CN104845642B

CN104845642B - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, phase difference film and method for producing same, polymer and compound

Info

Publication number: CN104845642B
Application number: CN201510053738.9A
Authority: CN
Inventors: 樫下幸志
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2014-02-13
Filing date: 2015-02-02
Publication date: 2020-11-24
Anticipated expiration: 2035-02-02
Also published as: CN104845642A; KR102209444B1; KR20150095561A; TWI709611B; JP6492564B2; TW201531530A; JP2015166844A

Abstract

The invention provides a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, a phase difference film and a manufacturing method thereof, a polymer and a compound. The liquid crystal aligning agent contains a polymer (P) obtained by using at least one compound (C') selected from the group consisting of a compound (C) having the following structure (a) and the following structure (b) and a compound (C1) in a reaction, wherein the compound (C1) has the following structure (a) and the following structure (b1) and no reactive group participating in polymerization is bonded to an aromatic ring group in the structure (a). (a) An aromatic amine structure in which 2 or 3 aromatic ring groups are bonded to the same nitrogen atom. (b) A chain structure such as a 2-valent chain hydrocarbon group having 6 or more carbon atoms. (b1) A C1-5 2-valent chain hydrocarbon group, -O-, -S-, and the like.

Description

Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, phase difference film and method for producing same, polymer and compound

Technical Field

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display device, a retardation film, a method for producing a retardation film, a polymer, and a compound.

Background

Conventionally, various driving methods such as a Twisted Nematic (TN) type, a Super Twisted Nematic (STN) type, a Vertical Alignment (VA) type, an In-Plane Switching (IPS) type, and a Fringe Field Switching (FFS) type have been developed for liquid crystal display elements, which have different electrode structures, physical properties of liquid crystal molecules used, and manufacturing steps. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. Polyamic acid or polyimide is generally used as a material of the liquid crystal alignment film in terms of its excellent properties such as heat resistance, mechanical strength, and affinity for liquid crystal.

In recent years, with the high definition of liquid crystal display elements, there have been increasing demands for reducing the image sticking phenomenon or suppressing the decrease in contrast, and various liquid crystal aligning agents have been proposed to meet the demands (for example, see patent documents 1 to 6). In the liquid crystal aligning agents described in patent documents 1 to 6, reduction of accumulated charges in the liquid crystal display element, suppression of contrast reduction, and the like are achieved by introducing a diphenylamine unit into the liquid crystal aligning agent.

Specifically, patent document 1 discloses that a polyamic acid or polyimide obtained by reacting a diamine containing 4, 4' -diaminodiphenylamine with a tetracarboxylic dianhydride is contained in a liquid crystal aligning agent. Patent document 2 discloses that a polyimide obtained by reacting a diamine containing an oligoaniline such as (4-aminophenyl) (4- ((4-aminophenyl) amino) phenylamine with a tetracarboxylic dianhydride is contained in a liquid crystal aligning agent, and patent document 3 discloses that a compound having 2 or more diphenylamine units is added separately to a polymer such as a polyamic acid or a polyimide, or that a polyamic acid obtained by reacting a diamine having 2 or more diphenylamine units with a tetracarboxylic dianhydride is contained in a liquid crystal aligning agent.

Patent document 4 discloses that a polyamic acid obtained by reacting a diamine containing 1, 3-bis-4- (N, N- (4-aminophenyl) propane as a compound having 2 diphenylamine structures in the molecule with a tetracarboxylic dianhydride is contained in a liquid crystal aligning agent. Further, patent documents 5 and 6 disclose that a polyamic acid obtained by reacting a diamine containing N, N '-bis (4-aminophenyl) -N, N' -dimethylethylenediamine with a tetracarboxylic dianhydride is contained in a liquid crystal aligning agent.

In addition, a variety of optical materials are used for liquid crystal display elements, and among them, a retardation film is used for the purpose of eliminating coloring of display or the purpose of eliminating viewing angle dependence of display color and contrast ratio which change with the viewing direction. The phase difference film is known to include: a liquid crystal alignment film formed on a surface of a substrate, such as a triacetyl cellulose (TAC) film, and a liquid crystal layer formed on a surface of the liquid crystal alignment film by hardening polymerizable liquid crystal. In recent years, the following photo-alignment methods have been used for producing a liquid crystal alignment film in a retardation film: irradiating a radiation-sensitive organic thin film formed on a substrate surface with polarized or unpolarized radiation to impart liquid crystal alignment ability to the organic thin film; a liquid crystal aligning agent for a retardation film used for producing a liquid crystal alignment film by the above-mentioned method has been proposed (for example, see patent document 7).

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent No. 4052307 publication

[ patent document 2] Japanese patent application laid-open No. 2000-44683

[ patent document 3] Japanese patent No. 4924832

[ patent document 4] Japanese patent application laid-open No. 2011-

[ patent document 5] Japanese patent laid-open No. 2012-155311

[ patent document 6] Japanese patent No. 5130907 publication

[ patent document 7] Japanese patent laid-open No. 2012-37868

Disclosure of Invention

[ problems to be solved by the invention ]

However, when the liquid crystal aligning agent of patent document 1 is used, the relaxation of Direct Current (DC) residual in the liquid crystal display element is insufficient, and the time until the residual image disappears tends to be long. In addition, in the conventional liquid crystal aligning agent containing a polymer using a diamine having a plurality of diphenylamine units as a monomer, the performance of alleviating DC residues is improved, but the transmittance of the liquid crystal alignment film is low due to an increase in the aromatic concentration. In addition, Alternating Current (AC) residual image performance, which is one of characteristics that affect the contrast of a liquid crystal display element, is insufficient, and various characteristics cannot be provided in a well-balanced manner. In addition, with the recent trend toward more versatile liquid crystal display devices, liquid crystal display devices are expected to be used under more severe conditions and are required to have excellent heat resistance.

A liquid crystal display is manufactured by disposing a pair of substrates on which liquid crystal alignment films are formed in an opposed manner and disposing liquid crystal between the pair of substrates disposed in the opposed manner. At this time, the pair of substrates is bonded using a sealant such as epoxy resin. Here, in a touch panel type display panel represented by a smartphone or a tablet computer, an attempt has been made to achieve a narrow frame in order to further increase the movable area of the touch panel and to achieve downsizing of a liquid crystal panel (element). As the liquid crystal panel is narrowed in the frame, display unevenness may be visually recognized around the sealant, and thus the display quality is not sufficiently satisfactory. In order to realize high definition and long life of a liquid crystal display, a liquid crystal display element in which display unevenness (high frame (bezel) unevenness resistance) around the sealant is difficult to visually recognize is required.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a liquid crystal alignment agent for obtaining a liquid crystal display element having a liquid crystal alignment film with good transmittance, less display unevenness around a sealant, and good balance with various characteristics such as an afterimage characteristic, high contrast, and heat resistance.

[ means for solving problems ]

The present inventors have conducted intensive studies to achieve the above-mentioned problems of the prior art, and have found that the above-mentioned problems can be solved by including a polymer having a specific structure as a polymer component in a liquid crystal aligning agent, and have completed the present invention. Specifically, the present invention provides the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, retardation film, method for producing retardation film, polymer and compound.

One aspect of the present invention provides a liquid crystal aligning agent containing a polymer (P) obtained by reacting at least one compound (C') selected from the group consisting of a compound (C) having the following structure (a) and the following structure (b) and a compound (C1) having the following structure (a) and the following structure (b1) in which a reactive group participating in polymerization is not bonded to an aromatic ring group in the structure (a).

(a) An aromatic amine structure in which 2 or 3 aromatic ring groups are bonded to the same nitrogen atom.

(b) Selected from a C6 or higher 2-valent chain hydrocarbon group and a group consisting of-O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-and-Si (CH) wherein at least 1 methylene group in the chain hydrocarbon group is substituted with a substituent₃)₂A chain structure of a group consisting of a 2-valent group substituted with (R is a hydrogen atom or a 1-valent organic group).

(b1) Selected from 2-valent chain hydrocarbon group with 1-5 carbon atoms, and at least 1 methylene in the chain hydrocarbon group is replaced by-O-, -S-, -CO-, -NR³-、-NR³CO-, -COO-, -COS-or-Si (CH)₃)₂A 2-valent radical formed by substitution, -O-, -S-, -CO-, -NR³CO-(R³Is a hydrogen atom or a 1-valent organic group), -COO-, -COS-, and-Si (CH)₃)₂-a structure in the group formed.

Another aspect of the present invention is to provide a liquid crystal alignment film formed using the liquid crystal aligning agent. In addition, a liquid crystal display element including the liquid crystal alignment film and a phase difference film including the liquid crystal alignment film are provided. Another aspect of the present invention provides a method for producing a retardation film, including: a step of coating the liquid crystal aligning agent on a substrate to form a coating film; irradiating the coating film with light; and a step of applying a polymerizable liquid crystal to the coating film irradiated with light and curing the coating film.

Another aspect of the present invention is to provide a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3). Also provided is a polymer selected from the group consisting of polyamic acids, polyamic acid esters, and polyimides obtained by reacting at least one compound selected from the group consisting of tetracarboxylic dianhydrides, tetracarboxylic diester compounds, and tetracarboxylic diester dihalides with diamines comprising at least one compound selected from the group consisting of compounds represented by the following formula (1-1), compounds represented by the following formula (1-2), and compounds represented by the following formula (1-3).

[ solution 1]

(in the formula (1-1), A¹And A³Each independently being a hydrogen atom or a 1-valent organic radical, A²And A⁴Each independently is a single bond or a 2-valent organic group; b is¹And B²Each independently is a single bond or a 2-valent organic group; wherein, in B¹In the case of a single bond, A¹And A²At least 1 of which is bonded to the nitrogen atom with an aromatic ring, in B¹In the case of a 2-valent organic radical, A¹、A²And B¹At least 2 of which are bonded to the nitrogen atom with an aromatic ring; b is²In the case of a single bond, A³And A⁴At least 1 of which is bonded to the nitrogen atom with an aromatic ring, in B²In the case of a 2-valent organic radical, A³、A⁴And B²At least 2 of which are bonded to the nitrogen atom with an aromatic ring; l is¹¹At least 1 methylene group in a chain hydrocarbon group having 2 valences of 6 or more carbon atoms is replaced by-O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-or-Si (CH)₃)₂A group having a valence of 2, wherein (R) is a hydrogen atom or a group having a valence of 1, which is substituted; wherein, at L¹¹In the case of having C1-5 alkanediyl group, A¹And A³At least any one of (A) is a hydrogen atom, or B¹And B²At least any one of (a) is a 2-valent organic group)

[ solution 2]

(in the formula (1-2), L¹²A 2-valent group containing a 2-valent chain hydrocarbon group having 6 or more carbon atoms; a. the¹、A²、A³、A⁴、B¹And B²Is the same as the formula (1-1); wherein, at L¹²When the alkyl group is an alkanediyl group having 6 to 10 carbon atoms, A¹And A³At least any one of (A) is a 1-valent organic group, or B¹And B²At least any one of (a) is a 2-valent organic group)

[ solution 3]

(in the formula (1-3), A⁷Is a hydrogen atom or a 1-valent organic radical, A⁸And A⁹Each independently is a single bond or a 2-valent organic group; wherein A is⁷、A⁸And A⁹At least 2 of which are bonded to the nitrogen atom with an aromatic ring; l is⁴As the structure (b1), L⁵Is a single bond or a 2-valent organic group)

[ Effect of the invention ]

By using the liquid crystal aligning agent containing the polymer (P) as a polymer component, a liquid crystal display element having less display unevenness around a sealant and having various characteristics such as low image sticking, high contrast, and heat resistance in a well-balanced manner can be obtained. Further, a liquid crystal alignment film having good transmittance can be obtained. Further, the polymer (P) has good solubility in a solvent, and the storage stability of the liquid crystal aligning agent is also good.

Drawings

Fig. 1 is a schematic configuration diagram of an FFS type liquid crystal cell.

Fig. 2(a) and 2(b) are schematic plan views of top electrodes used in the manufacture of liquid crystal display elements by the photo-alignment method. Fig. 2(a) is a plan view of the top electrode, and fig. 2(b) is a partial enlarged view of the top electrode.

Fig. 3 is a diagram showing a 4-system drive electrode.

Fig. 4(a) and 4(b) are schematic plan views of top electrodes used in the production of liquid crystal display elements by rubbing treatment. Fig. 4(a) is a plan view of the top electrode, and fig. 4(b) is a partial enlarged view of the top electrode.

Description of the symbols

10: liquid crystal display element

11a, 11 b: glass substrate

12: liquid crystal alignment film

13: top electrode

14: insulating layer

15: bottom electrode

16: liquid crystal layer

C1: part enclosed by a dotted line

d 1: line width of electrode

d 2: distance between electrodes

Detailed Description

Hereinafter, each component contained in the liquid crystal aligning agent of the present invention and other components optionally blended as necessary will be described.

< Polymer (P) >

The liquid crystal aligning agent of the present invention includes, as a polymer component, a polymer (P) obtained by using at least one compound (C') selected from the group consisting of a compound (C) having the structure (a) and the structure (b) and a compound (C1) having the structure (a) and the structure (b1) and having no reactive group participating in polymerization bonded to an aromatic ring group in the structure (a). Hereinafter, the structure (a) is also referred to as an "aromatic amine structure (a)", and the structure (b) is also referred to as a "chain structure (b)".

Compound (C)

(aromatic amine Structure (a))

The aromatic amine structure (a) of the compound (C) is a structure in which 2 or 3 aromatic ring groups are bonded to the same nitrogen atom. The aromatic ring group may be a group obtained by removing a hydrogen atom from the ring part of the aromatic ring, and specific examples thereof include a group obtained by removing a hydrogen atom from the ring part of an aromatic ring such as a benzene ring, a toluene ring, a naphthalene ring, or an anthracene ring, and an aromatic ring such as a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, or a triazine ring. Among these groups, a benzene ring is preferable from the viewpoint of good affinity with liquid crystals.

The number of the aromatic amine structures (a) in the molecule of the compound (C) is 1 or 2 or more, and preferably 2 or more from the viewpoint of improving the performance of residual DC mitigation. From the viewpoint of the transmittance of the liquid crystal alignment film and the solubility of the polymer, the number of the liquid crystal alignment film is more preferably 2 to 4, and particularly preferably 2 or 3.

(chain structure (b))

The chain structure (b) of the compound (C) is a C6 or more 2-valent chain hydrocarbon group, or at least 1 methylene group in the C6 or more 2-valent chain hydrocarbon group is replaced by-O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-or-Si (CH)₃)₂- (R is an amino atom or a 1-valent organic group).

The 2-valent chain hydrocarbon group in the chain structure (b) is a hydrocarbon group having a linear or branched chain structure alone, without having a cyclic structure in the main chain. The 2-valent chain hydrocarbon group in the chain structure (b) may have 6 or more carbon atoms, and specific examples thereof include: saturated hydrocarbon groups having 6 to 30 carbon atoms such as an hexanediyl group, a heptanedioyl group, a octanedioyl group, a nonanedioyl group, a decanedioyl group, a dodecanediyl group, a tetradecanediyl group, and an eicosanediyl group; and C6-30 unsaturated hydrocarbon groups in which at least 1C-C bond of the C6-30 saturated hydrocarbon groups is a double bond or a triple bond. These hydrocarbon groups may be linear or branched, and are preferably linear.

When the chain structure (b) is a 2-valent chain hydrocarbon group having 6 or more carbon atoms, the number of carbon atoms of the chain hydrocarbon group is preferably 6 to 30, more preferably 6 to 20.

The chain structure (b) is formed by substituting at least 1 methylene group in a 2-valent chain hydrocarbon group having 6 or more carbon atoms with-O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-or-Si (CH)₃)₂When- (R) is a hydrogen atom or a 1-valent organic group, the number of substitution may be 1 or more, and may be appropriately set depending on the number of carbon atoms. The number of carbons before the methylene group is substituted with the functional group is preferably 6 to 30, more preferably 7 to 20.

Examples of the 1-valent organic group of R include: a chain hydrocarbon group having 1 to 5 carbon atoms such as an alkyl group or an alkenyl group, a group having-O-, -CO-, or the like, between carbon-carbon bonds of the chain hydrocarbon group having 1 to 5 carbon atoms, a protecting group for an amino group, or the like. Specific examples of the protecting group of an amino group include: t-butoxycarbonyl, benzyloxycarbonyl, 1-dimethyl-2-haloethyloxycarbonyl, 1-dimethyl-2-cyanoethyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl, 2- (trimethylsilyl) ethoxycarbonyl and the like, with t-butoxycarbonyl being preferred.

The number of the chain structures (b) in the molecule of the compound (C) may be 1, or 2 or more. Preferably 1 to 5, more preferably 1 to 3. The compound (C) preferably has the aromatic amine structure (a) and the chain structure (b) in the main chain of the compound (C), specifically, the longest carbon chain in the compound (in the case of having a functional group, the longest carbon chain including the functional group).

