KR20220014816A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal element - Google Patents

Abstract

An objective of the present invention is to provide a liquid crystal aligning agent which is difficult to cause afterimage, provides excellent spreadability, and acquires a liquid crystal alignment film with high mechanical strength. According to the present invention, the liquid crystal aligning agent comprises: a polymer A including a structural unit U1 and not including a structural unit U2; and a polymer B including the structural unit U2 and a structural unit U3. The Structural unit U1 is a structural unit derived from diamine having a partial structure represented by the formula 1. The structural unit U2 is a structural unit derived from diamine having a partial structure represented by the Formula 2. The structural unit U3 is a structural unit derived from diamine having partial structure Y-CH2n- and the like. In the Formula 1, X^1 and X^2 are divalent aromatic ring groups, R^1 and R^2 are single-bond C1 to C4 alkanediyl group, Y^1 and Y^2 are -NR^3-CO-, and Z^1 is a divalent organic group or the like. In the Formula 2, A^1 and A^2 are divalent aromatic ring groups, and B^1 is -NR^4- or a divalent aromatic heterocyclic group.

Description

A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal element {LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT FILM AND LIQUID CRYSTAL ELEMENT}

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal element.

As a liquid crystal material of a liquid crystal element, a negative liquid crystal is used in a liquid crystal element such as a VA drive method or an MVA drive method, and a liquid crystal element such as a TN type, IPS (In-Plane Switching) drive method, FFS (Fringe Field Switching) drive method, etc. In this case, a positive liquid crystal is used. Moreover, in recent years, in order to achieve further high definition of a liquid crystal element, it is also proposed to use a negative liquid crystal in the liquid crystal element of an IPS drive system or an FFS drive system (for example, refer patent document 1).

DESCRIPTION OF RELATED ART In recent years, a liquid crystal element is applied to the wide use from comparatively large display apparatuses, such as a liquid crystal TV and an information display, to small display apparatuses, such as a smart phone. With the multipurpose use of such a liquid crystal element, further improvement of the quality of a liquid crystal element is calculated|required. Then, conventionally, while making a liquid crystal aligning agent contain the polymer which has nitrogen-containing metaarylene structure, a resistance value is low by this, and while obtaining the liquid crystal aligning film with high transparency, the burning resulting from an accumulation|storage electric charge (DC residual image) ) is proposed (for example, refer to Patent Document 2).

International Publication No. 2016/152928 International Publication No. 2019/093037

In the residual image which generate|occur|produces in a liquid crystal element, other than a DC residual image, there exists an AC residual image resulting from the orientation direction of a liquid crystal shifting|deviate from an initial stage orientation. In order to suppress generation|occurrence|production of an afterimage and aim at the further high definition of a liquid crystal element, in addition to a DC afterimage, it is calculated|required that it can suppress also about an AC afterimage. Moreover, when a metaarylene structure is introduce|transduced into a polymer like the technique of patent document 2, when a rigid structure is introduce|transduced into a principal chain, the solubility of a polymer falls and we are anxious that the applicability|paintability of a liquid crystal aligning agent falls. Moreover, when a case where a liquid crystal aligning film is obtained by the rubbing method, suppressing a yield fall, etc. are considered, high mechanical strength is calculated|required by the film|membrane formed using a liquid crystal aligning agent. However, it is difficult to make it satisfy|fill these some characteristics simultaneously, and there exists room for further improvement in a liquid crystal aligning agent.

This invention is made in view of the said subject, It is hard to generate|occur|produce an afterimage, and applicability|paintability is favorable, and its main object is to provide the liquid crystal aligning agent from which the liquid crystal aligning film with high dynamic strength can be obtained.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject, and by using the multiple types of polymers from which molecular structures differ, discovered that the said subject could be solved, and came to complete this invention. Specifically, the present invention provides the following means.

<1> containing a polymer [A] having the following structural unit (U1) and not having the following structural unit (U2), and a polymer [B] having the following structural unit (U2) and the following structural unit (U3); liquid crystal aligning agent.

