KR102521135B1 - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

This invention relates to the liquid crystal aligning agent containing the polymer obtained from diamine which has a structure represented by following formula (1), and an organic solvent, a liquid crystal aligning film, and a liquid crystal display element. In formula (1), X is a single bond or a divalent organic group, Y and Z are each independently a divalent organic group containing alkylene, 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. According to the present invention, a substrate having a liquid crystal alignment film for a horizontal electric field driven liquid crystal display element imparted with high efficiency in orientation control and excellent burn-in characteristics, a horizontal electric field driven liquid crystal display element having the substrate, and a compound imparting it, More specifically, with the addition of a small amount, a novel diamine capable of improving reliability without affecting orientation can be provided.

Description

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

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

BACKGROUND OF THE INVENTION [0002] Liquid crystal display elements are known as light weight, thin and low power consumption display devices, and in recent years they have made remarkable progress, such as being used for large-sized televisions. A liquid crystal display element is comprised, for example by sandwiching a liquid crystal layer with a pair of transparent board|substrates provided with electrodes. And in a liquid crystal display element, the organic film which consists of an organic material is used as a liquid crystal aligning film so that a liquid crystal may become a desired orientation state between board|substrates.

That is, the liquid crystal alignment film, as a constituent member of the liquid crystal display element, is formed on a surface in contact with the liquid crystal of a substrate holding the liquid crystal, and plays a role of orienting the liquid crystal in a certain direction between the substrates. And the role of controlling the pretilt angle of a liquid crystal may be requested|required of a liquid crystal aligning film in addition to the role of orienting a liquid crystal in fixed directions, such as a direction parallel to a board|substrate, for example. The ability (henceforth referred to as orientation control ability) of controlling the orientation of the liquid crystal in such a liquid crystal aligning film is provided by orientation-processing with respect to the organic film which comprises a liquid crystal aligning film.

As a method for orientation treatment of a liquid crystal aligning film for imparting orientation control ability, a rubbing method has conventionally been known. The rubbing method refers to rubbing the surface of an organic film such as polyvinyl alcohol, polyamide, or polyimide on a substrate with a cloth such as cotton, nylon, or polyester in a certain direction (rubbing), and rubbing in a rubbing direction (rubbing direction). It is a method of orienting the liquid crystal with Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements. And, as the organic film used for the liquid crystal alignment film, a polyimide-based organic film excellent in reliability such as heat resistance and electrical properties has been mainly selected.

However, the rubbing method which rubs the surface of the liquid crystal aligning film which consists of polyimide etc. has a case where generation|occurrence|production of dust generation or static electricity poses a problem. In addition, due to high definition of liquid crystal display elements in recent years and irregularities caused by electrodes on the corresponding substrates and switching active elements for driving liquid crystals, the surface of the liquid crystal alignment film cannot be uniformly rubbed with a cloth, and uniform alignment of liquid crystals can be realized. There were cases where it was not possible.

Then, as another orientation processing method of the liquid crystal aligning film which did not perform rubbing, the photo-alignment method is actively examined.

Although there are various methods for the optical alignment method, anisotropy is formed in the organic film constituting the liquid crystal alignment 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, polarized ultraviolet rays are irradiated to the polyimide film, and anisotropic decomposition occurs by using the polarization direction dependence of ultraviolet light absorption of molecular structure. Then, the liquid crystal is oriented by the polyimide remaining without being decomposed (for example, refer to Patent Document 1).

Moreover, the photo-alignment method of a photocrosslinking type or a photoisomerization type is also known. For example, a dimerization reaction (crosslinking reaction) occurs at the double bond portion of two side chains parallel to polarized light by irradiation with polarized ultraviolet rays using polyvinyl cinnamate. Then, the liquid crystal is aligned in a direction orthogonal to the polarization direction (see Non-Patent Document 1, for example). In addition, when a side chain type polymer having azobenzene in a side chain is used, polarized ultraviolet rays are irradiated to cause an isomerization reaction at the azobenzene portion of the side chain parallel to the polarization, and the liquid crystal is oriented in a direction orthogonal to the polarization direction ( For example, see Non-Patent Document 2).

As in the above example, in the alignment treatment method of the liquid crystal alignment film by the photo-alignment method, rubbing is not required, and there is no fear of dust generation or generation of static electricity. And orientation processing can be performed also on the board|substrate of a liquid crystal display element with unevenness|corrugation on the surface, and it becomes the method of orientation processing of a liquid crystal alignment film suitable for an industrial production process.

Japanese Patent Publication No. 3893659

M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992). K. Ichimura et al., Chem. Rev. 100, 1847 (2000).

As described above, the photo-alignment method does not require a rubbing step itself compared to the rubbing method conventionally used industrially as a method for alignment treatment of liquid crystal display elements, and therefore has a great advantage. And compared with the rubbing method in which orientation control ability becomes substantially constant by rubbing, in the photo-alignment method, the irradiation amount of polarized light can be changed and orientation control ability can be controlled. However, in the photo-alignment method, when trying to achieve the same degree of alignment control as in the case of the rubbing method, a large amount of polarized light irradiation is required, or there are cases where stable alignment of liquid crystals cannot be realized.

For example, in the decomposition type photo-alignment method described in Patent Literature 1 described above, ultraviolet light from a high-pressure mercury lamp with an output of 500 W needs to be irradiated for 60 minutes to the polyimide film. it becomes necessary Moreover, even in the case of a dimerization type or a photoisomerization type photo-alignment method, ultraviolet irradiation of a large amount of about several joules to several tens of J may be required. Further, in the case of a photo-crosslinking type or photo-isomerization type photo-alignment method, since the thermal stability and photostability of liquid crystal orientation are poor, when used as a liquid crystal display element, there is a problem that alignment failure or display burn-in occurs. In particular, since liquid crystal molecules are switched in-plane in a transverse electric field drive type liquid crystal display element, misalignment of the liquid crystal after driving the liquid crystal easily occurs, and display burn-in caused by AC driving is a major problem.

Therefore, in the photo-alignment method, realization of high efficiency of alignment treatment and stable liquid crystal orientation is required, and the liquid crystal aligning film and liquid crystal aligning agent capable of imparting high orientation control ability to the liquid crystal aligning film with high efficiency, and providing them compound is required.

The present invention provides a substrate having a liquid crystal alignment film for a horizontal electric field driven liquid crystal display element imparted with high efficiency in orientation control and excellent burn-in characteristics, a horizontal electric field driven liquid crystal display element having the substrate, and a compound imparting the same. Specifically, it is an object to provide a novel diamine capable of improving reliability without affecting orientation by adding a small amount.

The present inventors discovered the following inventions as a result of earnestly examining to achieve the above object.

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

[Formula 1]

(In Formula (1), X is a single bond or a divalent organic group, Y and Z are each independently a divalent organic group containing alkylene, 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 above 1 containing at least one polymer selected from the group consisting of a polyimide precursor which is a polymer of a diamine component containing the above diamine and tetracarboxylic dianhydride and a polyimide which is an imide thereof, and an organic solvent. The liquid crystal aligning agent described in .