The molecular weight of the compound (C) is preferably 1,200 or less in terms of reducing the surface roughness of the liquid crystal alignment film. Therefore, it is preferable to set the number of the aromatic amine structures (a) and the chain length of the chain structure (b) so that the molecular weight of the compound (C) falls within the above range. The molecular weight is more preferably 1,000 or less, and particularly preferably 800 or less.

Compound (C1)

The compound (C1) has the aromatic amine structure (a) and the structure (b 1). In the compound (C1), no reactive group participating in polymerization is bonded to the aromatic ring group in the aromatic amine structure (a). The reactive group differs depending on the main skeleton of the polymer (P), and for example, in the case where the main skeleton of the polymer (P) is a polyamic acid or a polyimide, the reactive group is an acid anhydride group or a primary amino group, in the case of a polyester, the reactive group is a hydroxyl group or a carboxyl group, and in the case of a polyamide, the reactive group is a carboxyl group or a primary amino group.

Description of the aromatic ring of the aromatic amine structure (a) contained in compound (C1) can be applied to the description of compound (C). The number of aromatic amine structures (a) in one molecule of compound (C1) is preferably 1.

The compound (C1) has a structure (b1) selected from a 2-valent chain hydrocarbon group having 1 to 5 carbon atoms, wherein at least 1 methylene group in the chain hydrocarbon group is replaced by-O-, -S-, -CO-, -NR³-、-NR³CO-, -COO-, -COS-or-Si (CH)₃)₂A 2-valent radical formed by substitution, -O-, -S-, -CO-, -NR³CO-, -COO-, -COS-, and-Si (CH)₃)₂-(R³Hydrogen atom or a 1-valent organic group). Further, the compound (C1) may have only 1 of these structures in the molecule, or may have 2 or more structures in the molecule.

Specific examples of the 2-valent chain hydrocarbon group having 1 to 5 carbon atoms in the structure (b1) include: methylene, ethylene, propylene, butylene, pentylene, vinylene, propylenediyl, butylenediyl, pentylenediyl, and the like. These hydrocarbon groups may be linear or branched, and are preferably linear.

The structure (b1) is formed by substituting at least 1 methylene group in a 2-valent chain hydrocarbon group having 1 to 5 carbon atoms with-O-, -S-, -CO-, -NR³-、-NR³CO-, -COO-, -COS-or-Si (CH)₃)₂In the case of a 2-valent group by substitution, the number of the substitution may be 1 or more, and may be appropriately set depending on the number of carbon atoms. R³The description of the 1-valent organic group of (C) can be applied to the description of R of the compound (C).

The number of the structures (b1) in the molecule of the compound (C1) may be 1, or 2 or more. Preferably 2 or more, and particularly preferably 2. Molecular weight of Compound (C1) the description of Compound (C) can be applied.

Examples of the main skeleton of the polymer (P) include a skeleton comprising polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polysiloxane, polyorganosiloxane, cellulose derivative, polyacetal derivative, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate derivative, and the like. The polymer (P) may be used by appropriately selecting 1 or 2 or more polymers selected from these depending on the use of the liquid crystal aligning agent and the like. Further, (meth) acrylate is meant to include both acrylate and methacrylate. The polymer (P) may have the aromatic amine structure (a) and the chain structure (b) or the structure (b1) in either the main chain or the side chain of the polymer, and preferably has the structure in the main chain of the polymer.

The main skeleton of the polymer (P) is preferably at least one selected from the group consisting of polyamic acids, polyimides, and polyamic acid esters, and more preferably at least one selected from the group consisting of polyamic acids, polyimides, and polyamic acid esters having the aromatic amine structure (a) and the chain structure (b) or the structure (b1) in the main chain. The polymer (P) is preferably a polymer obtained by using the compound (C') for a monomer.

The term "main chain" of a polymer in the present invention means a "dry" portion of the polymer containing the longest atom chain. In addition, the "stem" portion is allowed to contain a ring structure. Therefore, the phrase "having the aromatic amine structure (a) and the chain structure (b) or the structure (b1) in the main chain of the polymer" means that these structures constitute a part of the main chain. Note that, in the polymer (P), the case where the aromatic amine structure (a), the chain structure (b), and the structure (b1) are also present in a portion other than the main chain, for example, a side chain (a portion branched from the "trunk" of the polymer) is not excluded.

[ Polyamic acid (P) ]

In the case where the polymer (P) is a polyamic acid (hereinafter also referred to as "polyamic acid (P)"), it can be obtained by reacting a tetracarboxylic dianhydride with a diamine, for example.

(tetracarboxylic dianhydride)

Examples of tetracarboxylic acid dianhydride used for synthesizing the polyamic acid (P) include: aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride, and the like. Specific examples of the tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydrides such as: butane tetracarboxylic dianhydride, etc.;

examples of the alicyclic tetracarboxylic dianhydride include: 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3, 5-tricarboxylic cyclopentylacetic dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-c]Furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-8-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-c]Furan-1, 3-dione, 3-oxabicyclo [3.2.1]Octane-2, 4-dione-6-spiro-3 ' - (tetrahydrofuran-2 ',5' -dione), 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, 3,5, 6-tricarboxyl-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0]]Octane-2, 4,6, 8-tetracarboxylic acid 2: 4,6: 8-dianhydride, bicyclo [2.2.1 ]]Heptane-2, 3,5, 6-tetracarboxylic acid 2:3,5: 6-dianhydride, 4, 9-dioxatricyclo [5.3.1.0 ]^2，6]Undecane-3, 5,8, 10-tetraone, 1,2, 4, 5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2]Octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol bis (trimellitic anhydride ester), 1, 3-propanediol bis (trimellitic anhydride ester) (1, 3-propylene glycol bis (trimellitic anhydride ester)), and the like;

examples of the aromatic tetracarboxylic dianhydride include: pyromellitic dianhydride, etc.; in addition, tetracarboxylic dianhydrides described in Japanese patent application laid-open No. 2010-97188 can be used. Further, tetracarboxylic dianhydride used for synthesizing polyamic acid may be used by using 1 of these compounds alone or 2 or more in combination.

The tetracarboxylic dianhydride used for the synthesis of the polyamic acid (P) preferably comprises a compound selected from the group consisting of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c ] in view of satisfactory alignment of liquid crystals and solubility in a solvent]Furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-8-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-c]Furan-1, 3-dione, 3-oxabicyclo [3.2.1]Octane-2, 4-dione-6-spiro-3 ' - (tetrahydrofuran-2 ',5' -dione), 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, 3,5, 6-tricarboxyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4, 9-dioxatricyclo [5.3.1.0 ]^2，6]Undecane-3, 5,8, 10-tetraone, bicyclo [3.3.0]]At least one compound selected from the group consisting of octane-2, 4,6, 8-tetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, cyclopentanetetracarboxylic dianhydride, 1, 3-propanediol bis (trimellitic anhydride ester), and pyromellitic dianhydride (hereinafter also referred to as "specific tetracarboxylic dianhydride"). The amount of the specific tetracarboxylic dianhydride used is preferably 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 20 mol% or more, based on the total amount of the tetracarboxylic dianhydride used to synthesize the polyamic acid.

(diamine)

The diamine used for synthesizing the polyamic acid (P) preferably contains at least one compound (C') selected from the group consisting of a diamine having the aromatic amine structure (a) and the chain structure (b) (hereinafter also referred to as "diamine (C)"), and a compound (C1) having the structure (a1) and the structure (b 1).

Diamine (C)

The diamine (C) preferably has a structure capable of introducing the aromatic amine structure (a) and the chain structure (b) into the main chain of the polymer (P), and specifically preferably is a compound represented by the following formula (1).

[ solution 4]

(in the formula (1), A¹And A³Each independently being a hydrogen atom or a 1-valent organic radical, A²And A⁴Each independently is a single bond or a 2-valent organic group; b is¹And B²Each independently is a single bond or a 2-valent organic group; wherein, in B¹In the case of a single bond, A¹And A²At least 1 of which is bonded to the nitrogen atom with an aromatic ring, in B¹In the case of a 2-valent organic radical, A¹、A²And B¹At least 2 of which are bonded to the nitrogen atom with an aromatic ring; in B²In the case of a single bond, A³And A⁴At least 1 of which is bonded to the nitrogen atom with an aromatic ring, in B²In the case of a 2-valent organic radical, A³、A⁴And B²At least 2 of which are bonded to the nitrogen atom with an aromatic ring; l is¹Is a 2-valent radical comprising the structure (b)

With respect to said formula (1), A¹And A³Examples of the 1-valent organic group in (1) include: a 1-valent hydrocarbon group, a 1-valent group obtained by introducing a functional group such as-O-, -COO-, -CO-, -NHCO-, -S-, -NH-, or the like between carbon-carbon bonds in the 1-valent hydrocarbon group, and a protective group for an amino group. Furthermore, A¹And A³In the above-mentioned hydrocarbon group, the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) or a hydroxyl group, etc. Specific examples of the protecting group for an amino group include those exemplified in the description of R in the chain structure (b). Preferably tert-butoxycarbonyl.

Examples of the hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Here, the "chain hydrocarbon group" in the present specification is as described above. The "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. Among them, the structure of the alicyclic hydrocarbon does not need to be constituted only, and a hydrocarbon group having a chain structure in a part thereof is also included. The term "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. Among them, it is not necessary to constitute only an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure is included in a part thereof.

As A¹And A³Specific examples of the 1-valent hydrocarbon group in (2) include chain hydrocarbon groups such as: alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, eicosyl and the like; alkenyl groups having 2 to 30 carbon atoms such as an ethenyl group, a propenyl group, a butenyl group, etc.; an alkynyl group having 2 to 30 carbon atoms such as an ethynyl group and a propynyl group; these hydrocarbon groups may be linear or branched. Examples of the alicyclic hydrocarbon group include: cyclopentyl, cyclohexyl, norbornyl, adamantyl, and the like; examples of the aromatic hydrocarbon group include: phenyl, tolyl, benzyl, phenethyl, and the like.

A²、A⁴、B¹And B²Examples of the 2-valent organic group in (1) include: a 2-valent hydrocarbon group in which a functional group such as-O-, -COO-, -CO-, -NHCO-, -S-, -NH-or the like is introduced between carbon and carbon bonds in the 2-valent hydrocarbon group, and hydrogen atoms bonded to carbon atoms in these groups may be substituted by halogen atoms, hydroxyl groups, or the like. Specific examples of the 2-valent hydrocarbon group include groups obtained by removing 1 hydrogen atom from each of the groups exemplified in the 1-valent hydrocarbon group. In the compound represented by the formula (1), the structure surrounding the nitrogen atom in the formula (1) corresponds to the aromatic amine structure (a).

B¹And B²Preferably at least one is a single bond, more preferably B¹And B²Are all single bonds.

L¹Is a 2-valent group containing the chain structure (b). L is¹Preferable specific examples of (b) include: a group represented by the following formula (2), and the like.

[ solution 5]

(in the formula (2), L²And L³Each independently of the structure (b); q is a 2-valent group represented by the following formula (3) or formula (4); n is an integer of 0 to 4; "+" indicates a bond)

[ solution 6]

(in the formula (3), A⁵Is a hydrogen atom or a 1-valent organic group; r¹And R²The substituents may be the same as or different from each other; "+" indicates a bond)

[ solution 7]

(in the formula (4), A⁶Is a hydrogen atom or a 1-valent organic group; "+" indicates a bond)

In the formulas (3) and (4), A⁵And A⁶The 1-valent organic group of (A) may be used¹And A³Description of the 1-valent organic group(s). N in the formula (2) is preferably 0 or 1.

Specific examples of the group represented by the above formula (2) include groups represented by the following formulae (2-1) to (2-25).

[ solution 8]

[ solution 9]

(wherein "+" represents a bond)

Preferable specific examples of the compound represented by the formula (1) include a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2).

[ solution 10]

(in the formula (1-1), L¹¹At least 1 methylene group in a chain hydrocarbon group having 2 valences of 6 or more carbon atoms is replaced by-O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-or-Si (CH)₃)₂A group having a valence of 2, wherein (R) is a hydrogen atom or a group having a valence of 1, which is substituted; a. the¹、A²、A³、A⁴、B¹And B²Is the same as the formula (1); wherein, at L¹¹In the case of having C1-5 alkanediyl group, A¹And A³At least any one of (A) is a hydrogen atom, or B¹And B²At least any one of (a) is a 2-valent organic group)

[ solution 11]

(in the formula (1-2), L¹²A 2-valent group containing a 2-valent chain hydrocarbon group having 6 or more carbon atoms; a. the¹、A²、A³、A⁴、B¹And B²Is as defined for said formula (1)

L in the formula (1-1)¹¹May have only 1 methylene group in a 2-valent chain hydrocarbon group having 6 or more carbon atoms and may be replaced by-O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-or-Si (CH)₃)₂The substituted group may have a plurality of groups. L is¹¹As a preferred example of (3), a group represented by the formula (2) (wherein L is²And L³At least 1 methylene group in a 2-valent chain hydrocarbon group having 6 or more carbon atoms is replaced by-O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-or-Si (CH)₃)₂-substituted groups) and the like.

At L¹¹When the compound contains an alkanediyl group having 1 to 5 carbon atoms, A¹And A³At least one of (A) is a hydrogen atom, preferably A¹And A³Are all hydrogen atoms.

L in the formula (1-2)¹²The hydrocarbon group may have only 1 or more chain hydrocarbon groups having 2 valences and 6 or more carbon atoms, or may have a plurality of hydrocarbon groups. L is¹²As a preferred example of (3), a group represented by the formula (2) (wherein L is²And L³A 2-valent chain hydrocarbon group having 6 or more carbon atoms).

At L¹²When the alkanediyl group has 6 to 10 carbon atoms, the compound represented by the formula (1-2) is preferably A¹And A³At least any one of (A) is a 1-valent organic group, or B¹And B²At least any one of (a) and (b) is a 2-valent organic group. A in said formula (1-1)¹And A³In the case of a hydrogen atom, L¹²L is preferably a group represented by the formula (2)²And L³Is a 2-valent chain hydrocarbon group having 7 or more carbon atoms, and more preferably a 2-valent chain hydrocarbon group having 11 or more carbon atoms.

Preferable specific examples of the diamine (C) include compounds represented by the following formulae (DA-1) to (DA-10) and (DA-41). Further, the diamine (C) may be used alone in 1 kind or in combination of 2 or more kinds.

[ solution 12]

[ solution 13]

(wherein Ph represents a phenyl group)

Diamine (C1)

The diamine (C1) preferably has a structure in which the aromatic amine structure (a) and the structure (b1) can be introduced into the main chain of the polymer (P), and specifically preferably is a compound represented by the following formula (1-3).

[ solution 14]

With respect to said formula (1-3), A⁷The 1-valent organic group of the formula (1) can be used¹And A³Description of the 1-valent organic group(s). A. the⁸And A⁹The 2-valent organic group of the formula (1) can be used²And A⁴And (4) description. L is⁵Examples of the 2-valent organic group include: a 2-valent chain hydrocarbon group having 1 to 20 carbon atoms, wherein at least 1 methylene group in the chain hydrocarbon group is replaced by-O-, -S-, -CO-, -NR⁴-、-NR⁴CO-, -COO-, -COS-or-Si (CH)₃)₂A 2-valent group formed by substitution, -O-, -S-, -CO-, -NR⁴CO-, -COO-, -COS-, and-Si (CH)₃)₂-(R⁴Hydrogen atom or 1-valent organic group). In these organic radicals, L⁵The structure (b1) is preferable.

Preferable specific examples of the diamine (C1) include compounds represented by the following formulae (DA-22) to (DA-40). Further, the diamine (C1) may be used alone in 1 kind or in combination of 2 or more kinds.

[ solution 15]

[ solution 16]

The diamine used for the synthesis of the polyamic acid (P) may be the diamine (C ') alone, or a diamine other than the diamine (C') may be used in combination.

