crystal alignment, and a liquid crystal alignment film, a liquid crystal aligning agent, and a compound providing the same which can efficiently impart high alignment control ability to the liquid crystal alignment film are sought.

[0022] The object of the present invention is to provide a substrate having a liquid crystal orientation film for a lateral electric field driven liquid crystal display element which is efficiently endowed with orientation control capability and has excellent afterimage characteristics, a lateral electric field driven liquid crystal display element having the substrate, and a compound providing the same, more specifically, a new type of diamine which can improve reliability without affecting the orientation property by adding a small amount.

[0023] Solutions for solving problems

[0024] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found the following technical solutions.

[0025] 1. A liquid crystal aligning agent comprising a polymer obtained from a diamine component containing a diamine having a structure represented by the following formula (1), and an organic solvent.

[0026]

[0027] (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 Each independently is 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.

[0028] 2. The liquid crystal aligning agent according to item 1 above, comprising at least one polymer selected from the group consisting of polyimide precursors and imide products thereof, that is, polyimides, and an organic solvent, wherein the polyimide precursor is a polymer of a diamine component containing the above diamine and tetracarboxylic dianhydride.

[0029] 3. The liquid crystal aligning agent according to the above 1 or 2, wherein the diamine is represented by the following formula (2).

[0030]

[0031] (In formula (2), X, Y, Z, R 1 ~R 3 The definitions of m and n are the same as those in the above formula (1).

[0032] 4. The liquid crystal aligning agent according to any one of 1 to 3 above, wherein the polyimide precursor is represented by the following formula (3).

[0033]

[0034] (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 having a structure of formula (1), R 11 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 3 is an alkyl group having 1 to 4 carbon atoms. )

[0035] 5. The liquid crystal aligning agent according to 4 above, wherein in the formula (3), X 1 The structure is at least one selected from the group consisting of the following structural formulas (A-1) to (A-21).

[0036]

[0037] 6. The liquid crystal aligning agent according to the above 4 or 5, wherein the polymer having the structural unit represented by the formula (3) is contained in an amount of 10 mol % or more based on all polymers contained in the liquid crystal aligning agent.

[0038] 7. The liquid crystal aligning agent according to any one of 4 to 6 above, wherein the organic solvent contains at least one selected from the group consisting of 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether.

[0039] 8. A method for manufacturing a substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, the method comprising the following steps to obtain the liquid crystal alignment film endowed with an alignment control capability:

[0040] Step [I], coating the composition described in any one of 1 to 7 above on a substrate having a conductive film for lateral electric field driving to form a coating film;

[0041] Step [II], irradiating the coating film obtained in step [I] with polarized ultraviolet rays; and

[0042] In step [III], the coating film obtained in step [II] is heated.

[0043] 9. A substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element, which is produced by the method described in 8 above.

[0044] 10. A transverse electric field driven liquid crystal display element comprising the substrate described in 9 above.

[0045] 11. A method for manufacturing a lateral electric field driven liquid crystal display element, comprising the following steps to obtain the liquid crystal display element:

[0046] A step of preparing the substrate described in 9 above, i.e., the first substrate;

[0047] A step of obtaining a second substrate having a liquid crystal alignment film, wherein the liquid crystal alignment film having an alignment control capability is obtained by comprising the following steps [I'], [II'], and [III']; and

[0048] Step [IV], arranging the first substrate and the second substrate to face each other in such a manner that the liquid crystal alignment films of the first substrate and the second substrate face each other with the liquid crystal interposed therebetween, thereby obtaining a liquid crystal display element,

[0049] The steps [I'], [II'] and [III'] are:

[0050] Step [I'], coating the composition according to claims 1 to 7 on a second substrate to form a coating film;

[0051] Step [II'], irradiating the coating film obtained in [I'] with polarized ultraviolet rays;

[0052] In step [III'], the coating film obtained in step [II'] is heated.

[0053] 12. A transverse electric field driven liquid crystal display element manufactured by the method described in 11 above.

[0054] 13. A polymer, which is at least one polymer selected from the group consisting of a polyimide precursor and an imide product thereof, namely a polyimide, wherein the polyimide precursor is a polymer of a diamine component containing a diamine having a structure represented by the following formula (1) and tetracarboxylic dianhydride,

[0055]

[0056] (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 Each independently is 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.

[0057] 14. The polymer according to 13 above, wherein the diamine is represented by the following formula (2).

[0058]

[0059] (In formula (2), X, Y, Z, R 1 ~R 3 The definitions of m and n are the same as those in the above formula (1).

[0060] 15. The polymer according to 13 or 14 above, wherein the polyimide precursor is represented by the following formula (3).

[0061]

[0062] (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 having a structure of formula (1), R 11 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 3 is an alkyl group having 1 to 4 carbon atoms. )

[0063] 16. The polymer according to 15 above, wherein in the formula (3), X 1 The structure is at least one selected from the group consisting of the following structural formulas (A-1) to (A-21).

[0064]

[0065] 17. A diamine represented by the above formula (2).

[0066] Effects of the Invention

[0067] According to the present invention, there can be provided a substrate having a liquid crystal alignment film for a transverse electric field driven liquid crystal display element to which alignment control capability is efficiently imparted and excellent in afterimage characteristics, and a transverse electric field driven liquid crystal display element having the substrate.

[0068] Since the lateral electric field driven liquid crystal display element manufactured by the method of the present invention is endowed with the alignment control capability with high efficiency, the display characteristics are not impaired even if it is driven continuously for a long period of time.

[0069] The polymer composition used in the manufacture method of the present invention has a photosensitive main-chain polymer (hereinafter also referred to as main-chain polymer) that can show self-assembly ability, and the coating obtained using the aforementioned polymer composition is a film with a photosensitive main-chain polymer that can show self-assembly ability. The coating is not subjected to brushing treatment, but is oriented by polarized light irradiation. In addition, after irradiating polarized light, through the process of heating the main-chain polymer film, it becomes a coating (hereinafter also referred to as liquid crystal alignment film) endowed with orientation control ability. At this time, the tiny anisotropy shown 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 alignment film, it is possible to obtain a liquid crystal alignment film endowed with high orientation control ability by achieving efficient orientation treatment. DETAILED DESCRIPTION

[0070] Hereinafter, embodiments of the present invention will be described in detail.

[0071] The liquid crystal aligning agent of the present invention contains a polymer (hereinafter also referred to as a specific polymer or a main chain polymer) obtained from a diamine component containing a diamine having a structure represented by the following formula (1).

[0072] <Diamine having a specific structure>

[0073] The liquid crystal aligning agent of this invention is a liquid crystal aligning agent containing the polymer obtained from the diamine (it is also called a specific diamine in this invention) which has the structure of following formula (1), and an organic solvent.

[0074]

[0075] (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 Each independently is 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.

[0076] Examples of the monovalent organic group include alkyl, alkenyl, alkoxy, fluoroalkyl, fluoroalkenyl or fluoroalkoxy groups having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. Among them, the monovalent organic group is preferably a methyl group.