3. The liquid crystal aligning agent as described in said 1 or 2 in which the said diamine is represented by the following formula (2).

[Formula 2]

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

4. Liquid crystal aligning agent in any one of said 1-3 in which the said polyimide precursor is represented by following formula (3).

[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 having 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 as described in said 4 which is at least 1 sort(s) chosen from the group which the structure of X ^<1> becomes from following structural formula (A-1) - (A-21) in said Formula (3).

[Formula 4]

6. Liquid crystal aligning agent as described in said 4 or 5 which the polymer which has structural unit represented by said Formula (3) contains 10 mol% or more with respect to all the polymers contained in liquid crystal aligning agent.

7. The liquid crystal according to any one of 4 to 6 above, containing at least one selected from the group consisting of 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether in the organic solvent. orientation agent.

8. [I] A step of applying the composition according to any one of 1 to 7 above onto a substrate having a conductive film for driving a transverse electric field to form a coating film;

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

[III] Step of heating the coating film obtained in [II];

The manufacturing method of the board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements to which orientation control ability was provided by having.

9. The board|substrate which has the liquid crystal alignment film for horizontal electric field drive type liquid crystal display elements manufactured by the method of the said 8.

10. A transversal electric field drive type liquid crystal display device having the substrate described in 9 above.

11. Step of preparing the substrate (first substrate) described in 9 above;

[I'] a step of applying the composition according to claims 1 to 7 onto a second substrate to form a coating film;

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

[III'] Step of heating the coating film obtained in [II']; Process of obtaining the 2nd board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film to which orientation control ability was provided by having; and

[IV] Process of opposingly arranging the first and second substrates to obtain a liquid crystal display element so that the liquid crystal alignment films of the first and second substrates are opposed to each other through a liquid crystal; A method for producing a liquid crystal display element, wherein a horizontal electric field drive type liquid crystal display element is obtained by having a.

12. A transverse electric field drive type liquid crystal display device manufactured by the method described in 11 above.

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

[Formula 5]

(In Formula (1), X is a single bond or a divalent organic group, Y and Z are each independently a divalent organic group containing alkylene, 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 described in the above 13, in which the diamine is represented by the following formula (2).

[Formula 6]

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

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

[Formula 7]

(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 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 described in 15 above, wherein the structure of X ¹ in the formula (3) is at least one selected from the group consisting of the following structural formulas (A-1) to (A-21):

[Formula 8]

17. Diamine represented by the said formula (2).

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a horizontal electric field driven liquid crystal display element, which is highly efficient in orientation control and has excellent burn-in characteristics, and a horizontal electric field driven liquid crystal display element having the substrate.

The horizontal electric field drive type liquid crystal display device manufactured by the method of the present invention is highly efficient and has an orientation control capability, so that display characteristics are not impaired even when driven continuously for a long time.

The polymer composition used in the production method of the present invention has a photosensitive main chain polymer (hereinafter, simply referred to as a main chain polymer) capable of exhibiting self-organizing ability, and a coating film obtained by using the polymer composition. Silver is a film having a photosensitive main chain polymer capable of expressing self-assembly ability. This coating film is subjected to alignment treatment by polarized light irradiation without performing a rubbing treatment. And after polarized light irradiation, it becomes the coating film (henceforth also called a liquid crystal aligning film) to which orientation control ability was provided through the process of heating the main chain polymer film. At this time, the slight anisotropy expressed by polarized light irradiation becomes a driving force, and the main chain polymer itself is efficiently reorientated by self-organization. As a result, a highly efficient orientation treatment can be realized as a liquid crystal aligning film, and a liquid crystal aligning film with high orientation control ability can be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

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

<Diamine having a specific structure>

The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent containing a polymer obtained from diamine (in the present invention, it is also referred to as specific diamine) having a structure of formula (1) below, and an organic solvent.

[Formula 9]

(In Formula (1), X is a single bond or a divalent organic group, Y and Z are each independently a divalent organic group containing alkylene, 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 herein include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, or a fluoroalkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. Especially, as a monovalent organic group, a methyl group is preferable.

Examples of the divalent organic group include benzene, naphthalene, cyclohexyl groups, and groups obtained by substituting these hydrogen atoms with monovalent organic groups. Especially, as a divalent organic group, benzene is preferable.

The divalent organic group containing alkylene includes an alkylene group, a group composed of an alkylene and an ether bond, a group composed of an alkylene and an ester bond, and a group composed of an alkylene and ether bond in which some or all of hydrogen atoms are substituted with halogen. group, a group composed of an ester bond and an alkylene in which some or all of the hydrogen atoms are substituted with halogen. Especially, as a divalent organic group containing an alkylene, an alkylene and a group composed of an alkylene and an ether bond are preferable. It is preferable that they are 1 or more and 20 or less, and, as for carbon number, it is more preferable that they are 1 or more and 10 or less.

In addition, when the sum of the number of carbon atoms and the number of oxygen atoms involved in the length of the main chain is an even number among the total number of atoms of Y and Z, as a result of increasing the linearity of the obtained polymer, in the heating step after polarized light irradiation, more By reorienting in high order, since the liquid crystal aligning film to which high orientation control ability was provided can be obtained, it is preferable.

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

As m and n, 0 is preferable from the viewpoint that phenyl groups easily overlap each other due to less steric hindrance and rearrangement in a higher order.

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

[Formula 10]

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

Although the following can be illustrated as a specific example of the diamine which has the structure of said Formula (2), it is not limited to these.

[Formula 11]

[Formula 12]

[Formula 13]

<Synthesis method of specific diamine>

A method for synthesizing the specific diamine is not particularly limited. For example, a method in which a nitro compound represented by the following formula (5) is used and the nitro group it has is converted to an amino group by a reduction reaction is exemplified.

[Formula 14]

The catalyst used in the reduction reaction is preferably a commercially available activated carbon supporting metal, and examples thereof include palladium-activated carbon, platinum-activated carbon, and rhodium-activated carbon. In addition, it is not necessarily an activated carbon-supported metal catalyst, such as palladium hydroxide, platinum oxide, Raney nickel, iron, zinc, and tin. In general, iron, zinc, and tin, which are widely used, are preferable because good results are obtained.

In order to advance the reduction reaction more effectively, the reaction may be performed in the presence of activated carbon. At this time, the amount of activated carbon used is not particularly limited, but is preferably in the range of 1 to 30% by mass, more preferably 10 to 20% by mass, based on the dinitro compound X1. For the same reason, there are cases in which the reaction is performed under pressure. In this case, in order to avoid reduction of benzene nuclei, it is carried out in a pressurized range of up to 20 atm. Preferably, the reaction is carried out in a range of up to 10 atm. If necessary, an acid catalyst may be added to shorten the time.