Examples of other diamines which can be used here are: aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples of these diamines include aliphatic diamines such as: m-xylylenediamine, 1, 3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc.;

examples of the alicyclic diamine include: 1, 4-diaminocyclohexane, 4' -methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, and the like;

examples of the aromatic diamine include: o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4 '-diaminodiphenylmethane, 4' -diaminodiphenylsulfide, 4 '-diaminodiphenylamine, 1, 7-bis (4-aminophenoxy) heptane, 1, 5-diaminonaphthalene, 2' -dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4, 4 '-diaminobiphenyl, 4' -diaminodiphenylether, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 9-bis (4-aminophenyl) fluorene, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, 4, 4 '- (p-phenylenediisopropylidene) dianiline, 4' - (m-phenylenediisopropylidene) dianiline, 1, 4-bis (4-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) biphenyl, 2, 6-diaminopyridine, 2, 4-diaminopyrimidine, 3, 6-diaminocarbazole, N' -bis (4-aminophenyl) -benzidine, 1, 4-bis- (4-aminophenyl) -piperazine, 3, 5-diaminobenzoic acid, dodecanoyloxy-2, 4-diaminobenzene, tetradecanoyloxy-2, 4-diaminobenzene, pentadecanoyloxy-2, 4-diaminobenzene, hexadecanoyloxy-2, 4-diaminobenzene, octadecanoyloxy-2, 4-diaminobenzene, dodecanoyloxy-2, 5-diaminobenzene, tetradecanoyloxy-2, 5-diaminobenzene, pentadecanoyloxy-2, 5-diaminobenzene, hexadecanoyloxy-2, 5-diaminobenzene, octadecanoyloxy-2, 5-diaminobenzene, cholestayloxy-3, 5-diaminobenzene, cholestyryloxy-3, 5-diaminobenzene, cholestayloxy-2, 4-diaminobenzene, cholestyryloxy-2, 4-diaminobenzene, 3, 5-diaminobenzoic acid alkyl ester, cholestanyl ester of 3, 5-diaminobenzoic acid, lanostanyl ester of 3, 5-diaminobenzoic acid, 3, 6-bis (4-aminobenzoyloxy) cholestane, 3, 6-bis (4-aminophenoxy) cholestane, 4- (4 '-trifluoromethoxybenzoyloxy) cyclohexyl-3, 5-diaminobenzoate, 4- (4' -trifluoromethylbenzoyloxy) cyclohexyl-3, 5-diaminobenzoate, 1-bis (4- ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1-bis (4- ((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1-bis (4- ((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1-bis (4- ((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane 2, 4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1- (2, 4-diaminophenyl) piperazine-4-carboxylic acid, 1, 3-bis (N- (4-aminophenyl) piperidinyl) propane, alpha-amino-omega-aminophenylalkylene, 1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-5-amine, 1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-6-amine, 4-aminophenyl-4' -aminobenzoate, 2, 4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1- (2, 4-aminophenyl) piperazine-4-carboxylic acid, 1, 3-bis (N- (4-aminoph, 4, 4 '- [4, 4' -propane-1, 3-diylbis (piperidine-1, 4-diyl) ] diphenylamine, 4- (4-aminophenoxycarbonyl) -1- (4-aminophenyl) piperidine, represented by the following formula (DA-18)

[ solution 17]

A compound represented by the formula (D-1)

[ solution 18]

(in the formula (D-1), X^IAnd X^IIEach independently represents a single bond, -O-, COO-or-OCO- (-) representing a bond to the benzene ring in the formula¹Alkanediyl having 1 to 3 carbon atomsRadical, R^IIIs a single bond or C1-3 alkanediyl, a is 0 or 1, b is an integer of 0-2, c is an integer of 1-20, d is 0 or 1; wherein a and b are not both 0)

The compounds represented by the formula (I), etc.;

examples of the diaminoorganosiloxanes include: 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, and other diamines described in Japanese patent application laid-open No. 2010-97188 can be used.

-X in the formula (D-1)^I-(R^I-X^II)_dThe 2-valent group represented by- "is preferably an alkanediyl group having 1 to 3 carbon atoms, an-O-, -COO-group or an-O-C group₂H₄-O- (wherein the bond with the "-" is bonded to the diaminophenyl). radical-C_cH_2c+1Specific examples of "include: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and the like. The 2 amino groups in the diaminophenyl group are preferably located in the 2, 4-or 3, 5-positions relative to the other groups.

Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulae (D-1-1) to (D-1-3).

[ solution 19]

Further, 1 kind of these compounds may be used alone or 2 or more kinds may be appropriately selected and used as the other diamine for synthesizing the polyamic acid.

The diamine used for synthesizing the polyamic acid (P) of the present invention is preferably used in a proportion of 0.5 mol% or more based on the total amount of the diamine used for the synthesis. If the amount is less than 0.5 mol%, the effects of the present invention tend not to be sufficiently obtained. More preferably 2 mol% or more, particularly preferably 5 mol% or more, and particularly preferably 10 mol% or more. The upper limit of the amount of the diamine (C') used may be arbitrarily set within a range of 100 mol% or less with respect to the total amount of the diamine used in the synthesis. In the case where the improvement effect (for example, printability, voltage holding ratio, liquid crystal alignment property, and the like) by the addition of another diamine is achieved, the use ratio of the diamine (C') is preferably 95 mol% or less.

When the liquid crystal aligning agent of the present invention is used for producing a TN-type, STN-type or vertical alignment-type liquid crystal display element, at least a part of the polymer (P) contained in the liquid crystal aligning agent may be a polymer having a group capable of imparting pretilt angle expression ability to a coating film (hereinafter, also referred to as "pretilt angle-expressing group"). Examples of the pretilt angle-exhibiting groups include: an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having 17 to 51 carbon atoms and a steroid skeleton, a group having a polycyclic structure, and the like.

In order to obtain polyamic acid (P) having a pretilt angle-expressing group, it is preferable that the introduction of the pretilt angle-expressing group is facilitated by polymerization of a monomer composition containing a diamine having a pretilt angle-expressing group. Specifically, it can be synthesized by using a diamine having a pretilt angle-expressing group as another diamine.

In the case where a diamine having a pretilt angle-expressing group is used in synthesizing polyamic acid (P), the amount of the diamine used is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total diamine used in the synthesis, from the viewpoint of sufficiently exhibiting high pretilt angle characteristics.

When a coating film produced using the liquid crystal aligning agent of the present invention is imparted with liquid crystal aligning ability by a photo-alignment method, at least a part of the polymer (P) contained in the liquid crystal aligning agent may be a polymer having a photo-alignment structure. Here, the photo-alignment structure is a concept including two photo-alignment groups and a decomposition type photo-alignment portion. Specifically, the photo-alignment structure may employ a group that exhibits photo-alignment properties by photo-isomerization, photo-dimerization, photo-decomposition, or the like, and examples thereof include: an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, a polyimide-containing structure containing polyimide or a derivative thereof as a basic skeleton, and the like.

For example, when the polyamic acid, polyimide, and polyamic acid ester as the polymer (P) have a photo-alignment structure, a decomposition type photo-alignment portion is preferably provided as the photo-alignment structure, and specifically, a polymer having a bicyclo [2.2.2] octene skeleton or a cyclobutane skeleton is preferable. By having the specific skeleton as described above, the liquid crystal alignment property of the coating film can be further improved. For example, the polyamic acid (P) having a bicyclo [2.2.2] octene skeleton or a cyclobutane skeleton can be obtained by a reaction of a tetracarboxylic dianhydride comprising at least one of bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride and cyclobutane tetracarboxylic dianhydride, and a diamine comprising the diamine (C').

[ molecular weight modifier ]

When the polyamic acid (P) is synthesized, an end-modified polymer may be synthesized using an appropriate molecular weight modifier together with the tetracarboxylic dianhydride and the diamine as described above. By providing the above-mentioned end-modified polymer, the coating property (printability) of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention.

Examples of the molecular weight regulators include: acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like. Specific examples of these compounds include acid monoanhydrides: maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyltutanedioic anhydride, n-dodecylbutanedioic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylbutanedioic anhydride, and the like; examples of the monoamine compound include: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, and the like; examples of monoisocyanate compounds include: phenyl isocyanate, naphthyl isocyanate, and the like.

The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine used.

The diamine (C) and the diamine (C1) can be synthesized by appropriately combining the conventional methods of organic chemistry. As an example of the method, for example, with respect to the compound represented by the formula (1), the following method can be mentioned: a dinitro intermediate having a nitro group instead of the primary amino group in the formula is synthesized, and then the nitro group of the obtained dinitro intermediate is aminated using an appropriate reduction system.

The method for synthesizing the dinitro intermediate can be appropriately selected depending on the target compound. As an example of the method, the compound represented by the formula (1) is exemplified by the following methods: to have a corresponding A¹、A²And L¹A method of reacting the secondary amine compound with halogenated nitrobenzene; to have a corresponding A¹、A²And L¹A method of reacting a halide of (a) with a secondary amine compound containing a nitrophenyl group; reacting a carboxylic acid having a corresponding aminophenyl group and nitro group with a corresponding L¹A method of reacting the diol of (a); to have a corresponding A¹、A²And L¹And diamine compounds having the corresponding B¹A method of reacting the halogenated nitrobenzene; a hydroxyl group-containing compound having a corresponding aminophenyl group and nitro group, and a compound having a corresponding L group¹A method of reacting the halide of (1), and the like.

The reaction to obtain the nitro intermediate is preferably carried out in an organic solvent. The organic solvent may be any solvent that does not affect the reaction, and examples thereof include: methanol, ethanol, tetrahydrofuran, toluene, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and the like. In addition, the reaction can also be carried out in the presence of a catalyst as required.

The reduction reaction of the dinitro intermediate is preferably carried out in an organic solvent using a catalyst such as palladium on carbon, platinum oxide, zinc, iron, tin, or nickel. Examples of the organic solvent used herein include: ethyl acetate, toluene, tetrahydrofuran, alcohol, and the like. The procedure for synthesizing the diamine (C) and the diamine (C1) is not limited to the above-mentioned method.

[ Synthesis of Polyamic acid (P) ]

The ratio of the tetracarboxylic dianhydride to the diamine to be used in the synthesis reaction of the polyamic acid (P) of the present invention is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents, of the acid anhydride group of the tetracarboxylic dianhydride to 1 equivalent of the amino group of the diamine.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature in this case is preferably-20 to 150 ℃ and more preferably 0 to 100 ℃. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Examples of the organic solvent include: aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and the like. Specific examples of these organic solvents include the following aprotic polar solvents: n-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, γ -butyrolactone, tetramethylurea, hexamethylphosphoric triamide, and the like; examples of the phenolic solvent include: phenol, m-cresol, xylenol, halogenated phenols, and the like;

examples of alcohols include: methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1, 4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc.; examples of ketones are: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like; examples of the ester include: ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate, and the like; examples of ethers include: diethyl ether, diisoamyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, and the like; examples of the halogenated hydrocarbons include: dichloromethane, 1, 2-dichloroethane, 1, 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, and the like; examples of the hydrocarbon include: hexane, heptane, octane, benzene, toluene, xylene, and the like.

Among these organic solvents, it is preferable to use one or more selected from the group consisting of aprotic polar solvents and phenolic solvents (organic solvents of the first group), or a mixture of one or more selected from the group consisting of one or more selected from the first group and one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the use ratio of the organic solvent of the second group to the total amount of the organic solvent of the first group and the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 30% by weight or less. The amount (α) of the organic solvent used is preferably 0.1 to 50% by weight based on the total amount (α + β) of the tetracarboxylic dianhydride and the diamine.

As described above, the reaction solution in which the polyamic acid (P) is dissolved is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent, or the polyamic acid (P) contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent, or the isolated polyamic acid (P) may be purified and then supplied to the preparation of the liquid crystal aligning agent. In the case where the polyamic acid (P) is subjected to dehydration ring-closure to produce a polyimide, the reaction solution may be supplied directly to the dehydration ring-closure reaction, the polyamic acid (P) contained in the reaction solution may be isolated and then supplied to the dehydration ring-closure reaction, or the isolated polyamic acid (P) may be purified and then supplied to the dehydration ring-closure reaction. Isolation and purification of the polyamic acid can be carried out according to a known method.

[ Polyamic acid ester (P) ]

The polyamic acid ester (hereinafter also referred to as polyamic acid ester (P)) as the polymer (P) can be obtained, for example, by the following method: [I] a method of synthesizing by reacting polyamic acid (P) obtained by the synthesis reaction with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like; [ II ] a method for reacting a tetracarboxylic acid diester with a diamine; and [ III ] a method for reacting a tetracarboxylic acid diester dihalide with a diamine.

In the present specification, the term "tetracarboxylic diester" refers to a compound in which 2 of 4 carboxyl groups of a tetracarboxylic acid are esterified and the remaining 2 are carboxyl groups. By "tetracarboxylic acid diester dihalide", it is meant a compound in which 2 of the 4 carboxyl groups possessed by the tetracarboxylic acid are esterified and the remaining 2 are halogenated.

Examples of the hydroxyl group-containing compound used in the method [ I ] include: alcohols such as methanol, ethanol, propanol, etc.; phenols such as phenol and cresol. Examples of the halide include: methyl bromide, ethyl bromide, octadecyl bromide, methyl chloride, octadecyl chloride, 1, 1, 1-trifluoro-2-iodoethane, etc., and the epoxy group-containing compound may be, for example, propylene oxide, etc. The tetracarboxylic acid diester used in the method [ II ] can be obtained by ring-opening a tetracarboxylic acid dianhydride using the alcohol. The tetracarboxylic acid diester dihalide used in the method [ III ] can be obtained by reacting the tetracarboxylic acid diester obtained in the above manner with an appropriate chlorinating agent such as thionyl chloride. The diamine used in the process [ II ] or the process [ III ] preferably contains the diamine (C'), and the other diamine may be used as required. The polyamic acid ester (P) may have only an amic acid ester structure or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.

[ polyimide (P) ]

The polyimide (hereinafter also referred to as "polyimide (P)") as the polymer (P) can be obtained by subjecting, for example, the polyamic acid (P) synthesized in the above manner to dehydrative ring closure and imidization.

The polyimide (P) may be a complete imide compound obtained by dehydration ring closure of all the amic acid structures of the polyamic acid (P) as a precursor thereof, or may be a partial imide compound obtained by dehydration ring closure of only a part of the amic acid structures so that the amic acid structures and the imide ring structures coexist. The imidization ratio of the polyimide contained in the liquid crystal aligning agent of the present invention is preferably 30% or more, more preferably 40% to 99%, and particularly preferably 50% to 99%. The imidization ratio is a ratio of the number of imide ring structures to the total of the number of amic acid structures and the number of imide ring structures of the polyimide, and is expressed as a percentage. Here, a part of the imide ring may be an imide ring.

The dehydration ring-closing of the polyamic acid is preferably performed by the following method: a method of heating the polyamic acid; or a method in which the polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring-closure catalyst are added to the solution, followed by heating as necessary. Among these, the latter method is preferably used.

In the method of adding the dehydrating agent and the dehydration ring-closing catalyst to the solution of the polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride may be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles based on 1 mole of the amic acid structure of the polyamic acid. As the dehydration ring-closure catalyst, for example, a tertiary amine such as pyridine, collidine, lutidine or triethylamine can be used. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified for the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ℃, more preferably 10 to 150 ℃. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

The reaction solution containing the polyimide (P) was obtained as described above. The reaction solution can be directly provided for the preparation of the liquid crystal aligning agent, the dehydrating agent and the dehydration ring-closing catalyst can be removed from the reaction solution and then provided for the preparation of the liquid crystal aligning agent, the polyimide can be isolated and then provided for the preparation of the liquid crystal aligning agent, or the isolated polyimide can be purified and then provided for the preparation of the liquid crystal aligning agent. These purification operations may be carried out according to known methods. In addition, the polyimide (P) may be obtained by imidization of the polyamic acid ester (P).

The polyamic acid, polyamic acid ester, and polyimide as the polymer (P) obtained in this manner are preferably those having a solution viscosity of from 20 mPas to 1,800 mPas, more preferably from 50 mPas to 1,500 mPas, when prepared in a solution having a concentration of 15% by weight. The solution viscosity (mPa · s) of the polymer is a value measured at 25 ℃ with an E-type rotational viscometer for a 15 wt% polymer solution prepared using a good solvent for the polymer (e.g., γ -butyrolactone, N-methyl-2-pyrrolidone, etc.).

The polyamic acid, polyamic acid ester, and polyimide preferably have a weight average molecular weight (Mw) of 1,000 to 500,000, more preferably 2,000 to 300,000, in terms of polystyrene, as measured by Gel Permeation Chromatography (GPC). The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, and more preferably 10 or less. Within the above molecular weight range, good alignment properties and stability of the liquid crystal display element can be ensured.

< other ingredients >

The liquid crystal aligning agent of the present invention contains the polymer (P) as described above, and may contain other components as needed. Examples of the other components include: a polymer other than the polymer (P), a compound having at least one epoxy group in the molecule (hereinafter referred to as an "epoxy group-containing compound"), a functional silane compound, a metal chelate compound, a curing accelerator, a surfactant, and the like.

[ other Polymer ]

The other polymers may be used to improve solution characteristics or electrical characteristics. Examples of the other polymer include polymers obtained without using the compound (C'), and the main skeleton thereof is not particularly limited. Specifically, examples thereof include polymers having a main skeleton such as polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, and poly (meth) acrylate.

When another polymer is added to the liquid crystal aligning agent, the blending ratio of the other polymer is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and particularly preferably 0.1 to 30 parts by weight or less, based on 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent.

In addition, when a coating film formed using the liquid crystal aligning agent of the present invention is provided with liquid crystal aligning ability by a photo-alignment method, a polymer having a photo-alignment structure may be used as the other polymer. For example, in the case of a liquid crystal aligning agent for a retardation film, a polymer having a photo-alignment group as a photo-alignment structure can be preferably used, and specifically, a polymer having a group having a cinnamic acid structure (cinnamic acid or a derivative thereof) introduced thereinto, and the like can be mentioned. Among them, polyorganosiloxanes having a cinnamic acid structure can be preferably used in terms of ease of introduction of photo-alignment groups into the polymer.