[0077] Examples of the divalent organic group include benzene, naphthalene, cyclohexyl, and groups in which hydrogen atoms of these groups are substituted with monovalent organic groups. Among them, benzene is preferred as the divalent organic group.

[0078] As the divalent organic group containing an alkylene group, an alkylene group, a group consisting of an alkylene group and an ether bond, a group consisting of an alkylene group and an ester bond, a group consisting of an alkylene group in which some or all of the hydrogen atoms are substituted by halogen and an ether bond, and a group consisting of an alkylene group in which some or all of the hydrogen atoms are substituted by halogen and an ester bond can be cited. Among them, as the divalent organic group containing an alkylene group, an alkylene group and a group consisting of an alkylene group and an ether bond are preferred. The carbon number is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less.

[0079] In addition, when the sum of the number of carbon atoms and the number of oxygen atoms related to the main chain length in the total number of atoms of Y and Z is an even number, the linearity of the obtained polymer increases. As a result, the re-orientation is carried out more orderly in the heating process after polarized light irradiation, so that a liquid crystal orientation film endowed with high orientation control ability can be obtained, which is preferred.

[0080] As R 3 From the viewpoint of the ease of reaction during polymerization, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0081] As for m and n, 0 is preferable from the viewpoint that steric hindrance is small, phenyl groups are easily overlapped with each other, and realignment is more orderly.

[0082] As the above-mentioned diamine, a diamine represented by the following formula (2) is preferred.

[0083]

[0084] (In formula (2), X, Y, Z, R 1 ~R 3 The definitions of m and n are the same as those in the above formula (1).

[0085] Specific examples of the diamine having the structure of the above formula (2) include the following, but the diamine is not limited to these.

[0086]

[0087]

[0088]

[0089] <Method for synthesizing specific diamine>

[0090] The method for synthesizing the specific diamine is not particularly limited, and an example thereof includes a method of using a nitro compound represented by the following formula (5) and converting the nitro group thereof into an amino group by a reduction reaction.

[0091]

[0092] The catalyst used in the above-mentioned reduction reaction is preferably an activated carbon-supported metal that can be obtained with a commercial product, for example, palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon, etc. can be cited. In addition, it can also be palladium hydroxide, platinum oxide, Raney nickel, iron, zinc, tin, etc., which are not necessarily metal catalysts of activated carbon-supported type. Conventionally, widely used iron, zinc, and tin can obtain good results, so they are preferred.

[0093] In order to make the reduction reaction more effective, the reaction may be carried out in the presence of activated carbon. In this case, the amount of activated carbon used is not particularly limited, and is preferably in the range of 1 to 30% by mass, more preferably 10 to 20% by mass, relative to the dinitro compound X1. For the same reason, the reaction may be carried out under pressure. In this case, in order to avoid the reduction of the benzene nucleus, the reaction is carried out within a pressure range of up to 20 atmospheres. The reaction is preferably carried out within a range of up to 10 atmospheres. An acid catalyst may also be added as needed to shorten the time.

[0094] Any solvent can be used without limitation as long as it does not react with the raw materials. For example, non-protonic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers (Et2O, i-Pr2O, TBME, CPME, THF, dioxane, etc.); aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); halogen 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 solvents, polar organic solvents (methanol, ethanol, H2O, etc.), etc. These solvents can be appropriately selected in consideration of the ease of reaction, etc., and can be used alone or in combination of two or more. If necessary, the solvent may be dried using an appropriate dehydrating agent or drying agent to be used as a non-aqueous solvent.

[0095] The amount of the solvent used (reaction concentration) is not particularly limited, but is 0.1 to 100 times by mass, preferably 0.5 to 30 times by mass, and more preferably 1 to 10 times by mass, relative to the nitro compound.

[0096] The reaction temperature is not particularly limited, but is in the range of -100° C. to the boiling point of the solvent used, and is preferably -50 to 150° C. The reaction time is usually 0.05 to 350 hours, and preferably 0.5 to 100 hours.

[0097] [Preparation method of formula (5)]

[0098] The synthesis method of the compound of formula (5) is not particularly limited, and for example, a method of synthesizing the compound by reacting a nitrobenzene derivative having a leaving group X represented by the following formula (7) with a commercially available methylamine solution can be cited. Preferred leaving groups X include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, p-toluenesulfonate groups (-OTs), and methanesulfonate groups (-OMs).

[0099]

[0100] 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).

[0101] When a solvent is used, there is no particular limitation on the solvent used as long as it does not hinder the progress of the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; aliphatic halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene; ethers such as diethyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and 1,4-dioxane; esters such as ethyl acetate and ethyl propionate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; amines such as triethylamine, tributylamine, and N,N-dimethylaniline; pyridines such as pyridine and picoline; acetonitrile and dimethyl sulfoxide, etc. These solvents may be used alone or in combination of two or more thereof.

[0102] It is not necessary to add a base. When a base is used, for example, 1 to 4 equivalents of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, an alkali metal bicarbonate such as sodium bicarbonate or potassium bicarbonate, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, 4-(dimethylamino)pyridine, imidazole, an organic base such as 1,8-diazabicyclo[5,4,0]-7-undecene, etc. can be used relative to the compound represented by the general formula (7).

[0103] The reaction temperature can be set at any temperature from -60°C to the reflux temperature of the reaction mixture. The reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but can usually be set at any time within the range of 5 minutes to 100 hours.

[0104] In general, it is preferred that the reaction be carried out in the presence of 1 to 20 equivalents of methylamine and, if necessary, 1 to 4 equivalents of a base such as potassium carbonate, triethylamine, pyridine, 4-(dimethylamino)pyridine, etc., for 10 minutes to 24 hours without using a solvent or using a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, etc., for example, relative to 1 equivalent of the compound represented by the general formula (7), at a temperature within the range of 0°C to the reflux temperature of these solvents.

[0105] [Preparation method of formula (7)]

[0106] The synthesis method of the compound of formula (7) is not particularly limited, and for example, a method of synthesizing the compound by reacting a nitrobenzene derivative having a hydroxyl group represented by the following formula (8) with commercially available methanesulfonyl chloride can be cited. From the viewpoint of the ease of synthesis, the leaving group X is preferably a methanesulfonate group (-OMs), and other preferred leaving groups X include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonate group (-OTs), and the like.

[0107]

[0108] 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).

[0109] When a solvent is used, there is no particular limitation on the solvent used as long as it does not hinder the progress of the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; aliphatic halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene; ethers such as diethyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and 1,4-dioxane; esters such as ethyl acetate and ethyl propionate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; amines such as triethylamine, tributylamine, and N,N-dimethylaniline; pyridines such as pyridine and picoline; acetonitrile and dimethyl sulfoxide, etc. These solvents may be used alone or in combination of two or more thereof.

