KR20190028287A - Liquid crystal aligning agents for forming optical orientation type liquid crystal alignment films, liquid crystal alignment films, liquid crystal display elements using the same, polymers, and diamines - Google Patents

Abstract

The present invention relates to a liquid crystal aligning agent for optical orientation containing a polymer having a constituent unit including a photosensitive group represented by formula (1). According to the present invention, the liquid crystal aligning agent can form a liquid crystal alignment film which exhibits a high liquid crystal aligning properties and also has a high transmittance. The present invention also provides a new photosensitive diamine which is a raw material of a polymer used as the liquid crystal aligning agent for optical orientation. In formula (1), R^1 and R^2 are independently hydrogen or an alkyl having 1 to 10 carbon atoms, and a binding bond, of which a coupling position is not fixed to any one carbon forming a ring, exhibits that the coupling position in the ring is arbitrary, and hydrogen of a benzene ring may be substituted by a substituent.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a liquid crystal aligning agent for forming a liquid crystal alignment layer of a photo alignment type, a liquid crystal alignment layer, a liquid crystal display element using the same, a polymer, and a diamine ELEMENTS USING THE SAME, POLYMERS, AND DIAMINES}

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display device using the same. Specifically, a liquid crystal aligning agent for forming a liquid crystal alignment film of a photo alignment type (hereinafter sometimes abbreviated as a photo alignment film), a photo alignment type liquid crystal alignment film formed using this liquid crystal alignment agent, And a liquid crystal display element having a liquid crystal alignment film. Further, the present invention relates to a polymer such as polyamic acid or polyimide used for the liquid crystal aligning agent, and a diamine compound as a raw material thereof.

As a liquid crystal display device, a twisted nematic (TN) mode, a super twisted nematic (STN) mode, an in-plane switching (IPS) mode, a fringe field switching Have been known, and are used for various purposes such as television, mobile phone, and the like. In order to operate these liquid crystal display elements, it is necessary to orient the liquid crystal with regular regularity with respect to the substrate of the element. For this purpose, a liquid crystal alignment film is formed on a substrate. The liquid crystal alignment film is formed from a liquid crystal aligning agent. At present, a liquid crystal aligning agent mainly used is a solution (varnish) in which a polyamic acid, a soluble polyimide or a polyamic acid ester is dissolved in an organic solvent. This solution is applied to a substrate, and then formed into a film by a means such as heating to form a polyimide-based liquid crystal alignment film. After the film formation, an orientation treatment suitable for the above-described display mode is performed as necessary. As the alignment treatment method, a rubbing method and a photo alignment method are practically used. Since the photo alignment method is a non-contact alignment treatment method, there is an advantage that the film is not scratched and the cause of display defects of liquid crystal display elements such as oscillation and static electricity can be reduced.

The development of the technology of the liquid crystal display element is achieved not only by the improvement of the driving method and the device structure, but also by the constituent member used in the device. Of the constituent members used in the liquid crystal display element, in particular, the liquid crystal alignment film is one of important materials relating to the display quality, and it has become important to improve the performance of the liquid crystal alignment film as the quality of the liquid crystal display element is improved.

Even in the case of using the rubbing method and the photo alignment method, any alignment treatment method, there is a liquid crystal aligning property required for the liquid crystal alignment film. By using a liquid crystal alignment film having a high liquid crystal alignment property, it is possible to provide a liquid crystal display device having high contrast and afterimage characteristics (for example, Patent Documents 4 and 5). The photo alignment method has a higher alignment uniformity than the rubbing method. Among them, by applying the technique of photoisomerization described in Patent Documents 1 to 5, it is possible to provide a photo alignment film having a large anchoring energy and a good liquid crystal alignability. However, a further improvement in the quality of the display quality of the liquid crystal display element is required, and a higher liquid crystal alignment property is required in the liquid crystal alignment film.

Besides the liquid crystal alignability, there is a high transmittance as a property required for the liquid crystal alignment film. When a liquid crystal alignment film having a low transmittance in a liquid crystal display element is used, there arises a problem that the brightness of the liquid crystal display element is lowered. Patent Document 6 discloses a photo alignment film using an azine group and a diamine compound excellent in photosensitivity. In this photo alignment film, the transmittance was improved by shortening the conjugated system by a spacer group. However, even with this technology, there is still room for improvement because a higher transmittance is required to be improved.

Japanese Patent Application Laid-Open No. 2005-275364 Japanese Patent Application Laid-Open No. 2007-248637 Japanese Patent Application Laid-Open No. 2009-069493 Japanese Patent Application Laid-Open No. 2010-197999 International publication 2013/157463 Japanese Patent Publication No. 2014-205659

Disclosure of the Invention A problem to be solved by the present invention is to provide a liquid crystal alignment film which exhibits a high liquid crystal alignability and a high transmittance. Further, it is another object of the present invention to provide a liquid crystal aligning agent capable of forming the film, and a liquid crystal display element using the liquid crystal alignment film. It is another object of the present invention to provide a novel photosensitive diamine which can be used for the liquid crystal aligning agent.

The present inventors have found that a liquid crystal alignment film having a high orientation property and a high transmittance can be obtained by using the acylhydrazone structure represented by the formula (1) as a photosensitive group in a raw material of a liquid crystal aligning agent, and have reached the present invention. The present invention is as follows.

[1] a liquid crystal aligning agent for optical alignment, which comprises a polymer having a structural unit containing a photosensitive group represented by the following formula (1);

In the formula (1)

R ¹ and R ² are independently hydrogen or alkyl having 1 to 10 carbon atoms;

A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary and hydrogen in the benzene ring may be substituted with a substituent.

[2] A liquid crystal aligning agent for photo alignment comprising a polymer as a reaction product from a raw material containing a tetracarboxylic acid dianhydride and a diamine;

The diamine has at least one of diamines represented by the following formula (2): the liquid crystal aligning agent for photo-alignment described in item [1];

Here, the polymer is at least one selected from the group consisting of polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide;

In formula (2), R ¹ and R ² are independently hydrogen or alkyl having 1 to 10 carbon atoms;

R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃ ) , Or a single bond;

In R ⁴ and R ⁶ , one of -CH ₂ - of the straight chain alkylene or two non-adjacent ones may be substituted with -O-;

R ⁵ and R ⁷ are independently a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocyclic ring, or a single bond;

A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary and hydrogen in the benzene ring may be substituted with a substituent.

[3] The liquid crystal aligning agent for photo-alignment as described in [2], wherein the diamine contains at least one of diamines represented by the following formula (3).

In formula (3), R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃₎ -, or a single bond;

In R ⁴ and R ⁶ , one or two of -CH ₂ - of straight chain alkylene may be substituted with -O-;

R ⁵ and R ⁷ are independently a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocyclic ring, or a single bond;

A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary.

[4] The liquid crystal aligning agent for photo-alignment described in [2] or [3], wherein the diamine contains at least one of diamines represented by the following formulas (4) to (7)

In formulas (4) to (7), R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 2 carbon atoms or a single bond;

A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary.

(5-1), (5-2), (6-1), (6-2), and (6-2) The liquid crystal aligning agent for photo-alignment described in any one of [2] to [4], wherein the liquid crystal aligning agent contains at least one of diamines represented by formula (7-1) or formula (7-2)

[6] the liquid crystal aligning agent for photo-alignment described in any one of [2] to [5], wherein the raw material further comprises at least one selected from the group consisting of the following formulas (II) to (VI);

In formulas (II) to (VI), R ⁴ and R ⁵ are monovalent organic groups having -NH ₂ or monovalent organic groups having -CO-O-CO-;

In the formula (IV), R ⁶ is a divalent organic group;

In formula (VI), R ⁷ is an aromatic ring having -NH ₂ or -CO-O-CO-.

[7] The liquid crystal aligning agent for photo-alignment as described in any one of [1] to [6], which is used for producing a transverse electric field type liquid crystal display element.

[8] A liquid crystal alignment film formed by the liquid crystal aligning agent for photo-alignment described in any one of [1] to [7].

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

[10] A transverse electric field type liquid crystal display element having a liquid crystal alignment film according to [8].

[11] Expression (4-2), Expression (5-1), Expression (5-2), Expression (6-1), Expression (6-2), Expression (7-1) 2).

[12] A process for producing a polyamic acid, a polyimide, a partial polyimide, a polyamic acid ester, a polyamic acid-polyamide novolac resin, which is a reaction product of a tetracarboxylic acid dianhydride and a diamine containing at least one of diamines represented by formula (2) A polymer and at least one polymer selected from the group consisting of polyamideimide;

In formula (2), R ¹ and R ² are independently hydrogen or alkyl having 1 to 10 carbon atoms;

R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃ ) , Or a single bond;

In R ⁴ and R ⁶ , one of -CH ₂ - of the straight chain alkylene or two non-adjacent ones may be substituted with -O-;

R ⁵ and R ⁷ are independently a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocyclic ring, or a single bond;

A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary and hydrogen in the benzene ring may be substituted with a substituent.

[13] The polymer according to [12], wherein the diamine contains at least one of diamines represented by the following formula (3):

In formula (3), R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃₎ -, or a single bond;

In R ⁴ and R ⁶ , one or two of -CH ₂ - of straight chain alkylene may be substituted with -O-;

R ⁵ and R ⁷ are independently a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocyclic ring, or a single bond;

A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary.

[14] The polymer according to [12] or [13], wherein the diamine contains at least one of the diamines represented by the following formulas (4) to (7)

In formulas (4) to (7), R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 2 carbon atoms or a single bond;

A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary.

The diamine may be represented by the following formulas (4-1), (4-2), (5-1), (5-2), (6-1) The polymer according to any one of the items [12] to [14], which contains at least one of diamines represented by the formula (7-1) or (7-2)

The liquid crystal alignment film formed using the photo-alignment liquid crystal aligning agent containing a polymer having a structural unit containing a photosensitive group represented by the formula (1) of the present invention has a structure in which the absorption of light in the visible light region by the acyl hydrazone structure It is possible to obtain a liquid crystal alignment film having a high transmittance. The technique of the present invention exerts particularly excellent effects in the field of a liquid crystal alignment film of a photo alignment type.

1 is a UV-Vis spectrum of the liquid crystal alignment film (1) obtained in Example 1. Fig.
2 is a UV-Vis spectrum of the liquid crystal alignment film obtained in Comparative Example 1. Fig.

Hereinafter, the present invention will be described in detail. The constituent elements described below are described based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, the term " liquid crystal aligning agent of optical alignment method " is sometimes referred to as " liquid crystal aligning agent for optical alignment ". The above-mentioned " liquid crystal aligning agent of optical alignment method " or " liquid crystal aligning agent for optical alignment " may be abbreviated as " liquid crystal aligning agent ".

≪ Liquid crystal aligning agent for optical alignment of the present invention &

The liquid crystal aligning agent for photo-alignment of the present invention contains a polymer having a constituent unit represented by formula (1).

In the formula (1), R ¹ and R ² are independently hydrogen or alkyl having 1 to 10 carbon atoms, and the bonded hands in which the bonding position is not fixed to any one of the carbon atoms constituting the ring, The bonding position is arbitrary, and the hydrogen of the benzene ring may be substituted with a substituent.

In the formula (1), the alkyl in R ¹ and R ² may be any of linear, branched and cyclic. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms. Specific examples of alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert- Hexyl, isohexyl, 1-methylpentyl, 1-ethylbutyl and the like.

The hydrogen of the benzene ring in the formula (1) may be substituted with a substituent. Preferable examples of the substituent include alkyl, alkoxy, halogenated alkyl, halogen, and carboxyalkyl. The alkyl may be any of linear, branched and cyclic. The preferred number of carbon atoms of alkyl is 1 to 4, more preferably 1 to 2. Specific examples of alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like. The preferred number of carbon atoms of the alkoxy is 1 to 4, more preferably 1 to 2. Specific examples of the alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and the like. As specific examples of the halogenated alkyl, trifluoromethyl and the like can be mentioned. Specific examples of halogen include fluoro, chloro, bromo, iodo, and the like. Specific examples of carboxyalkyl include carboxymethyl, carboxyethyl and the like.

The structural unit represented by the formula (1) has an acylhydrazone structure. In the acylhydrazone structure, light is irradiated to cause an isomerization reaction between the trans-isomer and the cis-isomer.

The wavelength of the light in which the isomerization reaction is generated is not particularly limited, but is preferably 150 to 800 nm, more preferably 200 to 400 nm, and further preferably 300 to 400 nm. It is preferable that the light irradiation intensity required for the structural change in the photoreactive structure is 0.05 to 20 J / cm ² .

When the liquid crystal aligning agent of the present invention is coated on a substrate and dried by preliminary heating and then linearly polarized light is irradiated through a polarizing plate, the acylhydrazone structure of the polymer main chain which is substantially parallel to the polarization direction causes isomerization reaction. The main chain of the polymer which is substantially parallel to the polarization direction is selectively isomerized so that the main chain of the polymer forming the film becomes predominant in the component oriented substantially perpendicular to the polarization direction of the irradiated ultraviolet ray. Thereafter, the photo-aligned film is heated and fired to form a liquid crystal alignment film. When the polymer is at least one selected from the group consisting of polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide, Or may be conducted after heating to polyimide.