The polymer having a photo-alignment group can be synthesized by a conventionally known method. For example, polyorganosiloxane having photo-alignment groups as another polymer can be synthesized by reacting polyorganosiloxane having epoxy groups with carboxylic acid having photo-alignment groups, preferably in an organic solvent such as ether, ester, or ketone, in the presence of a catalyst such as a quaternary ammonium salt.

When the coating film is provided with a liquid crystal aligning ability by a photo-alignment method, the proportion of the polymer having the photo-alignment structure (the total amount of the polymer (P) and the other polymers in the case where the other polymers have the photo-alignment structure) is preferably 3 wt% or more, more preferably 5 wt% to 100 wt%, and particularly preferably 10 wt% to 100 wt% with respect to the total amount of the polymers used to prepare the liquid crystal aligning agent of the present invention.

[ epoxy group-containing Compound ]

The epoxy group-containing compound is useful for improving the adhesion of the liquid crystal alignment film to the substrate surface or the electrical characteristics. The epoxy group-containing compound is preferably exemplified by the following compounds: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2-dibromoneopentyl glycol diglycidyl ether, N, N, N ', N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N ' -tetraglycidyl-4, 4 ' -diaminodiphenylmethane, N, N-diglycidylcenzylamine, N, N-diglycidylaminomethylcyclohexane, N, n-diglycidyl-cyclohexylamine, and the like. In addition, as an example of the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in international publication No. 2009/096598 can be used.

When these epoxy-containing compounds are added to the liquid crystal aligning agent, the blending ratio of the epoxy-containing compounds is preferably 40 parts by weight or less, and more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent.

[ functional silane Compound ]

The functional silane compound may be used for the purpose of improving printability of the liquid crystal aligning agent. Examples of the functional silane compound include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4, 7-triazacyclodecane, 9-trimethoxysilyl-3, 6-diaza-nonyl acetate, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltrimethoxysilane, N-triethoxysilylpropyltriethoxysilane, N-trimethoxysilyl-1, 4, 7-triazacyclodecane, N-trimethoxysilyl-3, 6-diaza-nonyl-acetate, N-hydroxybutanes, N-, Methyl 9-trimethoxysilyl-3, 6-diazananonanoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and the like.

When these functional silane compounds are added to the liquid crystal aligning agent, the blending ratio of the functional silane compounds is preferably 2 parts by weight or less, and more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent.

[ Metal chelate Compound ]

The metal chelate compound is contained in a liquid crystal aligning agent (particularly, a liquid crystal aligning agent for a retardation film) in order to secure mechanical strength of a film formed by a low-temperature treatment when a polymer component of the liquid crystal aligning agent has an epoxy structure. The metal chelate compound is preferably an acetylacetone complex or an acetoacetic acid complex using a metal selected from aluminum, titanium, and zirconium. Specific examples thereof include: aluminum diisopropoxyethylacetoacetate, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), titanium diisopropoxybis (acetylacetonate), zirconium tris-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), and the like. When the metal chelate compound is added, the metal chelate compound is used in a proportion of preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and particularly preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of the components including the epoxy structure.

[ hardening accelerator ]

The hardening accelerator is contained in the liquid crystal aligning agent (particularly, a liquid crystal aligning agent for a retardation film) in order to ensure the mechanical strength of the formed liquid crystal aligning film and the stability of the liquid crystal aligning property with time when the polymer component in the liquid crystal aligning agent has an epoxy structure. Examples of the hardening accelerator include compounds having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, and a carboxylic anhydride group, and among them, compounds having a phenol group or a silanol group are preferable. Specific examples thereof include compounds having a phenol group such as: cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenophenol, 4-benzylphenol, etc.; examples of the compound having a silanol group include: trimethylsilanol, triethylsilanol, 1,3, 3-tetraphenyl-1, 3-disiloxane diol, 1, 4-bis (hydroxydimethylsilyl) benzene, triphenylsilanol, tri (p-tolyl) silanol, diphenylsilanediol, and the like. When the curing accelerator is added, the curing accelerator is used in a proportion of preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and particularly preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of the components including the epoxy structure.

[ surfactant ]

The surfactant may be contained in a liquid crystal aligning agent (particularly, a liquid crystal aligning agent for a retardation film) for the purpose of improving the coatability of the liquid crystal aligning agent to a substrate. Examples of such surfactants include: nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, fluorosurfactants, and the like. The use ratio of the surfactant is preferably 10 parts by weight or less, more preferably 1 part by weight or less, relative to 100 parts by weight of the total amount of the liquid crystal aligning agent.

In addition to the above components, examples of the other components include a compound having at least one oxetanyl group in the molecule, an antioxidant, and the like.

< solvent >

The liquid crystal aligning agent of the present invention is prepared as a liquid composition in which the polymer (P) and other components used as needed are preferably dispersed or dissolved in an appropriate solvent.

Examples of the organic solvent to be used include: n-methyl-2-pyrrolidone, gamma-butyrolactone, gamma-butyrolactam, N-dimethylformamide, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-N-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-N-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, gamma-butyrolactam, N-dimethylformamide, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxyp, Diisoamyl ether, ethylene carbonate, propylene carbonate, and the like. These organic solvents may be used alone or in combination of 2 or more.

The concentration of the solid component in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) may be appropriately selected in consideration of viscosity, volatility, and the like, and is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of a substrate as described below, and preferably heated to form a coating film as a liquid crystal alignment film or a coating film to be a liquid crystal alignment film. In this case, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent tends to increase to lower coatability.

The particularly preferable range of the solid content concentration varies depending on the application of the liquid crystal aligning agent or the method used when the liquid crystal aligning agent is applied to the substrate. For example, when the liquid crystal aligning agent for a liquid crystal alignment film is applied to a substrate by a spinner method, the solid content concentration (the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is particularly preferably in the range of 1.5 to 4.5 wt%. When the printing method is used, it is particularly preferable that the solution viscosity is set to a range of 12mPa · s to 50mPa · s by setting the solid content concentration to a range of 3 wt% to 9 wt%. In the case of using the ink jet method, it is particularly preferable to set the solution viscosity to a range of 3 to 15mPa · s by setting the solid content concentration to a range of 1 to 5 wt%. The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 10 to 50 ℃, more preferably 20 to 30 ℃. In addition, the solid content concentration of the liquid crystal aligning agent for the retardation film is preferably in the range of 0.2 to 10% by weight, more preferably in the range of 3 to 10% by weight, from the viewpoint of making the coatability of the liquid crystal aligning agent and the film thickness of the formed coating film appropriate.

Further, the results of the studies by the present inventors have revealed that a coating film having a flat surface (excellent surface unevenness) can be formed by using the liquid crystal aligning agent containing the polymer (P). The reason is not necessarily clear, but is presumed as follows. When the aromatic amine structure (a) is introduced to improve the performance of DC residue relaxation, the polymer becomes rigid (rigid) in addition to the increase in crystallinity, and thus it is considered that the polymer is easily aggregated (crystallized). In this case, it is assumed that polymer chains are entangled with each other at the time of forming a coating film, and the surface roughness of the coating film is reduced. On the other hand, in the polymer (P) obtained by using the compound (C) for the reaction, a chain structure (b) having a sufficiently long chain length is introduced as a spacer unit together with the aromatic amine structure (a), whereby the polymer chains are disentangled by heating (post-baking) at the time of forming the coating film, and it is considered that the surface unevenness is improved in the coating film after heating. It is also presumed that the above-mentioned effect is obtained for the same reason with respect to the polymer (P) obtained by using the compound (C1) in the reaction.

< liquid Crystal display element and retardation film >

The liquid crystal alignment film can be produced by using the liquid crystal aligning agent of the present invention described above. The liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention can be preferably applied to a liquid crystal alignment film for a liquid crystal display device and a liquid crystal alignment film for a retardation film. Hereinafter, the liquid crystal display element and the retardation film of the present invention will be described.

[ liquid Crystal display element ]

The liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal aligning agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited, and the liquid crystal display element can be applied to various driving methods such as TN type, STN type, VA type (including Vertical Alignment-Multidomain Vertical Alignment (VA-MVA) type, Vertical Alignment-pattern Vertical Alignment (VA-PVA) type, and the like), IPS type, FFS type, and Optically Compensated Bend (OCB) type. The liquid crystal display element of the present invention can be manufactured by, for example, the following steps (I-1) to (I-3). The step (I-1) uses different substrates according to the desired operation mode. The step (I-2) and the step (I-3) are common in each operation mode.

[ step (I-1): formation of coating film ]

First, the liquid crystal aligning agent of the present invention is applied to a substrate, and then the coated surface is heated, thereby forming a coating film on the substrate.

(I-1A) in the case of producing, for example, a TN, STN, or VA type liquid crystal display element, first, a pair of two substrates provided with a patterned transparent conductive film is formed, and the liquid crystal aligning agent of the present invention is applied to each of the surfaces on which the transparent conductive films are formed, preferably by an offset printing method, a spin coating method, a roll coater method, or an ink jet printing method. The substrate may be, for example: float glass, soda glass, and the like; transparent substrates comprising plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly (alicyclic olefin). The transparent conductive film provided on one surface of the substrate may contain tin oxide (SnO)₂) A film of (Nesa) (registered trademark of PPG Corp., USA) containing indium oxide-tin oxide (In)₂O₃-SnO₂) An ITO film of (2). In order to obtain a patterned transparent conductive film, for example, the following method can be used:a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern; a method of forming a transparent conductive film using a mask having a desired pattern. In the case of applying the liquid crystal aligning agent, the surface of the substrate on which the coating film is formed may be subjected to pretreatment such as application of a functional silane compound or a functional titanium compound in advance in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film.

After the liquid crystal aligning agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing sagging of the applied liquid crystal aligning agent and the like. The prebaking temperature is preferably from 30 ℃ to 200 ℃, more preferably from 40 ℃ to 150 ℃, and particularly preferably from 40 ℃ to 100 ℃. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Then, a firing (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally imidizing the amic acid structure present in the polymer. The firing temperature (post-baking temperature) at this time is preferably 80 to 300 ℃, more preferably 120 to 250 ℃. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film formed in this manner is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5. mu.m.

(I-1B) in the case of producing an IPS-type or FFS-type liquid crystal display element, the liquid crystal aligning agent of the present invention is applied to the electrode-forming surface of a substrate provided with an electrode comprising a transparent conductive film or a metal film patterned into a comb-tooth shape and the surface of a counter substrate not provided with an electrode, and the respective applied surfaces are heated to form a coating film. The materials of the substrate and the transparent conductive film used in this case, the coating method, the heating conditions after coating, the method for patterning the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferable film thickness of the formed coating film are the same as those in the above-mentioned (I-1A). As the metal film, a film containing a metal such as chromium can be used.

In both cases (I-1A) and (I-1B), a liquid crystal alignment agent is applied to a substrate, and then the organic solvent is removed to form a coating film as an alignment film. In this case, when the polymer contained in the liquid crystal aligning agent of the present invention is polyamic acid, polyamic acid ester, or imidized polymer having an imide ring structure and an amic acid structure, the polymer can be further heated after the formation of the coating film to perform a dehydration ring-closure reaction, thereby forming a further imidized coating film.

[ step (I-2): orientation ability imparting treatment

In the case of producing a liquid crystal display element of TN type, STN type, IPS type or FFS type, the coating film formed in the step (I-1) is subjected to a treatment for imparting liquid crystal aligning ability. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Examples of the treatment include the following: rubbing treatment, in which a coating film is wiped in a certain direction by a roller around which a cloth containing fibers such as nylon, rayon, and cotton is wound; and a photo-alignment treatment for irradiating the coating film with polarized or unpolarized radiation. On the other hand, in the case of producing a VA type liquid crystal display element, the coating film formed in the above-mentioned step (I-1) may be used as it is as a liquid crystal alignment film, or the coating film may be subjected to an alignment ability imparting treatment.

In the photo-alignment treatment, ultraviolet rays and visible rays including light having a wavelength of 150nm to 800nm, for example, can be used as the radiation irradiated to the coating film. When the radiation is polarized light, the radiation may be linearly polarized light or partially polarized light. When the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. When unpolarized radiation is irradiated, the irradiation direction is an oblique direction.

The light sources used may be, for example: low pressure mercury lamps, high pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and the like. Ultraviolet rays in a preferred wavelength range can be obtained by means of a light source used in combination with, for example, a filter, a diffraction grating, or the like. The irradiation dose of the radiation is preferably 100J/m²～50,000J/m²More preferably 300J/m²～20,000J/m². In addition, the coating film can be coated while improving the reactivityThe coating film was irradiated with light while heating. The temperature at the time of heating is usually from 30 ℃ to 250 ℃, preferably from 40 ℃ to 200 ℃, and more preferably from 50 ℃ to 150 ℃.

Further, the liquid crystal alignment film after the rubbing treatment may be further subjected to the following treatment to have different liquid crystal alignment ability for each region: a process of changing a pretilt angle of a partial region of the liquid crystal alignment film by irradiating ultraviolet rays to the partial region; or a process of forming a resist film on a part of the surface of the liquid crystal alignment film, rubbing the resist film in a direction different from the rubbing process, and then removing the resist film. In this case, the viewing characteristics of the resulting liquid crystal display element can be improved. The liquid crystal alignment film suitable for the VA-type liquid crystal display element can also be suitably used for a Polymer Stabilized Alignment (PSA) type liquid crystal display element.

[ step (I-3): construction of liquid Crystal cell

A liquid crystal cell was manufactured by preparing 2 substrates on which the liquid crystal alignment films were formed in the above manner, and disposing liquid crystal between the 2 substrates disposed opposite to each other. For example, the following 2 methods are used to produce a liquid crystal cell. The first method is a conventionally known method. First, 2 substrates were arranged to face each other through a gap (cell gap) so that the liquid crystal alignment films face each other, the peripheral portions of the 2 substrates were bonded to each other with a sealant, a liquid crystal was injected and filled into the cell gap defined by the substrate surface and the sealant, and then the injection hole was sealed, whereby a liquid crystal cell was produced. The second method is a method called a One Drop Fill (ODF) method. For example, a uv curable sealant is applied to a predetermined portion of one of the 2 substrates on which the liquid crystal alignment film is formed, liquid crystal is dropped onto predetermined portions of the liquid crystal alignment film surface, the other substrate is attached to the liquid crystal alignment film so as to face each other, the liquid crystal is spread over the entire surface of the substrate, and then the sealant is cured by irradiating uv light onto the entire surface of the substrate, whereby a liquid crystal cell can be manufactured. In either method, it is preferable that the liquid crystal cell manufactured as described above is further heated to a temperature at which the liquid crystal used has an isotropic phase, and then gradually cooled to room temperature to remove the flow alignment at the time of filling the liquid crystal.

As the sealant, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used. The liquid crystal includes nematic liquid crystal (nematic liquid crystal) and smectic liquid crystal (smectic liquid crystal), and among them, nematic liquid crystal is preferable, and for example, the following can be used: schiff base (Schiff base) liquid crystals, azoxy (azoxy) liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl (terphenyl) liquid crystals, diphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane (cubane) liquid crystals, and the like. In addition, the following substances may be added to these liquid crystals: cholesteric liquid crystals (cholesteric crystals), such as cholesterol chloride (cholesteryl chloride), cholesterol nonanoate (cholesteryl nonaate), and cholesterol carbonate (cholesteryl carbonate); chiral agents (chiral agents) sold under the trade names "C-15", "CB-15" (manufactured by Merck); ferroelectric liquid crystals (ferroelectric liquid crystals) such as p-decyloxybenzylidene-p-amino-2-methylbutylcyminate (p-decyloxybenzylidene-p-amino-2-methylbutylchinnamate) and the like.

Next, a polarizing plate is bonded to the outer surface of the liquid crystal cell to obtain the liquid crystal display element of the present invention. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include: a polarizing plate formed by sandwiching a polarizing film called "H film" which is a film obtained by absorbing iodine while stretching and orienting polyvinyl alcohol, or a polarizing plate including the H film itself, with a cellulose acetate protective film.

[ retardation film ]

In the case of producing a retardation film using the liquid crystal aligning agent of the present invention, it is preferable to use a photo-alignment method in terms of being able to suppress generation of dust or static electricity in the process and to form a uniform liquid crystal alignment film, and in terms of being able to form a plurality of regions having different liquid crystal alignment directions arbitrarily on a substrate by using an appropriate mask when radiation is irradiated. Specifically, the compound can be produced by performing the following steps (II-1) to (II-3).