The solvent can be used without limitation as long as it is a solvent that 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 (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); halogenated 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, H ₂ O, etc.) and the like can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction and the like, and can be used alone or in combination of two or more. If necessary, the solvent can be dried using an appropriate dehydrating agent or drying agent and used as a non-aqueous solvent.

The amount of solvent 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 to 30 times by mass, more preferably 1 to 10 times by mass.

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

[Preparation method of Formula (5)]

The method of synthesizing the compound of formula (5) is not particularly limited, but examples include 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 A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a tosylate (-OTs), a mesylate (-OMs) etc. are mentioned as a preferable leaving group X.

[Formula 15]

As for the amount of the reactive substrate, 1 to 20 equivalents of methylamine can be used with respect to 1 equivalent of the compound represented by the general formula (7).

In the case of using a solvent, the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction, but examples include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, and cyclohexane. alicyclic hydrocarbons such as chlorobenzene, aromatic halogenated hydrocarbons such as dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachlorethylene ethers such as aliphatic halogenated hydrocarbons such as diethyl ether, t-butylmethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 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; pyridine; pyridines such as picoline, acetonitrile, and dimethyl sulfoxide; and the like. These solvents may be used independently, or two or more of these may be mixed and used.

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

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

Generally, for example, 1 to 20 equivalents of methylamine, if necessary, 1 to 4 equivalents of potassium carbonate, triethylamine, pyridine, 4-(dimethylamino)pyridine, relative to 1 equivalent of the compound represented by the general formula (7) In the presence of a base such as, solventless 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, 10 minutes It is preferable to carry out the reaction within 24 hours.

[Preparation method of Formula (7)]

The method of synthesizing the compound of formula (7) is not particularly limited, but examples include a method of synthesizing a nitrobenzene derivative having a hydroxyl group represented by the following formula (8) by reacting it with commercially available mesyl chloride. there is. From the viewpoint of ease of synthesis, the leaving group X is preferably a mesylate (-Oms), but other preferable leaving groups X include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and tosylate (-OTs). there is.

[Formula 16]

As for the amount of the reaction substrate, 1 to 4 equivalents of mesyl chloride can be used with respect to 1 equivalent of the compound represented by Formula (8).

In the case of using a solvent, the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction, but examples include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, and cyclohexane. alicyclic hydrocarbons such as chlorobenzene, aromatic halogenated hydrocarbons such as dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachlorethylene ethers such as aliphatic halogenated hydrocarbons such as diethyl ether, t-butylmethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 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; pyridine; pyridines such as picoline, acetonitrile, and dimethyl sulfoxide; and the like. These solvents may be used independently, or two or more of these may be mixed and used.

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

The reaction temperature can be set to any temperature from -60°C to 25°C, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but can be set arbitrarily in the range of usually 5 minutes to 100 hours.

Generally, for example, 1 to 4 equivalents of mesyl chloride, if necessary, 1 to 4 equivalents of potassium carbonate, triethylamine, pyridine, 4-(dimethylamino)pyridine, etc., relative to 1 equivalent of the compound represented by formula (8). In the presence of a base, solventless or using a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, etc., in the range of 0 ℃ to 10 ℃, reaction for 10 minutes to 24 hours It is preferable to carry out

[Preparation of Formula (8)]

The method of synthesizing the compound of formula (8) is not particularly limited, but examples include a method of synthesizing by reacting a commercially available phenol derivative (9) with a nitrobenzene derivative having a leaving group represented by the following formula (10). there is. Preferred leaving group X include fluorine atom, chlorine atom, bromine atom, iodine atom, tosylate (-OTs), mesylate (-OMs) and the like.

[Formula 17]

As for the amount of the reactive 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).

In the case of using a solvent, the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction, but examples include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, and cyclohexane. alicyclic hydrocarbons such as chlorobenzene, aromatic halogenated hydrocarbons such as dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachlorethylene ethers such as aliphatic halogenated hydrocarbons such as diethyl ether, t-butylmethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 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; pyridine; pyridines such as picoline, acetonitrile, and dimethyl sulfoxide; and the like. These solvents may be used independently, or two or more of these may be mixed and used.

The addition of a base is not absolutely necessary, but when a base is used, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, or an alkali metal such as sodium hydrogen carbonate or potassium hydrogen carbonate. Bicarbonate, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, 4-(dimethylamino)pyridine, imidazole, 1,8-diazabicyclo[5,4,0]-7-undecene, etc. An organic base of 1 to 4 equivalents can be used relative to the compound represented by the general formula (10).

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

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

<Polymer>

The polymer of the present invention is a polymer obtained by using the above diamine. Although polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide, etc. are mentioned as a specific example, the polyimide precursor containing the structural unit represented by following formula (3) from a viewpoint of use as a liquid crystal aligning agent It is more preferable in it being at least 1 sort(s) chosen from polyimide which is , and its imide compound.

[Formula 18]

In the 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 the structure of formula (1), and R ¹¹ is A hydrogen atom or an alkyl group of 1 to 5 carbon atoms, and R ³ is an alkyl group of 1 to 4 carbon atoms. R ¹¹ is preferably a hydrogen atom, a methyl group or an ethyl group in view of the ease of imidation by heating. As R ³ , a methyl group is preferable from the viewpoint of easy 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 depends on the degree of required characteristics such as solubility in the solvent of the polymer, applicability of the liquid crystal aligning agent, orientation of the liquid crystal when used as a liquid crystal aligning film, voltage retention, and accumulated electric charge. It is appropriately selected depending on the type, and may be one type in the same polymer, or two or more types may be mixed.

If the specific example of X ^<1> is daringly shown, the structure of formula (X-1) - (X-46) published in the 13th term - 14th term of international publication 2015/119168, etc. are mentioned.

Although the structure of preferable X ^<1> is shown below, this invention is not limited to these.

[Formula 19]

Among the structures described above, (A-1), (A-2) and (A-4) are preferable from the viewpoint of optical orientation, and (A-1) is particularly preferable.

<diamine>

In Formula (3), as a specific example of Y ¹ , a structure obtained by removing an amino group and an alkylamino group from diamine having the structure of Formula (1) above is exemplified. Especially, as for Y ^<1> , it is especially preferable that it is a structure obtained by removing an amino group and an alkylamino group from the structure of the formula (2).

<Polymer (other structural units)>

The polyimide precursor containing the structural unit represented by formula (3) is at least selected from the structural unit represented by the following formula (4) and polyimide that is an imide product thereof within a range that does not impair the effect of the present invention. You may contain 1 type.

[Formula 20]

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 the definition of R ¹¹ in the formula (3) above.

Specific examples of X ² include the same structures as those exemplified for X ¹ in Formula (6), including preferred examples. Moreover, Y ^<2> in a polyimide precursor is a divalent organic group derived from diamine which does not contain the structure of Formula (1) in a principal chain direction, and the structure is not specifically limited. In addition, Y ² is appropriately selected according to the degree of required characteristics such as solubility in the solvent of the polymer, applicability of the liquid crystal aligning agent, orientation of the liquid crystal when used as a liquid crystal aligning film, voltage retention, and accumulated electric charge, One type may be sufficient in the same polymer, and two or more types may be mixed.