Structural unit (U1): Structural unit derived from diamine which has a partial structure represented by following formula (1)

Structural unit (U2): Structural unit derived from diamine which has a partial structure represented by following formula (2)

Structural unit (U3): a structural unit derived from a diamine having the following partial structure Y

Partial structure Y: In the structure represented by -(CH ₂ ) _n - (where n is an integer of 1 to 20), -(CH ₂ ) _n+1 - in the structure represented by -, any methylene group is -O-, -S-, -COO-, -NR ⁷ -, -NR ⁷ -CO-, -NR ⁷ -COO-, -NR ⁷ -CO-NR ⁸ -, or a structure substituted with a nitrogen-containing non-aromatic heterocyclic group (provided that R ⁷ and R ⁸ is each independently a hydrogen atom or a monovalent organic group, when n is 2 or more, -O-, -S-, -COO-, -NR ⁷ -, -NR ⁷ -CO-, -NR ⁷ -COO-, -NR ⁷ -CO-NR ⁸ - and nitrogen-containing non-aromatic heterocyclic groups are not adjacent to each other), -O-, -S-, -COO-, -NR ⁷ -CO-, -NR ⁷ -COO-, or -NR ⁷ -CO-NR ⁸ -

(In formula (1), X ¹ and X ² are each independently a divalent aromatic ring group. However, in the aromatic ring of X ¹ , the bonding position of R ¹ and the bonding position of the group bonded to “*” A substituent is not bonded to a position different from that, and to the aromatic ring of X ² , a substituent is not bonded to a position different from the bonding position of R ² and the bonding position of a group bonding to "*". ¹ and R ² are each independently a single bond, an alkanediyl group having 1 to 10 carbon atoms, or a substituted alkanediyl group having 1 to 10 carbon atoms Y ¹ and Y ² are each independently * ¹ -NR ³ -CO- or * ¹ -CO-NR ³ -. R ³ is a hydrogen atom or a monovalent organic group. “* ¹ ” represents a bond with Z ^{1. Z 1 is} a single bond or a divalent organic group m is 0 or 1. When m is 0, at least one of R ¹ and R ² is an alkanediyl group having 1 to 10 carbon atoms or a substituted alkanediyl group. “*” indicates a bond.)

(In formula (2), A ¹ and A ² are each independently a divalent aromatic ring group. B ¹ is -NR ⁴ - or a divalent aromatic heterocyclic group. When B ¹ is a divalent aromatic heterocyclic group, R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group When B ¹ is -NR ⁴ -, R ⁴ , R ⁵ and R ⁶ are (i) or (ii) below.

(i) R ⁴ is a hydrogen atom or a monovalent organic group. R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent organic group, or R ⁵ and R ⁶ combine with each other to represent a ring structure constituted with A ¹ , -NR ⁴ - and A ² .

(ii) R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, or a ring structure in which R ⁴ and R ⁵ combine with each other to form a ring structure together with A ¹ and a nitrogen atom. R ⁶ is a hydrogen atom or a monovalent organic group.

"*" indicates that it is a bond.)

<2> The liquid crystal aligning film formed with the liquid crystal aligning agent of said <1>.

<3> A liquid crystal element provided with the liquid crystal aligning film of said <2>.

ADVANTAGE OF THE INVENTION According to the liquid crystal aligning agent of this invention, an afterimage is hard to generate|occur|produce, it is excellent in applicability|paintability, and the liquid crystal aligning film with high dynamic strength can be obtained. According to the liquid crystal aligning agent of this invention especially, the liquid crystal aligning film which can make AC afterimage characteristic and DC afterimage characteristic compatible can be obtained.

(Form for implementing the invention)

The liquid crystal aligning agent of this indication contains a polymer [A] and the polymer [B] which is a polymer different from a polymer [A]. Below, each component contained in the liquid crystal aligning agent of this indication, and the other component mix|blended arbitrarily as needed are demonstrated.

In addition, in this specification, a "hydrocarbon group" is a meaning including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" means a straight-chain hydrocarbon group and a branched hydrocarbon group composed of only a chain structure without a cyclic structure in the main chain. However, saturated or unsaturated may be sufficient. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only the structure of an alicyclic hydrocarbon as a ring structure and not containing an aromatic ring structure. However, it is not necessary to be constituted only by the structure of an alicyclic hydrocarbon, and those having a chain structure in a part thereof are also included. An "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be constituted by only the aromatic ring structure, and a chain structure or a structure of an alicyclic hydrocarbon may be included in a part thereof. "Structural unit" refers to a unit mainly constituted by the main chain structure, and includes at least two or more units in the main chain structure. About each component and each compound, unless otherwise indicated, you may use individually by 1 type and may use in combination of 2 or more type.