[0110] It is not necessary to add a base. When a base is used, for example, 1 to 4 equivalents of an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, an alkali metal carbonate such as sodium carbonate and potassium carbonate, an alkali metal bicarbonate such as sodium bicarbonate and potassium bicarbonate, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, 4-(dimethylamino)pyridine, imidazole, an organic base such as 1,8-diazabicyclo[5,4,0]-7-undecene, etc. can be used relative to the compound represented by the general formula (8).

[0111] The reaction temperature can be set at any temperature within the range of -60°C to 25°C. The reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but can usually be set at any time within the range of 5 minutes to 100 hours.

[0112] Generally speaking, it is preferred that the reaction be carried out in the presence of 1 to 4 equivalents of methanesulfonyl chloride and, if necessary, 1 to 4 equivalents of a base such as potassium carbonate, triethylamine, pyridine, 4-(dimethylamino)pyridine, etc., for 10 minutes to 24 hours at 0°C to 10°C, for example, relative to 1 equivalent of the compound represented by formula (8), without using a solvent or using a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, etc.

[0113] [Preparation method of formula (8)]

[0114] The synthesis method of the compound of formula (8) is not particularly limited. For example, a method of synthesizing the compound by reacting a commercially available phenol derivative (9) with a nitrobenzene derivative having a leaving group represented by the following formula (10) can be cited. Preferred leaving groups X include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, p-toluenesulfonate groups (-OTs), and methanesulfonate groups (-OMs).

[0115]

[0116] 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).

[0117] When a solvent is used, there is no particular limitation on the solvent used as long as it does not hinder the progress of the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; aliphatic halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene; ethers such as diethyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and 1,4-dioxane; esters such as ethyl acetate and ethyl propionate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; amines such as triethylamine, tributylamine, and N,N-dimethylaniline; pyridines such as pyridine and picoline; acetonitrile and dimethyl sulfoxide, etc. These solvents may be used alone or in combination of two or more thereof.

[0118] It is not necessary to add a base. When a base is used, for example, 1 to 4 equivalents of an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, an alkali metal carbonate such as sodium carbonate and potassium carbonate, an alkali metal bicarbonate such as sodium bicarbonate and potassium bicarbonate, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, 4-(dimethylamino)pyridine, imidazole, an organic base such as 1,8-diazabicyclo[5,4,0]-7-undecene, etc. can be used relative to the compound represented by the general formula (10).

[0119] The reaction temperature can be set at any temperature from -60°C to the reflux temperature of the reaction mixture. The reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but can usually be set at any time within the range of 5 minutes to 100 hours.

[0120] In general, it is preferred that, for example, 1 to 4 equivalents of the compound represented by formula (9) are used relative to 1 equivalent of the compound represented by formula (10), in the presence of 1 to 4 equivalents of a base such as potassium carbonate, triethylamine, pyridine, 4-(dimethylamino)pyridine, etc., as required, without using a solvent or using a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, and the reaction is carried out in the range of 0°C to the reflux temperature of these solvents for 10 minutes to 24 hours.

[0121] <Polymer>

[0122] The polymer of the present invention is a polymer obtained using the above diamine. As specific examples, polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide, etc. can be cited. From the viewpoint of use as a liquid crystal aligning agent, it is more preferably selected from at least one of a polyimide precursor containing a structural unit represented by the following formula (3) and its imide, i.e., a polyimide.

[0123]

[0124] 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 having a structure of formula (1), R 11 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 3 is an alkyl group having 1 to 4 carbon atoms. From the viewpoint of the ease of imidization by heating, R 11 A hydrogen atom, a methyl group or an ethyl group is preferred. 3 From the viewpoint of the ease of reaction during polymerization, a methyl group is preferred.

[0125] <Tetracarboxylic dianhydride>

[0126] X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited.1 It can be appropriately selected based on the solubility of the polymer in the solvent, the coating properties of the liquid crystal alignment agent, the orientation of the liquid crystal when it is made into a liquid crystal alignment film, the voltage holding rate, the degree of accumulated charge and other required properties. One type can be used in the same polymer, or two or more types can be mixed.

[0127] If you have to show X 1 Specific examples thereof include structures of formulae (X-1) to (X-46) described in International Publication No. 2015 / 119168, pages 13 to 14.

[0128] The following shows the preferred X 1 However, the present invention is not limited to these structures.

[0129]

[0130] Among the above structures, (A-1), (A-2), and (A-4) are preferred, and (A-1) is particularly preferred, from the viewpoint of photo-alignment.

[0131] <Diamine>

[0132] In formula (3), as Y 1 A specific example of Y is a structure obtained by removing an amino group and an alkylamino group from a diamine having the structure of the formula (1). 1 Particularly preferred is a structure obtained by removing an amino group and an alkylamino group from the structure of the above formula (2).

[0133] <Polymer (other structural units)>

[0134] The polyimide precursor containing the structural unit represented by formula (3) may contain at least one selected from the group consisting of structural units represented by formula (4) below and imide products thereof, that is, polyimides, within a range not impairing the effects of the present invention.

[0135]

[0136] 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 a structure of formula (1) in the main chain direction, R 12 With R in the formula (3) 11 The definition is the same.

[0137] As X 2 Specific examples include X of formula (6) including preferred examples. 1 The same structure as the example listed in. In addition, Y in the polyimide precursor 2is a divalent organic group derived from a diamine that does not contain the structure of formula (1) in the main chain direction. Its structure is not particularly limited. 2 It can be appropriately selected based on the solubility of the polymer in the solvent, the coating properties of the liquid crystal alignment agent, the orientation of the liquid crystal when it is made into a liquid crystal alignment film, the voltage holding rate, the degree of accumulated charge and other required properties. One type can be used in the same polymer, or two or more types can be mixed.

[0138] If you have to show Y 2 Specific examples include the structure of formula (2) described on page 4 of International Publication No. 2015 / 119168, and the structures of formulas (Y-1) to (Y-97), (Y-101) to (Y-118) described on pages 8 to 12; a divalent organic group obtained by removing two amino groups from formula (2) described on page 6 of International Publication No. 2013 / 008906; a divalent organic group obtained by removing two amino groups from formula (2) described on page 8 of International Publication No. 2015 / 122413 a divalent organic group obtained by removing two amino groups from the formula (1) described in ; a structure of formula (3) described on page 8 of International Publication Gazette 2015 / 060360; a divalent organic group obtained by removing two amino groups from the formula (1) described in page 8 of Japanese Patent Publication 2012-173514; a divalent organic group obtained by removing two amino groups from formulas (A) to (F) described on page 9 of International Publication Gazette 2010-050523, etc.

[0139] As the preferred 2 The structure of can be exemplified by the structure of the following formula (11).

[0140]

[0141] In formula (11), R 32 It is a single bond or a divalent organic group, and is preferably a single bond.

[0142] R 33 -(CH2) r - is a structure shown in FIG. r is an integer of 2 to 10, preferably 3 to 7. In addition, any -CH2- can be optionally replaced by an ether, ester, amide, urea or urethane bond under the condition that they are not adjacent to each other.