If the specific example of ^Y2 is shown, the structure of formula (2) published in item 4 of International Publication No. 2015/119168, and the formulas (Y-1) to (Y-97) published in items 8 to 12 , the structures of (Y-101) to (Y-118); The divalent organic group which removed 2 amino groups from formula (2) published in the 6th term of International Publication No. 2013/008906; The divalent organic group which removed 2 amino groups from Formula (1) published in 8 paragraph of International Publication No. 2015/122413; structure of formula (3) published in paragraph 8 of International Publication No. 2015/060360; The divalent organic group which removed 2 amino groups from Formula (1) described in 8th term of Unexamined-Japanese-Patent No. 2012-173514; The divalent organic group etc. which removed 2 amino groups from formula (A) - (F) published in the 9th term of International Publication No. 2010-050523 are mentioned.

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

[Formula 21]

In Formula (11), R ³² is a single bond or a divalent organic group, and a single bond is preferable.

R ³³ is a structure represented by -(CH ₂ ) _r -. r is an integer of 2 to 10, preferably 3 to 7. In addition, arbitrary -CH ₂ - may be substituted with an ether, ester, amide, urea or carbamate bond 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 may be substituted with a monovalent organic group, and a fluorine atom or a methyl group is preferable.

Although the following structures are specifically mentioned as a structure represented by Formula (11), It is not limited to these.

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

Especially, the benzene ring of specific diamine (2) from the point which does not inhibit the reorientation of at least 1 sort(s) chosen from the polyimide precursor containing the structural unit represented by Formula (3), and the polyimide which is an imide product It is preferable to include a partial structure common to the -Y-benzene ring moiety.

When the polyimide precursor containing the structural unit represented by Formula (3) simultaneously contains the structural unit represented by Formula (4), the liquid-crystal orientation may improve more when there are few structural units represented by Formula (3) . The reason for this is that when R ₂₁ in Formula (3) is an alkyl group, imidation is not achieved by heating, and the orientation ability of liquid crystal molecules is reduced. Therefore, the structural unit represented by formula (3) is preferably from 1 to 70 mol%, more preferably from 5 to 50 mol%, particularly preferably from the total of formulas (3) and (4) is 10 to 30 mol%.

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

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

As a method of imidating the polyimide precursor, thermal imidation in which the solution of the polyimide precursor is heated as it is or catalyst imidation in which a catalyst is added to the solution of the polyimide precursor is exemplified.

<liquid crystal aligning agent>

Although 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), in the limit which exhibits the effect described in this invention, of a different structure You may contain 2 or more types of specific polymers. Moreover, in addition to a specific polymer, you may contain the polymer which does not have a bivalent group represented by another polymer, ie, Formula (1). Examples of other polymers include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or its derivative, poly(styrene-phenylmaleimide) ) derivatives, poly(meth)acrylates, and the like. When the liquid crystal aligning agent of this invention contains other polymers, 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 of it.

A liquid crystal aligning agent is used in order to manufacture a liquid crystal aligning film, and generally takes the form of a coating liquid from a viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of this invention, it is preferable that it is a coating liquid containing said polymer component and the organic solvent which dissolves this polymer component. In that case, 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. It is preferably 1% by mass or more from the point of forming a uniform and defect-free coating film, and from the point of storage stability of the solution, it is preferably set to 10% by mass or less. A particularly preferred concentration of the polymer is 2 to 8% by mass.

The organic solvent contained in a liquid crystal aligning agent will not be specifically limited if a polymer component melt|dissolves uniformly. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-buty Rolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, etc. are mentioned. Especially, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone.

In addition, as for the organic solvent contained in the liquid crystal aligning agent, in addition to the above solvents, it is common to use a mixed solvent in which a solvent that improves the coating property at the time of applying the liquid crystal aligning agent and the surface smoothness of the coating film is used in combination, and this Also in the liquid crystal aligning agent of the invention, such a mixed solvent is preferably used. Although the specific example of the organic solvent used together is given below, it is not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl alcohol, tert-pentyl alcohol, 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-methyl Cyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 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-penta Paddy, 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 mono Methyl 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, 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, 3- Methoxymethylpropionate, 3-ethoxymethylethylpropionate, 3-methoxyethylpropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropylpropionate, 3-methoxybutylpropionate, methyl lactate, Lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, solvents represented by the following formulas [D-1] to [D-3], and the like are exemplified.

[Formula 27]

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-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2- It is preferable to use pentanone, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether. The type and content of such a solvent are appropriately selected depending on the application device, application conditions, and application environment of the liquid crystal aligning agent.

The liquid crystal aligning agent of this invention may further 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 additional components, an adhesion auxiliary agent for enhancing the adhesion between the liquid crystal alignment film and the substrate or the adhesion between the liquid crystal alignment film and the sealing material, a crosslinking agent for increasing the strength of the liquid crystal alignment film, and a dielectric or conductive material for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film. etc. can be mentioned. Specific examples of these additional components are as disclosed in various known literatures related to liquid crystal aligning agents, but if an example is shown, pages 53 to 55 of pamphlet No. ], and the like.

<Method of manufacturing a substrate having a liquid crystal alignment film> and <Method of manufacturing a liquid crystal display element>

The method for manufacturing a substrate having a liquid crystal alignment film of the present invention,

[I] (A) Applying a polymer obtained from a diamine component containing a diamine having a structure represented by formula (1) and (B) a polymer composition containing an organic solvent on a substrate having a conductive film for transverse electric field drive to form a coating film;

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

[III] Step of heating the coating film obtained in [II];

have

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

Further, by preparing a second substrate in addition to the substrate (first substrate) obtained above, a transverse electric field drive type liquid crystal display device can be obtained.

For the second substrate, a substrate having no conductive film for transverse electric field driving is used instead of a substrate having a conductive film for transverse electric field driving, and steps [I] to [III] (the conductive film for transverse electric field driving) are used. Since the substrate which does not have is used, for convenience, in this application, it may abbreviate as process [I'] - [III']) by using) The 2nd board|substrate which has a liquid crystal aligning film provided with orientation control ability can be obtained there is.

A method for manufacturing a transversal electric field driven liquid crystal display device,

[IV] Process of arranging the 1st and 2nd board|substrates obtained above so that the liquid crystal aligning films of a 1st and 2nd board|substrate may face each other through a liquid crystal, and obtaining a liquid crystal display element;

have As a result, a transversal electric field drive type liquid crystal display element can be obtained.

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

<Process [I]>

In Step [I], a polymer composition containing a photosensitive template polymer and an organic solvent is applied onto a substrate having a conductive film for driving a transverse electric field to form a coating film.