<Polymer>

The polymer used in the liquid crystal aligning agent of the present invention is characterized by having a photosensitive group represented by formula (1) in its main chain. The polymer used in the liquid crystal aligning agent of the present invention may be one kind of polymer or two or more kinds. The polymer is not particularly limited and includes, for example, a polyamic acid, a polyamic acid derivative, a polyester, a polyamide, a polysiloxane, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly (styrene-phenylmaleimide) ) Acrylate, and the like.

Here, the polyamic acid is a polymer synthesized by a polymerization reaction of a diamine represented by the formula (DI) and a tetracarboxylic acid dianhydride represented by the formula (AN), and has a structural unit represented by the formula (PAA). By subjecting the polyamic acid to dehydration cyclization, a polyimide liquid crystal alignment film having a constituent unit represented by formula (PI) can be formed. As the diamine, the structure represented by the formula (1) can be easily introduced into the main chain by using a compound having a structure in which an amino group is linked to the bonding position of the structure represented by the formula (1). The amino group in the diamine may be directly bonded to the bonding position of the structure represented by the formula (1), or may be connected via a divalent linking group.

In the formula (AN), the formula (PAA), and the formula (PI), X ¹ represents a tetravalent organic group. In the formulas (DI), (PAA), and (PI), X ² represents a divalent organic group. For a preferable range and specific examples of the tetravalent organic group in X ¹ , reference can be made to the corresponding structure of the tetracarboxylic acid dianhydride described in the tetracarboxylic dianhydride column below. The preferable range and specific examples of the divalent organic group in X ² are the same as in the formula (1) or a description of the corresponding structure of the diamine or dihydrazide described in the column of the conventional diamine, dihydrazide below Can be referenced.

A derivative of polyamic acid is a component which is dissolved in a solvent when it is used as a liquid crystal aligning agent to be described later and is a component capable of forming a liquid crystal alignment film containing polyimide as a main component when the liquid crystal aligning agent is used as a liquid crystal alignment film . Examples of such derivatives of polyamic acid include soluble polyimides, polyamic acid esters, and polyamic acid amides, and more specifically 1) polyimides obtained by dehydration ring-closure reaction of all amino groups of polyamic acid with carboxyl groups, 2) a partial polyimide partially dehydrated ring closure reaction, 3) a polyamic acid ester in which the carboxyl of the polyamic acid is converted into an ester, 4) a part of the acid dianhydride contained in the tetracarboxylic acid dianhydride is replaced with an organic dicarboxylic acid A polyamic acid-polyamide copolymer obtained, and 5) a polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to dehydration ring closure reaction. Among these derivatives, examples of the polyimide include those having a structural unit represented by the formula (PI), and examples of the polyamic acid ester include those having a structural unit represented by the following formula (PAE) have.

In the formula (PAE), X ¹ represents a tetravalent organic group, X ² represents a divalent organic group, and Y represents independently alkyl. X ^1, it is possible to see the description of the X ^1, X ² in the desired range for the specific example of X ^2, equation (PAA). As for the description, preferable range, and specific examples of Y, reference can be made to the description, preferable range, and specific examples of alkyl as a substituent of the benzene ring of the formula (1).

Of these polymers, at least one selected from the group consisting of polyamic acid and derivatives thereof is preferable. Hereinafter, the case where the polymer is a polyamic acid and a derivative thereof will be described in detail.

<Polyamic acid and derivatives thereof>

The polyamic acid and the derivative thereof according to the embodiment of the present invention are characterized by having a photosensitive group represented by the formula (1) in the main chain. For example, at least one of the raw material monomers may be at least one compound represented by the formula (2) 1 &lt; / RTI &gt; The polyamic acid and the derivative thereof may be a polymer having a structure of the reaction product of tetracarboxylic acid dianhydride and diamine and may be prepared by using other raw materials to obtain a reaction product by reaction other than the reaction of tetracarboxylic acid dianhydride and diamine You can.

The polyamic acid or the derivative thereof according to the embodiment of the present invention can be produced in the same manner as the known polyamic acid or derivative thereof used for forming the polyimide film. The total amount of the tetracarboxylic dianhydride to be added is preferably approximately equal to the total number of moles of the diamine (molar ratio of about 0.9 to 1.1).

When the polyamic acid according to the embodiment of the present invention is a polyamic acid derivative polyimide, the obtained polyamic acid solution is mixed with an acid anhydride such as acetic anhydride, dehydrated propionic acid, anhydrous trifluoroacetic acid, Can be obtained by carrying out an imidization reaction at a temperature of 20 to 150 ° C together with a tertiary amine such as triethylamine, pyridine or coridine, which is a ring-closing catalyst. Alternatively, polyamic acid may be precipitated from the obtained polyamic acid solution by using a large amount of a poor solvent (an alcohol solvent such as methanol, ethanol, isopropanol, or a glycol solvent), and the precipitated polyamic acid may be dissolved in a solvent such as toluene, Imidization reaction may be carried out at a temperature of from 20 to 150 ° C together with the same dehydrating agent and dehydration ring-closing catalyst.

In the imidization reaction, the total amount of the dehydrating agent and the dehydration cyclization catalyst is preferably 1.5 to 10 times the molar amount of the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid. The ratio of the dehydrating agent to the dehydration ring-closing catalyst is preferably 0.1 to 10 (molar ratio). By adjusting the dehydrating agent, the amount of catalyst, the reaction temperature and the reaction time of the chemical imidization of both, the degree of imidization can be controlled to obtain the partial polyimide. The obtained polyimide may be used as a liquid crystal aligning agent or may be used as a liquid crystal aligning agent without being separated from a solvent by redissolving the polyimide in the above-described solvent separately from the solvent.

The polyamic acid ester may be synthesized by reacting the above-described polyamic acid with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound or the like, or a method of reacting a tetracarboxylic acid diester or tetracarboxylic acid diester dichloride derived from a tetracarboxylic acid dianhydride And then reacting it with a diamine. The tetracarboxylic acid diester derived from the tetracarboxylic acid dianhydride can be obtained, for example, by reacting tetracarboxylic dianhydride with two equivalents of alcohol and ring opening, and the tetracarboxylic acid diester dichloride is obtained by reacting the tetracarboxylic acid diester with 2 equivalents of With a chlorinating agent (for example, thionyl chloride or the like). The polyamic acid ester may have only an amic acid ester structure or may be a partial esterified amic acid structure and an amic ester structure. The liquid crystal aligning agent for photo-alignment of the present invention may contain one or more of these polyamic acid, polyamic acid ester and polyimide obtained by imidizing them.

The molecular weight of the polyamic acid or its derivative according to the embodiment of the present invention is preferably 7,000 to 500,000, more preferably 10,000 to 200,000, in terms of weight average molecular weight (Mw) in terms of polystyrene. The molecular weight of the polyamic acid or its derivative can be determined by measurement by gel permeation chromatography (GPC).

The polyamic acid or its derivative according to the embodiment of the present invention can be confirmed by analyzing the solid content obtained by precipitating with a large amount of a poor solvent by IR and NMR. Also, the monomer used can be identified by analyzing an extract of the decomposition product of the polyamic acid or its derivative by an aqueous solution of a strong alkali such as KOH or NaOH with an organic solvent by GC, HPLC or GC-MS.

&Lt; Diamine of the present invention &

The diamine represented by the formula (2) according to the embodiment of the present invention will be described.

In the formula (2), R ¹ and R ² are independently hydrogen or alkyl having 1 to 10 carbon atoms. Equation (2) Examples of R ¹ and R ² in the, reference can be made to examples of R ¹ and R ² in the formula (1).

R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃ ) , Or a single bond. In R ⁴ and R ⁶ , one of -CH ₂ - of straight chain alkylene or two non-adjacent ones may be substituted with -O-. R ⁵ and R ⁷ are monocyclic hydrocarbons, condensed polycyclic hydrocarbons, heterocyclic rings, or single bonds.

The monocyclic hydrocarbons in R ⁵ and R ⁷ may be alicyclic or aromatic rings. The number of carbon atoms of the monocyclic hydrocarbon is preferably from 6 to 12, more preferably from 6 to 10, and even more preferably from 6 to 8. Specific examples of the monocyclic hydrocarbon include a benzene ring, a cyclohexane ring, and a cyclohexane ring.

The condensed polycyclic hydrocarbon in R ⁵ and R ⁷ preferably has 10 to 20 carbon atoms, more preferably 10 to 18 carbon atoms, and even more preferably 10 to 14 carbon atoms. Concrete examples of the condensed polycyclic hydrocarbon include naphthalene ring, anthracene ring and phenanthrene ring.

The heterocyclic rings in R ⁵ and R ⁷ may be alicyclic or aromatic rings. The number of carbon atoms in the heterocycle is preferably 1 to 26, more preferably 3 to 14, and even more preferably 3 to 8. As the hetero atom contained in the heterocycle as a ring member, nitrogen, oxygen, and sulfur can be exemplified. Specific examples of the heterocyclic ring include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazin ring, an indole ring and an oxazole ring.

A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary and hydrogen in the benzene ring may be substituted with a substituent. With regard to the preferable range and specific examples of the substituent, in the above-mentioned general formula (1), a preferable range of the substituent which can be substituted with a benzene ring and specific examples can be referred to.

Among the formula (2), the diamine compound represented by the following formula (3) is preferable from the height of the orientation.

In formula (3), R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃₎ -, or a single bond. In R ⁴ and R ⁶ , one of -CH ₂ - of straight chain alkylene or two non-adjacent ones may be substituted with -O-. R ⁵ and R ⁷ are monocyclic hydrocarbons, condensed polycyclic hydrocarbons, heterocyclic rings, or single bonds. R ⁵ and the examples of the monocyclic hydrocarbon group, condensed polycyclic hydrocarbon or a heterocyclic ring in R ⁷ is, it is possible to see an example of R ⁵ and R ⁷ in the formula (2). A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary.

Among the formula (3), the diamine compounds represented by the following formulas (4) to (7) are preferable from the viewpoint of easiness of obtaining the raw materials.

In the formulas (4) to (7), R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 2 carbon atoms or a single bond. A joining hand in which the joining position is not fixed to any carbon constituting the ring indicates that the joining position in the ring is arbitrary.

(4-1), (4-2), (5-1), (5-2), (6-1), and , The formula (6-2), the formula (7-1), or the formula (7-2).

&Lt; Synthesis of diamine of the present invention &gt;

Expressions (4-1), (4-2), (5-1), (5-2), (6-1), (6-2), The diamine represented by the formula (7-2) can be synthesized as follows.

The diamines represented by the formulas (4-1) and (4-2) according to the embodiment of the present invention are obtained by hydrazidizing a commercially available methyl benzoate and then providing commercially available nitrobenzaldehyde to obtain a dinitro compound . And then reducing the nitro group.

The diamines represented by the formulas (5-1) and (5-2) according to the embodiment of the present invention can be synthesized by cross-coupling commercially available 4-bromobenzoic acid with nitrophenylboronic acid, Lt; / RTI &gt;

The diamines represented by the formulas (6-1) and (6-2) according to the embodiment of the present invention can be synthesized by cross-coupling commercially available bromonitrobenzene with 4-formylphenylboronic acid, Lt; / RTI &gt;

The diamines represented by the formulas (7-1) and (7-2) according to the embodiment of the present invention are obtained by a combination of the above-described methods.

These compounds may be purified by recrystallization or column chromatography.

(4-1), (5-1), (6-1), and (7-1) are preferably added to the raw material among these compounds in order to provide a liquid crystal aligning agent capable of becoming a liquid crystal alignment film having higher orientation. ) Is preferably used as the diamine compound.

&Lt; Tetracarboxylic acid dianhydride &gt;

The tetracarboxylic acid dianhydride used for producing the polyamic acid and the derivative thereof according to the embodiment of the present invention will be described. The tetracarboxylic acid dianhydride used in the present invention can be selected without limitation from known tetracarboxylic acid dianhydrides. Such tetracarboxylic acid dianhydrides include aromatic (including a complex aromatic ring system) in which a dicarboxylic acid anhydride is directly bonded to an aromatic ring, and aliphatic (heterocyclic ring systems in which a direct dicarboxylic acid anhydride is not bonded to the aromatic ring ). &Lt; / RTI &gt;

Suitable examples of such tetracarboxylic acid dianhydrides include tetracarboxylic acid dianhydrides represented by the formulas (AN-I) to (AN-V) in view of ease of raw material availability, ease of production of the polymer, have.

In the formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or -CH ₂ -. In the formula (AN-II), G represents a single bond, alkylene, -CO-, -O-, -S-, -SO 2 of carbon number 1 ~ 20 -, -C (CH 3) 2 -, or - C (CF ₃ ) ₂ -. In the formulas (AN-II) to (AN-IV), Y is independently selected from the group consisting of the following trivalent groups and the bonding hand is connected to any carbon, Hydrogen may be substituted with methyl, ethyl or phenyl.