[0143] R 34 It is a single bond or a divalent organic group.

[0144] Any hydrogen atom on the benzene ring may be substituted with a monovalent organic group, preferably a fluorine atom or a methyl group.

[0145] Specific examples of the structure represented by formula (11) include the following structures, but the structure is not limited thereto.

[0146]

[0147]

[0148] Among them, it is preferred to contain the same partial structure as the benzene ring-Y-benzene ring part of the specific diamine (2) from the viewpoint of not inhibiting the reorientation of at least one selected from the polyimide precursor containing the structural unit represented by formula (3) and its imide product, i.e., polyimide.

[0149] When the polyimide precursor containing the structural unit represented by formula (3) also contains the structural unit represented by formula (4), the liquid crystal orientation may be further improved when the structural unit represented by formula (3) is less. The reason is that R 21 When the alkyl group is heated, imidization will not occur, and the orientation ability of the liquid crystal molecules will be reduced. Therefore, the structural unit represented by 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 formula (3) and formula (4).

[0150] The molecular weight of the polyimide precursor used in the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and further preferably 10,000 to 100,000 in terms of weight average molecular weight.

[0151] Examples of polyimides having a divalent group represented by formula (1) in the main chain include polyimides obtained by ring-closing the aforementioned polyimide precursor. The ring-closure ratio (also referred to as imidization ratio) of the amic acid group in the polyimide is not necessarily 100% and can be arbitrarily adjusted according to the application and purpose.

[0152] As a method of imidating a polyimide precursor, thermal imidation in which a solution of a polyimide precursor is heated as it is, or catalytic imidation in which a catalyst is added to a solution of a polyimide precursor is mentioned.

[0153] <Liquid crystal alignment agent>

[0154] The liquid crystal aligning agent of the present invention contains a polymer (specific polymer) obtained by a diamine component containing a diamine having a structure shown in formula (1), but it may also contain two or more specific polymers with different structures within the limit of the effect described in the present invention. In addition, in addition to the specific polymer, other polymers may also be contained, that is, polymers that do not have a divalent group shown in formula (1) may also be contained. As the types of other polymers, polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetals, polystyrene or its derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, etc. can be cited. When the liquid crystal aligning agent of the present invention contains other polymers, the ratio of the specific polymer to the total polymer components is preferably 5% by mass or more, and as an example, 5 to 95% by mass can be cited.

[0155] Liquid crystal alignment agents are used to make liquid crystal alignment films. From the perspective of forming a uniform film, they are generally in the form of a coating liquid. The liquid crystal alignment agent of the present invention is also preferably a coating liquid containing the aforementioned polymer component and an organic solvent that can dissolve the polymer component. At this time, the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed according to the setting of the thickness of the coating to be formed. From the perspective of forming a uniform and defect-free coating, it is preferably 1% by mass or more, and from the perspective of the storage stability of the solution, it is preferably set to 10% by mass or less. The concentration of the particularly preferred polymer is 2 to 8% by mass.

[0156] The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as it is an organic solvent in which the polymer component can be uniformly dissolved. If specific examples are given, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, etc. can be cited. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferably used.

[0157] In addition, for the organic solvent contained in the liquid crystal alignment agent, a mixed solvent formed by a solvent that can improve the coating property and surface smoothness of the coating film when the liquid crystal alignment agent is applied is usually used on the basis of the above-mentioned solvent, and such a mixed solvent is also preferably used in the liquid crystal alignment agent of the present invention. Specific examples of the organic solvents used in combination are listed below, but are not limited to these examples.

[0158] For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentanol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 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-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene ... 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 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 propylene 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 dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, Ethylene 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 acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, solvents represented by the following formulas [D-1] to [D-3], and the like.

[0159]

[0160] In formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms, wherein in the formula [D-2], D 2represents an alkyl group having 1 to 3 carbon atoms, wherein D 3 It represents an alkyl group having 1 to 4 carbon atoms.

[0161] Among them, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether are preferably used. The type and content of such solvents can be appropriately selected according to the coating device, coating conditions, coating environment, etc. of the liquid crystal alignment agent.

[0162] The liquid crystal aligning agent of the present invention may also contain additional components other than polymer components and organic solvents within the scope of not impairing the effect of the present invention. As such additional components, there can be cited: a close adhesion aid for improving the close adhesion between the liquid crystal aligning film and the substrate, and the close adhesion between the liquid crystal aligning film and the sealing material; a cross-linking agent for improving the strength of the liquid crystal aligning film; a dielectric or conductive material for adjusting the dielectric constant and resistance of the liquid crystal aligning film, etc. Specific examples of these additional components are various components disclosed in the known literature on liquid crystal aligning agents. If an example must be shown, the components disclosed on pages 53

[0105] to 55

[0116] of the Public Gazette No. 2015 / 060357 can be cited.

[0163] <Method for producing substrate having liquid crystal alignment film> and <Method for producing liquid crystal display element>

[0164] The method for manufacturing a substrate having a liquid crystal alignment film of the present invention comprises the following steps:

[0165] Step [I], coating a polymer composition containing (A) a polymer obtained from a diamine component including a diamine having a structure represented by formula (1) and (B) an organic solvent on a substrate having a conductive film for lateral electric field driving, thereby forming a coating film;

[0166] Step [II], irradiating the coating film obtained in step [I] with polarized ultraviolet rays; and

[0167] In step [III], the coating film obtained in step [II] is heated.

[0168] Through the above-mentioned steps, a liquid crystal alignment film for a transverse electric field driven liquid crystal display element to which an alignment control capability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

[0169] Furthermore, by preparing a second substrate in addition to the substrate (first substrate) obtained as described above, a transverse electric field driven liquid crystal display element can be obtained.

[0170] In addition to using a substrate without a conductive film for driving a lateral electric field instead of a substrate with a conductive film for driving a lateral electric field, the second substrate having a liquid crystal orientation film endowed with an orientation control capability can be obtained by using the above-mentioned steps [I] to [III] (due to the use of a substrate without a conductive film for driving a lateral electric field, for convenience, these steps are sometimes referred to as steps [I'] to [III'] in this application).

[0171] A method for manufacturing a lateral electric field driven liquid crystal display element comprises:

[0172] Step [IV]: The first substrate and the second substrate obtained above are arranged to face each other so that the liquid crystal alignment films of the first substrate and the second substrate face each other with the liquid crystal interposed therebetween, thereby obtaining a liquid crystal display element. Thus, a transverse electric field driven liquid crystal display element can be obtained.

[0173] Hereinafter, each step [I] to [III] and [IV] included in the production method of the present invention will be described.

[0174] <Process [I]>

[0175] In step [I], a polymer composition containing a photosensitive main chain polymer and an organic solvent is applied on the substrate having the conductive film for transverse electric field driving to form a coating film.

[0176] <Substrate>

[0177] There is no particular limitation on the substrate, but when the manufactured liquid crystal display element is a transmission type, a substrate with high transparency is preferably used. In this case, there is no particular limitation, and a glass substrate, or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.