<substrate>

The substrate is not particularly limited, but when the liquid crystal display element to be produced is of a transmissive type, a highly transparent substrate is preferably used. In that case, it is not particularly limited, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate 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 ITO (Indium Tin Oxide: Indium Tin Oxide) and IZO (Indium Zinc Oxide: Indium Zinc Oxide) when the liquid crystal display element is of a transmissive type, but is not limited thereto.

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

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

The method of applying the polymer composition described above onto a substrate having a conductive film for transverse electric field driving is not particularly limited.

As for the coating method, industrially, a method performed by screen printing, offset printing, flexographic printing, or an inkjet method is common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method (rotational coating method), or a spray method, and these may be used depending on the purpose.

After the polymer composition is applied on the substrate having the conductive film for driving the transverse electric field, the temperature is 50 to 300° C., preferably 50 to 180° C. A coating film can be obtained by evaporating the solvent at °C. The drying temperature at this time is preferably lower than that of the step [III] from the viewpoint of liquid crystal orientation stability.

If the thickness of 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. 150 nm.

It is also possible to provide a step of cooling the substrate on which the coating film is formed to room temperature after the step [I] and before the subsequent step [II].

<Process [II]>

In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When irradiating the film surface of a coating film with polarized ultraviolet rays, polarized ultraviolet rays are irradiated through a polarizing plate in a certain direction with respect to the substrate. As the ultraviolet ray to be used, an ultraviolet ray within a wavelength range of 100 nm to 400 nm can be used. Preferably, an optimal wavelength is selected through a filter or the like according to the type of coating film to be used. And, for example, it is possible to select and use ultraviolet rays in a wavelength range of 240 nm to 400 nm so as to selectively cause a photolysis reaction. As the ultraviolet light, 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 amount is 1 of the amount of polarized ultraviolet rays that achieves the maximum value of ΔA (hereinafter also referred to as ΔAmax), which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays in the coating film and the ultraviolet absorbance in the direction perpendicular to the direction It is preferable to set it in the range of % - 70%, and it is more preferable to set it in the range of 1% - 50%.

<Process [III]>

In process [III], the coating film to which the ultraviolet-ray polarized in process [II] was irradiated is heated. By heating, orientation control ability can be provided to a coating film.

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

The heating temperature is preferably within a temperature range in which the main chain polymer exhibits good liquid-crystal orientation stability. When the heating temperature is too low, the effect of amplifying anisotropy by heat or thermal imidization tends to be insufficient, and when the heating temperature is too high above the temperature range, the anisotropy imparted by polarized light exposure tends to disappear, and this In some cases, self-organization makes it difficult to reorient in one direction.

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

By having the above steps, in the manufacturing method of the present invention, highly efficient anisotropic introduction to the coating film can be realized. And a board|substrate with a liquid crystal aligning film can be manufactured with high efficiency.

<Process [IV]>

Step [IV] is a substrate (first substrate) having a liquid crystal alignment film on the conductive film for transverse electric field drive obtained in [III], and similarly to the substrate obtained in [I'] to [III'] that does not have the conductive film It is a process of opposingly arranging a substrate (second substrate) with a liquid crystal alignment film so that both liquid crystal alignment films are facing each other through a liquid crystal, manufacturing a liquid crystal cell by a known method, and manufacturing a horizontal electric field drive type liquid crystal display element. Further, steps [I'] to [III'] include using a substrate having no conductive film for transverse electric field driving in place of the substrate having a conductive film for transverse electric field driving in step [I], and step [ I] to [III] can be carried out in the same way. Since the difference between steps [I] to [III] and steps [I'] to [III'] is only the presence or absence of the above-described conductive film, description of steps [I'] to [III'] is omitted.

If an example of production of a liquid crystal cell or a liquid crystal display element is given, the first and second substrates described above are prepared, spacers are spread on the liquid crystal alignment film of one side substrate, the liquid crystal alignment film surface is on the inside, and the other A method of bonding unilateral substrates and injecting a liquid crystal under reduced pressure to seal the liquid crystal, or dropping a liquid crystal onto a surface of a liquid crystal aligning film having a spacer dispersed thereon, followed by a method of bonding the substrates together to seal the liquid crystal. can be exemplified. At this time, it is preferable to use a substrate having an electrode having a comb-like structure for driving the transverse electric field as the substrate on one side. The diameter of the spacer at this time is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. The diameter of this spacer determines the distance between a pair of substrates 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 to form a coating film, polarized ultraviolet-ray is irradiated. Next, by heating, highly efficient anisotropic introduction to the main chain polymer film is realized, and a substrate with a liquid crystal alignment film equipped with orientation control capability of liquid crystal is manufactured.

In the coating film used in the present invention, highly efficient anisotropic introduction into the coating film is realized by utilizing the principle of molecular reorientation caused by self-organization based on photoreaction of the main chain. In the production method of the present invention, in the case of a structure having a photodecomposable group as a photoreactive group in the main chain polymer, after forming a coating film on a substrate using the main chain polymer, irradiated with polarized ultraviolet rays, and then heating After carrying out, a liquid crystal display element is manufactured.

Therefore, the coating film used for the method of this invention can be made into a liquid crystal aligning film excellent in orientation control ability by introducing anisotropy with high efficiency by sequentially performing irradiation of polarized ultraviolet rays and heat treatment to the coating film.

And in the coating film used for the method of this invention, the irradiation amount of the polarized ultraviolet-ray to the coating film and the heating temperature in heat treatment are optimized. As a result, highly efficient anisotropic introduction to the coating film can be realized.

The amount of irradiation of polarized ultraviolet rays that is optimal for introducing high-efficiency anisotropy into the coating film used in the present invention corresponds to the amount of irradiation of polarized ultraviolet rays that optimizes the amount of photolysis reaction of photosensitive groups in the coating film. As a result of irradiation of polarized ultraviolet rays to the coating film used in the present invention, if there are few photosensitive groups that undergo photolysis, a sufficient amount of photoreaction is not obtained. In that case, even if it is heated after that, sufficient self-organization does not progress.

Therefore, in the coating film used in the present invention, the optimal amount of photolysis reaction of the photosensitive group by irradiation with polarized ultraviolet rays is preferably 0.1 mol% to 90 mol%, and 0.1 mol% to 80 mol% of the polymer film. It is more preferable to By setting the amount of the photosensitive groups to be photoreacted within such a range, self-organization in the subsequent heat treatment proceeds efficiently, and highly efficient anisotropic formation in the film becomes possible.