In the formulas (AN-III) to (AN-V), ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, Hydrogen may be substituted with methyl, ethyl or phenyl, and the bonding hands attached to the ring may be connected to any carbon constituting the ring, and two bonding hands may be connected to the same carbon.

More specifically, the tetracarboxylic acid dianhydride represented by the following formulas (AN-1) to (AN-16-15) can be mentioned.

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

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

When G ¹² is &gt; CH-, the hydrogen of &gt; CH- may be substituted with -CH ₃ . When G ¹² is> N-, G ¹¹ is not a single bond and -CH ₂ -, and X ¹¹ is not a single bond. And R ¹¹ is hydrogen or -CH _3.

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

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

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

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

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-2) include compounds represented by the following formulas.

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

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

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

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

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

In the formula (G13-1), G ^13a and ^13b G is a bivalent group represented by a single bond independently, -O-, or -NHCO-. Phenylene is preferably 1,4-phenylene and 1,3-phenylene.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-4) include the compounds represented by the following formulas.

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

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

In formula (AN-5), R ¹¹ is independently hydrogen or -CH ₃ . R ¹¹ in which the bonding position is not fixed to the carbon constituting the benzene ring indicates that the bonding position in the benzene ring is arbitrary.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-5) include compounds represented by the following formulas.

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

In the formula (AN-6), X ¹¹ is independently a single bond or -CH ₂ -. X ¹² is -CH ₂ -, -CH ₂ CH ₂ - or -CH = CH-. n is 1 or 2;

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

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

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

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-7) include the compounds represented by the following formulas.

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

In formula (AN-8), X ¹¹ is a single bond or -CH ₂ -. R ¹² is hydrogen, -CH ₃ , -CH ₂ CH ₃ , or phenyl, and ring A ¹² is a cyclohexane ring or a cyclohexane ring.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-8) include the compounds represented by the following formulas.

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

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

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

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

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

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

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

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

In the formula (AN-12), each of the rings A &lt; ¹¹ &gt; is independently a cyclohexane ring or a benzene ring.

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

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

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

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

As the tetracarboxylic acid dianhydride other than the above, the following compounds may be mentioned.

Refers to a material suitable for improving the properties of the liquid crystal alignment layer described later in the tetracarboxylic acid dianhydride. (AN-1), (AN-3), and (AN-4) are preferable, and the compounds represented by formulas (AN-1-2) More preferably a compound represented by the formula (AN-1-13), a formula (AN-3-2), a formula (AN-4-17), and a formula (AN- M is 4 or 8, and in the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

(AN-1-1), (AN-1-2), (AN-3-1), (AN-4-17), AN-10-1, AN-16-3, AN-16, and AN-15, (AN-4-17) and (AN-2-1) are preferable, and in the formula (AN-1-2), m is preferably 4 or 8, ), M = 4 or 8 is preferable, and m = 8 is more preferable.

(AN-1-1), (AN-1-2), (AN-3-1), and (AN-2-1) are given when it is important to improve the voltage holding ratio of the liquid crystal display element AN-4-17, AN-4-30, AN-7-2, AN-10-1, AN-16-3, AN-16, (AN-4-17) and (AN-2-1) are preferable, and m is preferably 4 or 8 in the formula (AN-1-2) , M = 4 or 8 is preferable, and m = 8 is more preferable.

It is effective as one of the methods for preventing the baking by decreasing the volume resistivity of the liquid crystal alignment film and improving the relaxation rate of the residual charge (residual DC) in the liquid crystal alignment film. (AN-1-13), (AN-3-2), AN-4-21, AN-4-29, and AN-11 -3) is preferable.

&Lt; Diamines and dihydrazides other than the diamines represented by the formula (2) &gt;

The diamines and dihydrazides used to prepare the polyamic acids and derivatives thereof according to the embodiments of the present invention will be described. In the production of the polyamic acid or the derivative thereof according to the embodiment of the present invention, other than the diamine represented by the formula (2), it may be selected without limitation from known diamines and dihydrazides.

The diamine can be divided into two types according to its structure. That is, when a skeleton connecting two amino groups is taken as a main chain, it is a group branching from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. In the following description, the diamine having such a side chain group may be referred to as a side chain type diamine. The diamine having no such side chain group may be referred to as a non-branched chain diamine. This side chain group is a group having an effect of increasing the pretilt angle.

By suitably separating the non-branched diamine and the branched-chain diamine, they can correspond to the respective pre-tilt angles.

The side chain type diamine is preferably used in combination so as not to impair the characteristics of the present invention. In addition, it is preferable that the side chain type diamine and the non-side chain type diamine are selected and used for the purpose of improving the vertical alignment property, the voltage holding ratio, the burning property and the orientation property to the liquid crystal.

Existing diamines and dihydrazides are shown below.

In the formula (DI-1), G ²⁰ is -CH ₂ - or the formula (DI-1-a), and when G ²⁰ is -CH ₂ -, at least one -CH ₂ - -NH-, -O-, m is an integer of 1 to 12, m at least one hydrogen of -CH ₂ - may be substituted with -OH or methyl, G ²⁰ may be substituted by the formula (DI-1 -a), m is zero.

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

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

In formula (DI-5), G ³³ is independently a single bond, -NH-, -NCH ₃ -, -O-, -S-, -SS-, -SO ₂ -, -CO-, _{, -CONCH 3 -, -CONH-, -C} (CH 3) 2 -, -C (CF 3) 2 -, - (CH 2) m -, -O- (CH 2) m -O-, -N _{(CH 3) - (CH 2} ) k -N (CH 3) -, - (OC 2 H 4) m -O-, -O-CH 2 -C (CF 3) 2 -CH 2 -O-, - _{O-CO- (CH 2) m} -CO-O-, -CO-O- (CH 2) m -O-CO-, - (CH 2) m -NH- (CH 2) m -, -CO- _{(CH 2) k -NH- (CH} 2) k -, - (NH- (CH 2) m) k -NH-, -CO-C 3 H 6 - (NH-C 3 H 6) n -CO- , or _{-S- (CH 2) m -S-,} -N (Boc) - (CH 2) e -N (Boc) -, -NH- (CH 2) e -N (Boc) -, -N ( _{Boc) - (CH 2) e} -, - (CH 2) m -N (Boc) -CONH- (CH 2) m -, - (CH 2) m -N (Boc) - (CH 2) m -, Is a group represented by the following formula (DI-5-a) or (DI-5-b), m is independently an integer of 1 to 12, k is an integer of 1 to 5, Lt; / RTI &gt; and n is 1 or 2. Boc is a t-butoxycarbonyl group

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

Formula (DI-2) ~ formula (DI-7) of the cyclohexane ring and benzene ring, at least one hydrogen, -F, -Cl, alkyl, -OCH _3, -OH, -CF ₃ having a carbon number of 1 to 3, _{-CO 2 H, -CONH 2, -NHC} 6 H 5, phenyl, or benzyl is optionally substituted with, in addition to formula (DI-4) in cyclohexane ring and benzene ring, at least one hydrogen has the following formula (DI in (DI-4-a) to (DI-4-i). In the formula (DI-5), when G ³³ is a monovalent bond, a cyclohexane ring and benzene At least one hydrogen of the ring may be substituted with NHBoc or N (Boc) ₂ .

At least one hydrogen of a cyclohexane ring and a benzene ring indicates that a bonding position in which the bonding position is not fixed to the carbon constituting the ring is arbitrary. The bonding position of -NH ₂ to the cyclohexane ring or the benzene ring is any position other than the bonding position of G ²¹ , G ²² or G ³³ .

In the formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ . M is an integer of 0 to 12, and Boc is a t-butoxycarbonyl group.

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

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

In formula (DI-12), R ²¹ and R ²² are independently alkyl having 1 to 3 carbon atoms or phenyl, G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms, w is an integer of 1 to 10;

In formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4 to be.

(DI-14), ring B is a monocyclic heterocyclic aromatic group, R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbon atoms, alkoxy, alkenyl, alkynyl, q is independently It is an integer from 0 to 4. In the formula (DI-15), the ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1. A bonding hand in which the bonding position is not fixed to the carbon constituting the ring indicates that the bonding position in the ring is arbitrary. In the formulas (DI-13) to (DI-16), the bonding position of -NH ₂ bonded to the ring is an arbitrary position.

Specific examples of the following formulas (DI-1-1) to (DI-16-1) may be mentioned as diamines having no side chain of the formulas (DI-1) to (DI-16).

Examples of the diamine represented by the formula (DI-1) are shown below.

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

Examples of the diamines represented by the formulas (DI-2) to (DI-3) are shown below.

Examples of the diamine represented by the formula (DI-4) are shown below.

In the formulas (DI-4-20) and (DI-4-21), m is independently an integer of 1 to 12.

Examples of the diamine represented by the formula (DI-5) are shown below.

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

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

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

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

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

(DI-5-42) to Formula (DI-5-44), e is an integer of 2 to 10, and R ⁴³ is hydrogen, NHBoc or N (Boc) ₂ . In the formulas (DI-5-42) to (DI-5-44), Boc is a t-butoxycarbonyl group.

Examples of the diamine represented by the formula (DI-6) are shown below.

Examples of the diamine represented by the formula (DI-7) are shown below.

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

Examples of the diamine represented by the formula (DI-8) are shown below.

Examples of the diamine represented by the formula (DI-9) are shown below.

Examples of the diamine represented by the formula (DI-10) are shown below.

Examples of the diamine represented by the formula (DI-11) are shown below.

Examples of the diamine represented by the formula (DI-12) are shown below.

Examples of the diamine represented by the formula (DI-13) are shown below.

Examples of the diamine represented by the formula (DI-14) are shown below.

Examples of the diamine represented by the formula (DI-15) are shown below.

Examples of the diamine represented by the formula (DI-16) are shown below.

Describes dihydrazide. Examples of the dihydrazide having no existing side chain include the following formulas (DIH-1) to (DIH-3).

In the formula (DIH-1), G ²⁵ represents a single bond, alkylene, -CO-, -O- having a carbon number of _{1 ~ 20, -S-, -SO 2} -, -C (CH 3) 2 -, or - (CF ₃ ) ₂ -.

In the formula (DIH-2), the ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of the group may be substituted with methyl, ethyl or phenyl. In the formula (DIH-3), each of the rings E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of the group may be substituted with methyl, ethyl or phenyl, Y is a single bond, -CO-, -O-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, or -C (CF ₃ ) ₂ -. In the formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary position.

Examples of the formulas (DIH-1) to (DIH-3) are shown below.

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

Such diamines and dihydrazides have the effect of improving the electrical characteristics, such as lowering the ion density of the liquid crystal display element.

A diamine suitable for the purpose of increasing the pre-tilt angle will be described. (DI-31) to (DI-35), and the formulas (DI-36-1) to (DI-36-8) as the diamine having a side chain group suitable for the purpose of increasing the pretilt angle have.

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O -, -OCF ₂ -, or - (CH ₂ ) _{m '} -, and m' is an integer of 1 to 12. Preferred examples of G ²⁶ are a single bond, -O-, -COO-, -OCO-, -CH ₂ O-, and alkylene having 1 to 3 carbon atoms, particularly preferred examples are a single bond, -O-, -COO -, -OCO-, -CH ₂ O-, -CH ₂ - and -CH ₂ CH ₂ -. R ²⁵ is alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In this alkyl, at least one hydrogen may be substituted with -F, and at least one -CH ₂ - may be substituted with -O-, -CH = CH-, or -C≡C-. Hydrogen of the phenyl _{is, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, or may be substituted by alkoxy of 3 to 30 carbon atoms or alkyl of 3 to 30 carbon atoms. The bonding position of -NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, and the bonding position is preferably meta or para. That is, when the bonding position of the group &quot; R ²⁵ -G ²⁶ - &quot; is taken as 1 position, it is preferable that the two bonding positions are 3 position and 5 position or 2 position and 5 position.

In formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are bonding groups and independently represent a single bond or an alkylene group having 1 to 12 carbon atoms, and at least one -CH ₂ - May be substituted with -O-, -COO-, -OCO-, -CONH- or -CH = CH-. Ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, , 5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or an anthracene-9,10-diyl, ring B ^21, B ²² ring, ring B and ²³ in ring B ^24, at least one hydrogen is substituted by -F, or -CH _3, s, t and u are independently an integer from 0 to 2, their sum is 1 ~ 5, s, t Or when u is 2, the two couplers in each parenthesis may be the same or different and the two rings may be the same or different. R ²⁶ is hydrogen, -F, -OH, C 1 -C 30 alkyl, C 1 -C 30 fluorine-substituted alkyl, _{alkoxy, -CN, -OCH 2 F, -OCHF} 2, or -OCF of 1 to 30 carbon atoms in the ₃ , And at least one -CH ₂ - of the alkyl having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-31-b).