[ step (II-1): formation of coating film Using liquid Crystal Aligning agent ]

First, the liquid crystal aligning agent of the present invention is applied to a substrate to form a coating film. The substrate used herein may suitably be exemplified by: transparent substrates containing synthetic resins such as triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, polymethyl methacrylate, and polycarbonate. Among these substrates, TAC is generally used as a protective layer for a polarizing film in a liquid crystal display element. Further, polymethyl methacrylate is preferably used as a substrate for a retardation film in terms of low hygroscopicity of a solvent, good optical properties, and low cost. In addition, for the substrate used for coating the liquid crystal aligning agent, a conventionally known pretreatment may be applied to the surface of the substrate on which the coating film is formed, in order to improve the adhesion between the substrate surface and the coating film.

In many cases, a phase difference film is used in combination with a polarizing film. In this case, in order to exhibit desired optical characteristics, it is necessary to precisely control the angle of the retardation film with respect to the polarizing axis of the polarizing film to a specific direction and bond the retardation film. Therefore, here, by forming a liquid crystal alignment film having liquid crystal alignment ability in a direction of a predetermined angle on a substrate such as TAC film or polymethyl methacrylate, a step of bonding a retardation film to a polarizing film while controlling the angle of the retardation film can be omitted. In addition, this can contribute to improvement in productivity of the liquid crystal display element. In order to form a liquid crystal alignment film having liquid crystal alignability in a direction of a predetermined angle, it is preferable to use the liquid crystal aligning agent of the present invention and perform the formation by a photo-alignment method.

The liquid crystal aligning agent can be applied to the substrate by a suitable application method, for example, the following methods can be used: a roll coater method, a spinner method, a printing method, an ink jet method, a bar coater method, an extrusion die method, a direct gravure coater (direct gravure coater) method, a chamber doctor blade coater (chamber coater) method, an indirect gravure coater (offset gravure coater) method, a single roll kiss coater method, a reverse kiss coater (reverse kiss coater) method using a small-diameter gravure roll, a three reverse roll coater (reverse roll coater) method, a four reverse roll coater method, a slot die method, an air knife coater (air sector coater) method, a positive rotary roll coater (positive rotary coater) method, a blade coater method, a knife coater method, a MB method, an impregnation method, and the like.

After the coating, the coated surface is heated (baked) to form a coating film. The heating temperature in this case is preferably 40 to 150 ℃, more preferably 80 to 140 ℃. The heating time is preferably 0.1 to 15 minutes, and more preferably 1 to 10 minutes. The film thickness of the coating film formed on the substrate is preferably 1nm to 1,000nm, more preferably 5nm to 500 nm.

[ step (II-2): light irradiation step ]

Then, the coating film formed on the substrate in this manner is irradiated with light to impart liquid crystal alignment ability to the coating film. Here, the description of the photo-alignment process in the step (I-2) can be applied to the description of the wavelength of light to be irradiated, the kind of light, and the light source to be used. The irradiation amount of light is preferably set to 0.1mJ/cm²～1,000mJ/cm²More preferably 1mJ/cm²～500mJ/cm²Particularly preferably 2mJ/cm²～200mJ/cm²。

[ step (II-3): formation of liquid Crystal layer

Then, a polymerizable liquid crystal is applied to the coating film irradiated with light in the above-described manner and cured. Thereby, a coating film (liquid crystal layer) containing polymerizable liquid crystal is formed. The polymerizable liquid crystal used herein is a liquid crystal compound or a liquid crystal composition that is polymerized by at least one treatment of heating and light irradiation. As the polymerizable liquid crystal, conventionally known liquid crystals can be used, and specifically, for example, nematic liquid crystals described in non-patent document 1 (ultraviolet (UV) -curable liquid crystal and application thereof, liquid crystal 3, vol.1 (1999), pages 34 to 42) can be mentioned. In addition, it may be: a cholesteric liquid crystal; discotic liquid crystal (discotic liquid crystal); a twisted nematic alignment liquid crystal to which a chiral agent is added, and the like. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may be a composition further containing a known polymerization initiator, an appropriate solvent, and the like.

For coating the polymerizable liquid crystal on the coating film formed using the liquid crystal aligning agent, an appropriate coating method such as a bar coater method, a roll coater method, a spinner method, a printing method, and an ink jet method can be used.

Then, the polymerizable liquid crystal coating film formed in the above manner is subjected to one or more treatments selected from heating and light irradiation, and the coating film is cured to form a liquid crystal layer. These treatments are preferably performed in a superposed manner, because good alignment can be obtained.

The heating temperature of the coating film can be appropriately selected depending on the kind of polymerizable liquid crystal used. For example, in the case of using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40 ℃ to 80 ℃. The heating time is preferably 0.5 to 5 minutes.

As the irradiation light, unpolarized ultraviolet rays having a wavelength in the range of 200nm to 500nm can be preferably used. The irradiation amount of light is preferably 50mJ/cm²～10,000mJ/cm²More preferably, it is 100mJ/cm²～5,000mJ/cm²。

The thickness of the formed liquid crystal layer is appropriately set according to the desired optical characteristics. For example, in the case of manufacturing an 1/2-wavelength plate of visible light having a wavelength of 540nm, the retardation film to be formed is selected to have a retardation of 240nm to 300nm, and in the case of a 1/4-wavelength plate, the retardation film is selected to have a retardation of 120nm to 150 nm. The thickness of the liquid crystal layer to obtain the target phase difference differs depending on the optical characteristics of the polymerizable liquid crystal used. For example, in the case of RMS03-013C manufactured by Merck (Merck), the thickness of the plate used to manufacture 1/4 wavelength plates ranged from 0.6 μm to 1.5 μm.

The retardation film obtained in the above manner can be preferably applied as a retardation film of a liquid crystal display element. The liquid crystal display element to which the retardation film produced using the liquid crystal aligning agent of the present invention is applied is not limited in its driving method, and can be applied to various known methods such as TN type, STN type, IPS type, FFS type, and VA type. The retardation film is used by attaching the substrate side of the retardation film to the outer surface of the polarizing plate disposed on the viewing side of the liquid crystal display element. Therefore, it is preferable to adopt the following aspect: the substrate of the retardation film is made of TAC or acrylic base material, and functions as a protective film of a polarizing film.

Here, a roll-to-roll (roll-to-roll) method is a method for producing a retardation film on an industrial scale. The method is a method for preparing a film subjected to the following steps into a wound body and recycling the wound body by performing the following steps in a continuous manner: a process of winding a film from a long-shaped roll of a base material film and forming a liquid crystal alignment film on the wound film; coating a polymerizable liquid crystal on the liquid crystal alignment film and hardening the liquid crystal; and a process of laminating the protective film as necessary. The retardation film formed using the liquid crystal aligning agent of the present invention has good adhesion to a substrate, and is difficult to peel off from the substrate even when the retardation film is stored in a roll. Therefore, the reduction of the product yield in the production of the retardation film by the roll-to-roll method can be suppressed.

The liquid crystal display element of the present invention can be effectively applied to various devices, for example, to: a clock, a portable game machine, a word processor (word processor), a notebook Personal computer (note type Personal computer), a car navigation system (car navigation system), a camcorder (camrecorder), a Personal Digital Assistant (PDA), a Digital camera (Digital camera), a mobile phone, a smart phone, various monitors, a liquid crystal television, various display devices such as an information display, and the like.

[ examples ]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

In the following examples and synthetic examples, the weight average molecular weight Mw of the polymer, the imidization ratio and the epoxy equivalent, and the solution viscosity of the polymer solution were measured by the following methods.

[ weight-average molecular weight Mw of Polymer ]

Mw is a polystyrene equivalent measured by GPC under the following conditions.

Pipe column: TSKgelGRCXLII manufactured by Tosoh (Strand, Tosoh)

Solvent: n, N-dimethylformamide solution containing tetrahydrofuran, or lithium bromide and phosphoric acid

Temperature: 40 deg.C

Pressure: 68kgf/cm²

[ imidization ratio of Polymer ]

Adding a solution containing polyimide into pure water, drying the obtained precipitate at room temperature under sufficiently reduced pressure, dissolving in deuterated dimethyl sulfoxide, measuring at room temperature using tetramethylsilane as reference substance¹H-Nuclear Magnetic Resonance (NMR). According to what is obtained¹The imidization ratio was determined by H-NMR spectroscopy using the following numerical formula (EX-1).

Imidization rate (%) - (1-E)¹/E²×α)×100 (EX-1)

(in the numerical formula (EX-1), E¹Is the peak area of the NH group-derived proton appearing in the vicinity of a chemical shift of 10ppm, E²Is the peak area derived from other protons, and α is the number ratio of the other protons to 1 proton of NH group in the precursor (polyamic acid) of the polymer)

[ epoxy equivalent ]

The epoxy equivalent is measured by the hydrochloric acid-methylethylketone method described in JIS C2105.

[ solution viscosity of Polymer solution ]

The solution viscosity (mPas) of the polymer solution was measured at 25 ℃ using an E-type rotational viscometer.

< Synthesis of Compound (C) >

Synthetic examples 1 to 1: synthesis of Compound (DA-1)

Compound (DA-1) was synthesized according to the following scheme 1. In the formula, Bn represents a benzyl group (the same applies hereinafter).

[ solution 20]

The first-stage reaction is a Williamson reaction (Williamson reaction). First, 83.7g (0.2 mol) of N-benzyl-4-hydroxyaniline, 46g (0.42 mol) of 1, 5-dibromopentane, 121.5g (0.8 mol) of cesium fluoride and 800mL of dimethylformamide were mixed and dissolved in a 2L three-necked flask equipped with a dropping funnel, and the mixture was stirred at 60 ℃ for 4 hours to effect a reaction. After the reaction, 2000mL of ethyl acetate was added for extraction, and 200mL of distilled water was added for liquid separation purification. After the extractive purification was repeated 5 times, the solvent was removed from the organic layer by distillation under the reduced pressure, whereby 76.4g (0.16 mol) of the dibenzyl intermediate (the compound represented by the formula (DA-1-1)) was obtained.

The second reaction stage is synthesized by Ullmann condensation reaction. 76.4g (0.16 mol) of the above-mentioned dibenzyl intermediate (DA-1-1), 81.5g (0.33 mol) of 4-iodonitrobenzene, 59g (0.33 mol) of phenanthroline (phenanthroline), 139g (0.65 mol) of tripotassium phosphate, 9.4g (0.05 mol) of copper iodide and 600mL of dimethylacetamide were added to a 2L three-necked flask under a nitrogen stream, mixed and dissolved, and stirred under reflux for 24 hours to effect a reaction. After the reaction was completed, the reaction solution was filtered to remove the catalyst, and the filtrate was poured into 2000mL of distilled water to precipitate crystals. The precipitated solid was recovered by filtration, sufficiently washed with ethanol, and recrystallized in tetrahydrofuran to obtain 35g (0.05 mol) of a nitro intermediate (the compound represented by the formula (DA-1-2)).

The reaction of the third stage is synthesized by hydrogen reduction reaction. 35g, 3g of 5% Pd/C, 50mL of ethanol, 50mL of tetrahydrofuran, and 35mL of hydrazine monohydrate were added to a 500mL three-necked flask under a nitrogen stream, and then replaced with hydrogen again, followed by reaction at room temperature in the presence of hydrogen. The reaction was followed by High Performance Liquid Chromatography (HPLC), and filtration was performed after confirming the progress of the reaction. To the filtrate, 1000mL of ethyl acetate and 100mL of distilled water were added to conduct liquid separation purification. After repeating the extraction and purification 5 times, the solvent was removed from the organic layer by distillation under reduced pressure, whereby a solid was precipitated. The precipitated solid was recrystallized from a mixed solvent of tetrahydrofuran and ethanol, whereby 18.5g (0.04 mol) of the compound (DA-1) was obtained.

Synthetic examples 1 to 2: synthesis of Compound (DA-2)

Compound (DA-2) is obtained according to scheme 2 below using the same synthesis reaction recipe as compound (DA-1).

[ solution 21]

Synthetic examples 1 to 3: synthesis of Compound (DA-3)

Compound (DA-3) is obtained according to scheme 3 below using the same synthesis reaction recipe as compound (DA-1). The reaction of The second stage is synthesized by a method described in non-patent document 2 (Journal of Organic Chemistry 2002, 67, 6479).

[ solution 22]

Synthetic examples 1 to 4: synthesis of Compound (DA-4)

Compound (DA-4) is obtained according to scheme 4 below using the same synthetic reaction recipe as compound (DA-1). Further, the reaction in the second stage is synthesized by hydrolysis, and the reaction in the third stage is synthesized by condensation reaction using 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride.

[ solution 23]

Synthetic examples 1 to 5: synthesis of Compound (DA-5)

Compound (DA-5) is obtained according to scheme 5 below using the same synthetic reaction recipe as compound (DA-1).

[ solution 24]

Synthetic examples 1 to 6: synthesis of Compound (DA-6)

Compound (DA-6) is obtained according to scheme 6 below using the same synthetic reaction recipe as compound (DA-1).

[ solution 25]

Synthetic examples 1 to 7: synthesis of Compound (DA-7)

Compound (DA-7) is obtained according to scheme 7 below using the same synthetic reaction recipe as compound (DA-1).

[ solution 26]

Synthetic examples 1 to 8: synthesis of DA-8

Compound (DA-8) is obtained according to scheme 8 below using the same synthetic reaction recipe as compound (DA-1). Further, the mononitromonoiodo intermediate (the compound represented by the formula (DA-8-1)) is synthesized in the first stage by Friedel-Crafts reaction (Friedel-Crafts reaction), and in the second stage by reduction reaction of a silane carbonyl group with triethylsilane in the presence of trifluoromethanesulfonic acid as a strong acid.

[ solution 27]

Synthetic examples 1 to 9: synthesis of Compound (DA-9)

Compound (DA-9) is obtained according to scheme 9 below using the same synthetic reaction recipe as compound (DA-1).

[ solution 28]

Synthetic examples 1 to 10: synthesis of Compound (DA-10)

Compound (DA-10) is obtained according to scheme 10 below using the same synthetic reaction recipe as compound (DA-1). Further, the mononitromonohydroxy intermediate (the compound represented by the formula (DA-10-1)) is synthesized in the first stage by friedel-crafts reaction, in the second stage by deprotection reaction of methoxy group by lithium bromide, and in the third stage by reduction reaction of silane carbonyl group by triethylsilane in the presence of trifluoromethanesulfonic acid as a strong acid.

[ solution 29]

< Synthesis of Compound (C1) >

Synthetic examples 1 to 11: synthesis of Compound (DA-22)

Compound (DA-22) is obtained according to scheme 11 below. In addition, the first-stage synthesis was carried out by a Knoevenagel reaction (Knoevenagel reaction) to obtain an intermediate (a compound represented by the following formula (DA-22-1)). The second stage is reduced by the same method as that for the compound (DA-1).

[ solution 30]

Synthetic examples 1 to 12: synthesis of Compound (DA-23)

According to the following scheme 12, the compound (DA-22-1) is reduced in the presence of zinc using water as a catalyst, thereby obtaining a compound (DA-23).

[ solution 31]

< Synthesis of Polymer >

Synthesis of Polyamic acid

Synthetic example 2-1: synthesis of Polymer (PAm-1) ]

In a reaction vessel, tetracarboxylic dianhydride and diamine were added at a mixing ratio (molar parts) shown in table 1 below so that the total weight was 30g, and 170g of N-methyl-2-pyrrolidone (NMP) was further added and dissolved, and the reaction was carried out at 60 ℃ for 6 hours. Then, the resulting reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried at 40 ℃ for 15 hours under reduced pressure, thereby obtaining a polymer (PAm-1). In addition, as for tetracarboxylic dianhydrides, the values in table 1 represent the usage ratio (mol%) relative to the total amount of tetracarboxylic dianhydrides used in the reaction, and as for diamines, the values in table 1 represent the usage ratio (mol%) relative to the total amount of diamines used in the reaction. Then, the obtained polymer (PAm-1) was dissolved in NMP so as to be 15 wt%, and the respective solution viscosities were measured. The measurement results are shown in Table 1 below. The polymer solution obtained as described above did not undergo gelation after standing at 20 ℃ for 3 days, and was good in storage stability.

Synthesis examples 2-2 to 2-18: synthesis of polymers (PAm-2) to (PAm-18) ]

Polymers (PAm-2) to (PAm-18) were obtained in the same manner as in Synthesis example 2-1, except that the mixing ratio of the tetracarboxylic dianhydride and the diamine was changed to the values shown in Table 1 and Table 2 below. The results of measuring the solution viscosity of each polymer in the same manner as in synthesis example 2-1 are shown in tables 1 and 2 below. Further, each of the polymer solutions obtained above was allowed to stand at 20 ℃ for 3 days, and as a result, gelation did not occur except for the polymer (PAm-14), and the storage stability was good. The polymer (PAm-14) gelled and the fluidity disappeared.

Synthesis of polyimide

[ Synthesis examples 3-1: synthesis of Polymer (PIm-1)

A polyamic acid was synthesized in the same manner as in Synthesis example 2-1, except that tetracarboxylic dianhydride and diamine were added at the mixing ratios (molar parts) shown in Table 2 below so that the total weight was 30g, and further 170g of NMP was added. Then, 200g of NMP was added, pyridine and acetic anhydride were added in amounts shown in Table 2 below (the numerical values represent molar parts per 100 molar parts of the total amount of acid dianhydrides), and a dehydration ring-closure reaction was carried out at 80 ℃ for 6 hours. Then, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried at 40 ℃ for 15 hours under reduced pressure, thereby obtaining polymer (PIm-1).