[0178] In addition, in consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer may be used.

[0179] <Conductive film for lateral electric field driving>

[0180] The substrate has a conductive film for lateral electric field driving.

[0181] When the liquid crystal display element is a transmission type, examples of the conductive film include ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide), but the conductive film is not limited to these.

[0182] In the case of a reflective liquid crystal display element, examples of the conductive film include materials that reflect light, such as aluminum, but are not limited to these.

[0183] As a method of forming a conductive film on a substrate, a conventionally known method can be used.

[0184] The method for applying the polymer composition onto the substrate having the conductive film for transverse electric field driving is not particularly limited.

[0185] The coating method is generally industrially performed by screen printing, offset printing, flexographic printing or inkjet method, etc. Other coating methods include dipping, roll coating, slit coating, spin coating (spin coating method) or spray coating, and these methods can be used according to the purpose.

[0186] After coating the polymer composition on the substrate having the conductive film for lateral electric field driving, the solvent can be evaporated at 50 to 300° C., preferably 50 to 180° C., by heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven to obtain a coating film. From the viewpoint of liquid crystal alignment stability, the drying temperature at this time is preferably lower than that in step [III].

[0187] If the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm.

[0188] Note that, after step [I] and before the next step [II], a step of cooling the substrate on which the coating film is formed to room temperature may be provided.

[0189] <Process [II]>

[0190] In step [II], the coating obtained in step [I] is irradiated with polarized ultraviolet rays. When the film surface of the coating is irradiated with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays from a specific direction through a polarizing plate. As the ultraviolet rays used, ultraviolet rays with a wavelength in the range of 100nm to 400nm can be used. Preferably, the optimal wavelength is selected with the aid of a filter or the like depending on the type of coating used. In addition, for example, in order to selectively induce a photolysis reaction, ultraviolet rays with a wavelength in the range of 240nm to 400nm can be selected. As ultraviolet rays, for example, light emitted by a high-pressure mercury lamp or a metal halide lamp can be used.

[0191] The irradiation amount of polarized ultraviolet rays depends on the coating film used. The irradiation amount is preferably set in the 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 in the range of 1% to 50%, wherein ΔA 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.

[0192] <Step [III]>

[0193] In step [III], the coating film irradiated with polarized ultraviolet rays in step [II] is heated. Heating can impart orientation control capability to the coating film.

[0194] The heating may be performed by using a heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven. The heating temperature may be determined in consideration of a temperature at which the coating film to be used exhibits good liquid crystal alignment stability and electrical properties.

[0195] The heating temperature is preferably within the temperature range in which the main chain polymer exhibits good liquid crystal orientation stability. When the heating temperature is too low, there is a tendency for the anisotropy amplification effect brought about by heat and insufficient thermal imidization, and when the heating temperature is excessively higher than the temperature range, there is a tendency for the anisotropy imparted by polarized light exposure to disappear, and in this case, it is sometimes difficult to re-orient in one direction by self-assembly.

[0196] For the same reason as described in step [I], the thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm.

[0197] By having the above steps, the production method of the present invention can efficiently introduce anisotropy into the coating film and can efficiently produce a substrate with a liquid crystal alignment film.

[0198] <Step [IV]>

[0199] Step [IV] is a step in which the substrate (first substrate) having a liquid crystal alignment film on the conductive film for lateral electric field driving obtained in step [III] and the substrate (second substrate) with a liquid crystal alignment film without a conductive film obtained in the above steps [I'] to [III'] are arranged opposite to each other in such a manner that the liquid crystal alignment films of the two are opposite to each other with liquid crystals interposed therebetween, and a liquid crystal unit is produced by a known method to produce a lateral electric field driven liquid crystal display element. It should be noted that steps [I'] to [III'] can be carried out in the same manner as steps [I] to [III] except that a substrate without a conductive film for lateral electric field driving is used instead of a substrate with the conductive film for lateral electric field driving in step [I]. The difference between steps [I] to [III] and steps [I'] to [III'] is only the presence or absence of the conductive film, so the description of steps [I'] to [III'] is omitted.

[0200] If a production example of a liquid crystal unit or a liquid crystal display element is given, the following method can be illustrated: prepare the above-mentioned first substrate and second substrate, spread spacers on the liquid crystal alignment film of one substrate, adhere the other substrate with the liquid crystal alignment film surface as the inner side, and inject liquid crystal under reduced pressure and seal; or, after dripping liquid crystal on the surface of the liquid crystal alignment film with spacers, adhere the substrates and seal. At this time, the substrate on one side preferably uses a substrate with an electrode structure like a comb tooth for lateral electric field driving. The diameter of the spacer at this time is preferably 1μm to 30μm, and more preferably 2μm to 10μm. The diameter of the spacer will determine the distance between a pair of substrates used to clamp the liquid crystal layer, that is, the thickness of the liquid crystal layer.

[0201] In the method for manufacturing a substrate with a coating film of the present invention, a polymer composition is coated on a substrate to form a coating film, and then polarized ultraviolet rays are irradiated. Subsequently, anisotropy is efficiently introduced into the main chain polymer film by heating, thereby manufacturing a substrate with a liquid crystal alignment film having the ability to control liquid crystal alignment.

[0202] The coating film used in the present invention utilizes the principle that the main chain self-assembly based on the photoreaction induces the molecular reorientation, thereby efficiently introducing anisotropy into the coating film. In the manufacturing method of the present invention, when the main chain polymer has a structure with a photolyzable group as a photoreactive group, a coating film is formed on a substrate using the main chain polymer, and then polarized ultraviolet rays are irradiated and then heated to produce a liquid crystal display element.

[0203] Therefore, the coating film used in the method of the present invention can be efficiently introduced with anisotropy by sequentially irradiating the coating film with polarized ultraviolet rays and performing a heat treatment, thereby making it possible to obtain a liquid crystal alignment film having excellent alignment controllability.

[0204] Furthermore, for the coating film used in the method of the present invention, the irradiation amount of polarized ultraviolet rays irradiated to the coating film and the heating temperature in the heat treatment are optimized, thereby achieving efficient introduction of anisotropy into the coating film.

[0205] The optimal amount of polarized ultraviolet irradiation for efficiently introducing anisotropy into the coating used in the present invention corresponds to the amount of polarized ultraviolet irradiation that makes the photosensitive groups in the coating film to undergo photolysis reaction reach the optimal amount. As a result of irradiating the coating used in the present invention with polarized ultraviolet rays, if the photosensitive groups undergoing photolysis reaction are small, a sufficient amount of photoreaction cannot be achieved. In this case, sufficient self-assembly will not be performed even if it is subsequently heated.

[0206] Therefore, in the coating film used in the present invention, the optimal amount of the photosensitive group that undergoes photolysis reaction by irradiation with polarized ultraviolet rays is preferably set to 0.1 mol% to 90 mol%, more preferably 0.1 mol% to 80 mol% of the polymer film. By setting the amount of the photosensitive group that undergoes photoreaction to this range, self-assembly in the subsequent heat treatment is efficiently promoted, and anisotropy can be efficiently formed in the film.