<Polymer [A]>

Polymer [A] is a polymer which has a structural unit (U1) derived from the diamine (henceforth "specific diamine (A)") which has a partial structure represented by following formula (1).

(In formula (1), X ¹ and X ² are each independently a divalent aromatic ring group. However, in the aromatic ring of X ¹ , the bonding position of R ¹ and the bonding position of the group bonded to “*” A substituent is not bonded to a position different from that, and to the aromatic ring of X ² , a substituent is not bonded to a position different from the bonding position of R ² and the bonding position of a group bonding to "*". ¹ and R ² are each independently a single bond, an alkanediyl group having 1 to 10 carbon atoms, or a substituted alkanediyl group having 1 to 10 carbon atoms Y ¹ and Y ² are each independently * ¹ -NR ³ -CO - or * ¹ -CO-NR ³ -. R ³ is a hydrogen atom or a monovalent organic group. "* ¹ " represents a bond with Z ^{1. Z 1 is} a single bond or a divalent organic group m is 0 or 1. At least one of R ¹ and R ² is an alkanediyl group having 1 to 10 carbon atoms or a substituted alkanediyl group. “*” represents a bond.)

・Structural unit (U1)

The structural unit (U1) is a structural unit derived from diamine containing two aromatic rings and at least one amide bond (-NR ³ -CO-). In the formula (1), the divalent aromatic ring group of X ¹ and X ² is preferably an aromatic hydrocarbon group. Specific examples of X ¹ and X ² include groups obtained by removing any two hydrogen atoms bonded to carbon atoms constituting rings of aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring and an anthracene ring.

In addition, the aromatic ring which X< ¹ > and X< ² > has does not have a substituent. That is, the substituent is not couple|bonded with the aromatic ring which X< ¹ > has at the position different from the bond position of R< ¹ > and the bond position of the group couple|bonded with the bond shown by "*". Moreover, similarly, also in the aromatic ring which X2 has, a substituent is not ^couple |bonded with the position different from the bonding position of the bonding position with ^R2 , and the bonding position of the group couple|bonded with the bond shown by "*".

A phenylene group is preferable and a 1, 4- phenylene group is especially preferable as the divalent aromatic ring group of X< ¹ > and X< ² > from a viewpoint of aiming at densification of a liquid crystal aligning film, and making the reduction effect of an afterimage and the mechanical strength of a film|membrane high.

When R ¹ and R ² are an alkanediyl group having 1 to 10 carbon atoms, R ¹ and R ² are methylene group, ethylene group, 1,3-propanediyl group, 1,4-butanediyl group, 1,5- linear alkanediyl groups such as pentanediyl groups; and branched alkanediyl groups such as 1,2-propanediyl group, 1,2-butanediyl group and 2-methyl-1,3-propanediyl group. When R ¹ and R ² are a substituted alkanediyl group having 1 to 10 carbon atoms, examples of the substituent include a halogen atom, a hydroxyl group, an amino group, a cyano group, an alkoxy group, a protected hydroxyl group, and a protected amino group.

At least one of R ¹ and R ² is preferably an alkanediyl group having 1 to 10 carbon atoms or a substituted alkanediyl group having 1 to 10 carbon atoms, and R It is preferable that both ¹ and ^R2 are a C1-C10 alkanediyl group or a C1-C10 substituted alkanediyl group. From the point which shows favorable voltage retention characteristic and liquid-crystal orientation, 1-8 are preferable and, as for carbon number of R< ¹ > and R< ² >, C2-C8 is more preferable. It is preferable that liquid-crystal orientation can be made high and R< ¹ > and R< ² > are linear at the point with the high effect of afterimage reduction.

Y ¹ and Y ² are amide bonds (* ¹ -NR ³ -CO- or * ¹ -CO-NR ³ -). It is preferable that the monovalent organic group of R< ³ > is a C1-C10 monovalent|monohydric hydrocarbon group, or that it is a group (protecting group) which generate|occur|produces a hydrogen atom by desorption. When R ³ is a monovalent hydrocarbon group, the monovalent hydrocarbon group is preferably an alkyl group or phenyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

When R ³ is a protecting group, the protecting group is preferably a monovalent group that is released by heat, and examples thereof include a carbamate protecting group, an amide protecting group, an imide protecting group, and a sulfonamide protecting group. Among these, a carbamate-type protecting group is preferable from the viewpoint of high desorption property by heat, and specific examples thereof include a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, Allyloxycarbonyl group, 2-(trimethylsilyl)ethoxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, etc. are mentioned. From the viewpoints of excellent thermal detachability and the ability to reduce the residual amount in the film of the deprotected portion, a tert-butoxycarbonyl group (Boc group) is particularly preferable among these.