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

In formula (DI-32) and formula (DI-33), G ³⁰ represents a single bond independently, -CO- or -CH ₂ -, and, R ²⁹ are independently hydrogen or -CH _3, R ³⁰ is hydrogen , Alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms. At least one hydrogen of the benzene ring in formula (DI-33) may be substituted with alkyl having 1 to 20 carbon atoms or phenyl. A joining hand in which the joining position is not fixed to any carbon constituting the ring indicates that the joining position in the ring is arbitrary. 2 groups of the formula (DI-32) "- phenylene -G ³⁰ -O-", one of the steroids bonded to the 3-position of the nucleus, and the other one is preferably bonded to the 6-position of the steroid nucleus . Formula (DI-33) 2 group of from the "- phenylene -G ³⁰ -O-", binding position of the benzene ring are in, it is desirable for the bonding position of the steroid nucleus, wherein each meta-position or para-position . In the formulas (DI-32) and (DI-33), -NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

In the formulas (DI-34) and (DI-35), G ³¹ is independently -O- or alkylene having 1 to 6 carbon atoms, and G ³² is a single bond or alkylene having 1 to 3 carbon atoms. R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one -CH ₂ - of the alkyl may be substituted with -O-, -CH = CH- or -C≡C-. R ³² is alkyl having 6 to 22 carbon atoms, and R ³³ is hydrogen or alkyl having 1 to 22 carbon atoms. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. And -NH ₂ bonded to the benzene ring represents an arbitrary bonding position in the ring, and it is preferable that it is independently a meta position or a para position with respect to the bonding position of G ³¹ .

Examples of the compound represented by the formula (DI-31) are shown below.

In the formulas (DI-31-1) to (DI-31-11), R ³⁴ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, preferably alkyl having 5 to 25 carbon atoms, Lt; / RTI &gt; R ³⁵ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, preferably alkyl having 3 to 25 carbon atoms or alkoxy having 3 to 25 carbon atoms.

In the formulas (DI-31-12) to (DI-31-17), R ³⁶ is alkyl of 4 to 30 carbon atoms, preferably alkyl of 6 to 25 carbon atoms. R ³⁷ is alkyl having 6 to 30 carbon atoms, preferably 8 to 25 carbon atoms.

In the formulas (DI-31-18) to (DI-31-43), R ³⁸ is alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms, preferably alkyl having 3 to 20 carbon atoms or 3 Lt; / RTI &gt; R ³⁹ is hydrogen, -F, a C 1 -C 30 alkyl, _{alkoxy, -CN, -OCH 2 F, -OCHF} 2 or -OCF of 1 to 30 carbon atoms of _3, preferably an alkyl, or with a carbon number of 3 to 25 Alkoxy of 3 to 25 carbon atoms. And G ³³ is alkylene having 1 to 20 carbon atoms.

Examples of the compound represented by the formula (DI-32) are shown below.

Examples of the compound represented by the formula (DI-33) are shown below.

Examples of the compound represented by the formula (DI-34) are shown below.

In formula (DI-34-1) ~ formula (DI-34-12), R ⁴⁰ is hydrogen or alkyl of 1 to 20 carbon atoms, preferably hydrogen or alkyl of 1 to 10 carbon atoms, and R ⁴¹ is hydrogen Or alkyl having 1 to 12 carbon atoms.

Examples of the compound represented by the formula (DI-35) are shown below.

In formulas (DI-35-1) to (DI-35-3), R ³⁷ is alkyl having 6 to 30 carbon atoms and R ⁴¹ is hydrogen or alkyl having 1 to 12 carbon atoms.

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

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

Refers to a material suitable for improving the properties of the liquid crystal alignment film described below in the above-mentioned diamine and dihydrazide. (DI-5-1), the formula (DI-5-5), the formula (DI-5-9), the formula (DI-5-12), Formula (DI-5-13), Formula (DI-5-29), Formula (DI- 6-7) -2) is preferably used. In the formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is more preferable. In the formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In the formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable.

(DI-3-1), formula (DI-2-1), formula (DI-5-1), formula (DI- 5-5) 5-24) and the diamine represented by the formula (DI-7-3) are preferably used, and the compound represented by the formula (DI-2-1) is more preferable. In the formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is more preferable. In the formula (DI-7-3), m = 2 or 3, n = 1 or 2 is preferable, and m = 3 and n = 1 are more preferable.

(DI-2-1), (DI-4-1), (DI-4-2), and (DI-4-10) The compound represented by the formula (DI-4-15), the formula (DI-4-22), the formula (DI-5-28), the formula (DI- 5-30) And diamines represented by the formulas (DI-2-1), (DI-5-1) and (DI-13-1) are more preferable. In the formula (DI-5-1), m = 1 is preferable. In the formula (DI-5-30), k = 2 is preferable.

It is effective as one of the methods for blocking the baking to improve the relaxation speed of the residual charge (residual DC) in the liquid crystal alignment film by lowering the volume resistance value of the liquid crystal alignment film. (DI-4-1), (DI-4-2), (DI-4-10), (DI-4-15) and (DI-5- 1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28) It is preferable to use compounds represented by the formulas (DI-7-12) and (DI-16-1) -13) is more preferable. In the formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is more preferable. In the formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In the formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable. In the formula (DI-7-12), m = 3 or 4 is preferable, and m = 4 is more preferable.

In each of the diamines, a part of the diamine may be substituted with a monoamine in the range of the proportion of the monoamine to the diamine being 40 mol% or less. Such substitution can cause termination of the polymerization reaction at the time of producing the polyamic acid, and further suppress the progress of the polymerization reaction. Therefore, by such substitution, the molecular weight of the obtained polymer (polyamic acid or its derivative) can be easily controlled, and the application property of the liquid crystal aligning agent can be improved without impairing the effect of the present invention . The diamine substituted with a monoamine may be used in one kind or in two or more types if the effect of the present invention is not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, Octadecylamine, and n-eicosylamine.

The polyamic acid or derivative thereof according to the embodiment of the present invention may further comprise a monoisocyanate compound in its monomer. By incorporating the monoisocyanate compound into the monomer, the terminal of the resulting polyamic acid or its derivative is modified and the molecular weight is controlled. By using the polyamic acid of the terminal modification type or a derivative thereof, for example, the coating property of the liquid crystal aligning agent can be improved without impairing the effect of the present invention. The content of the monoisocyanate compound in the monomer is preferably from 1 to 10 mol% based on the total amount of the diamine and tetracarboxylic acid dianhydride in the monomer from the viewpoint of the above. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

&Lt; Monomer having photoreactive structure &gt;

In the production of the polyamic acid or its derivative according to the embodiment of the present invention, in addition to the diamine represented by the formula (2), it may be used together with a monomer having another photoreactive structure. Other photoreactive structures include, for example, optical isomerization structures represented by formulas (P-1) to (P-3) causing isomerization by ultraviolet irradiation, formulas (P-5) P-7), and the like.

Examples of the compound having a photoisomerization structure represented by the formulas (P-1) to (P-3) include compounds having at least one compound selected from the group of compounds represented by the following formulas (II) to (VI) , And a compound represented by the formula (V) is more preferable.

In the formulas (II) to (V), R ² and R ³ are each a monovalent organic group having -NH ₂ or a monovalent organic group having -CO-O-CO-, and R ⁴ is a divalent organic group, and in formula (VI), R ⁵ is independently an aromatic ring having -NH ₂ or -CO-O-CO-.

The photoisomerization structure can be incorporated into either the main chain or the side chain of the polyamic acid or its derivative in the present invention, but it can be suitably used for a liquid crystal display device of the transverse electric field system by incorporating into the main chain.

(III-1), (III-2), (III-2), (IV-1) ), At least one compound selected from the group of compounds represented by formulas (V-1) to (V-3), formula (VI-1) and formula (VI-2)

In the formula (IV-3), r represents an integer of from 1 to 3, and R &lt; 2 &gt; represents an alkyl group having 1 to 4 carbon atoms. in an integer from to 10, formula (V-2), R ⁶ is independently selected from _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, a is independently an integer from 0 to 2, the expression (V-3), ring A and ring B are each independently at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocyclic rings, R ¹¹ is straight chain alkylene having 1 to 20 carbon atoms, -COO -, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, or -CON (CH ₃ ) -, and R ¹² is straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO- or -CON (CH ₃ ) -, and in R ¹¹ and R ¹² , one of -CH ₂ - Or two of them may be substituted with -O-, and R ⁷ to R ¹⁰ are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ , or - OH, and b to e are each independently an integer of 0 to 4.

The compounds represented by the formulas (V-1), (V-2) and (VI-2) can be suitably used particularly in view of their photosensitivity. In the formula (V-2) and the compound represented by the formula (VI-2), the compound in which the bonding position of the amino group is the para position and the compound in the formula (V-2) And can be suitably used. The compound represented by the formula (IV-3) may be used for purposes other than the expression of photosensitivity.

The tetracarboxylic acid dianhydride or diamine having a structure capable of causing isomerization by ultraviolet irradiation represented by the formula (II-1) to (VI-2) is represented by the following formula (II- 3).

In the formula (IV-3-1), r is an integer of 1 to 10.

Among these compounds, it is preferable to use a compound having a structure capable of causing isomerization by ultraviolet irradiation of the formula (VI-1-1) to the formula (V-3-8) to provide a liquid crystal aligning agent for photo- Can be obtained. V-2-1, V-2-1, V-2-4 to V-2-11 and V-3-1 to V- -8) having a structure capable of causing isomerization by irradiation with ultraviolet rays, it is possible to obtain a liquid crystal aligning agent for optical alignment capable of more uniformly orienting liquid crystal molecules. Among them, a compound represented by the formula (V-2-1) can more suitably be used because it exhibits greater anisotropy when the liquid crystal alignment film is formed.

Examples of the compound having a photoreactive structure represented by the formulas (P-5) to (P-7) include diamine compounds represented by the following formulas (PDI-9) to (PDI-13).

In formula (PDI-12), R ⁵⁴ is alkyl or alkoxy having 1 to 10 carbon atoms, and at least one hydrogen of alkyl or alkoxy may be substituted with fluorine.

The above formulas (PDI-9) and (PDI-11) can be suitably used.

In the case of using a tetracarboxylic acid dianhydride having no photoreactive structure (non-photosensitive) and a (photosensitive) tetracarboxylic acid dianhydride having a photoreactive structure, in order to prevent the sensitivity of the liquid crystal alignment film to light, The amount of the photosensitive tetracarboxylic acid dianhydride is preferably 0 to 70 mol%, more preferably 0 to 50 mol%, relative to the total amount (total amount) of the tetracarboxylic acid dianhydride used as a raw material in the production of the polyamic acid or the derivative thereof according to the embodiment More preferable. Further, two or more photosensitive tetracarboxylic acid dianhydrides may be used in combination in order to improve the above-described characteristics such as sensitivity to light, electrical characteristics, residual image characteristics and the like.

In the case of using the (photosensitive) diamine having no photoreactive structure (photosensitive) and the (photosensitive) diamine having a photoreactive structure in combination, in order to prevent the sensitivity of the liquid crystal alignment film to the sensitivity to light, The photosensitive diamine is preferably used in an amount of from 20 to 100 mol%, and more preferably from 50 to 100 mol%, based on the total amount of the diamine used as a raw material in the production of the resin or the derivative thereof. Further, two or more photosensitive diamines may be used in combination in order to improve the above-mentioned various characteristics such as sensitivity to light, residual image characteristics and the like. As described above, the embodiment of the present invention includes the case where the total amount of the tetracarboxylic dianhydride is in the non-photosensitive tetracarboxylic acid dianhydride, in which case at least 20 mol% of the total amount of the diamine is required to be the photosensitive diamine.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention may be composed of one kind of polymer according to the embodiment of the present invention, or two or more kinds of polymers according to the embodiment of the present invention may be mixed. However, considering the storage stability of the liquid crystal aligning agent, the printing property of the liquid crystal aligning agent on the display element substrate, and the properties of the liquid crystal alignment film to be formed, the mixing of the polyamic acid or its derivatives or the polyamic acid or its derivative is expressed by formula (2) A liquid crystal aligning agent obtained by mixing a polyamic acid or a derivative thereof which does not use a diamine as a raw material is preferable. Further, in the present specification, the liquid crystal aligning agent composed of one kind of the above polymer may be referred to as a single layer type liquid crystal aligning agent. A liquid crystal aligning agent for mixing two or more of the above polymers may be referred to as a blended liquid crystal aligning agent.

The above-mentioned tetracarboxylic acid dianhydride, diamine and dihydrazide are suitably used for the production of the polyamic acid and the derivative thereof, which does not use the diamine represented by the formula (2) as a raw material.

When such a two-component polymer is used, for example, there is a mode in which a polymer having a performance excellent in liquid crystal aligning ability is selected on one side and a polymer having excellent performance in improving electrical characteristics of the liquid crystal display element on the other side is selected . In this case, it is preferable that a liquid crystal aligning agent in which these polymers are dissolved in a solvent by controlling the structure and molecular weight of each polymer is applied to the substrate as described later, and preliminary drying is performed to form a thin film, It is possible to segregate the polymer having the performance in the upper layer of the thin film and the polymer having the excellent performance in improving the electrical characteristics of the liquid crystal display element in the lower layer of the thin film. For this, a phenomenon in which a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer can be applied to a mixed polymer. Confirmation of such layer separation can be confirmed to be that the surface energy of the formed liquid crystal alignment film is equal to or close to the surface energy of the film formed by the liquid crystal aligning agent containing only the polymer intended to be segregated in the upper layer.