[0207] 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, the anisotropy is efficiently introduced into the coating film used in the present invention together with the subsequent heat treatment. At this time, the appropriate amount of polarized ultraviolet rays can be evaluated based on the ultraviolet absorption of the coating film used in the present invention.

[0208] That is, for the coating used in the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet and the ultraviolet absorption in the direction perpendicular to the polarization direction of the polarized ultraviolet are measured respectively after the polarized ultraviolet irradiation. ΔA is evaluated based on the measurement result of ultraviolet absorption, and the ΔA is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet in the coating. Then, the maximum value (ΔAmax) of ΔA that can be achieved in the coating used in the present invention and the amount of polarized ultraviolet irradiation that achieves this value are calculated. In the manufacturing method of the present invention, the amount of polarized ultraviolet irradiation that achieves this ΔAmax is used as a reference to determine the preferred amount of polarized ultraviolet irradiation in the manufacture of the liquid crystal alignment film.

[0209] As described above, in the manufacturing method of the present invention, in order to realize the efficient introduction of anisotropy into the coating film, the temperature range in which the main chain polymer imparts liquid crystal orientation stability can be used as a reference to determine the above-mentioned suitable heating temperature. Therefore, for example, the temperature range in which the main chain polymer used in the present invention imparts liquid crystal orientation stability can be determined by considering the temperature at which the coating film used exhibits good liquid crystal orientation stability and electrical properties, and can be set according to the temperature range corresponding to the liquid crystal orientation film formed by polyimide, etc. in the past. That is, it is preferred to set the heating temperature after polarized ultraviolet irradiation to 100°C to 300°C, and it is more ideal to set it to 150°C to 250°C. By doing so, the coating film used in the present invention will be given greater anisotropy.

[0210] By doing so, the liquid crystal display element provided by the present invention can show high reliability against external stress such as light and heat.

[0211] As described above, the substrate for a lateral electric field driven liquid crystal display element manufactured using the polymer of the present invention or the lateral electric field driven liquid crystal display element having the substrate has excellent reliability and can be suitably used in large-screen and high-definition liquid crystal televisions, etc. In addition, the liquid crystal alignment film manufactured by the method of the present invention has excellent liquid crystal alignment stability and reliability, and can therefore also be used in a variable phase shifter using liquid crystals, which can be suitably used in, for example, an antenna with a variable resonance frequency, etc.

[0212] Example

[0213] The abbreviations used in the examples are as follows.

[0214] DMF: N,N-dimethylformamide

[0215] MeOH: Methanol

[0216] NMP: N-methyl-2-pyrrolidone

[0217] BCS: Butyl Cellosolve

[0218] DA-1: The compound represented by the following structural formula (DA-1)

[0219] DA-2: The compound represented by the following structural formula (DA-2)

[0220] DA-3: The compound represented by the following structural formula (DA-3)

[0221] CA-1: The compound represented by the following structural formula (CA-1)

[0222]

[0223] < 1 HNMR measurement>

[0224] Apparatus: Fourier transform superconducting nuclear magnetic resonance apparatus (FT-NMR) "INOVA-400" (manufactured by Varian), 400 MHz.

[0225] Solvent: deuterated N,N-dimethyl sulfoxide (DMSO-d6).

[0226] Reference substance: tetramethylsilane (TMS).

[0227] <Viscosity measurement>

[0228] In the synthesis examples, the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) under the conditions of a sample volume of 1.1 mL, a conical rotor TE-1 (1°34', R24), and a temperature of 25°C.

[0229] <Diamine compounds>

[0230] DA-1 is a novel compound that has not been disclosed in literature, and its synthesis method is described in detail in the following Synthesis Example 1.

[0231] <Synthesis example 1>

[0232] [DA-1]: Synthesis of 4-(2-(4-(2-(methylamino)ethyl)phenoxy)ethoxy)aniline

[0233] The aromatic diamine compound (DA-1) was synthesized according to the four-step route shown below. It should be noted that the aromatic diamine compound (DA-1) belongs to the above-mentioned specific diamine compound.

[0234] Step 1: Synthesis of 2-(4-(2-(4-nitrophenoxy)ethoxy)phenyl)ethanol (DA-1-1)

[0235]

[0236] 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 a solution obtained by dissolving β-bromo-4-nitrophenyl ethyl ether (29.4 g, 119.4 mmol) in DMF (22.5 g) was added dropwise at 80°C. The mixture was stirred at 80°C for 5 hours, and the disappearance of the raw material was confirmed by high performance liquid chromatography (hereinafter referred to as HPLC). Then, the reaction solution was naturally cooled to room temperature, water (540.0 g) was added, and then dichloroethane (270.0 g) was added to perform a liquid separation operation to extract the organic layer. The mixture was extracted again with pure water (540.0 g), dried with magnesium sulfate (5.0 g), and concentrated. Tetrahydrofuran (50.0 g) and heptane (40.0 g) were added to the concentrated crude product, and all of the mixture was dissolved at 60° C., then 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%).

[0237] 1 H NMR (DMSO-d6): δ8.22 (d, J=9.2Hz, 2H, C6H4), 7.22 (d, J=9.2Hz, 2H, C6H4), 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=7.2Hz, 2H, CH2).

[0238] Step 2: Synthesis of 4-(2-(4-nitrophenoxy)ethoxy)phenethyl methanesulfonate (DA-1-2)

[0239]

[0240] 2-(4-(2-(4-nitrophenoxy)ethoxy)phenyl)ethanol (5.0 g, 16.5 mmol) was dissolved in dichloroethane (30.0 g), triethylamine (2.50 g, 24.7 mmol) was added, and the mixture was cooled to 5°C. A solution obtained by dissolving methanesulfonyl chloride (2.3 g, 19.8 mmol) in dichloroethane (15.0 g) was added dropwise while being careful about heat generation. The mixture was stirred at 5°C for 1 hour, and the disappearance of the raw material was confirmed by HPLC. Then, water (60.0 g) was added to the reaction solution, followed by dichloroethane (40.0 g), and a liquid separation operation was performed to extract the organic layer. The organic layer was extracted again with water (50.0 g), and the mixture was dried over sodium sulfate (5.0 g) together with the previous organic layer, and then concentrated. The concentrate was used as a crude product to obtain 4-(2-(4-nitrophenoxy)ethoxy)phenethyl methanesulfonate (white powder, yield: 6.3 g, yield rate: 99%).

[0241] 1 H NMR (DMSO-d6): δ8.22 (d, J=9.2Hz, 2H, C6H4), 7.23-7.20 (m, 4H, C6H4), 7.14 (d, J=8.4Hz, 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=6.8Hz, 2H, CH2).