R ³ is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a protecting group, and particularly preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a tert-butoxycarbonyl group.

Z ¹ is a single bond or a divalent organic group. It is preferable that Z< ¹ > is a divalent organic group at the point which can make the voltage preservation characteristic of a liquid crystal element, and the liquid-crystal orientation high.

When Z ¹ is a divalent organic group, the divalent organic group is a divalent hydrocarbon group having 1 to 20 carbon atoms and -O-, -S- or -NR ³ - (provided that between the carbon-carbon bonds of the hydrocarbon group, and R ³ is a divalent group having the same meaning as R ³ in Y ¹ and Y ² ). Moreover, Z1 is ^couple |bonded with the hydrocarbon group with respect to ^the amide bond ^of Y1 and Y2.

From the viewpoint of making the solubility of the polymer [A] high, the divalent organic group of Z ¹ is, among these, a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a chain A divalent group having -O-, -S- or -NR ³ - between the carbon-carbon bonds of the hydrocarbon group is preferable, and an alkanediyl group having 1 to 20 carbon atoms or a cycloalkylene group having 4 to 12 carbon atoms is particularly preferable. .

1-12 are preferable and, as for carbon number of Z< ¹ >, 1-10 are more preferable.

m is 0 or 1, and 1 is preferable at the point which can make the reduction effect of an AC afterimage higher.

It is preferable that the specific diamine (A) is an aromatic diamine, and it is especially preferable that it is an aromatic diamine which has a structure which can introduce|transduce the partial structure represented by said Formula (1) into the main chain of a polymer [A]. It is especially preferable that specific diamine (A) is a compound specifically, represented by a following formula (DA). In addition, the "main chain" means the part of the "stem" which consists of the chain of the longest atom in a polymer. It is permissible for this "stem" part to contain a ring structure. For example, "having a specific structure in the main chain" means that the specific structure constitutes a part of the main chain. A "side chain" means the part branched from the "stem" of a polymer.

(In formula (DA), R ¹ , R ² , Y ¹ , Y ² , Z ¹ and m have the same meaning as in Formula (1) above.)

In the formula (DA), the description of the formula (1) applies to the examples and preferred examples of R ¹ , R ² , Y ¹ , Y ² , Z ¹ and m.

As a specific example of a specific diamine (A), the compound etc. which are represented by each of a following formula (DA-1) - a formula (DA-23) are mentioned.

(In the formula, "Boc" represents a tert-butoxycarbonyl group.)

The polymer [A] may be a polymer having a structural unit (U1), but since a liquid crystal aligning film with high affinity and mechanical strength with liquid crystal and high reliability can be formed, polyamic acid, polyamic acid ester, and polyamic acid It is preferable that it is at least 1 sort(s) chosen from the group which consists of mids. When the polymer [A] is at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, the partial structure represented by the formula (1) can be introduced into the main chain of the polymer [A]. Moreover, when the partial structure represented by said Formula (1) is introduce|transduced into the main chain of a polymer, the reduction of an afterimage and the improvement effect of a film|membrane strength can be made higher, and it is suitable.

(polyamic acid)

When the polymer [A] is polyamic acid, the polyamic acid (hereinafter also referred to as "polyamic acid [A]") is, for example, a reaction between tetracarboxylic dianhydride and a diamine compound containing a specific diamine (A). can be obtained by doing

・Tetracarboxylic acid dianhydride

As tetracarboxylic dianhydride used for the synthesis|combination of polyamic acid [A], aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. Specific examples thereof include 1,2,3,4-butanetetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, and the like as aliphatic tetracarboxylic dianhydride; As alicyclic tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3 ,5-tricarboxycyclopentylacetic acid dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan- 1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1 ,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2 anhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride My back; As aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycolbisanhydrotrimellitate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, etc.; In addition to those mentioned respectively, the tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 can be used. As tetracarboxylic dianhydride, 1 type can be used individually or in combination of 2 or more types.