Then, the obtained polymer (PIm-1) was dissolved in NMP so as to be 15% by weight, and the respective solution viscosities were measured. The imidization ratio was also measured. The measurement results are shown in table 2 below. Further, the polymer solution obtained as described above was allowed to stand at 20 ℃ for 3 days, and as a result, gelation did not occur, and the storage stability was good.

[ Synthesis examples 3-2: synthesis of Polymer (PIm-2)

A polymer (PIm-2) was obtained in the same manner as in Synthesis example 3-1, except that the mixing ratio of the tetracarboxylic dianhydride and the diamine was changed to the values shown in Table 2 below. The results of measuring the solution viscosity of the polymer (PIm-2) in the same manner as in Synthesis example 3-1 and the results of measuring the imidization ratio are shown in Table 2 below. The polymer solution obtained as described above did not undergo gelation after standing at 20 ℃ for 3 days, and was good in storage stability.

[ Table 1]

[ Table 2]

The compounds in tables 1 and 2 are abbreviated as follows. In table 2, the numerical values of pyridine and acetic anhydride represent molar parts relative to 100 molar parts of the total tetracarboxylic dianhydrides used in the reaction.

(tetracarboxylic dianhydride)

AN-1: 1,2,3, 4-cyclobutanetetracarboxylic dianhydride

AN-2: pyromellitic dianhydride

AN-3: 2,3, 5-tricarboxylic cyclopentyl acetic dianhydride

AN-4: ethylenediaminetetraacetic dianhydride

AN-5: 5- (2, 5-Trioxotetrahydrofuran-3-yl) -8-methyl-3 a,4,5,9 b-tetrahydronaphtho [1,2-c ] furan-1, 3-dione

AN-6: bicyclo [3.3.0] octane-2, 4,6, 8-tetracarboxylic acid 2: 4,6: 8-dianhydrides

AN-7: 1, 3-propanediol bis (trimellitic anhydride)

AN-8: 1,2,3, 4-cyclopentanetetracarboxylic dianhydride

(diamine)

DA-11: 1, 7-bis (4-aminophenoxy) heptane

DA-12: 4, 4' -diaminodiphenylamine

DA-13: a compound represented by the following formula (DA-13)

DA-14: a compound represented by the following formula (DA-14)

DA-15: a compound represented by the following formula (DA-15)

DA-16: 4, 4' -diaminodiphenylmethane

DA-17: 4-aminophenyl-4' -aminobenzoic acid ester

DA-18: a compound represented by the formula (DA-18)

DA-19: 4- (4-Aminophenoxycarbonyl) -1- (4-aminophenyl) piperidine

DA-20: 4- (tetradecanoyloxy) benzene-1, 3-diamine

DA-21: 3, 5-diaminobenzoic acid cholestanyl ester

[ solution 32]

Synthesis of polyorganosiloxane containing photo-alignment group

Synthesis examples 4-1: synthesis of Polymer (PSi-1) ]

100.0g of 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 500g of methyl isobutyl ketone and 10.0g of triethylamine were charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and mixed at room temperature. 100g of deionized water was added dropwise to the mixture over 30 minutes from the addition funnel, and the mixture was mixed under reflux and reacted at 80 ℃ for 6 hours. After the reaction was completed, the organic layer was taken out, washed with a 0.2 wt% ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure, whereby the polyorganosiloxane having the oxetanyl group was obtained as a viscous transparent liquid. The polyorganosiloxane having an oxetanyl group is subjected to¹As a result of H-NMR analysis, a peak based on the oxetanyl group was obtained as shown by the theoretical intensity in the vicinity of chemical shift () (3.2 ppm), and it was confirmed that no side reaction of the oxetanyl group occurred in the reaction. The epoxy equivalent of the polyorganosiloxane with an oxetanyl group was measured and found to be 186 g/eq.

Then, 9.3g of the thus-obtained polyorganosiloxane with an oxetanyl group, 26g of methyl isobutyl ketone, 3g of 4-phenoxycinnamic acid, and 0.10g of UCAT 18X (trade name, manufactured by San-Apro corporation) were charged in a 100mL three-necked flask, and the reaction was carried out at 80 ℃ for 12 hours with stirring. After the reaction, a precipitate produced by charging the reaction mixture into methanol was collected, and the precipitate was dissolved in ethyl acetate to prepare a solution, and the solution was washed with water 3 times, and then the solvent was distilled off, whereby 6.3g of polyorganosiloxane (PSi-1) having an oxetanyl group and a cinnamic acid structure was obtained as a white powder. The weight-average molecular weight Mw of this polyorganosiloxane (PSi-1) was 3,500 in terms of polystyrene as measured by GPC.

Examples 1 to 1: light-oriented FFS type liquid crystal display element

(1) Preparation of liquid crystal aligning agent

50 parts by weight of the polymer (PAm-4) obtained in synthesis examples 2 to 4 and 50 parts by weight of the polymer (PAm-11) obtained in synthesis examples 2 to 11 were dissolved in a mixed solvent containing γ -butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP) and Butyl Cellosolve (BC) (GBL: NMP: BC: 40: 20 (weight ratio)) to prepare a solution having a solid content concentration of 3.5 wt%. The solution was filtered through a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent.

(2) Evaluation of surface roughness of coating film

The prepared liquid crystal aligning agent was coated on a glass substrate using a spinner, prebaked on a hot plate at 80 ℃ for 1 minute, and then heated (postbaked) in a 200 ℃ oven with a nitrogen gas substitution in the chamber for 1 hour to form a film having an average thickness of

Coating film of (3). The coating film was observed with an Atomic Force Microscope (AFM), and the center average roughness (Ra) was measured. The evaluation was carried out in the following manner: the surface roughness was evaluated as "good" when the Ra was less than 2.0nm, as "acceptable" when the Ra was 2.0nm or more and less than 5.0nm, and as "poor" when the Ra was 5.0nm or more. In this example, Ra is 0.8nm, and the surface roughness is "good".

(3) Evaluation of transmittance

The obtained coating film was evaluated for light transmittance (%) at a wavelength of 400nm using a spectrophotometer (150-20 type double beam manufactured by hitachi corporation). The evaluation was carried out in the following manner: the light transmittance was evaluated as "good" when the light transmittance was 97% or more, as "ok" when the light transmittance was 95% or more and less than 97%, and as "bad" when the light transmittance was less than 95%. As a result, the light transmittance of the coating film was 99.0%, and the transmittance was "good".

(4) Evaluation of orientation

The obtained coating film was irradiated with polarized ultraviolet light 300J/m containing 313nm bright lines from the substrate normal direction using an Hg-Xe lamp and a Glan-Taylor prism (Glan-Taylor prism)²To perform the orientation process. The refractive index anisotropy (nm) of the glass substrate with the alignment film was measured using a liquid crystal alignment film inspection apparatus (rasscann) manufactured by Morris (MORITEX). The evaluation was carried out in the following manner: the evaluation was "good" when the wavelength was 0.020nm or more, "good" when the wavelength was less than 0.020nm and 0.010nm or more, and "bad" when the wavelength was less than 0.010 nm. As a result, the refractive index anisotropy of the substrate was 0.037nm, and the alignment property was "good".

(5) Manufacture of FFS type liquid crystal display element using optical alignment method

An FFS type liquid crystal display device 10 shown in fig. 1 was produced. First, a glass substrate 11a having an electrode pair on one surface thereof, the electrode pair being formed in this order of a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and a top electrode 13 patterned in a comb-tooth shape, and a counter glass substrate 11b having no electrode are formed as a pair, and the liquid crystal alignment agent prepared in (1) above is applied to the surface of the glass substrate 11a having a transparent electrode and the one surface of the counter glass substrate 11b using a spinner, thereby forming a coating film. Then, the coating film was prebaked on a hot plate at 80 ℃ for 1 minute, and then heated at 230 ℃ for 15 minutes in an oven with a nitrogen gas substitution in the storage (postbaking) to form an average film thickness

Coating film of (3). A schematic plan view of the top electrode 13 used here is shown in fig. 2(a) and 2 (b). Fig. 2(a) is a plan view of the top electrode 13, and fig. 2(b) is an enlarged view of a portion C1 surrounded by a broken line in fig. 2 (a). In this example, a substrate having a top electrode with a line width d1 of 4 μm and an inter-electrode distance d2 of 6 μm was used. The top electrode 13 is a 4-system drive electrode using the electrode a, the electrode B, the electrode C, and the electrode D. Fig. 3 shows a structure of a driving electrode of the liquid crystal display element. In this case, the bottom electrode 15 acts as a common electrode on all the 4-system drive electrodes, and the regions of the 4-system drive electrodes are pixel regions.

Then, polarized ultraviolet light 300J/m containing 313nm bright line was irradiated from the substrate normal direction onto each surface of the coating films using Hg-Xe lamp and Glan Taylor prism, respectively²A pair of substrates having liquid crystal alignment films was obtained. At this time, the irradiation direction of the polarized ultraviolet rays is set to be from the substrate normal direction, and after setting the polarization plane direction so that the direction of the line segment projecting the polarization plane of the polarized ultraviolet rays onto the substrate becomes the direction of the double-headed arrow in fig. 2(a) and 2(b), the light irradiation treatment is performed.

Then, an epoxy resin adhesive containing alumina balls having a diameter of 5.5 μm was applied to the outer periphery of the surface having the liquid crystal alignment film of 1 of the substrates by screen printing, and then 1 pair of substrates were pressed and laminated so that the directions of polarization planes of polarized ultraviolet rays projected onto the substrates were parallel to each other, and the adhesive was thermally cured at 150 ℃ for 1 hour. Then, a liquid crystal "MLC-6221" manufactured by Merck corporation was filled into the substrate gap from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, it was heated to 150 ℃ and then slowly cooled to room temperature.

Then, polarizing plates are bonded to both outer surfaces of the substrate, thereby manufacturing an FFS type liquid crystal display device. In this case, 1 of the polarizing plates was attached so that the polarization direction thereof was parallel to the projection direction of the substrate surface of the polarized ultraviolet ray polarized light of the liquid crystal alignment film, and the other was attached so that the polarization direction thereof was orthogonal to the polarization direction of the immediately preceding polarizing plate.

The above-described method was repeated to manufacture a total of 5 FFS type liquid crystal display elements, and 1 of the following liquid crystal alignment property evaluation, heat resistance evaluation, frame unevenness resistance, image sticking property, and contrast property evaluation was provided. In either case, ultraviolet irradiation under voltage application was not performed. In addition, the liquid crystal cell used for evaluation of the contrast characteristics was not laminated with a polarizing plate.

(6) Evaluation of liquid Crystal alignment Properties

In the FFS type liquid crystal display device manufactured as described above, the presence or absence of an abnormal region in a change in brightness when a voltage of 5V is turned ON/OFF (ON/OFF) (applied/released) was observed with a microscope at a magnification of 50 times. The evaluation was carried out in the following manner: the case where no abnormal region was observed was evaluated as "good" liquid crystal alignment, and the case where an abnormal region was observed was evaluated as "poor" liquid crystal alignment. The liquid crystal display element has "good" liquid crystal alignment properties.

(7) Evaluation of Voltage holding ratio

In the FFS type liquid crystal display device manufactured as described above, after applying a voltage of 5V at 23 ℃ for an application time of 60 microseconds and a span of 167 milliseconds, a Voltage Holding Ratio (VHR) after 167 milliseconds from the release of the application was measured, and as a result, the voltage holding ratio was 99.4%. The measurement apparatus was VHR-1 manufactured by Toyang Technica (Toyo technical) (Inc.).

(8) Evaluation of Heat resistance

The voltage holding ratio was measured in the same manner as in the evaluation of the voltage holding ratio (7), and the value thereof was regarded as the initial VHR (VHR)_BF). Then, the liquid crystal display element after the initial VHR measurement was left to stand in an oven at 100 ℃ for 500 hours. Then, the liquid crystal display element was left to stand at room temperature and was left to cool to room temperature, and then the voltage holding ratio was measured in the same manner as described above, and the value thereof was regarded as VHR_AF. Further, according to the following formula (EX-2),the rate of change of the voltage holding ratio (Δ VHR (%)) before and after application of thermal stress was determined.

ΔVHR(％)＝((VHR_BF-VHR_AF)÷VHR_BF)×100 (EX-2)

The heat resistance was evaluated as follows: the heat resistance was evaluated as "good" when the change rate Δ VHR was less than 4%, as "good" when the change rate Δ VHR was 4% or more and less than 5%, and as "poor" when the change rate Δ VHR was 5% or more. As a result, Δ VHR was 2.9%, and the heat resistance of the liquid crystal display element was "good".

(9) Unevenness resistance of sealant periphery (frame unevenness resistance)

The manufactured FFS type liquid crystal display device was stored at 25 ℃ and 50% RH for 30 days, and then was driven at an ac voltage of 5V to observe a lighting state. The evaluation was carried out in the following manner: if no difference in brightness (more black or more white) is visually recognized around the sealant, it is evaluated as "excellent"; if the difference in brightness disappeared within 5 minutes after lighting, it was evaluated as "good", although visually recognized; if the brightness difference disappears within more than 5 minutes and 20 minutes, the evaluation is "ok"; if the luminance difference was visually recognized even after 20 minutes had elapsed, the evaluation was "poor". As a result, the luminance difference of the liquid crystal display element was not visually recognized, and it was judged as "excellent".

(10) Evaluation of residual image characteristics (DC residual image evaluation)

The fabricated photo-alignment liquid crystal display device was placed at 25 ℃ under 1 atmosphere. The bottom electrode was set to be a common electrode for all the 4-system drive electrodes, and the potential of the bottom electrode was set to 0V potential (ground potential). The electrode B and the electrode D were brought into a 0V applied state by short-circuiting the common electrode, and a combined voltage including an AC voltage of 3.5V and a DC voltage of 1V was applied to the electrode A and the electrode C for 2 hours. After 2 hours had elapsed, an alternating voltage of 1.5V was applied to all of the electrodes A to D. Next, the time from the time when the application of the ac 1.5V voltage to all the drive electrodes was started until the difference in luminance between the drive stress applied region (the pixel region of the electrode a and the electrode C) and the drive stress non-applied region (the pixel region of the electrode B and the electrode D) could not be visually confirmed was measured and used as the afterimage erasing time. Further, the shorter the time, the more difficult afterimages are generated. The liquid crystal display element of the present example was evaluated as "good" when the afterimage erasing time was less than 30 seconds, as "ok" when the afterimage erasing time was 30 seconds or more and less than 120 seconds, and as "bad" when the afterimage erasing time was 120 seconds or more, and as a result, the liquid crystal display element of the present example was evaluated as "good" when the afterimage erasing time was 1 second.

(11) Evaluation of contrast characteristics after driving stress (AC afterimage evaluation)

After the manufactured FFS type liquid crystal cell (liquid crystal cell without a polarizing plate attached thereto) was driven at an ac voltage of 10V for 30 hours, the minimum relative transmittance (%) represented by the following formula (EX-3) was measured using a device in which a polarizer and an analyzer were disposed between a light source and a light quantity detector.

Minimum relative transmittance (%) ═ β -B₀)/(B₁₀₀-B₀)×100 (EX-3)

(in the numerical formula (EX-3), B₀A transmission amount of light under a blank and crossed nicols; b is₁₀₀The amount of light transmitted under the blank and parallel nicols; beta is the minimum light transmission amount under crossed Nichol by sandwiching the liquid crystal display element between the polarizer and the analyzer

The black level (black level) in the dark state is expressed by the minimum relative transmittance of the liquid crystal display element, and the smaller the black level in the dark state is, the better the contrast characteristics are. The minimum relative transmittance was evaluated as "good" when it was less than 0.5%, as "ok" when it was 0.5% or more and less than 1.0%, and as "bad" when it was 1.0% or more. As a result, the minimum relative transmittance of the liquid crystal display element was 0.2%, and the contrast characteristic was judged to be "good".

Examples 1-2, examples 1-3 and comparative examples 1-1

Liquid crystal aligning agents were prepared and liquid crystal display elements were manufactured and evaluated in the same manner as in example 1-1, except that the kinds and amounts of the polymers used for the preparation of the liquid crystal aligning agents were as described in table 3 below. The evaluation results are shown in table 3 below.

[ example 2-1: friction FFS type liquid crystal display element

(1) Preparation of liquid crystal aligning agent

The polymer (PAm-1) obtained in synthesis example 2-1 as a polymer was dissolved in a mixed solvent containing γ -butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP), and Butyl Cellosolve (BC) (GBL: NMP: BC 40: 20 (weight ratio)) to prepare a solution having a solid content concentration of 3.5 wt%. The solution was filtered through a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent.