As a method for expressing the layer separation, the case where the molecular weight of the polymer to be segregated in the upper layer is reduced can be mentioned.

In the liquid crystal aligning agent comprising a mixture of polyamic acids, it is also possible to express the layer separation by making the polymer to be segregated in the upper layer polyimide.

The diamine represented by the formula (2) according to the embodiment of the present invention may be used as the raw material monomer of the polymer segregated in the upper layer of the thin film or may be used as the raw material monomer of the polymer segregated in the lower layer of the thin film. It may also be used as a raw material monomer for both polymers.

The tetracarboxylic acid dianhydride used for synthesizing the polyamic acid or its derivative segregated in the upper layer of the thin film may be selected without limitation from the known tetracarboxylic acid dianhydride exemplified above.

(AN-1-1), (AN-4-17), and (AN-2-1), the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid or the derivative thereof segregated in the upper layer of the thin film can be obtained, (AN-4-17) is more preferable. In the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

The diamine and dihydrazide used for synthesizing the polyamic acid or its derivative segregated in the upper layer of the thin film can be selected without limitation from the known diamines and dihydrazides exemplified above.

The diamines and dihydrazides used for synthesizing the polyamic acid or derivatives thereof segregated in the upper layer of the thin film may be represented by the following formulas (DI-4-1), (DI-5-1) and (DI- 3) is preferably used. Among them, in the formula (DI-5-1), m = 1, 2 or 4 is preferable, and m = 4 is more preferable. In the formula (DI-7-3), m = 3 and n = 1 are preferable.

The non-photosensitive diamine used for synthesizing the polyamic acid or its derivative segregated in the upper layer of the thin film preferably contains 30 mol% or more of the aromatic diamine in the total amount of the diamine, more preferably 50 mol% or more.

The acid dianhydride and diamine having the above-described photo-isomerization structure are suitably used for synthesizing a polyamic acid or a derivative thereof segregated in the upper layer of the thin film.

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

(AN-1-1), formula (AN-1-13), formula (AN-3-2) or the like may be used as the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid or its derivative segregated in the lower layer of the thin film. , And (AN-4-21) are preferable, and the compounds represented by formulas (AN-1-1) and (AN-3-2) are more preferable.

The tetracarboxylic acid dianhydride used for synthesizing the polyamic acid or the derivative thereof segregated in the lower layer of the thin film preferably contains 10 mol% or more of the aromatic tetracarboxylic acid dianhydride in the total amount of the tetracarboxylic dianhydride, more preferably 30 mol% or more .

The diamine and dihydrazide used for synthesizing the polyamic acid or its derivative segregated in the lower layer of the thin film can be selected without limitation from the known diamines and dihydrazides exemplified above.

(DI-4-1), (DI-4-2), and (DI-4-10) which are used for synthesizing polyamic acid or derivatives thereof segregated in the lower layer of the thin film, ), Formula (DI-5-9), Formula (DI-5-28), Formula (DI-5-30) and Formula (DIH-2-1) are preferable. Among them, in the formula (DI-5-30), a diamine in which k = 2 is preferable.

The diamine used for synthesizing the polyamic acid or its derivative segregated in the lower layer of the thin film is preferably one containing at least 30 mol% of the aromatic diamine with respect to the total diamine and at least 50 mol% More preferable.

The polyamic acid or its derivative segregated in the upper layer of the thin film and the polyamic acid or the derivative segregated in the lower layer of the thin film are all methods of synthesizing polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention Can be synthesized in accordance with the description.

The proportion of the polyamic acid or its derivative segregated in the upper layer of the thin film relative to the total amount of the polyamic acid or the derivative segregated in the upper layer of the thin film and the total amount of the polyamic acid or the derivative segregated in the lower layer of the thin film is preferably 5 wt% %, More preferably 10% by weight to 40% by weight.

<Solvent>

For example, the liquid crystal aligning agent of the present invention may further contain a solvent from the viewpoint of the application of the liquid crystal aligning agent and the adjustment of the concentration of the polyamic acid or its derivative. The solvent can be applied without particular limitation as long as it is a solvent capable of dissolving a polymer component. The solvent widely includes a solvent commonly used in the production process or application of a polymer component such as polyamic acid and soluble polyimide, and may be appropriately selected depending on the purpose of use. The solvent may be one kind or two or more kinds of mixed solvents.

Examples of the solvent include a hydrophilic solvent for the polyamic acid or a derivative thereof, and other solvents for improving the applicability.

Examples of the aprotic polar organic solvent which is a hydrophilic solvent for the polyamic acid or a derivative thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, N, N-dimethylisobutylamide, N, N-dimethylacetamide, and lactone such as? -butyrolactone.

Examples of other solvents for the purpose of improving coatability include diisobutyl ketone, alkyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, tetralin, isophorone and ethylene glycol monobutyl ether Diethylene glycol monoalkyl ethers such as ethylene glycol monoalkyl ether and diethylene glycol monoethyl ether, diethylene glycol dialkyl ethers such as diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and diethylene glycol butyl methyl ether, Propylene glycol monoalkyl ethers such as ethylene glycol monoalkyl or phenylacetate, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether and propylene glycol monobutyl ether, dialkyl malonates such as diethyl malonate, dipropylene glycol monomethyl ether and the like Dipropylene glycol monoalkyl ether, and ester compounds such as acetate .

Among them, the solvent is preferably selected from the group consisting of N-methyl-2-pyrrolidone, dimethylimidazolidinone,? -Butyrolactone, diisobutylketone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, Methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether are preferable.

The concentration of the polyamic acid in the liquid crystal aligning agent of the present invention is preferably 0.1 to 40% by weight. When this liquid crystal aligning agent is applied to the substrate, it may be necessary to dilute the polyamic acid contained in advance with a solvent in order to adjust the film thickness.

The solid concentration of the liquid crystal aligning agent of the present invention is not particularly limited, and an optimum value may be selected in accordance with the following various application methods. The amount is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight based on the weight of the varnish in order to suppress unevenness and pinholes at the time of coating.

The viscosity of the liquid crystal aligning agent of the present invention differs depending on the method of application, the concentration of the polyamic acid or its derivative, the type of the polyamic acid or derivative thereof, and the type and ratio of the solvent. For example, in the case of application by a printing machine, it is 5 to 100 mPa · s (more preferably, 10 to 80 mPa · s). When it is less than 5 mPa · s, it is difficult to obtain a sufficient film thickness, and when it is more than 100 mPa · s, printing unevenness may become large. In the case of application by spin-coating, 5 to 200 mPa · s (more preferably 10 to 100 mPa · s) is suitable. In the case of coating using an inkjet coating apparatus, 5 to 50 mPa · s (more preferably 5 to 20 mPa · s) is suitable. The viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measurement method and measured (measured temperature: 25 ° C) using, for example, a rotational viscometer (TVE-20L type manufactured by TOKI INDUSTRIES, LTD.).

&Lt; Alkenyl-substituted nadimide compound &gt;

For example, the liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadimide compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long term. The alkenyl-substituted nadimide compound may be used singly or in combination of two or more. The content of the alkenyl-substituted nadimide compound is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and more preferably 1 to 50% by weight, based on the polyamic acid or the derivative thereof, More preferable.

The alkenyl-substituted nadimide compound is preferably a compound capable of dissolving in the solvent for dissolving the polyamic acid or the derivative thereof used in the present invention. Preferred examples of the alkenyl-substituted nadimide compounds include alkenyl-substituted nadimide compounds disclosed in JP-A-2013-242526 and the like. More preferred alkenyl-substituted nadimide compounds include bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} methane, N, N'- (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis Ene-2,3-dicarboxyimide).

<Compound Having Radical Polymerizable Unsaturated Double Bond>

For example, the liquid crystal aligning agent of the present invention may further contain a compound having a radically polymerizable unsaturated double bond for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long term. The compound having a radically polymerizable unsaturated double bond may be a single compound or two or more compounds. The compound having a radically polymerizable unsaturated double bond does not contain an alkenyl-substituted nadimide compound. The content of the compound having a radically polymerizable unsaturated double bond is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and more preferably 1 to 50% by weight, based on the polyamic acid or the derivative thereof, %.

The ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl-substituted nadimide compound is preferably in the range of from 0.1 to 5 parts by weight based on 100 parts by weight of the liquid crystal display element, , The weight ratio of the compound having a radically polymerizable unsaturated double bond / alkenyl-substituted nadimide compound is preferably 0.1 to 10, more preferably 0.5 to 5.

Preferred examples of the compound having a radically polymerizable unsaturated double bond include compounds having a radically polymerizable unsaturated double bond disclosed in JP-A-2013-242526 and the like.

&Lt;

For example, the liquid crystal aligning agent of the present invention may further contain an oxazine compound in order to stabilize the electric characteristics of the liquid crystal display element for a long term. The oxazine compound may be a single compound or two or more compounds. The content of the oxazine compound is preferably from 0.1 to 50% by weight, more preferably from 1 to 40% by weight, and still more preferably from 1 to 20% by weight, based on the polyamic acid or the derivative thereof .

The oxazine compound is soluble in a solvent which dissolves the polyamic acid or its derivative, and is preferably an oxazine compound having ring-opening polymerizability. Preferred examples of the oxazine compound include oxazine compounds represented by formulas (OX-3-1) and (OX-3-2), and oxazine compounds disclosed in JP-A-2013-242526 have.

<Oxazoline compound>

For example, the liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electric characteristics in the liquid crystal display element for a long term. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be a single compound or two or more compounds. The content of the oxazoline compound is preferably from 0.1 to 50% by weight, more preferably from 1 to 40% by weight, and even more preferably from 1 to 20% by weight, based on the polyamic acid or the derivative thereof for the above purpose . Alternatively, the content of the oxazoline compound is preferably 0.1 to 40% by weight based on the amount of the polyamic acid or its derivative when the oxazoline structure in the oxazoline compound is converted to oxazoline.

Preferable oxazoline compounds include oxazoline compounds disclosed in JP-A-2013-242526 and the like. More preferred is 1,3-bis (4,5-dihydro-2-oxazolyl) benzene.

<Epoxy Compound>

For example, the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long term. The epoxy compound may be one kind of compound or two or more kinds of compounds. The content of the epoxy compound is preferably from 0.1 to 50% by weight, more preferably from 1 to 40% by weight, and still more preferably from 1 to 20% by weight, based on the polyamic acid or the derivative thereof.

Examples of the epoxy compound include an epoxy compound disclosed in JP-A-2013-242526 and the like. Preferred epoxy compounds include N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- glycidoxypropyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyl triethoxysilane, (3,3 ', 4,4'-diepoxy) bicyclohexyl (trade name: CELLOXIDE 8000) .

<Additives>

For example, the liquid crystal aligning agent of the present invention may further contain various additives. Examples of various additives include polymer compounds other than polyamic acid and derivatives thereof, and low molecular weight compounds, and they can be selected depending on the purpose.

For example, the polymer compound may be a polymer compound soluble in an organic solvent. The addition of such a polymer compound to the liquid crystal aligning agent of the present invention is preferable from the viewpoint of controlling the electrical characteristics and orientation of the liquid crystal alignment film to be formed. Examples of the polymer compound include polyamides, polyurethanes, polyureas, polyesters, polyepoxides, polyester polyols, silicone modified polyurethanes, and silicone modified polyesters.

Examples of the low-molecular compound include the following materials. 1) When it is desired to improve the coating property, the surfactant for this purpose. 2) Antistatic agent when it is necessary to improve antistatic property. 3) A silane coupling agent or a titanium-based coupling agent when it is desired to improve the adhesion with the substrate. 4) Imidization catalyst in the case where imidization proceeds at a low temperature. Examples of the silane coupling agent include silane coupling agents disclosed in JP-A-2013-242526 and the like. A preferred silane coupling agent is 3-aminopropyltriethoxysilane. As the imidization catalyst, there can be mentioned imidization catalysts disclosed in JP-A-2013-242526 and the like.

&Lt; Liquid Crystal Alignment Film of Optical Alignment Type (Photo Alignment Film) &gt;

The photo alignment layer of the present invention will be described in detail. The photo alignment layer of the present invention can be obtained by a conventional method for producing a photo alignment layer from a photo alignment liquid crystal alignment agent. The photo alignment layer of the present invention can be obtained by, for example, a step of forming a coating film of the photo alignment liquid crystal aligning agent of the present invention, a step of heating and drying, a step of irradiating light to impart anisotropy, You can get it by hovering. With respect to the photo alignment layer of the present invention, anisotropy may be imparted by irradiating light after the coating process, the heating and drying process, if necessary, or anisotropy may be imparted by irradiating light after the heating and firing process.

The coating film can be formed by applying the liquid crystal aligning agent of the present invention to a substrate in a liquid crystal display element in the same manner as in the production of an ordinary liquid crystal alignment film. The substrate, ITO (Indium Tin Oxide), IZO (In 2 O 3 -ZnO), IGZO (In-Ga-ZnO 4) The silicon nitride, glass, which may include the electrode and the color filter, such as the electrodes is installed acrylic claim, Polycarbonate, polyimide, and the like.