In the coating film used in the method of the present invention, the amount of photolysis reaction of photosensitive groups in the main chain of the polymer film is optimized by optimizing the irradiation amount of polarized ultraviolet rays. And, together with the subsequent heat treatment, highly efficient anisotropic introduction to the coating film used in the present invention is realized. In that case, it is possible to determine the preferable amount of polarized ultraviolet rays based on 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, ultraviolet absorption in a direction parallel to the polarization direction of polarized ultraviolet rays after irradiation with polarized ultraviolet rays and ultraviolet absorption in a direction perpendicular to the polarization direction are measured, respectively. From the measurement result of ultraviolet absorption, ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light in the coating film and the ultraviolet absorbance in the direction perpendicular to the polarization direction, is evaluated. Then, the maximum value of ΔA realized in the coating film used in the present invention (ΔAmax) and the irradiation amount of polarized ultraviolet rays that realize it are obtained. In the manufacturing method of this invention, the amount of polarized ultraviolet rays of a preferable quantity irradiated in manufacture of a liquid crystal aligning film can be determined on the basis of the polarization|polarized-light ultraviolet irradiation amount which realizes this (DELTA)Amax.

From the above, in the production method of the present invention, in order to realize highly efficient anisotropic introduction into the coating film, the preferred heating temperature as described above is based on the temperature range in which the main chain polymer imparts liquid crystal alignment stability It is desirable to determine Therefore, for example, the temperature range at which the main chain polymer used in the present invention imparts liquid crystal alignment stability can be determined in consideration of the temperature at which good liquid crystal alignment stability and electrical properties are exhibited in the coating film to be used. It can set in the temperature range according to the liquid crystal aligning film which consists of polyimide etc. That is, it is preferable to set it as 100 degreeC - 300 degreeC, and, as for the heating temperature after polarized light ultraviolet irradiation, it is more preferable to set it as 150 degreeC - 250 degreeC. By doing in this way, a larger anisotropy is provided 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 or heat.

As described above, the substrate for a horizontal electric field driven liquid crystal display element manufactured using the polymer of the present invention or the horizontal electric field driven liquid crystal display element having the substrate is excellent in reliability, and a large-screen, high-definition liquid crystal television etc. can be used suitably. Moreover, since the liquid crystal alignment film manufactured by the method of this invention has excellent liquid-crystal orientation stability and reliability, it can also be used for a variable phase machine using a liquid crystal, and this variable phase machine is an antenna which can change a resonance frequency, for example. etc. can be used suitably.

Example

The abbreviation used in the Example is 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: 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)

[Formula 28]

<Measurement of ¹ HNMR>

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

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

Standard substance: 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.) at a sample amount of 1.1 ml, a cone rotor TE-1 (1 ° 34 ', R24), and a temperature of 25 ° C. did

<Diamine compound>

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

<Synthesis Example 1>

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

An aromatic diamine compound (DA-1) was synthesized in the course of 4 steps shown below. In addition, an aromatic diamine compound (DA-1) corresponds to the specific diamine compound mentioned above.

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

[Formula 29]

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-nitro A solution in which phenetol (29.4 g, 119.4 mmol) was dissolved in DMF (22.5 g) was added dropwise at 80°C. It stirred at 80 degreeC as it was for 5 hours, and the loss|disappearance of the raw material was confirmed by high-performance liquid chromatography (it abbreviates as HPLC hereafter). Thereafter, the reaction solution was allowed to cool to room temperature, water (540.0 g) was added, and then dichloroethane (270.0 g) was added, followed by liquid separation operation, and the organic layer was taken out. Extraction was performed again with pure water (540.0 g), and concentration was performed after drying with magnesium sulfate (5.0 g). Tetrahydrofuran (50.0 g) and heptane (40.0 g) were added to the concentrated crude, and after diluting at 60 ° C., it 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%).

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

[Formula 30]

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) ) was added, cooled to 5°C, and a solution in which mesyl chloride (2.3 g, 19.8 mmol) was dissolved in dichloroethane (15.0 g) was added dropwise, paying attention to heat generation. It stirred at 5 degreeC as it was for 1 hour, and the disappearance of the raw material was confirmed by HPLC. Thereafter, water (60.0 g) was added to the reaction mixture, and then dichloroethane (40.0 g) was added, followed by liquid separation operation, and the organic layer was taken out. The organic layer was extracted again with water (50.0 g), combined with the previous organic layer, dried over sodium sulfate (5.0 g), and then concentrated. The concentrate was cruded to obtain 4-(2-(4-nitrophenoxy)ethoxy)phenethylmethanesulfonate (white powder, yield: 6.3 g, yield: 99%).

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

[Formula 31]

4-(2-(4-nitrophenoxy)ethoxy)phenethylmethanesulfonate (20.0 g, 52.4 mmol) was dissolved in tetrahydrofuran (200.0 g), and a 40% MeOH solution of methylamine (81.4 g , 1048.8 mmol) was added, and the temperature was raised to 40°C. It stirred at 40 degreeC as it was for 24 hours, and the disappearance of the raw material was confirmed by HPLC. Thereafter, the reaction liquid was concentrated, ethyl acetate (400.0 g) was added, and after adding 2 wt% aqueous sodium hydroxide solution (400.0 g) thereafter, liquid separation operation was performed, and the organic layer was taken out. The organic layer was extracted again with water (400.0 g), combined with the previous organic layer, dried over sodium sulfate (10.0 g), and then concentrated. Heptane (80.0 g) was added to the concentrated crude, 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%).

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

[Formula 32]

N-methyl-2-(4-(2-(4-nitrophenoxy)ethoxy)phenyl)ethanamine (10.0 g, 31.6 mmol) was dissolved in tetrahydrofuran (100.0 g), and 5% palladium- Carbon (0.5 g) was added, and the mixture was stirred at 50°C for 5 hours under a hydrogen atmosphere. Disappearance of the raw material was confirmed by HPLC, dissolved in tetrahydrofuran (50.0 g), and after removing the catalyst by filtration, the filtrate was concentrated. This 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%).

Polymerization example, preparation example of orientation agent

<Synthesis Example 2>

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 equipped with a stirrer and a nitrogen inlet tube, and 37.6 g of NMP was added. , and dissolved by stirring while sending nitrogen. Stirring this diamine solution under water cooling, 2.59g (13.2 mmol) of CA-1 was added, and also 9.41g of NMP was added, and it stirred at 23 degreeC under nitrogen atmosphere for 15 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of this polyamic acid solution was 270 mPa*s.

14.5 g of this polyamic acid solution was put into a 100 ml Erlenmeyer flask with a stirrer, 12.6 g of NMP and 11.6 g of BCS were added, stirred with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (A-1) got

<Comparative Synthesis Example 1>

4.09 g (15.0 mmol) of DA-2 was weighed and taken into a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet pipe, 39.3 g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. Stirring this diamine solution under water cooling, 2.77g (14.1 mmol) of CA-1 was added, and also 9.83g of NMP was added, and it stirred at 23 degreeC under nitrogen atmosphere for 3 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of this polyamic acid solution was 263 mPa*s.