(2) Evaluation of surface roughness of coating film

The prepared liquid crystal alignment agent was coated on a glass substrate using a spinner, prebaked for 1 minute on a 80 ℃ hot plate, and then heated (postbaked) for 1 hour in a 200 ℃ oven in which nitrogen gas was substituted in the chamber, thereby forming a film having an average film thickness of

Coating film of (3). For this coating film, evaluation of the surface unevenness of the coating film was performed in the same manner as in (2) of the above-mentioned example 1-1. As a result, the Ra of the coating film was 0.9nm, and the surface roughness was "good".

(3) Evaluation of transmittance

For the obtained coating film, the transmittance was evaluated in the same manner as in (3) of the example 1-1. As a result, the transmittance of the coating film was 98.5%, and the transmittance was "good".

(4) Evaluation of Friction resistance

The obtained coating film was subjected to rubbing treatment 7 times at a roller rotation speed of 1000rpm, a table moving speed of 20 cm/sec and a capillary penetration length of 0.4mm by using a rubbing machine having a roller around which cotton cloth was wound. The number of foreign matters (fragments of coating film) in a 500 μm × 500 μm region on the obtained substrate was measured by observing the foreign matters by rubbing and grinding with an optical microscope. The evaluation was carried out in the following manner: the number of foreign matters was 3 or less, the friction resistance was "good", the number of foreign matters was 4 or more and 7 or less, the number of foreign matters was "ok", and the number of foreign matters was 8 or more, the friction resistance was "poor". As a result, no foreign matter was observed, and the abrasion resistance of the coating film was "good".

(5) Evaluation of orientation

With respect to the obtained glass substrate with an alignment film subjected to rubbing alignment treatment, alignment properties were evaluated in the same manner as in (4) of example 1-1. As a result, the refractive index anisotropy of the substrate was 0.031nm, which was "good".

(6) Manufacture of FFS type liquid crystal display element using rubbing method

In the same manner as in (5) of the above-described example 1-1, an FFS type liquid crystal display element shown in fig. 1 was produced. Fig. 4(a) and 4(b) show schematic plan views of the top electrode 13 used here. Fig. 4(a) is a plan view of the top electrode 13, and fig. 4(b) is an enlarged view of a portion C1 surrounded by a broken line in fig. 4 (a). In this example, a substrate having a top electrode with a line width d1 of 4 μm and an inter-electrode distance d2 of 6 μm was used.

Then, rubbing treatment was performed on each surface of the coating film formed on the glass substrate with cotton to prepare a liquid crystal alignment film 12. In fig. 4(b), the rubbing direction of the coating film formed on the glass substrate 11a is shown by an arrow. These substrates were bonded to each other via a spacer having a diameter of 3.5 μm so that the rubbing directions of the substrates 11a and 11b were antiparallel to each other, and a liquid crystal MLC-6221 (manufactured by Merck) was injected to form the liquid crystal layer 16. Further, polarizing plates (not shown) were bonded to both outer surfaces of the substrates 11a and 11b so that the polarization directions of the 2 polarizing plates were orthogonal to each other, thereby producing the liquid crystal display element 10.

(7) Evaluation of liquid Crystal alignment Properties

For the produced rubbed FFS type liquid crystal display element, the liquid crystal alignment property was evaluated in the same manner as in (6) of the example 1-1. As a result, the liquid crystal alignment property in the liquid crystal display element was "good".

(8) Evaluation of Voltage holding ratio and Heat resistance

With respect to the produced rubbed FFS type liquid crystal display element, the Voltage Holding Ratio (VHRBF) was measured in the same manner as in (7) of the example 1-1, and the heat resistance of the liquid crystal display element was evaluated from the rate of change in the voltage holding ratio before and after application of thermal stress in the same manner as in (8) of the example 1-1. As a result, VHR_BFThe content was 99.4%. Further, Δ VHR was 1.6%, and it was judged that the heat resistance was "good".

(9) Unevenness resistance of sealant periphery (frame unevenness resistance)

The frame unevenness resistance was evaluated in the same manner as in (9) of the above-mentioned example 1-1. As a result, the luminance difference of the liquid crystal display element was not visually recognized, and it was judged that the frame unevenness resistance was "excellent".

DC afterimage evaluation was performed in the same manner as in examples 1-1 (10). As a result, the liquid crystal display element had an afterimage erasing time of 2 seconds, and was evaluated as "good".

The evaluation of AC afterimage was carried out in the same manner as in the examples 1-1 (10). In this case, a liquid crystal cell to which a polarizing plate is not attached was also used for evaluation. As a result, the minimum relative transmittance was 0.1%, and the contrast characteristic was judged to be "good".

Example 2-2 to example 2-15 and comparative example 2-1 to comparative example 2-5

Liquid crystal aligning agents were prepared and liquid crystal display elements were manufactured and evaluated in the same manner as in example 2-1, except that the kinds and amounts of the polymers used for the preparation of the liquid crystal aligning agents were as shown in table 4 below. In comparative examples 2 to 4, the liquid crystal alignment was poor, and the liquid crystal cell was not evaluated. The evaluation results are shown in tables 4 and 5 below.

[ Table 4]

[ Table 5]

As shown in tables 3 to 5, the liquid crystal aligning agents containing the polymers obtained by using the compound (C') gave good results with respect to the surface unevenness, transmittance, rubbing resistance and alignment properties of the coating film. In addition, in the liquid crystal display element manufactured by using these liquid crystal aligning agents, good results are obtained with respect to all of the alignment property, voltage holding ratio, heat resistance, frame unevenness resistance, residual image characteristics (DC residual image), and contrast characteristics (AC residual image) of liquid crystal molecules, and various characteristics are simultaneously obtained with good balance.

On the other hand, in comparative example 2-1 in which a diamine having no aromatic amine structure but only a chain structure was used, the image retention characteristics were "poor", and the frame unevenness resistance and the heat resistance were inferior to those of the examples, and thus the object of the present invention was not sufficiently achieved.

In comparative examples 1-1, 2-2 and 2-3 in which diamines having only an aromatic amine structure were used, the liquid crystal display elements were "poor" in heat resistance, frame unevenness resistance and contrast characteristics. Further, the polymer of comparative example 4 using PAm-14 was not sufficiently useful as a liquid crystal display device because of poor storage stability, surface irregularity of a coating film, and transmittance, and poor alignment properties of liquid crystal. Further, in comparative examples 2 to 5, the heat resistance and the frame unevenness resistance were "poor". In addition, considering the transmittance, rubbing resistance and alignment property of the coating film, and the alignment property, voltage holding ratio, heat resistance, frame unevenness resistance, image sticking property and contrast property of the liquid crystal in the liquid crystal display device in a comprehensive manner, any of the comparative examples was inferior to the examples.

Example 3-1: TN type liquid crystal display element

(1) Preparation of liquid crystal aligning agent

50 parts by weight of the polymer (PAm-3) obtained in synthesis examples 2 to 3 and 50 parts by weight of the polymer (PAm-16) obtained in synthesis examples 2 to 16 were dissolved in a mixed solvent of NMP and BC (NMP: BC 50: 50 (weight ratio)) to prepare a solution having a solid content concentration of 6.5 wt%. The solution was sufficiently stirred and then filtered through a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent.

(2) Evaluation of printability

The liquid crystal aligning agent prepared in (1) was applied to the transparent electrode surface of a glass substrate having a transparent electrode including an ITO film using a liquid crystal alignment film printer (manufactured by Nippon ink jet printing (jet) Co., Ltd.), heated (prebaked) on a hot plate at 80 ℃ for 1 minute to remove the solvent, and then heated (postbaked) on a hot plate at 200 ℃ for 10 minutes to form a film having an average thickness of

Coating film of (3). The coating film was observed with a microscope at a magnification of 20 times to examine the presence or absence of uneven printing and pinholes. The evaluation was carried out in the following manner: the case where neither of the uneven printing and the pinholes was observed was evaluated as "good" in printability, the case where at least either of the uneven printing and the pinholes was slightly observed was evaluated as "good" in printability, and the case where at least either of the uneven printing and the pinholes was largely observed was evaluated as "poor" in printability. In the present example, neither uneven printing nor pinholes were observed, and the printability was "good".

(3) Evaluation of transmittance

For the obtained coating film, the transmittance was evaluated in the same manner as in (3) of the example 1-1. As a result, the transmittance of the coating film was 98.4%, which was "good".

(4) Production of TN type liquid crystal cell

Using a liquid crystal alignment film printer (manufactured by Nippon ink jet printing), the (1)) The liquid crystal aligning agent prepared in (1) is coated on the transparent electrode surface of a glass substrate having a transparent electrode comprising an ITO film, and after removing the solvent by heating (prebaking) for 1 minute on a hot plate at 80 ℃, heating (postbaking) for 10 minutes on a hot plate at 200 ℃ to form a film having an average thickness of

Coating film of (3). The coating film was rubbed by a rubbing machine having a roll around which a rayon cloth was wound at a roll rotation speed of 500rpm, a table moving speed of 3 cm/sec and a fluff pressing length of 0.4mm to impart liquid crystal alignment ability. Then, ultrasonic washing was performed in ultrapure water for 1 minute, followed by drying in a clean oven at 100 ℃ for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. Further, the above operation was repeated to obtain a pair of (2) substrates having liquid crystal alignment films.

Next, an epoxy adhesive containing alumina balls having a diameter of 5.5 μm was applied to the outer edge of the surface having the liquid crystal alignment film on one of the pair of substrates, and then the pair of substrates were stacked with the liquid crystal alignment films facing each other and pressure bonded to each other, thereby curing the adhesive. Then, a nematic liquid crystal (MLC-6221, manufactured by Merck) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curable adhesive to manufacture a TN liquid crystal cell.

(5) Evaluation of liquid Crystal alignment Properties

With respect to the liquid crystal cell manufactured in the above (4), the presence or absence of an abnormal region when the voltage of 5V was turned on and off was observed at a magnification of 50 times under crossed nicols using a microscope. Evaluation was performed in the same manner as in (6) of the example 1-1. As a result, the liquid crystal alignment property in the liquid crystal display element was "good".

(6) Evaluation of pretilt Angle stability

In the liquid crystal cell manufactured in the above (4), the angle at which the liquid crystal molecules are tilted from the substrate surface is measured by the crystal rotation method using He — Ne laser light, and this value is used as the initial pretilt angle θ_IN. The crystal rotation method is based on non-patent document 3 (T.J)Scheffer et al, Applied to Journal of Physics (Journal of Applied Physics, J.Appl. Phys.) No. 48, page 1783 (1977), and non-patent document 4(F. Zhongye (F.Nakano) et al, Japanese Journal of Applied Physics, JPN.J.Appl. Phys.) No. 19, page 2013 (1980)).

Then, for the measurement of initial pretilt angle θ_INThe subsequent liquid crystal cell was applied with an alternating voltage of 5V for 100 hours. Then, the pretilt angle was measured again by the same method as described above, and the value was used as the pretilt angle θ after voltage application_AF. These measurement values are substituted into the following equation (EX-4) to obtain the amount of change in pretilt angle (Delta theta (DEG)) before and after voltage application.

Δθ＝|θ_AF-θ_IN| (EX-4)

When Δ θ was less than 3%, the pretilt angle stability was evaluated as "good", when 3% or more and less than 4% were evaluated as "acceptable", and when 4% or more were evaluated as "poor", the pretilt angle change rate of the liquid crystal display element was 1.6%, and the pretilt angle stability was judged as "good".

(7) Evaluation of Voltage holding ratio and Heat resistance

The Voltage Holding Ratio (VHR) was measured in the same manner as in (7) of the example 1-1_BF) Further, in the same manner as in (8) of the above-mentioned embodiment 1-1, the heat resistance of the liquid crystal display device was evaluated from the rate of change in the voltage holding ratio before and after application of the thermal stress. As a result, VHR_BFThe content was 98.6%. In addition, Δ VHR was 2.1%, and heat resistance was judged to be "good".

(8) Unevenness resistance of sealant periphery (frame unevenness resistance)

The frame unevenness resistance was evaluated in the same manner as in (9) of the above-mentioned example 1-1. As a result, the luminance difference of the liquid crystal display element was not visually recognized, and it was judged as "excellent".

(9) Evaluation of residual image characteristics (DC residual image evaluation)

DC afterimage evaluation was performed in the same manner as in examples 1-1 (10). As a result, the liquid crystal display element had an afterimage erasing time of 12 seconds, and was evaluated as "good".

[ example 4-1: VA type liquid crystal display element

(1) Preparation of liquid crystal aligning agent

20 parts by weight of the polymer (PIm-2) obtained in Synthesis example 3-2 and 80 parts by weight of the polymer (PAm-3) obtained in Synthesis example 2-3 were added to NMP and BC to prepare a solution having a solid content of 6.5% by weight and a solvent mixing ratio of NMP to BC of 50 to 50 (weight ratio). The solution was sufficiently stirred and then filtered through a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent.

(2) Evaluation of printability

The printability was examined in the same manner as in (2) of example 3-1 using the liquid crystal aligning agent prepared in (1), and neither of uneven printing and pinholes was observed, and the printability was "good".

(3) Evaluation of transmittance

For the obtained coating film, the transmittance was evaluated in the same manner as in (3) of the example 1-1. As a result, the coating film had a transmittance of 99.2% and was "good".

(4) Manufacture of VA type liquid crystal cell

The prepared liquid crystal aligning agent was coated on a transparent electrode surface of a glass substrate (thickness of 1mm) provided with a transparent electrode including an ITO film using a liquid crystal alignment film printer (manufactured by japan portrait printing (ply)). Then, the film was heated on a hot plate at 80 ℃ for 1 minute (prebaking), and further heated on a hot plate at 200 ℃ for 60 minutes (postbaking) to form an average film thickness of

The coating film (liquid crystal alignment film) of (1). This operation was repeated to obtain a pair of (2) glass substrates each having a liquid crystal alignment film on a transparent conductive film. Then, one of the substrates was coated with an epoxy resin adhesive containing alumina balls having a diameter of 5.5 μm on the outer edge of the surface having the liquid crystal alignment film, and then the surfaces were opposed to each otherThe pair of substrates are overlapped and pressed to cure the adhesive. Then, a nematic liquid crystal (MLC-6608, manufactured by Merck) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to manufacture a VA liquid crystal cell.

(5) Evaluation of liquid Crystal alignment, Voltage holding ratio and Heat resistance

As a result of evaluating the liquid crystal alignment properties of the liquid crystal cell produced in (4) above in the same manner as in (6) of example 1-1, the liquid crystal alignment properties of the liquid crystal cell were "good". In addition, the Voltage Holding Ratio (VHR) was measured in the same manner as in (7) of example 1-1_BF) And the heat resistance (rate of change in voltage holding ratio before and after application of thermal stress) was evaluated in the same manner as in (8) of the above-described example 1-1. As a result, VHR_BFThe content was 99.0%. In addition, Δ VHR was 2.3%, and heat resistance was judged to be "good".

(6) Unevenness resistance of sealant periphery (frame unevenness resistance)

The frame unevenness resistance was evaluated in the same manner as in (9) of the above-mentioned example 1-1. As a result, the luminance difference of the liquid crystal cell was not visually recognized, and it was determined to be "good".

[ example 5-1: retardation film

(1) Preparation of liquid crystal aligning agent

100 parts by weight of the polymer (PAm-1) obtained in synthesis example 2-1 and 10 parts by weight of the polymer (PSi-1) obtained in synthesis example 4-1 were dissolved in a mixed solvent containing NMP and BC (NMP: BC 50: 50 (weight ratio)) to prepare a solution having a solid content concentration of 3.5 wt%. The solution was filtered through a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent.

(2) Production of retardation film

The prepared liquid crystal alignment agent was applied to one surface of a TAC film as a substrate using a bar coater, and baked in an oven at 120 ℃ for 2 minutes to form a coating film having a film thickness of 100 nm. Then, the surface of the coating film was irradiated perpendicularly from the substrate normal line with polarized violet containing 313nm bright line using Hg-Xe lamp and a Glan Taylor prismOuter line 10mJ/cm². Then, a polymerizable liquid crystal (RMS03-013C, manufactured by Merck) was filtered through a filter having a pore size of 0.2 μm, and the resultant polymerizable liquid crystal was applied to the coating film after the light irradiation by a bar coater to form a coating film of the polymerizable liquid crystal. After baking the film in an oven at 50 ℃ for 1 minute, the film was irradiated with unpolarized ultraviolet light 1,000mJ/cm containing 365nm bright rays from the vertical direction using an Hg-Xe lamp²The polymerizable liquid crystal is cured to form a liquid crystal layer, thereby producing a retardation film.

(3) Evaluation of liquid Crystal alignment Properties

The retardation film produced in (2) was observed for the presence or absence of an abnormal region by visual observation under crossed nicols and a polarization microscope (magnification of 2.5 times), and thereby evaluated for liquid crystal alignment properties (photo-alignment properties). The evaluation was carried out in the following manner: the liquid crystal alignment property was evaluated as "good" when the alignment property was good under visual observation and no abnormal region was observed with a polarization microscope; the case where no abnormal region was observed by visual observation but the abnormal region was observed by a polarization microscope was evaluated as "good" liquid crystal alignment property; the abnormal region observed visually or by a polarization microscope was evaluated as "poor" liquid crystal alignment. As a result, the retardation film was evaluated to have "good liquid crystal alignment properties".