[0242] Step 3: Synthesis of N-methyl-2-(4-(2-(4-nitrophenoxy)ethoxy)phenyl)ethaneamine (DA-1-3)

[0243]

[0244] 4-(2-(4-nitrophenoxy)ethoxy)phenethyl methanesulfonate (20.0 g, 52.4 mmol) was dissolved in tetrahydrofuran (200.0 g), and a 40% methylamine solution in MeOH (81.4 g, 1048.8 mmol) was added, and the temperature was raised to 40°C. The mixture was stirred at 40°C for 24 hours, and the disappearance of the raw material was confirmed by HPLC. Then, the reaction solution was concentrated, ethyl acetate (400.0 g) was added, and then a 2wt% sodium hydroxide aqueous solution (400.0 g) was added to perform a liquid separation operation, and the organic layer was extracted. The organic layer was extracted again with water (400.0 g), and after drying with the previous organic layer over sodium sulfate (10.0 g), it was 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)ethanamine (yellow powder, yield: 15.6 g, yield: 94%).

[0245] 1 H NMR (DMSO-d6): δ8.22 (d, J=9.2Hz, 2H, C6H4), 7.21 (d, J=9.2Hz, 2H, C6H4), 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).

[0246] Step 4: Synthesis of 4-(2-(4-(2-methylamino)ethyl)phenoxy)ethoxy)aniline (DA-1)

[0247]

[0248] N-methyl-2-(4-(2-(4-nitrophenoxy)ethoxy)phenyl)ethanamine (10.0 g, 31.6 mmol) was dissolved in tetrahydrofuran (100.0 g), 5% palladium-carbon (0.5 g) was added, and the mixture was stirred at 50° C. for 5 hours under a hydrogen atmosphere. The disappearance of the raw material was confirmed by HPLC, and the mixture was dissolved in tetrahydrofuran (50.0 g), the catalyst was removed by filtration, and the filtrate was concentrated. The solid was washed with heptane (50.0 g), and 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%).

[0249] 1H NMR (DMSO-d6): δ7.11 (d, J=9.2Hz, 2H, C6H4), 6.87 (d, J=9.2Hz, 2H, C6H4), 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).

[0250] Polymerization example, preparation example of alignment agent

[0251] <Synthesis example 2>

[0252] 1.00 g (3.50 mmol) of DA-1 and 2.86 g (10.5 mmol) of DA-2 were weighed into a 100 mL four-necked flask with a stirrer and a nitrogen inlet tube, and 37.6 g of NMP was added, and the mixture was dissolved by stirring while nitrogen was supplied. 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 added, and the mixture was stirred at 23 ° C for 15 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 270 mPa·s.

[0253] 14.5 g of the polyamic acid solution was taken out and added to a 100 mL Erlenmeyer flask equipped with a stirrer, 12.6 g of NMP and 11.6 g of BCS were added, and the mixture was stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal aligning agent (A-1).

[0254] <Comparative Synthesis Example 1>

[0255] 4.09 g (15.0 mmol) of DA-2 was weighed into a 100 mL four-necked flask with a stirrer and a nitrogen inlet tube, and 39.3 g of NMP was added, and the mixture was dissolved by stirring while nitrogen was supplied. 2.77 g (14.1 mmol) of CA-1 was added while the diamine solution was stirred under water cooling, and 9.83 g of NMP was added, and the mixture was stirred at 23 ° C for 3 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 263 mPa·s.

[0256] 14.9 g of the polyamic acid solution was taken out and added to a 100 mL Erlenmeyer flask equipped with a stirrer, 12.9 g of NMP and 11.9 g of BCS were added, and the mixture was stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal aligning agent (B-1).

[0257] <Comparative Synthesis Example 2>

[0258] 2.86 g (10.5 mmol) of DA-2 and 0.526 g (3.50 mmol) of DA-3 were weighed into a 100 mL four-necked flask with a stirrer and a nitrogen inlet tube, and 34.8 g of NMP was added, and the mixture was dissolved by stirring while nitrogen was supplied. 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 added, and the mixture was stirred at 23 ° C for 15 hours under a nitrogen atmosphere to obtain a polyamic acid solution. The viscosity of the polyamic acid solution at a temperature of 25 ° C was 299 mPa·s.

[0259] 14.6 g of the polyamic acid solution was taken out and added to a 100 mL Erlenmeyer flask equipped with a stirrer, 12.6 g of NMP and 11.7 g of BCS were added, and the mixture was stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal aligning agent (B-2).

[0260] <Preparation of Liquid Crystal Cell for Evaluation of Liquid Crystal Orientation>

[0261] The method for producing a liquid crystal cell for evaluating the liquid crystal orientation is shown below.

[0262] A liquid crystal unit having a liquid crystal display element structure of the FFS mode is prepared. First, a substrate with electrodes is prepared. The substrate is a glass substrate with a size of 30 mm × 35 mm and a thickness of 0.7 mm. On the substrate, as the first layer, an IZO electrode constituting a counter electrode is formed on the entire surface. On the counter electrode of the first layer, as the second layer, a SiN (silicon nitride) film formed by a CVD method is formed. The film 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 the third layer, a comb-shaped pixel electrode formed by patterning the IZO film is arranged to form two pixels, the first pixel and the second pixel. The size of each pixel is 10 mm in length and about 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 due to the action of the SiN film of the second layer.

[0263] The pixel electrode of the third layer is the same as the figure described in Japanese Patent Laid-Open 2014-77845 (Japanese Patent Gazette), and has a comb-like shape composed of a plurality of "<"-shaped electrode elements with a bent central portion. The width of each electrode element in the width direction is 3μm, and the interval between the electrode elements is 6μm. The pixel electrode forming each pixel is composed of a plurality of "<"-shaped electrode elements with a bent central portion, so the shape of each pixel is not a rectangle, but has a shape similar to a bold "<" character that is bent in the central portion like the electrode elements. Furthermore, each pixel is divided into upper and lower parts with the central bent portion as the boundary, and has a first area on the upper side of the bent portion and a second area on the lower side.

[0264] When comparing the first area and the second area of ​​each pixel, the electrode elements constituting the pixel electrodes are formed in different directions. That is, when the line segment direction when the polarization plane of the polarized ultraviolet rays described later is projected onto the substrate is used as a reference, in the first area of ​​the pixel, the electrode elements of the pixel electrode are formed at an angle of +10° (clockwise), and in the second area of ​​the pixel, the electrode elements of the pixel electrode are formed at an angle of -10° (clockwise). That is, the first area and the second area of ​​each pixel are constructed as follows: the directions of the rotational movement (plane switching) of the liquid crystal within the substrate surface induced by applying a voltage between the pixel electrode and the counter electrode are opposite to each other.