14.9 g of this solution of polyamic acid was put into a 100 ml Erlenmeyer flask with a stirrer, 12.9 g of NMP and 11.9 g of BCS were added, stirred with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (B-1) got

<Comparative Synthesis Example 2>

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 equipped with a stirrer and a nitrogen inlet pipe, and 34.8 g of NMP was added. , and dissolved by stirring while sending nitrogen. Stirring this diamine solution under water cooling, 2.62g (13.4 mmol) of CA-1 was added, 8.71g of NMP was added, and it stirred at 23 degreeC under nitrogen atmosphere for 15 hours, and obtained the solution of a polyamic acid. The viscosity in the temperature of 25 degreeC of this polyamic acid solution was 299 mPa*s.

14.6 g of this solution of polyamic acid was placed in a 100 ml Erlenmeyer flask with a stirrer, 12.6 g of NMP and 11.7 g of BCS were added, stirred with a magnetic stirrer for 2 hours, and liquid crystal aligning agent (B-2) got

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

Below, the manufacturing method of the liquid crystal cell for evaluating liquid-crystal orientation is shown.

The liquid crystal cell provided with the structure of the liquid crystal display element of FFS system was manufactured. At the very beginning, a substrate with attached electrodes was prepared. The substrate is a glass substrate having a size of 30 mm x 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, as a second layer, a SiN (silicon nitride) film formed into a film by the CVD method was formed. The film thickness of the SiN film of the 2nd layer is 500 nm, and it functions as an interlayer insulating film. On the SiN film of the 2nd layer, as a 3rd layer, the comb-shaped pixel electrode formed by patterning the IZO film was arrange|positioned, and two pixels, a 1st pixel and a 2nd pixel, were formed. The size of each pixel is 10 mm long and about 5 mm wide. 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 configured by arranging a plurality of ""-shaped electrode elements with curved central portions, similarly to the drawing described in Japanese Unexamined Patent Publication No. 2014-77845 (Japanese Unexamined Patent Publication). The width of each electrode element in the width direction is 3 μm, and the interval between the electrode elements is 6 μm. Since the pixel electrode constituting each pixel is configured by arranging a plurality of ""-shaped electrode elements with bent central portions, the shape of each pixel is not a rectangular shape, but has a bold character curved at the central portion similarly to the electrode element. It has a shape similar to the character く. Then, each pixel is divided up and down with the central bending part as a boundary, and has a first region above the bending part and a second region below the bending part.

Comparing the 1st area and the 2nd area|region of each pixel, the formation direction of the electrode element of the pixel electrode which comprises them differs. That is, when the direction of the line segment projected onto the substrate is the reference to the polarization plane of the polarization ultraviolet rays described later, in the first region of the pixel, the electrode elements of the pixel electrode are formed so as to form an angle of +10 ° (clockwise direction), In the second region of the pixel, the electrode element of the pixel electrode was formed to form an angle of -10° (clockwise direction). That is, in the first area and the second area of each pixel, directions of rotational motion (in-plane switching) in the substrate surface of the liquid crystal caused by application of a voltage between the pixel electrode and the opposite electrode are opposite to each other. composed.

Next, after filtering the liquid crystal aligning agent obtained by the synthesis example and the comparative synthesis example with a 1.0 micrometer filter, it apply|coated to the prepared said board|substrate with an electrode by spin-coating. Then, it was dried for 90 seconds on a hot plate set at 70°C. Next, using an exposure apparatus manufactured by Ushio Electric Co., Ltd.: APL-L050121S1S-APW01, linearly polarized light of ultraviolet rays was irradiated in a direction perpendicular to the substrate through a wavelength selection filter and a polarizing plate. At this time, the direction of the polarization plane was set so that the direction of the line segment projected on the substrate by the polarization plane of the polarized light was inclined by 10° with respect to the third-layer IZO comb electrode. It baked for 30 minutes in the IR (infrared) type|mold oven set to then, 230 degreeC, and obtained the board|substrate with a polyimide liquid crystal aligning film of 100 nm of film thickness in which the orientation process was performed. Moreover, the board|substrate with a polyimide liquid crystal aligning film on which the orientation process was performed also as the counter substrate in the same manner as the above was obtained also for the glass substrate which has a columnar spacer of 4 micrometers in height in which the ITO electrode was formed on the back surface. These two substrates with a liquid crystal alignment film are used as one set, and a sealing compound is printed in a form leaving a liquid crystal injection port on one side substrate, and the liquid crystal alignment film surface faces the other substrate, and the polarization plane of polarized ultraviolet rays is a substrate. It was bonded and compressed so that the direction of the projected line segment was parallel. Thereafter, the sealing compound was cured to prepare an empty cell having a cell gap of 4 µm. Liquid crystal MLC-7026-100 (negative liquid crystal manufactured by Merck & Co., Ltd.) was injected into this empty cell by the vacuum injection method, the injection port was sealed, and the liquid crystal cell of the FFS system was obtained. Then, after heating the obtained liquid crystal cell at 120 degreeC for 30 minute(s) and leaving it to stand at 23 degreeC overnight, it was used for evaluation of the liquid-crystal orientation.

<Evaluation of liquid crystal orientation>

Using this liquid crystal cell, the alternating voltage of 16 VPP was applied on the frequency of 30 Hz in a 70 degreeC constant temperature environment for 120 hours. Then, it was set as the state which short-circuited between the pixel electrode of a liquid crystal cell and a counter electrode, and it was left as it was at 23 degreeC overnight.

After standing, the liquid crystal cell was installed between two polarizing plates arranged so that the polarization axes were orthogonal, and the backlight was turned on in a state where no voltage was applied, and the angle of arrangement of the liquid crystal cell was adjusted so that the luminance of the transmitted light was the smallest. And the rotation angle at the time of rotating the liquid crystal cell from the angle at which the 2nd area|region of the 1st pixel becomes the darkest to the angle at which the 1st area|region becomes the darkest was computed as angle (DELTA). Similarly, also in the second pixel, the second area and the first area were compared, and the same angle Δ was calculated. And the average value of the angle Δ value of the 1st pixel and the 2nd pixel was computed as angle Δ of a liquid crystal cell. When the value of the angle Δ of this liquid crystal cell was less than 0.3°, when the value of “good” and the angle Δ was 0.3° or more, it was defined as “defective” and evaluated.

<Manufacture of liquid crystal cell for voltage retention evaluation>

Using a glass substrate with an ITO electrode, except having spread a 4 μm bead spacer on the liquid crystal aligning film surface on one side substrate before printing of the sealing compound, in the same procedure as in the production of the liquid crystal cell for evaluating the liquid crystal orientation, voltage retention A liquid crystal cell for measurement was prepared.