(4) Adhesion property

The adhesion between the coating film formed by the liquid crystal aligning agent and the substrate was evaluated by using the retardation film produced in (2). First, slits were cut into the liquid crystal layer side surface of the retardation film with a dicing blade using an equally-spaced spacer with a guide, and 10 × 10 lattice patterns were formed in a range of 1cm × 1 cm. The depth of each notch is set to be half of the thickness of the substrate from the surface of the liquid crystal layer. Then, a cellophane sheet is adhered so as to cover the entire surface of the lattice pattern, and then the cellophane sheet is peeled. The cut portion of the grid pattern after peeling was observed by visual observation under crossed nicols to evaluate the adhesiveness. The evaluation was carried out in the following manner: the case where no peeling was confirmed at the portion along the cut line and the intersection portion of the lattice pattern was evaluated as "good adhesion"; the number of lattices in which peeling was observed in the portion was less than 15% with respect to the number of the whole lattice pattern was evaluated as "ok"; the case where the number of lattices from which peeling was observed in the above-mentioned portion was 15% or more with respect to the number of the whole lattice pattern was evaluated as "poor adhesion". As a result, the retardation film had "good adhesion".

Claims

1. A liquid crystal aligning agent characterized in that: comprising a polymer (P) obtained by reacting at least one compound (C') selected from the group consisting of a compound (C) and a compound (C1), wherein the polymer (P) is at least one polymer selected from the group consisting of a polyamic acid, a polyamic acid ester, and a polyimide, and the compound (C) is a compound represented by the following formula (1),

in the formula (1), A¹And A³Each independently being a hydrogen atom or a 1-valent organic radical, A²And A⁴Each independently is a single bond or a 2-valent organic group; b is¹And B²Each independently is a single bond or a 2-valent organic group; wherein, in B¹In the case of a single bond, A¹And A²At least 1 of which is bonded to the nitrogen atom with an aromatic ring, in B¹In the case of a 2-valent organic radical, A¹、A²And B¹At least 2 of which are bonded to the nitrogen atom with an aromatic ring; in B²In the case of a single bond, A³And A⁴At least 1 of which is bonded to the nitrogen atom with an aromatic ring, in B²In the case of a 2-valent organic radical, A³、A⁴And B²At least 2 of which are bonded to the nitrogen atom with an aromatic ring; l is¹The polymer (P) comprises a 2-valent chain hydrocarbon group having 6 or more carbon atoms and at least 1 methylene group in the chain hydrocarbon group is replaced by-O-, -S-, -CO-, -NR-, -NRCO-, -COO--COS-or-Si (CH)₃)₂-a 2-valent group of a chain structure in the group consisting of substituted 2-valent groups, wherein R is a hydrogen atom or a 1-valent organic group; wherein, at L¹When the alkyl group is an alkanediyl group having 6 to 10 carbon atoms, A¹And A³At least any one of (A) is a 1-valent organic group, or B¹And B²At least any one of (a) is a 2-valent organic group,

the compound (C1) is a compound represented by the following formula (1-3),

in the formula (1-3), A⁷Is a hydrogen atom or a 1-valent organic radical, A⁸And A⁹Each independently represents a single bond, a 2-valent hydrocarbon group or a 2-valent group in which 1 or more functional groups-O-, -COO-, -CO-, -NHCO-or-S-are introduced between carbon-carbon bonds in the 2-valent hydrocarbon group, and hydrogen atoms bonded to carbon atoms of the group may be substituted with halogen atoms or hydroxyl groups; wherein A is⁷、A⁸And A⁹At least 2 of which are bonded to the nitrogen atom with an aromatic ring; a reactive group participating in polymerization is not bonded to an aromatic ring group in an aromatic amine structure in which 2 or 3 aromatic ring groups are bonded to the same nitrogen atom, the reactive group being an acid anhydride group or a primary amino group, L⁴Is selected from 2-valent chain hydrocarbon group with 1-5 carbon atoms, at least 1 methylene in the chain hydrocarbon group is replaced by-O-, -S-, -CO-, -NR³-、-NR³CO-, -COO-, -COS-or-Si (CH)₃)₂A 2-valent radical formed by substitution, -O-, -S-, -CO-, -NR³CO-, -COO-, -COS-, and-Si (CH)₃)₂-a structure of the group consisting of, wherein R³Is a hydrogen atom or a 1-valent organic radical, L⁵Is a 2-valent chain hydrocarbon group having 1 to 20 carbon atoms, wherein at least 1 methylene group in the chain hydrocarbon group is replaced by-O-, -S-, -CO-, -NR⁴-、-NR⁴CO-, -COO-, -COS-or-Si (CH)₃)₂A 2-valent radical formed by substitution, -O-, -S-, -CO-, -NR⁴CO-, -COO-, -COS-, or-Si (CH)₃)₂-, wherein R⁴Is a hydrogen atom or a 1-valent organic group.

2. The liquid crystal aligning agent according to claim 1, wherein: b is¹And said B²At least any one of (a) and (b) is a single bond.

3. The liquid crystal aligning agent according to claim 1, wherein: said L¹Is represented by the following formula (2),

in the formula (2), L²And L³Each independently selected from a 2-valent chain hydrocarbon group having 6 or more carbon atoms, and at least 1 methylene group in the chain hydrocarbon group is replaced by-O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-or-Si (CH)₃)₂-a chain structure in the group consisting of substituted 2-valent groups, wherein R is a hydrogen atom or a 1-valent organic group; q is a 2-valent group represented by the following formula (3) or formula (4); n is an integer of 0 to 4; "+" indicates a bond;

in the formula (3), A⁵Is a hydrogen atom or a 1-valent organic group; r¹And R²The substituents may be the same as or different from each other; "+" indicates a bond;

in the formula (4), A⁶Is a hydrogen atom or a 1-valent organic group; "" indicates a bond.

4. The liquid crystal aligning agent according to claim 1, wherein: the compound (C) is a compound represented by the following formula (1-1),

in the formula (1-1), L¹¹At least 1 methylene group in a chain hydrocarbon group having 2 valences of 6 or more carbon atoms is replaced by-O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-or-Si (CH)₃)₂-a 2-valent radical of a substituted radical, wherein R is a hydrogen atom or a 1-valent organic radical; a. the¹、A²、A³、A⁴、B¹And B²Is the same as the formula (1); wherein, at L¹¹In the case of having C1-5 alkanediyl group, A¹And A³At least any one of (A) is a hydrogen atom, or B¹And B²At least any one of (a) and (b) is a 2-valent organic group.

5. The liquid crystal aligning agent according to claim 1, wherein: the compound (C) is a compound represented by the following formula (1-2),

in the formula (1-2), L¹²A 2-valent group containing a 2-valent chain hydrocarbon group having 6 or more carbon atoms; a. the¹、A²、A³、A⁴、B¹And B²Is as defined for formula (1).

6. The liquid crystal aligning agent according to claim 1, wherein: the polymer (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide obtained by reacting tetracarboxylic dianhydride with diamine containing the compound (C'), and is characterized in that

The tetracarboxylic dianhydride comprises 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentyl acetic dianhydride, 1,3,3a,45,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-c]Furan-1, 3-dione, 1,3,3a,4,5,9 b-hexahydro-8-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-c]Furan-1, 3-dione, 3-oxabicyclo [3.2.1]Octane-2, 4-dione-6-spiro-3 ' - (tetrahydrofuran-2 ',5' -dione), 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, 3,5, 6-tricarboxyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4, 9-dioxatricyclo [5.3.1.0 ]^2,6]Undecane-3, 5,8, 10-tetraone, bicyclo [3.3.0]]Octane-2, 4,6, 8-tetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, cyclopentanetetracarboxylic dianhydride, 1, 3-propanediol bis (trimellitic anhydride ester), and pyromellitic dianhydride.

7. The liquid crystal aligning agent according to claim 1, wherein: the molecular weight of the compound (C') is 1,000 or less.

8. A liquid crystal alignment film characterized in that: which is formed using the liquid crystal aligning agent according to any one of claims 1 to 7.

9. A liquid crystal display element, characterized in that: comprising the liquid crystal alignment film according to claim 8.

10. A phase difference film, characterized in that: comprising the liquid crystal alignment film according to claim 8.

11. A method for producing a retardation film, comprising: a step of applying the liquid crystal aligning agent according to any one of claims 1 to 7 to a substrate to form a coating film, a step of irradiating the coating film with light; and a step of applying a polymerizable liquid crystal to the coating film irradiated with light and curing the coating film.

12. A polymer selected from the group consisting of polyamic acids, polyamic acid esters, and polyimides, wherein the polymer is a polymer selected from the group consisting of polyamic acids, polyamic acid esters, and polyimides

Which is obtained by reacting at least one compound selected from the group consisting of tetracarboxylic dianhydrides, tetracarboxylic diester compounds and tetracarboxylic diester dihalides with a diamine containing at least one selected from the group consisting of compounds represented by the following formula (1-1), compounds represented by the following formula (1-2) and compounds represented by the following formula (1-3),

in the formula (1-1), A¹And A³Each independently being a hydrogen atom or a 1-valent organic radical, A²And A⁴Each independently is a single bond or a 2-valent organic group; b is¹And B²Each independently is a single bond or a 2-valent organic group; wherein, in B¹In the case of a single bond, A¹And A²At least 1 of which is bonded to the nitrogen atom with an aromatic ring, in B¹In the case of a 2-valent organic radical, A¹、A²And B¹At least 2 of which are bonded to the nitrogen atom with an aromatic ring; in B²In the case of a single bond, A³And A⁴At least 1 of which is bonded to the nitrogen atom with an aromatic ring, in B²In the case of a 2-valent organic radical, A³、A⁴And B²At least 2 of which are bonded to the nitrogen atom with an aromatic ring; l is¹¹At least 1 methylene group in a chain hydrocarbon group having 2 valences of 6 or more carbon atoms is replaced by-O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-or-Si (CH)₃)₂-a 2-valent radical of a substituted radical, wherein R is a hydrogen atom or a 1-valent organic radical; wherein, at L¹¹In the case of having C1-5 alkanediyl group, A¹And A³At least any one of (A) is a hydrogen atom, or B¹And B²At least any one of (a) is a 2-valent organic group;

in the formula (1-2), L¹²A 2-valent group containing a 2-valent chain hydrocarbon group having 6 or more carbon atoms; a. the¹、A²、A³、A⁴、B¹And B²Is the same as the formula (1-1); wherein, at L¹²When the alkyl group is an alkanediyl group having 6 to 10 carbon atoms, A¹And A³At least any one of (A) is a 1-valent organic group, or B¹And B²At least any one of (a) is a 2-valent organic group;

in the formula (1-3), A⁷Is a hydrogen atom or a 1-valent organic radical, A⁸And A⁹Each independently represents a single bond, a 2-valent hydrocarbon group or a 2-valent group in which 1 or more functional groups-O-, -COO-, -CO-, -NHCO-or-S-are introduced between carbon-carbon bonds in the 2-valent hydrocarbon group, and hydrogen atoms bonded to carbon atoms of the group may be substituted with halogen atoms or hydroxyl groups; wherein A is⁷、A⁸And A⁹At least 2 of which are bonded to the nitrogen atom with an aromatic ring; a reactive group participating in polymerization is not bonded to an aromatic ring group in an aromatic amine structure in which 2 or 3 aromatic ring groups are bonded to the same nitrogen atom, and the reactive group is an acid anhydride group or a primary amino group; l is⁴Is a 2-valent chain hydrocarbon group having 1 to 5 carbon atoms, wherein at least 1 methylene group in the chain hydrocarbon group is replaced by-O-, -S-, -CO-, -NR³-、-NR³CO-, -COO-, -COS-or-Si (CH)₃)₂-substituted 2-valent radicals, -O-, -S-, -CO-, -NR-³CO-, -COO-, -COS-, or-Si (CH)₃)₂-, wherein R³Is a hydrogen atom or a 1-valent organic group; l is⁵Is a 2-valent chain hydrocarbon group having 1 to 20 carbon atoms, wherein at least 1 methylene group in the chain hydrocarbon group is replaced by-O-, -S-, -CO-, -NR⁴-、-NR⁴CO-, -COO-, -COS-or-Si (CH)₃)₂A 2-valent radical formed by substitution, -O-, -S-, -CO-, -NR⁴CO-, -COO-, -COS-, or-Si (CH)₃)₂-, wherein R⁴Is hydrogenAn atom or a 1-valent organic group.

13. A compound characterized by being represented by the following formula (1-1),

in the formula (1-1), A¹And A³Each independently being a hydrogen atom or a 1-valent organic radical, A²And A⁴Each independently is a single bond or a 2-valent organic group; b is¹And B²Each independently is a single bond or a 2-valent organic group; wherein, in B¹In the case of a single bond, A¹And A²At least 1 of which is bonded to the nitrogen atom with an aromatic ring, in B¹In the case of a 2-valent organic radical, A¹、A²And B¹At least 2 of which are bonded to the nitrogen atom with an aromatic ring; in B²In the case of a single bond, A³And A⁴At least 1 of which is bonded to the nitrogen atom with an aromatic ring, in B²In the case of a 2-valent organic radical, A³、A⁴And B²At least 2 of which are bonded to the nitrogen atom with an aromatic ring; l is¹¹At least 1 methylene group in a chain hydrocarbon group having 2 valences of 6 or more carbon atoms is replaced by-O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-or-Si (CH)₃)₂-a 2-valent radical of a substituted radical, wherein R is a hydrogen atom or a 1-valent organic radical; wherein, at L¹¹In the case of having C1-5 alkanediyl group, A¹And A³At least any one of (A) is a hydrogen atom, or B¹And B²At least any one of (a) and (b) is a 2-valent organic group.

14. A compound characterized by being represented by the following formula (1-2),

in the formula (1-2), A¹And A³Each independently being a hydrogen atom or a 1-valent organic radical, A²And A⁴Each independently is a single bond or a 2-valent organic group; b is¹And B²Each independently is a single bond or a 2-valent organic group; wherein, in B¹In the case of a single bond, A¹And A²At least 1 of which is bonded to the nitrogen atom with an aromatic ring, in B¹In the case of a 2-valent organic radical, A¹、A²And B¹At least 2 of which are bonded to the nitrogen atom with an aromatic ring; in B²In the case of a single bond, A³And A⁴At least 1 of which is bonded to the nitrogen atom with an aromatic ring, in B²In the case of a 2-valent organic radical, A³、A⁴And B²At least 2 of which are bonded to the nitrogen atom with an aromatic ring; l is¹²A 2-valent group containing a 2-valent chain hydrocarbon group having 6 or more carbon atoms; wherein, at L¹²When the alkyl group is an alkanediyl group having 6 to 10 carbon atoms, A¹And A³At least any one of (A) is a 1-valent organic group, or B¹And B²At least any one of (a) and (b) is a 2-valent organic group.

15. A compound characterized by being represented by the following formula (1-3),

in the formula (1-3), A⁷Is a hydrogen atom or a 1-valent organic radical, A⁸And A⁹Each independently represents a single bond, a 2-valent hydrocarbon group or a 2-valent group in which 1 or more functional groups-O-, -COO-, -CO-, -NHCO-or-S-are introduced between carbon-carbon bonds in the 2-valent hydrocarbon group, and hydrogen atoms bonded to carbon atoms of the group may be substituted with halogen atoms or hydroxyl groups; wherein A is⁷、A⁸And A⁹At least 2 of which are bonded to the nitrogen atom with an aromatic ring; a reactive group participating in polymerization is not bonded to the aromatic ring group in the aromatic amine structure in which 2 or 3 aromatic ring groups are bonded to the same nitrogen atom, and the reactive group is an acid anhydride group or a mono-groupA secondary amino group; l is⁴Is a 2-valent chain hydrocarbon group having 1 to 5 carbon atoms, wherein at least 1 methylene group in the chain hydrocarbon group is replaced by-O-, -S-, -CO-, -NR³-、-NR³CO-, -COO-, -COS-or-Si (CH)₃)₂-substituted 2-valent radicals, -O-, -S-, -CO-, -NR-³CO-, -COO-, -COS-, or-Si (CH)₃)₂-, wherein R³Is a hydrogen atom or a 1-valent organic group; l is⁵Is a 2-valent chain hydrocarbon group having 1 to 20 carbon atoms, wherein at least 1 methylene group in the chain hydrocarbon group is replaced by-O-, -S-, -CO-, -NR⁴-、-NR⁴CO-, -COO-, -COS-or-Si (CH)₃)₂A 2-valent radical formed by substitution, -O-, -S-, -CO-, -NR⁴CO-, -COO-, -COS-, or-Si (CH)₃)₂-, wherein R⁴Is a hydrogen atom or a 1-valent organic group.