The tetracarboxylic dianhydride used for the synthesis|combination of polyamic acid [A] has high solubility with respect to a solvent, and since the liquid crystal aligning film which shows favorable electrical properties and a low residual image characteristic can be obtained, aliphatic tetracarboxylic dianhydride and alicyclic It is preferable to contain the at least 1 sort(s) of compound chosen from the group which consists of formula tetracarboxylic dianhydride, and it is more preferable to contain alicyclic tetracarboxylic dianhydride. The use ratio of the alicyclic tetracarboxylic dianhydride is preferably 20 mol% or more, more preferably 40 mol% or more, with respect to the total amount of tetracarboxylic dianhydride used for the synthesis of polyamic acid [A], It is more preferable that it is 50 mol% or more.

・Diamine compound

The diamine compound used for the synthesis of the polyamic acid [A] may be only the specific diamine (A), but together with the specific diamine (A), a diamine different from the specific diamine (A) (hereinafter also referred to as “another diamine (A)”) ) may be used. As another diamine (A), an aliphatic diamine, an alicyclic diamine, an aromatic diamine, diaminoorganosiloxane, etc. are mentioned. Specific examples of the other diamine (A) include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl Propane, 4-aminophenyl-4-aminobenzoate, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4 -Aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,6-bis(4-aminophenoxy)hexane, 4,4'-diaminodiphenyl ether, N,N' -di(5-amino-2-pyridyl)-N,N'-di(tert-butoxycarbonyl)ethylenediamine, 6,6'-(pentamethylenedioxy)bis(3-aminopyridine), 2 ,2'-dimethyl-4,4'-diaminobiphenyl etc. are mentioned.

In the synthesis of polyamic acid [A], the ratio of specific diamine (A) is used for synthesis of polyamic acid [A] from the viewpoint of sufficiently reducing the afterimage and from the viewpoint of obtaining a liquid crystal aligning film with high mechanical strength It is preferable that it is 10 mol% or more with respect to the whole amount of a diamine compound, It is more preferable that it is 15 mol% or more, It is still more preferable that it is 20 mol% or more, It is still more preferable that it is 30 mol% or more, It is still more preferable that it is 40 mol% or more. It is preferable, and it is especially preferable that it is 60 mol% or more. In addition, the ratio of a specific diamine (A) can be set in the range of 100 mol% or less with respect to the whole quantity of the diamine compound used for the synthesis|combination of polyamic acid [A].

Synthesis of polyamic acid

Polyamic acid [A] can be obtained by making tetracarboxylic dianhydride and a diamine compound react with a molecular weight modifier as needed. In the synthesis reaction of polyamic acid, the use ratio of tetracarboxylic dianhydride and diamine compound is preferably such that the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 2 equivalents with respect to 1 equivalent of the amino group of the diamine compound. . Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate, etc. can be heard It is preferable that the usage-rate of a molecular weight modifier shall be 20 mass parts or less with respect to a total of 100 mass parts of the tetracarboxylic dianhydride and diamine compound to be used.

The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, and the reaction time is preferably 0.1 to 24 hours. Examples of the organic solvent used for the reaction include aprotic polar solvents, phenolic solvents, alcohol solvents, ketone solvents, ester solvents, ether solvents, halogenated hydrocarbons, and hydrocarbons. Specific examples of these include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphotria. At least one selected from the group consisting of mide, m-cresol, xylenol and halogenated phenol is used as the reaction solvent, or at least one of these and another organic solvent (eg, butylcellosolve, diethylene It is preferable to use a mixture with glycol diethyl ether, etc.). It is preferable that the usage-amount (a) of an organic solvent sets it as the quantity from which the total amount (b) of tetracarboxylic dianhydride and diamine will be 0.1-50 mass % with respect to the total amount (a+b) of a reaction solution.

As described above, a polymer solution obtained by dissolving polyamic acid [A] is obtained. You may use this polymer solution for preparation of a liquid crystal aligning agent as it is, and after isolating polyamic acid [A] contained in a polymer solution, you may provide for preparation of a liquid crystal aligning agent.