[0265] Next, the liquid crystal alignment agent obtained in the synthesis example and the comparative synthesis example is filtered with a 1.0 μm filter, and then applied to the prepared substrate with electrodes by spin coating. Then, dry on a hot plate set at 70°C for 90 seconds. Next, use an exposure device manufactured by Ushio Electric Co., Ltd.: APL-L050121S1S-APW01, and irradiate linearly polarized light of ultraviolet rays from a direction perpendicular to the substrate through a wavelength selection filter and a polarizing plate. At this time, the direction of the polarization plane is set so that the line direction of the polarized ultraviolet rays when projected onto the substrate is inclined 10° relative to the third layer of IZO comb-tooth electrodes. Next, bake in an IR (infrared) type oven set at 230°C for 30 minutes to obtain a substrate with a polyimide liquid crystal alignment film with a film thickness of 100 nm that has been subjected to orientation treatment. In addition, as a counter substrate, a glass substrate with an ITO electrode formed on the back and a columnar spacer with a height of 4 μm was subjected to an orientation treatment in the same manner as described above to obtain a substrate with a polyimide liquid crystal orientation film. These two substrates with liquid crystal orientation films are taken as a group, and a sealant is printed on one substrate in the form of a liquid crystal injection port, and the other substrate is bonded and crimped in a manner that the liquid crystal orientation film faces each other and the polarization plane of the polarized ultraviolet rays is projected onto the substrate in a parallel direction. Then, the sealant is cured to produce an empty cell with a cell gap of 4 μm. Liquid crystal ML-7026-100 (negative liquid crystal manufactured by Merck) is injected into the empty cell by a reduced pressure injection method, and the injection port is sealed to obtain an FFS mode liquid crystal cell. Then, the resulting liquid crystal cell is heated at 120°C for 30 minutes, and is placed at 23°C for one night before being used for the evaluation of liquid crystal orientation.

[0266] <Evaluation of Liquid Crystal Orientation>

[0267] Using this liquid crystal cell, a 16 VPP AC voltage was applied at a frequency of 30 Hz for 120 hours in a constant temperature environment of 70° C. Then, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left at 23° C. overnight.

[0268] After placement, the liquid crystal unit is set between two polarizing plates configured in a manner that the polarization axes are orthogonal, the backlight is turned on without voltage application, and the configuration angle of the liquid crystal unit is adjusted to minimize the brightness of the transmitted light. Then, the rotation angle when the liquid crystal unit is rotated from the angle at which the second area of ​​the first pixel becomes darkest to the angle at which the first area becomes darkest is calculated as the angle △. For the second pixel, the second area and the first area are also compared in the same way, and the same angle △ is calculated. Then, the average value of the angle △ values ​​of the first pixel and the second pixel is calculated as the angle △ of the liquid crystal unit. The case where the angle △ value of the liquid crystal unit is less than 0.3° is defined and evaluated as "good", and the case where the angle △ value is greater than 0.3° is defined and evaluated as "poor".

[0269] <Preparation of Liquid Crystal Cell for Voltage Holding Ratio Evaluation>

[0270] A liquid crystal cell for voltage holding ratio measurement was prepared in the same manner as the liquid crystal cell for liquid crystal orientation evaluation, except that a glass substrate with an ITO electrode was used and 4 μm spacer microspheres were spread on the liquid crystal alignment film surface on one substrate before printing the sealant.

[0271] <Evaluation of voltage holding ratio>

[0272] The voltage holding ratio is evaluated using the liquid crystal unit. Specifically, a 2VPP AC voltage is applied to the liquid crystal unit obtained by the above method for 60 microseconds at a temperature of 70°C, the voltage is measured after 1 second, and the voltage can be maintained as the voltage holding ratio (also called VHR) calculated. It should be noted that the voltage holding ratio measuring device (VHR-1, manufactured by Dongyang Technica) is used, and the measurement is performed with the settings of voltage (Voltage): ±1V, pulse width (Pulse Width): 60 microseconds, and frame period (Flame Period): 1000 milliseconds. The case where the voltage holding ratio of the liquid crystal unit is 80% or more is defined and evaluated as "good", and the case where the voltage holding ratio is less than 80% is defined and evaluated as "poor".

[0273] (Example 1)

[0274] Using the liquid crystal aligning agent (A-1) obtained in Synthesis Example 2, two liquid crystal units were prepared as described above. Polarized ultraviolet rays were irradiated using a high-pressure mercury lamp through a wavelength selection filter: 240LCF and a 254nm polarizing plate. The amount of polarized ultraviolet rays was measured using an illuminometer UVD-S254SB manufactured by Ushio Electric Co., Ltd., with a wavelength of 254nm and a range of 600 to 1800mJ / cm 2 The method is implemented by changing the amount of polarized ultraviolet light irradiation one by one within a range of , thereby producing three or more liquid crystal units with different amounts of polarized ultraviolet light irradiation.

[0275] The liquid crystal orientation of these liquid crystal cells was evaluated and the polarized ultraviolet irradiation dose at the best angle △ was 1800 mJ / cm 2 , the angle △ is 0.15°, which is good.

[0276] Furthermore, the voltage holding ratio of the liquid crystal cell produced by irradiating the same polarized ultraviolet ray was evaluated and found to be 92.4%, which was good.

[0277] (Comparative Examples 1-2)

[0278] The liquid crystal orientation and the voltage holding ratio were evaluated by the same method as in Example 1, except having used the liquid crystal aligning agent obtained in Comparative Synthesis Examples 1 and 2.

[0279] Table 1 shows the polarized ultraviolet irradiation amount at which the angle Δ is optimal when the liquid crystal aligning agents obtained in the synthesis examples and the comparative synthesis examples are used, the evaluation results of the liquid crystal alignment, and the evaluation results of the voltage holding ratio.

[0280] [Table 1]

[0281]

[0282] As shown in Table 1, in Example 1, the difference in the orientation azimuth before and after AC driving, that is, the angle △, is less than 0.3°, which is good. At the same time, the voltage holding rate is more than 80%, which also shows good characteristics, and both are good afterimage characteristics. Therefore, the improvement of the display quality of the liquid crystal display element is excellent. In Comparative Examples 1 and 2, the characteristics of both the angle △ and the voltage holding rate were not confirmed.

[0283] This confirmed that the liquid crystal display element produced by the method of the present invention exhibits extremely excellent image sticking characteristics.

[0284] Industrial Applicability

[0285] The substrate for a lateral electric field driven liquid crystal display element manufactured using the composition of the present invention or the lateral electric field driven liquid crystal display element having the substrate has excellent reliability and can be suitably used in large-screen and high-definition liquid crystal televisions, etc. In addition, the liquid crystal alignment film manufactured by the method of the present invention has excellent liquid crystal alignment stability and reliability, and can therefore also be used in a variable phase shifter using liquid crystals, which can be suitably used in, for example, an antenna with a variable resonance frequency, etc.

Claims

1. A diamine represented by the following formula (2): In formula (2), X is a single bond or a benzene ring, Y and Z are each independently an alkylene group having 1 to 10 carbon atoms or a group consisting of an alkylene group and an ether bond having 1 to 10 carbon atoms, and R 1 and R 2 are each independently selected from the group consisting of an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, and a fluoroalkoxy group having 1 to 10 carbon atoms, and R 3 It is an alkyl group having 1 to 4 carbon atoms, and m and n are each independently an integer of 0 to 4.

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