<Evaluation of voltage retention>

Voltage retention was evaluated using this liquid crystal cell. Specifically, a 2VPP alternating voltage was applied to the liquid crystal cell obtained by the above method for 60 μsec at a temperature of 70°C, the voltage after 1 second was measured, and how much the voltage was maintained was measured as voltage retention (also known as VHR). ) was calculated as In addition, the measurement was carried out using a voltage retention measuring device (VHR-1, manufactured by Toyo Technica Co., Ltd.) under the settings of Voltage: ±1 V, Pulse Width: 60 μs, and Flame Period: 1000 ms. When the value of the voltage retention of this liquid crystal cell was 80% or more, when the value of "good" and the voltage retention was less than 80%, it 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 the polarized ultraviolet rays was performed using a high-pressure mercury lamp through a wavelength selection filter: 240 LCF and a 254 nm type polarizing plate. The amount of irradiation of polarized ultraviolet rays was determined by measuring the amount of light using an illuminometer UVD-S254SB manufactured by Ushio Electric Co., Ltd., and changing the amount of light in the range of 600 to 1800 mJ/cm 2 at a wavelength of 254 nm, respectively, to obtain three different irradiation amounts of polarized ultraviolet rays. The above liquid crystal cell was manufactured.

About these liquid crystal cells, as a result of evaluating the liquid-crystal orientation, the polarization|polarized-light ultraviolet irradiation amount which angle (DELTA) was the best was 1800 mJ/cm<2>, and the angle (DELTA) was 0.15 degree and was favorable.

Moreover, when voltage retention was evaluated about the liquid crystal cell manufactured with the same amount of polarized light ultraviolet irradiation, the voltage retention was 92.4 % and was favorable.

(Comparative Examples 1 to 2)

Except having used the liquid crystal aligning agent obtained in Comparative Synthesis Examples 1-2, it is the method similar to Example 1, and evaluated the liquid-crystal orientation and voltage retention.

Angle Δ at the time of using the liquid crystal aligning agent obtained by the synthesis example and the comparative synthesis example in Table 1 shows the polarization|polarized-light ultraviolet irradiation quantity which was the best, the result of evaluation of liquid-crystal orientation, and the result of evaluation of voltage retention.

As shown in Table 1, in Example 1, the angle Δ, which is the difference between the alignment azimuths before and after the AC drive, was good at less than 0.3°, and the voltage retention also exhibited good characteristics of 80% or more, all of which had good afterimage characteristics. , The display quality improvement of the liquid crystal display element is excellent. On the other hand, in Comparative Examples 1 and 2, the characteristic which made angle (DELTA) and voltage holding ratio compatible was not confirmed.

Thus, it was confirmed that the liquid crystal display device manufactured by the method of the present invention exhibits very excellent afterimage characteristics.

A substrate for a horizontal electric field driven liquid crystal display device manufactured using the composition of the present invention or a horizontal electric field driven liquid crystal display device having the substrate has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television or the like. there is. Moreover, since the liquid crystal alignment film manufactured by the method of this invention has excellent liquid-crystal orientation stability and reliability, it can also be used for a variable phase machine using a liquid crystal, and this variable phase machine is an antenna which can change a resonance frequency, for example. etc. can be used suitably.

Claims (17)

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

(In formula (1), X is selected from a single bond, a benzene ring, or an alkyl group in which the hydrogen atom of the benzene ring has 1 to 10 carbon atoms, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, and a fluoroalkoxy group. Y and Z are each independently a group consisting of an alkylene group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms and an ether bond, and R ¹ and R ² are each independently 1 is a valent 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) According to claim 1,
A liquid crystal aligning agent containing at least one polymer selected from the group consisting of a polyimide precursor which is a polymer of a diamine component containing the above diamine and tetracarboxylic dianhydride, and a polyimide which is an imide product thereof, and an organic solvent. . According to claim 1,
The liquid crystal aligning agent in which the said diamine is represented by the following formula (2).

(In Formula (2), the definitions of X, Y, Z, R ¹ to R ³ , m and n are the same as in Formula (1) above) According to claim 2,
The liquid crystal aligning agent in which the 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 having the structure of formula (1), and R ¹¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²¹ is an alkyl group having 1 to 4 carbon atoms) According to claim 4,
The liquid crystal aligning agent whose structure of X ^<1> is at least 1 sort(s) chosen from the group which consists of following structural formula (A-1) - (A-21) in said Formula (3).

According to claim 4,
The liquid crystal aligning agent in which the polymer which has a structural unit represented by said Formula (3) is contained 10 mol% or more with respect to all the polymers contained in a liquid crystal aligning agent. According to claim 4,
The liquid crystal aligning agent containing at least 1 sort(s) chosen from the group which consists of 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether in the said organic solvent. [I] A step of applying the liquid crystal aligning agent according to any one of claims 1 to 7 on a substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] Step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and
[III] Step of heating the coating film obtained in [II];
The manufacturing method of the board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements to which orientation control ability was provided by having. A substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display device manufactured by the method according to claim 8. A transversal electric field drive type liquid crystal display device comprising the substrate according to claim 9. [I] A step of applying the liquid crystal aligning agent according to any one of claims 1 to 7 on a substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] Step of irradiating polarized ultraviolet rays to the coating film obtained in [I];
[III] Step of heating the coating film obtained in [II];
Process of preparing the board|substrate (1st board|substrate) with the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements to which orientation control ability was provided by having;
[I'] Step of applying the liquid crystal aligning agent according to any one of claims 1 to 7 on a second substrate to form a coating film;
[II'] Step of irradiating polarized ultraviolet rays to the coating film obtained in [I']; and
[III'] Step of heating the coating film obtained in [II'];
Process of obtaining the 2nd board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film to which orientation control ability was provided by having; and
[IV] Process of opposingly arranging the first and second substrates to obtain a liquid crystal display element so that the liquid crystal alignment films of the first and second substrates are opposed to each other through a liquid crystal;
A method for producing a liquid crystal display element, wherein a horizontal electric field drive type liquid crystal display element is obtained by having a. A transverse electric field drive type liquid crystal display device manufactured by the method according to claim 11. At least one polymer selected from the group consisting of a polyimide precursor that is a polymer of a diamine component containing diamine having a structure represented by the following formula (1) and tetracarboxylic dianhydride, and a polyimide that is an imide product thereof.

(In formula (1), X is selected from a single bond, a benzene ring, or an alkyl group in which the hydrogen atom of the benzene ring has 1 to 10 carbon atoms, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, and a fluoroalkoxy group. Y and Z are each independently a group consisting of an alkylene group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms and an ether bond, and R ¹ and R ² are each independently 1 is a valent 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) According to claim 13,
A polymer in which the diamine is represented by the following formula (2).

(In Formula (2), the definitions of X, Y, Z, R ¹ to R ³ , m and n are the same as in Formula (1) above) According to claim 13 or 14,
The polymer which the 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 having 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) According to claim 15,
The polymer whose structure of X ^<1> in said Formula (3) is at least 1 sort(s) selected from the group which consists of the following structural formulas (A-1) - (A-21).

Diamine represented by following formula (2).

(In formula (2), X is selected from a single bond, a benzene ring, or an alkyl group in which the hydrogen atom of the benzene ring has 1 to 10 carbon atoms, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, and a fluoroalkoxy group. Y and Z are each independently a group consisting of an alkylene group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms and an ether bond, and R ¹ and R ² are each independently 1 is a valent 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)