(polyamic acid ester)

When the polymer [A] is a polyamic acid ester, the polyamic acid ester is, for example, [I] a method of reacting the polyamic acid [A] with an esterifying agent, [II] a tetracarboxylic acid diester, and a specific diamine ( It can be obtained by the method of making the diamine compound containing A) react, the method of making [III] tetracarboxylic-acid diester dihalide and the diamine compound containing the specific diamine (A) react, etc. The polyamic acid ester may have only a dark acid ester structure, and may be a partial esterified product in which a dark acid structure and a dark acid ester structure coexist. The reaction solution formed by dissolving polyamic acid ester may be used for preparation of a liquid crystal aligning agent as it is, and after isolating the polyamic acid ester contained in a reaction solution, you may provide for preparation of a liquid crystal aligning agent.

(Polyimide)

When the polymer [A] is a polyimide, the polyimide can be obtained, for example, by imidizing the polyamic acid [A] synthesized as described above by dehydration and ring closure. The polyimide may be a complete imidized product in which all of the amic acid structure of the polyamic acid, which is its precursor, is cyclized by dehydration, or a partial imidized product in which only a part of the amic acid structure is cyclized by dehydration and coexisting with a amic acid structure and an imide ring structure. good. It is preferable that it is 20 to 99 %, and, as for the imidation rate of a polyimide, it is more preferable that it is 30 to 90 %. In addition, the imidation ratio represents the ratio which the number of imide ring structures occupies with respect to the sum total of the number of the male acid structures of a polyimide, and the number of imide ring structures, in percentage. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of polyamic acid is preferably carried out by dissolving polyamic acid in an organic solvent, adding a dehydrating agent and dehydration ring closure catalyst to the solution, and heating if necessary. In this method, as a dehydrating agent, acid anhydrides, such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride, can be used, for example. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles with respect to 1 mole of the amic acid structure of the polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring closure catalyst to be used is preferably 0.01 to 10 moles with respect to 1 mole of the dehydrating agent to be used. Examples of the organic solvent used for the dehydration ring closure reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180°C. The reaction time is preferably 1.0 to 120 hours. Moreover, the reaction solution containing a polyimide may be used for preparation of a liquid crystal aligning agent as it is, and after isolating a polyimide, you may provide for preparation of a liquid crystal aligning agent.

<Polymer [B]>

The polymer [B] is a polymer having a structural unit (U2) and a structural unit (U3). Hereinafter, each structural unit which the polymer [B] has is demonstrated in detail.

・Structural unit (U2)

Structural unit (U2) is a structural unit derived from the diamine (henceforth "specific diamine (B1)") which has a partial structure represented by following formula (2). By structural unit (U2), the function which relieve|moderates the accumulation|storage electric charge in a liquid crystal aligning film is provided to polymer [B]. Further, the aforementioned polymer [A] does not have a structural unit (U2), and in this respect, the polymer [B] is different from the polymer [A].

(In formula (2), A ¹ and A ² are each independently a divalent aromatic ring group. B ¹ is -NR ⁴ - or a divalent aromatic heterocyclic group. When B ¹ is a divalent aromatic heterocyclic group, R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group When B ¹ is -NR ⁴ -, R ⁴ , R ⁵ and R ⁶ are (i) or (ii) below.

(i) R ⁴ is a hydrogen atom or a monovalent organic group. R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent organic group, or R ⁵ and R ⁶ combine with each other to represent a ring structure constituted with A ¹ , -NR ⁴ - and A ² .

(ii) R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, or a ring structure in which R ⁴ and R ⁵ combine with each other to form a ring structure together with A ¹ and a nitrogen atom. R ⁶ is a hydrogen atom or a monovalent organic group.

"*" indicates that it is a bond.)

In addition, in this specification, it is another polymer that another polymer "does not have" the structural unit (henceforth a "specific unit") which at least 1 type of polymer has among multiple types of polymers contained in a liquid crystal aligning agent. In the range that does not impair the effects of the present invention, it is an acceptable meaning to have the specific unit. When the other polymer does not have a specific unit, the content of the specific unit in the other polymer is preferably 1 mol% or less, more preferably 0.5 mol% or less, with respect to all the structural units of the other polymer, More preferably, it is 0.1 mol% or less.