As a method of applying a liquid crystal aligning agent to a substrate, a spinner method, a printing method, a dipping method, a dropping method, an ink jet method, and the like are generally known. These methods are also applicable to the present invention.

The heating and drying process is generally known as a heating process in an oven or an infrared room, a heating process on a hot plate, and the like. The heating and drying step is preferably carried out at a temperature within a range in which evaporation of the solvent is possible, and more preferably at a temperature relatively lower than the temperature in the heating and firing step. Specifically, the heating and drying temperature is preferably in the range of 30 ° C to 150 ° C, more preferably in the range of 50 ° C to 120 ° C.

The heating and firing step may be carried out under conditions necessary for the polyamic acid or its derivative to exhibit a dehydration / ring-closing reaction. The firing of the coating film is generally known as a method of performing a heat treatment in an oven or an infrared ray, a method of performing heat treatment on a hot plate, and the like. These methods are also applicable to the present invention. It is generally preferable to carry out the reaction at a temperature of about 100 to 300 ° C for 1 minute to 3 hours, more preferably 120 to 280 ° C, and even more preferably 150 to 250 ° C. It is also possible to heat and fuse a plurality of times at different temperatures. A plurality of heating apparatuses set at different temperatures may be used, or one heating apparatus may be used while sequentially changing the temperature to a different temperature. In the case of performing the heat firing twice at different temperatures, it is preferable to perform the firing at 90-180 캜 for the first time and 185 캜 or higher for the second time. In addition, firing can be performed by changing the temperature from low temperature to high temperature. When firing is performed by changing the temperature, the initial temperature is preferably 90 to 180 占 폚. The final temperature is preferably 185 to 300 占 폚, and more preferably 190 to 230 占 폚.

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

The method of forming the liquid crystal alignment film of the present invention by the photo alignment method will be described in detail. The liquid crystal alignment film of the present invention using the photo alignment method can be formed by irradiating linearly polarized light or non-polarized light of radiation to a thin film obtained by heating and drying a coating film, imparting anisotropy to the thin film, and heating and firing the film. Alternatively, the coating film can be formed by heating and drying the film, heating and baking the film, and irradiating the film with linearly polarized light or unpolarized light. From the standpoint of the orientation property, it is preferable that the irradiation step of the radiation is performed before the heating and firing step.

In addition, in order to enhance the liquid crystal alignment capability of the liquid crystal alignment film, it is also possible to irradiate linearly polarized light or unpolarized light of radiation while heating the coating film. The irradiation of the radiation may be performed in the step of heating and drying the coating film or the step of heating and firing, or may be carried out between the heating and drying step and the heating and firing step. The heating and drying temperature in the above step is preferably in the range of 30 ° C to 150 ° C, more preferably in the range of 50 ° C to 120 ° C. The heating and firing temperature in the above step is preferably in the range of 30 ° C to 300 ° C, more preferably in the range of 50 ° C to 250 ° C.

As the radiation, for example, ultraviolet light or visible light including light having a wavelength of 150 to 800 nm may be used, and ultraviolet light containing light of 300 to 400 nm is preferable. In addition, linearly polarized light or unpolarized light can be used. The light is not particularly limited as long as it is light capable of imparting liquid crystal aligning ability to the thin film, but linear polarization is preferable when a strong alignment regulating force is desired to be exerted on the liquid crystal.

The liquid crystal alignment film of the present invention can exhibit a high liquid crystal aligning ability even with light irradiation with low energy. The irradiation amount of the linearly polarized light in the above-mentioned irradiation step is preferably 0.05 to 20 J / cm ² , more preferably 0.5 to 10 J / cm ² . The wavelength of the linearly polarized light is preferably 200 to 400 nm, more preferably 300 to 400 nm. The irradiation angle with respect to the film surface of the linearly polarized light is not particularly limited, but when it is desired to exhibit a strong alignment regulating force with respect to the liquid crystal, it is preferable that the angle perpendicular to the film surface is as short as possible from the viewpoint of shortening the orientation treatment time. The liquid crystal alignment film of the present invention can orient the liquid crystal in a direction perpendicular to the polarization direction of linearly polarized light by irradiating linearly polarized light.

Examples of the light source used in the step of irradiating linearly polarized light or unpolarized light of radiation include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a Deep UV lamp, a halogen lamp, a metal halide lamp, a high power metal halide lamp, A xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, and a microwave excitation non-electrode lamp.

The liquid crystal alignment film of the present invention is suitably obtained by a method further including a step other than the above-described step. For example, in the liquid crystal alignment film of the present invention, the step of cleaning the film after baking or irradiation with radiation is not essential, but a cleaning step can be provided for other processes.

Examples of the cleaning method using a cleaning liquid include brushing, jet spraying, steam cleaning, ultrasonic cleaning, and the like. These methods may be performed alone or in combination. As the cleaning liquid, pure water or various alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, halogen solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone are used But is not limited thereto. Needless to say, these cleaning liquids are used with a sufficiently low amount of purified impurities. These cleaning methods can also be applied to the cleaning step in the formation of the liquid crystal alignment film of the present invention.

In order to enhance the liquid crystal alignment performance of the liquid crystal alignment film of the present invention, annealing treatment by heat or light can be used before, after, or before and after irradiation of polarized or unpolarized light. In the annealing treatment, the annealing temperature is 30 to 180 占 폚, preferably 50 to 150 占 폚, and the time is preferably 1 minute to 2 hours. Examples of the annealing light used in the annealing process include a UV lamp, a fluorescent lamp, and an LED lamp. The irradiation amount of light is preferably 0.3 to 10 J / cm ² .

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

The liquid crystal alignment film of the present invention is characterized by having anisotropy particularly in a large orientation. The magnitude of such anisotropy can be evaluated by a method using polarized IR described in Japanese Patent Application Laid-Open No. 2005-275364. It can also be evaluated by a method using an ellipsometer. Specifically, the retardation value of the liquid crystal alignment film can be measured by the spectroscopic ellipsometer. The retardation value of the film becomes larger in proportion to the degree of orientation of the polymer main chain. That is, the polymer film having a large retardation value has a large degree of orientation, and when used as a liquid crystal alignment film, it is considered that a liquid crystal alignment film having a larger anisotropy has a large alignment restraining force for the liquid crystal composition.

The liquid crystal alignment film of the present invention can be suitably used for a liquid crystal display device of a transverse electric field system. When used in a liquid crystal display element of a transverse electric field system, the lower the Pt angle and the higher the liquid crystal aligning ability, the higher the black display level in the dark state and the contrast is improved. The Pt angle is preferably 0.1 DEG or less.

The liquid crystal alignment film of the present invention can be used for alignment control of a liquid crystal composition for a liquid crystal display, such as a smart phone, a tablet, a vehicle monitor, and a television. In addition to the orientation of the liquid crystal composition for a liquid crystal display, it can be used for orientation control of optical compensation materials and all other liquid crystal materials. Since the liquid crystal alignment film of the present invention has a large anisotropy, it can be used alone as an optical compensation material.

<Liquid crystal display element>

The liquid crystal display element of the present invention will be described in detail. The present invention relates to a plasma display panel comprising a pair of substrates disposed opposite to each other, an electrode formed on one or both of opposite surfaces of each of the pair of substrates, A liquid crystal display element having a liquid crystal alignment film, a liquid crystal layer formed between the pair of substrates, and a pair of polarizing films, a backlight, and a driving device provided so as to sandwich the opposing substrate, A liquid crystal display element which is a liquid crystal alignment film of the invention is provided.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such electrodes include a vapor-deposited film of ITO or a metal. The electrode may be formed on the entire surface of one side of the substrate, or may be formed into a desired shape that is patterned, for example. The desired shape of the electrode is, for example, a comb-like or zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both of the substrates. For example, in the case of an IPS type liquid crystal display device, electrodes are disposed on one side of the above-described pair of substrates, and in the case of other liquid crystal display devices, Electrodes are disposed on both sides of the pair of substrates. The liquid crystal alignment film is formed on the substrate or the electrode.

In the case of a homogeneous liquid crystal display element (for example, IPS, FFS or the like), at least a backlight, a first polarizing film, a first substrate, a first liquid crystal alignment film, a liquid crystal layer, 2 substrate and a second polarizing film, and the polarizing axis of the polarizing film is provided such that the polarizing axis of the first polarizing film (direction of polarization absorption) and the polarizing axis of the second polarizing film intersect (preferably perpendicular). At this time, the polarizing axis of the first polarizing film and the liquid crystal alignment direction may be parallel or perpendicular to each other. A liquid crystal display element provided so that the polarization axis of the first polarizing film and the liquid crystal alignment direction are parallel to each other is set to be O-mode and orthogonal to each other, is referred to as an E- mode. The liquid crystal alignment film of the present invention can be applied to either the O-mode or the E-mode, and can be selected in accordance with the purpose.

Many dichromatic compounds are used for many photoisomerizable materials. Therefore, when the polarization axis of the polarized light to be irradiated for adding anisotropy to the liquid crystal aligning agent is made parallel to the polarization axis of the polarized light from the polarizing film disposed on the backlight side (when the liquid crystal aligning agent of the present invention is used, O -Mode), the transmittance in the light absorption wavelength region of the liquid crystal alignment film increases. As a result, the transmittance of the liquid crystal display element can be further improved.

The liquid crystal layer is formed in such a form that the liquid crystal composition is sandwiched by the pair of substrates facing each other on which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, a spacer, such as fine particles or a resin sheet, which forms an appropriate gap between the pair of substrates can be used as needed.

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

In the vacuum injection method, a gap (cell gap) is provided so that the liquid crystal alignment film faces are opposed to each other, and a sealant is printed leaving the injection port of the liquid crystal and the substrates can be bonded together. A liquid crystal is injected and filled in a cell gap defined by a substrate surface and a sealing agent by using a vacuum differential pressure, and then an injection port is sealed to manufacture a liquid crystal display device.

In the ODF method, a sealing agent is printed on the outer periphery of one liquid crystal alignment film surface of a pair of substrates, liquid crystal is dropped to the inside region of the sealing agent, and then the other substrate is bonded so that the liquid crystal alignment film faces face each other have. Then, the liquid crystal is expanded on the front surface of the substrate, and then the ultraviolet light is irradiated to the entire surface of the substrate to cure the sealing agent, thereby manufacturing a liquid crystal display element.

As the sealing agent used for bonding the substrates, a thermosetting type other than the UV curing type is also known. The sealing agent can be printed by, for example, a screen printing method.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having a positive dielectric anisotropy include those described in JP 3086228 A, JP 2635435 A, JP 5-501735 A, JP 8-157826 A, JP 8-231960 A, 9-241644 (EP885272A1), 9-302346 (EP806466A1), 8-199168 (EP722998A1), 9-235552, 9-255956 Japanese Patent Application Laid-Open No. 9-241643 (EP885271A1), Japanese Patent Application Laid-Open No. 10-204016 (EP844229A1), Japanese Patent Application Laid-Open No. 10-204436, Japanese Patent Application Laid-Open No. 10-231482, , And JP-A-2001-48822.

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

There is no problem that one or more optically active compounds are added to a liquid crystal composition having a positive or negative dielectric anisotropy.

For example, the liquid crystal composition used in the liquid crystal display element of the present invention may further contain an additive, for example, from the viewpoint of improving the orientation. Such additives include photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerization initiators, polymerization inhibitors and the like. Examples of the preferable photopolymerizable monomer, optically active phosphorus compound, antioxidant, ultraviolet absorber, dye, defoamer, polymerization initiator and polymerization inhibitor include compounds disclosed in International Publication No. 2015/146330.

The polymerizable compound may be mixed into the liquid crystal composition so as to be suitable for a liquid crystal display device of a PSA (polymer sustained alignment) mode. Preferable examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Preferred compounds include those disclosed in International Publication No. 2015/146330.

[Example]

Hereinafter, the present invention will be described by way of examples. The evaluation methods and compounds used in the examples are as follows.

1. Weight average molecular weight (Mw)

The weight average molecular weight of the polyamic acid was determined by the GPC method using a 2695 separation module 2414 differential refractometer (manufactured by Waters) and the polystyrene conversion was carried out. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that the concentration of polyamic acid was about 2% by weight. The column was subjected to the measurement under the conditions of a column temperature of 50 캜 and a flow rate of 0.40 mL / min using the above-mentioned mixed solution as a developing agent, using HSPgel RT MB-M (manufactured by Waters). Standard polystyrene was TSK standard polystyrene manufactured by Tohto Corporation.

2. Transmittance

The transmittance of a transparent glass substrate on which a liquid crystal alignment film was not formed was set to 100%, and the transmittance of a substrate on which a liquid crystal alignment film described later was formed was measured to calculate an average value of transmittances of 390 nm to 410 nm. An ultraviolet visible spectrophotometer V-660 (manufactured by Nippon Bunko K.K.) was used for the ultraviolet visible spectrophotometer. When a single-layer liquid crystal aligning agent was used, it was judged that the transmittance was at least 75%, and 80% or more was the best. In the case of using a blend type liquid crystal aligning agent, it was judged that the transmittance was 90% or more, and 92% or more was the best.