In the formula (2), examples of the divalent aromatic ring group of A ¹ and A ² include a divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group. Examples of the divalent aromatic heterocyclic group include a nitrogen-containing aromatic heterocyclic group, an oxygen-containing aromatic heterocyclic group, and a sulfur-containing aromatic heterocyclic group, and a nitrogen-containing aromatic heterocyclic group is preferable. In addition, A ¹ and A ² may have a substituent in the aromatic ring part. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms and a halogen atom.

Specific examples of A ¹ and A ² include a divalent aromatic hydrocarbon group obtained by removing any two hydrogen atoms bonded to carbon atoms constituting a benzene ring, a naphthalene ring, or an anthracene ring; a divalent nitrogen-containing aromatic heterocyclic group obtained by removing any two hydrogen atoms bonded to carbon atoms constituting a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring; as a divalent oxygen-containing aromatic heterocyclic group, a group formed by removing any two hydrogen atoms bonded to carbon atoms constituting the furan ring; Examples of the divalent sulfur-containing aromatic heterocyclic group include groups obtained by removing any two hydrogen atoms bonded to carbon atoms constituting the thiophene ring. ^{A divalent} aromatic hydrocarbon group is preferable and, as for the divalent aromatic ring group of A1 and A2 from a viewpoint of aiming at densification of a liquid crystal aligning film, and high transmittance|permeability-ization, a phenylene group is more preferable.

B ¹ is -NR ⁴ - or a divalent aromatic heterocyclic group. When B ¹ is a divalent aromatic heterocyclic group, examples of the aromatic heterocyclic group include the divalent aromatic heterocyclic groups exemplified by A ¹ and A ² . Among these, the divalent aromatic heterocyclic group of B ¹ has a high effect of alleviating the accumulated charge by removing any two hydrogen atoms bonded to carbon atoms constituting the pyrrole ring, furan ring and thiophene ring. It is preferable to be a group formed.

When B ¹ is a divalent aromatic heterocyclic group, R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group. For specific examples and preferred examples of R ⁵ , the description of R ³ can be referred to. Examples of the monovalent organic group for R ⁶ include an alkyl group having 1 to 3 carbon atoms, a halogen atom, and a cyano group.

When B ¹ is -NR ⁴ -, R ⁴ , R ⁵ and R ⁶ satisfy (i) or (ii) above. When R ⁴ , R ⁵ and R ⁶ satisfy the above (i), R ⁴ is a hydrogen atom or a monovalent organic group. For specific examples and preferred examples of R ⁴ , the description of R ³ can be referred to. In the case where R ⁵ and R ⁶ are a hydrogen atom or a monovalent organic group, the description of R ³ can be similarly cited for specific examples and preferred examples. When R ⁵ and R ⁶ are combined with R ⁵ and R ⁶ to form a ring structure together with A ¹ , -NR ⁴ - and A ² , the ring structure is a carbazole structure or a 9-methylcarbazole structure. , a 9-ethylcarbazole structure, and the like.

When R ⁴ , R ⁵ and R ⁶ satisfy the above (ii), the description of R ³ can be cited for specific examples and preferred examples when R ⁴ is a hydrogen atom or a monovalent organic group. When R ⁵ and R ⁶ are a hydrogen atom or a monovalent organic group, examples of the monovalent organic group include an alkyl group having 1 to 3 carbon atoms, a halogen atom, and a cyano group.

When R ⁴ and R ⁵ are combined with R ⁴ and R ⁵ to form a ring structure together with A ¹ and a nitrogen atom, examples of the ring structure include an indoline structure and an isoindoline structure.

As a preferable specific example of the partial structure represented by said Formula (2), when B< ¹ > is -NR ⁴ -, the partial structure etc. which are represented by each of following formula (2-1) - Formula (2-7); As a case where B< ¹ > is a bivalent aromatic heterocyclic group, the partial structure etc. represented by each of following formula (2-8) - formula (2-10) are mentioned.

(In formulas (2-1) to (2-10), R ⁴ and R ³³ each independently represent a hydrogen atom or a monovalent organic group. “*” represents a bond.)

Specific diamine (B1) may have one partial structure represented by said formula (2), and may have two or more. From a viewpoint of ensuring the solubility of polymer [B], Preferably it is 1 or 2 pieces. It is preferable that the specific diamine (B1) is an aromatic diamine, and it is especially preferable that it is an aromatic diamine which has a structure in which the partial structure represented by said formula (2) can be introduce|transduced into the main chain of polymer [B]. As a specific example of specific diamine (B1), the compound etc. which are represented by each of a following formula (DB-1) - a formula (DB-21) are mentioned. In addition, the specific diamine (B1) does not have the partial structure Y which a structural unit (U3) has.