3. Measurement of AC residual image (evaluation of liquid crystal orientation)

The luminance-voltage characteristic (B-V characteristic) of the liquid crystal cell to be described later was measured. This is regarded as a luminance-voltage characteristic before the stress application: B (before). Next, an alternating current of 4.5 V and 60 Hz was applied to the liquid crystal cell for 20 minutes, followed by a short circuit for 1 second, and the luminance-voltage characteristic (B-V characteristic) was measured again. This is regarded as a luminance-voltage characteristic after the application of the stress: B (after). Based on these values, the luminance change rate? B (%

B (%) = [B (after) - B (before)] / B (before) (Formula AC1)

Of the total population. These measurements were made with reference to WO 2000/043833. It can be said that the smaller the value of? B (%) at the voltage of 1.3 V is, the less the occurrence of the afterglow of AC can be suppressed. If it is 6.0% or more, . International Publication No. 2000/043833 discloses a technique that suppresses the generation of AC afterimage with the improvement of the alignment restraining force of the alignment film, resulting in a reduction in display unevenness. Japanese Patent Application Laid-Open No. 2016-095537, which deals with the invention relating to the improvement of photo-alignment treatment, discloses that the improvement of the alignment order of the liquid crystal alignment film is particularly effective for reducing the AC after-image. From these, it is considered that the liquid crystal alignability of the liquid crystal alignment film used in the liquid crystal display device can be evaluated by measuring? B (%) of the liquid crystal display device.

&Lt; Diamine of the present invention &

&Lt; Tetracarboxylic acid dianhydride &gt;

<Diamine>

<Solvent>

N-methyl-2-pyrrolidone

Butyl cellosolve (ethylene glycol monobutyl ether)

? -butyrolactone

Diisobutyl ketone

<Additives>

Additive (Ad1): N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

Additive (Ad2): 1,3-bis (4,5-dihydro-2-oxazolyl) benzene

Additive (Ad3): 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

Additive (Ad4): CELLOXIDE 8000 (trade name, manufactured by Daicel Co., Ltd.)

[Synthesis Example 1] Synthesis of compound (4-1)

<Step 1: Synthesis of hydrazide>

Methyl 4-nitrobenzoate (25.0 g, 138.0 mmol), hydrazine monohydrate (35.0 mL) and ethanol (600 mL) were added to a 1000 mL three-necked flask equipped with a reflux condenser, thermometer and nitrogen inlet tube. Thereafter, the solution was refluxed and stirred in a nitrogen atmosphere for 5 hours. Water (150 mL) was added to the reaction solution, followed by filtration to obtain 4-nitrobenzohydrazide (yield 18.8 g, yield 75%).

<Step 2: Dehydration reaction>

Nitrobenzohydrazide (18.8 g, 103.8 mmol), 4-nitrobenzaldehyde (15.7 g, 103.9 mmol) and trifluoroacetic acid (1.02 g, 103.8 mmol) were added to a 500 mL three-necked flask equipped with a thermometer and a reflux condenser, , 10.4 mmol), and ethanol (200 mL). The solution was refluxed and stirred for 1 hour under a nitrogen atmosphere, cooled, and then filtered to obtain the following compound (yield: 32.7 g, yield: 100%).

<Step 3: Reduction reaction>

(32.7 g, 103.8 mmol), sodium sulfide hydrate (149.9 g, 624.1 mmol), ethanol (2000 mL), and water (100 mL) were added to a 500 mL three-necked flask equipped with a reflux condenser, (700 mL). After that, the solution was refluxed and stirred for 6 hours under a nitrogen atmosphere. After the solvent was distilled off under reduced pressure, water (1000 mL) and ethyl acetate (1000 mL) were added and extraction operation was carried out. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the compound (4-1) (yield: 16.4 g, yield: 62%).

[Synthesis Example 2] Synthesis of compound (5-1)

<First step: Suzuki reaction>

Methylbenzoate (25.0 g, 116.3 mmol), 4-nitrophenylboronic acid (21.3 g, 127.9 mmol) and potassium carbonate (32.1 g, , 232.6 mmol), PdCl ₂ (dppf) CH ₂ Cl ₂ (1.90 g, 2.33 mmol), water (200 mL) and 1,4-dioxane (200 mL). Thereafter, the solution was refluxed and stirred for 3 hours under a nitrogen atmosphere. The reaction solution was poured into saturated aqueous sodium hydrogencarbonate (200 mL), and ethyl acetate (300 mL) was added to perform extraction operation. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield: 29.6 g, yield: 99%).

&Lt; Step 2: Synthesis of hydrazide &gt;

(29.6 g, 115.1 mmol), hydrazine monohydrate (30.0 mL) and ethanol (750 mL) were added to a 2000 mL three-necked flask equipped with a reflux condenser, a thermometer and a nitrogen inlet tube. Thereafter, the solution was refluxed and stirred in a nitrogen atmosphere for 5 hours. Water (150 mL) was added to the reaction solution, followed by filtration to obtain the following compound (yield 20.7 g, yield 70%).

<Third step: dehydration reaction>

(20.7g, 80.57mmol), 4-nitrobenzaldehyde (12.2g, 80.57mmol), trifluoroacetic acid (0.79g, 80.57mmol) were added to a 1000mL three-necked flask equipped with a reflux condenser, , 8.06 mmol), and ethanol (500 mL). The solution was refluxed under nitrogen atmosphere for 1 hour, cooled, and then filtered to obtain the following compound (yield: 27.7 g, yield: 88%).

<Step 4: Reduction reaction>

(27.7 g, 70.90 mmol), sodium sulfide hydrate (51.1 g, 212.7 mmol), ethanol (1500 mL), and water (100 mL) were added to a 3000 mL three-necked flask equipped with a reflux condenser, (500 mL). After that, the solution was refluxed and stirred for 6 hours under a nitrogen atmosphere. After the solvent was distilled off under reduced pressure, water (1000 mL) and ethyl acetate (500 mL) were added to carry out the extraction operation. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the compound (5-1) (yield: 13.6 g, yield: 58%).

[Synthesis Example 3] Synthesis of compound (6-1)

<First step: Suzuki reaction>

Bromo-4-nitrobenzene (25.0 g, 123.8 mmol), 4-formylphenylboronic acid (20.4 g, 136.2 mmol), and carbonic acid were added to a 1000 mL three-necked flask equipped with a thermometer and a reflux condenser, Potassium (34.2 g, 247.6 mmol), PdCl ₂ (dppf) CH ₂ Cl ₂ (2.02 g, 2.48 mmol), water (200 mL) and 1,4-dioxane (200 mL) were added. Thereafter, the solution was refluxed and stirred for 3 hours under a nitrogen atmosphere. The reaction solution was poured into saturated aqueous sodium hydrogencarbonate (200 mL), and ethyl acetate (300 mL) was added to perform extraction operation. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain the following compound (yield: 27.6 g, yield: 98%).

<Step 2: Dehydration reaction>

(27.6 g, 121.3 mmol), 4-nitrobenzohydrazide (22.0 g, 121.3 mmol), and trifluoroacetic acid 1.19 g, 12.1 mmol), and ethanol (500 mL). The solution was refluxed and stirred for 1 hour under a nitrogen atmosphere, cooled, and then filtered to obtain the following compound (yield: 43.6 g, yield: 92%).

<Step 3: Reduction reaction>

(43.6 g, 111.6 mmol), sodium sulfide hydrate (80.4 g, 334.8 mmol), ethanol (2400 mL) and water (100 mL) were added to a 500 mL three-necked flask equipped with a reflux condenser, (800 mL). After that, the solution was refluxed and stirred for 6 hours under a nitrogen atmosphere. After the solvent was distilled off under reduced pressure, water (200 mL) and ethyl acetate (1000 mL) were added to perform extraction operation. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography to obtain Compound (6-1) (yield: 18.8 g, yield: 51%).

[Synthesis Example 4] Synthesis of varnish

2.3092 g of the compound represented by the formula (4-1) was added to a 100 mL three-necked flask equipped with a stirrer and a nitrogen inlet tube, and 74.0 g of N-methyl-2-pyrrolidone was added. The solution was warmed to a liquid temperature of 60 占 폚 and then 3.6908 g of a compound represented by the formula (AN-4-17, m = 8) was added and stirred at room temperature for 12 hours. 10.0 g of? -Butyrolactone and 10.0 g of butyl cellosolve were added thereto and the solution was stirred and heated to 80 占 폚 until the weight average molecular weight of the polymer of the solute became the desired weight average molecular weight, Varnish 1 having a molecular weight of about 11,000 and a resin content of 6 wt% was obtained.

[Synthesis Examples 5 to 31]

Varnish 2 to varnish 28 having a polymer solid content concentration of 6% by weight were prepared in accordance with Synthesis Example 4, except that tetracarboxylic acid dianhydride and diamine were changed. The weight average molecular weight was adjusted to 5,000 to 20,000 in the case of using the compound (2) in one of the raw materials and to 45,000 to 50,000 in the case of using the compound (2) in one of the raw materials. The weight average molecular weights of the tetracarboxylic acid dianhydrides and diamines used and the obtained polymer are shown in Tables 1 to 2. Numerical values in angle brackets indicate compounding ratio (molar ratio). Synthesis Example 4 is also shown in Table 1 again.

[Table 1]

[Table 2]

[Comparative Synthesis Examples 1 and 2]

Varnish 29 to varnish 30 having a polymer solid content concentration of 6% by weight were prepared in accordance with Synthesis Example 4, except that tetracarboxylic acid dianhydride and diamine were changed. The weight average molecular weights of the tetracarboxylic acid dianhydrides and diamines used and the obtained polymer are shown in Table 3. &lt; tb &gt; &lt; TABLE &gt;

[Table 3]

[Example 1] Preparation of single-layer type liquid crystal aligning agent, formation of liquid crystal alignment film, measurement of transmittance

10.0 g of the varnish 1 synthesized in Synthesis Example 4 was weighed in a 50 mL Naris flask equipped with a stirrer and a nitrogen introducing tube, 1.0 g of N-methyl-2-pyrrolidone, 0.5 g of butyl cellosolve, 0.5 g of butyl ketone was added and the mixture was stirred at room temperature for 1 hour to obtain a liquid crystal alignment layer 1 having a resin concentration of 5% by weight. This liquid crystal alignment material 1 was applied to a transparent glass substrate by a spinner method (2,000 rpm, 15 seconds). After the application, the substrate was heated at 60 占 폚 for 1 minute to evaporate the solvent. Then, using the Multilight ML-501C / B manufactured by Ushio Electric Co., the linear polarization of ultraviolet rays . The exposure energy at this time was measured by using UV ultraviolet light intensity meter UIT-150 (receiver: UVD-S365) manufactured by Ushio Inc., and the exposure time was set to 2.0 ± 0.1 J / cm ² at a wavelength of 365 nm Respectively. Followed by baking at 230 DEG C for 30 minutes to form a film having a film thickness of about 100 nm. The UV-Vis spectrum of the obtained liquid crystal alignment film 1 was measured using V-660 manufactured by Nippon Shokubu Co., and it is shown in Fig. The average value of the transmittances of 390 nm to 410 nm was calculated as the transmittance of the liquid crystal alignment film 1, and it was found to be 85%.

[Examples 2 to 20]

The liquid crystal alignment film was formed and the transmittance was measured in accordance with Example 1 except that the varnish used was changed. The varnish used and the measurement results are shown in Table 4 together with Example 1.

[Table 4]

In Examples 1 to 3, 10 to 14, and 17 to 20 using the diamine of the present invention alone as a raw material having a photoreactive structure, the transmittance was at least 80% and was the best. Also in Examples 4 to 9, 15, and 16, in which diamines represented by the formula (V-2-1) having a structure of a diamine and azobenzene of the present invention were used as raw materials having a photoreactive structure, transmittance Was 75% to 81%, which was good.

[Comparative Examples 1 and 2]

The UV-Vis spectrum was measured according to Example 1 except that the varnish used was changed. The varnishes used and the measurement results are shown in Table 5. The UV-Vis spectrum of Comparative Example 1 is shown in Fig.

[Table 5]

In Comparative Examples 1 and 2, the transmittance was 67% and 71%, respectively, and was lower than in Examples 1 to 20. This is because the varnish 29 and the varnish 30 use only the formulas (V-2-1) and (V-3-1) having an azobenzene structure as raw materials having a photoreactive structure. Since azobenzene is absorbed in a visible light region, it is considered that a liquid crystal alignment film formed of a liquid crystal aligning agent using only azobenzene has not obtained good results in the value of transmittance.

[Example 21] Fabrication and evaluation of a liquid crystal cell for AC residual image measurement

Separately, the liquid crystal alignment layer 1 was applied (2,000 rpm, 15 seconds) to a glass substrate with an FFS electrode and a glass substrate with a column spacer by a spinner method. After the application, the substrate was heated at 60 占 폚 for 1 minute to evaporate the solvent. Then, using the Multilight ML-501C / B manufactured by Ushio Electric Co., the linear polarization of ultraviolet rays . The exposure energy at this time was measured by using UV ultraviolet light intensity meter UIT-150 (receiver: UVD-S365) manufactured by Ushio Inc., and the exposure time was set to 2.0 ± 0.1 J / cm ² at a wavelength of 365 nm Respectively. Followed by baking at 230 DEG C for 30 minutes to form a film having a film thickness of about 100 nm. Subsequently, two substrates on which these liquid crystal alignment films were formed were opposed to each other with a surface on which the liquid crystal alignment film was formed facing each other, and voids were formed between the opposed liquid crystal alignment films for injecting the liquid crystal composition. At this time, the polarization directions of linearly polarized light irradiated on each liquid crystal alignment film were made parallel. Negative liquid crystal composition A was vacuum-injected into these cells, and the injection port was sealed with a photo-curing agent to prepare a liquid crystal cell (liquid crystal display element) having a cell thickness of 4 mu m. The resultant AC residual image of the obtained liquid crystal display element was measured and found to be 3.1%.

&Lt; Negative-type liquid crystal composition A &

Property: NI 75.7 ° C; ?? -4.1;? N 0.101;? 14.5mPa 占 퐏.

[Example 22]

A liquid crystal cell (liquid crystal display element) was produced in accordance with Example 21 except that the liquid crystal aligning agent to be used was changed to the liquid crystal aligning agent 4. [ As a result of measurement of the AC afterimage of the obtained liquid crystal display element,? B was 2.0%.

From the results of Examples 21 and 22, it was confirmed that the liquid crystal display element using the liquid crystal aligning agent of the present invention had good orientation.

[Example 23] Preparation of blend type liquid crystal aligning agent, formation of liquid crystal alignment film, measurement of transmittance

3.0 g of the varnish 1 synthesized in Synthesis Example 4 and 7.0 g of the varnish 21 synthesized in Synthesis Example 24 were weighed in a 50 mL Naris flask equipped with a stirrer and a nitrogen inlet tube and N-methyl-2-pyrrolidone , 1.0 g of butyl cellosolve and 1.0 g of diisobutyl ketone were added and stirred at room temperature for 1 hour to obtain a liquid crystal aligning agent 23 having a resin concentration of 4% by weight. Using the obtained liquid crystal aligning agent 23, a liquid crystal alignment film 23 was formed on a transparent glass substrate in accordance with the method described in Example 1. As a result of measuring the UV-Vis spectrum, the average value of the transmittance of 390 nm to 410 nm was 93%.

[Examples 24 to 66]

The UV-Vis spectrum was measured in accordance with Example 23 except that the used varnish was changed. The varnish used and the measurement results are shown in Table 6 together with Example 23. Further, in Table 6, the varnish A is a varnish containing a polymer using a raw material having a photoreactive structure, and the varnish B is a varnish containing a polymer which does not use a raw material having a photoreactive structure.

[Table 6]

In Examples 23 to 66, the transmittance was 90% or more, which was good. By using the blend type liquid crystal aligning agent, a higher transmittance than that using a single layer type liquid crystal aligning agent was obtained.

[Comparative Examples 3 to 4]

The UV-Vis spectrum was measured in accordance with Example 23 except that the used varnish was changed. The varnishes used and the measurement results are shown in Table 7. Further, in Table 7, the varnish A is a varnish containing a polymer using a raw material having a photoreactive structure, and the varnish B is a varnish containing a polymer which does not use a raw material having a photoreactive structure.

[Table 7]

In Comparative Example 3 and Comparative Example 4, the transmittance was inferior to those in Examples 23 to 66. This is because the varnish 29 and the varnish 30 use only the formulas (V-2-1) and (V-3-1) having azobenzene as a raw material having a photoreactive structure. Even in the case of using a blend type liquid crystal aligning agent, it is considered that azobenzene absorbs in the visible light region, and therefore, a liquid crystal alignment film formed of a liquid crystal aligning agent using only azobenzene has not obtained good results in terms of transmittance.

[Example 67]

3.0 g of the varnish 1 synthesized in Synthesis Example 4 and 7.0 g of the varnish 21 synthesized in Synthesis Example 24 were weighed in a 50 mL Naris flask equipped with a stirrer and a nitrogen inlet tube and N-methyl-2-pyrrolidone 1.0 g of butyl cellosolve and 30 mg of additive Ad1 were added and stirred at room temperature for 1 hour to obtain liquid crystal aligning agent 69 having a resin concentration of 4% by weight and an additive concentration of 5 parts by weight per 100 parts by weight of resin. Using the obtained liquid crystal aligning agent 69, a liquid crystal alignment film 69 was formed on a transparent glass substrate in accordance with the method described in Example 1. As a result of measuring the UV-Vis spectrum, the average value of the transmittance at 380 to 780 nm was 93%.

[Examples 68 to 110]

The UV-Vis spectrum was measured in accordance with Example 67 except that the varnish used was changed. The varnish to be used and the measurement results are shown in Table 8 together with Example 67. Further, in Table 8, the varnish A is a varnish containing a polymer using a raw material having a photoreactive structure, and the varnish B is a varnish containing a polymer which does not use a raw material having a photoreactive structure.

[Table 8]

In Examples 67 to 110, the transmittance was 90% or more, which was good. It was found that the liquid crystal aligning agent containing the additive also exhibited a high transmittance.

[Comparative Examples 5 to 6]

The UV-Vis spectrum was measured in accordance with Example 67 except that the varnish to be used and the additives were changed. The varnishes used and the measurement results are shown in Table 9. Further, in Table 9, the varnish A is a varnish containing a polymer using a raw material having a photoreactive structure, and the varnish B is a varnish containing a polymer which does not use a raw material having a photoreactive structure.

[Table 9]

In Comparative Example 5 and Comparative Example 6, the transmittance was inferior to those in Examples 67 to 110. This is because varnish 29 and varnish 30 use only formulas (V-2-1) and (V-3-1) having azobenzene as a raw material having a photoreactive structure. Even in the case of a liquid crystal aligning agent containing an additive, it is considered that azobenzene is absorbed in a visible light region, and therefore, a liquid crystal alignment film formed of a liquid crystal aligning agent using only azobenzene has not obtained good results in terms of transmittance.

[Synthesis Examples 32 to 42]

Varnish 31 to varnish 41 having a polymer solid content concentration of 6% by weight were prepared in accordance with Synthesis Example 4, except that tetracarboxylic acid dianhydride and diamine were changed. The weight average molecular weight of the polymer was adjusted to about 5,000 to 20,000 for one of the raw materials of the compound (2) and to 45,000 to 50,000 for the one of the raw materials of the compound (2). The weight average molecular weights of the tetracarboxylic acid dianhydrides and diamines used and the obtained polymers are shown in Table 10.

[Table 10]

[Examples 111 to 116]

The liquid crystal alignment film was formed and the transmittance was measured in accordance with Example 1 except that the varnish used was changed. The varnish used and the measurement results are shown in Table 11.

[Table 11]

In Examples 111 to 116 using the diamine of the present invention singly as a raw material having a photoreactive structure, the transmittance was at least 80%, which was the best.

[Examples 117 to 139]

The UV-Vis spectrum was measured in accordance with Example 23 except that the used varnish was changed. The varnish to be used and the measurement results are shown in Table 12. Further, in Table 12, the varnish A is a varnish containing a polymer using a raw material having a photoreactive structure, and the varnish B is a varnish containing a polymer which does not use a raw material having a photoreactive structure.

[Table 12]

In Examples 117 to 139, the transmittance was 90% or more, which was good. By using the blend type liquid crystal aligning agent, a higher transmittance than that using a single layer type liquid crystal aligning agent was obtained.

[Examples 140 to 162]

The UV-Vis spectrum was measured in accordance with Example 67 except that the varnish used was changed. The varnish to be used and the measurement results are shown in Table 13. Further, in Table 13, the varnish A is a varnish containing a polymer using a raw material having a photoreactive structure, and the varnish B is a varnish containing a polymer which does not use a raw material having a photoreactive structure.

[Table 13]

In Examples 140 to 162, the transmittance was 90% or more and was good. It was found that the liquid crystal aligning agent containing the additive also exhibited a high transmittance.

[Industrial Availability]

By using a liquid crystal aligning agent using a polyamic acid or a derivative thereof based on a diamine as a raw material according to an embodiment of the present invention, a liquid crystal alignment film having a high transmittance and high orientation can be obtained. This liquid crystal aligning agent can be suitably applied to a transverse electric field type liquid crystal display element.

Claims (15)

A liquid crystal aligning agent for photo-alignment comprising a polymer having a structural unit containing a photosensitive group represented by the following formula (1).

(In the formula (1)
R ¹ and R ² are independently hydrogen or alkyl having 1 to 10 carbon atoms;
A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary and hydrogen in the benzene ring may be substituted with a substituent. The method according to claim 1,
1. A liquid crystal aligning agent for photo alignment comprising a polymer which is a reaction product from a raw material containing a tetracarboxylic acid dianhydride and a diamine,
Wherein the diamine contains at least one of diamines represented by the following formula (2).
Wherein the polymer is at least one selected from the group consisting of polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide;

In formula (2), R ¹ and R ² are independently hydrogen or alkyl having 1 to 10 carbon atoms;
R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃ ) , Or a single bond;
In R ⁴ and R ⁶ , one of -CH ₂ - of the straight chain alkylene or two non-adjacent ones may be substituted with -O-;
R ⁵ and R ⁷ are independently a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocyclic ring, or a single bond;
A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary and hydrogen in the benzene ring may be substituted with a substituent. The method of claim 2,
Wherein the diamine contains at least one of diamines represented by the following formula (3).

(In the formula (3), R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO- , -CON (CH ₃₎ -, or a single bond;
In R ⁴ and R ⁶ , one or two of -CH ₂ - of straight chain alkylene may be substituted with -O-;
R ⁵ and R ⁷ are independently a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocyclic ring, or a single bond;
A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary.) The method according to claim 2 or 3,
Wherein the diamine contains at least one of diamines represented by the following formulas (4) to (7).

(In formulas (4) to (7), R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 2 carbon atoms or a single bond;
A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary.) The method according to any one of claims 2 to 4,
The diamine is represented by the following formulas (4-1), (4-2), (5-1), (5-2), (6-1) 1) or the diamine represented by the formula (7-2).

The method according to any one of claims 2 to 5,
Wherein the raw material further comprises at least one selected from the group consisting of the following formulas (II) to (VI).

(In formulas (II) to (VI), R ⁴ and R ⁵ are monovalent organic groups having -NH ₂ or monovalent organic groups having -CO-O-CO-;
In the formula (IV), R ⁶ is a divalent organic group;
In formula (VI), R ⁷ is an aromatic ring having -NH ₂ or -CO-O-CO-.) The method according to any one of claims 1 to 6,
A liquid crystal aligning agent for photo-alignment used for manufacturing a transverse electric field type liquid crystal display element. A liquid crystal alignment film formed by the liquid crystal aligning agent for photo-alignment described in any one of claims 1 to 7. A liquid crystal display element having the liquid crystal alignment film according to claim 8. A transverse electric field type liquid crystal display element having the liquid crystal alignment film according to claim 8. (7-2), (5-1), (5-2), (6-1), (6-2), (7-1), or The indicated diamine.

A polyamic acid, a polyimide, a partial polyimide, a polyamic acid ester, a polyamic acid-polyamide copolymer, and a polyamic acid, which are reaction products of a tetracarboxylic acid dianhydride and a diamine containing at least one of diamines represented by formula (2) And at least one polymer selected from the group consisting of polyamideimide.

(In the formula (2), R ¹ and R ² are independently hydrogen or alkyl having 1 to 10 carbon atoms;
R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO-, -CON (CH ₃ ) , Or a single bond;
In R ⁴ and R ⁶ , one of -CH ₂ - of the straight chain alkylene or two non-adjacent ones may be substituted with -O-;
R ⁵ and R ⁷ are independently a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocyclic ring, or a single bond;
A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary and hydrogen in the benzene ring may be substituted with a substituent. The method of claim 12,
The diamine contains at least one of the diamines represented by the following formula (3).

(In the formula (3), R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N (CH ₃ ) CO- , -CON (CH ₃₎ -, or a single bond;
In R ⁴ and R ⁶ , one or two of -CH ₂ - of straight chain alkylene may be substituted with -O-;
R ⁵ and R ⁷ are independently a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, a heterocyclic ring, or a single bond;
A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary.) The method according to claim 12 or 13,
Wherein the diamine contains at least one of the diamines represented by the following formulas (4) to (7).

(In formulas (4) to (7), R ⁴ and R ⁶ are independently straight chain alkylene having 1 to 2 carbon atoms or a single bond;
A bonding hand in which the bonding position is not fixed to any carbon constituting the ring indicates that the bonding position in the ring is arbitrary.) The method according to any one of claims 12 to 14,
The diamine is represented by the following formulas (4-1), (4-2), (5-1), (5-2), (6-1) 1), or a diamine represented by the formula (7-2).

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