・Structural unit (U3)

The structural unit (U3) is a structural unit derived from a diamine having the following partial structure Y (hereinafter also referred to as “specific diamine (B2)”). In addition, specific diamine (B2) is a compound which does not have the partial structure represented by said Formula (2), Comprising: It differs from specific diamine (B1). When the polymer [B] has the structural unit (U3) together with the structural unit (U2), the solubility of the polymer [B] can be increased, and a liquid crystal aligning film showing low afterimage characteristics (particularly, reduction of AC afterimage) is obtained. can

Partial structure Y: In the structure represented by -(CH ₂ ) _n - (where n is an integer of 1 to 20), -(CH ₂ ) _n+1 - in the structure represented by -, any methylene group is -O-, -S-, -COO-, -NR ⁷ -, -NR ⁷ -CO-, -NR ⁷ -COO-, -NR ⁷ -CO-NR ⁸ -, or a structure substituted with a nitrogen-containing non-aromatic heterocyclic group (provided that R ⁷ and R ⁸ is each independently a hydrogen atom or a monovalent organic group, when n is 2 or more, -O-, -S-, -COO-, -NR ⁷ -, -NR ⁷ -CO-, -NR ⁷ -COO-, -NR ⁷ -CO-NR ⁸ - and nitrogen-containing non-aromatic heterocyclic groups are not adjacent to each other), -O-, -S-, -COO-, -NR ⁷ -CO-, -NR ⁷ -COO-, or -NR ⁷ -CO-NR ⁸ -

Partial structure Y WHEREIN: The solubility improvement effect of polymer [B] can be made high, and also from a viewpoint of the improvement effect of a low afterimage characteristic (reduction of AC afterimage and DC afterimage), and the dynamic strength of a liquid crystal aligning film, n is 1 -14 are preferable and 1-12 are more preferable. When partial structure Y is a structure in which arbitrary methylene groups are substituted with -O- or the like in a structure represented by -(CH ₂ ) _n+1 - (hereinafter also referred to as “hetero atom-containing structure”), n is preferably 2 or more And it is more preferable that it is 2-14.

In partial structure Y, examples of the nitrogen-containing non-aromatic heterocyclic group include a piperidine-1,4-diyl group, a piperazine-1,4-diyl group, and 2-oxo-4-imidazolidinone-1,3- Diary, etc. are mentioned.

For the examples and preferred examples of R ⁷ and R ⁸ , the description of R ³ can be referred to.

As partial structure Y, among these, a structure represented by -(CH ₂ ) _n -, a structure containing a hetero atom, or -O- is preferable, and a structure represented by -(CH ₂ ) _n - or a structure containing a hetero atom is more desirable.

The specific diamine (B2) is not particularly limited as long as it is a diamine having the partial structure Y, and examples thereof include aliphatic diamine, alicyclic diamine, aromatic diamine, and diaminoorganosiloxane. It is preferable that specific diamine (B2) has a structure which can introduce|transduce partial structure Y into the main chain of polymer [B], and it is preferable that it is a compound specifically, represented by a following formula (DB2).

(in formula (DB2), Y ³ is -(CH ₂ ) _n -, in the structure represented by -(CH ₂ ) _n+1 -, any methylene group is -O-, -S-, -COO-, -NR ⁷ -, -NR ⁷ -CO-, -NR ⁷ -COO-, -NR ⁷ -CO-NR ⁸ -, or a structure substituted with a nitrogen-containing non-aromatic heterocyclic group (hetero atom-containing structure), -O -, -S-, -COO-, -NR ⁷ -CO-, -NR ⁷ -COO-, or -NR ⁷ -CO-NR ⁸ - A ³ and A ⁴ are each independently a single bond; A substituted or unsubstituted cyclohexylene group, or a substituted or unsubstituted phenylene group. The definitions of n, R ⁷ and R ⁸ have the same meaning as above. When n is 2 or more, in the heteroatom containing structure, -O-, -S-, -COO-, -NR ⁷ -, -NR ⁷ -CO-, -NR ⁷ -COO-, -NR ⁷ -CO-NR ⁸ - and nitrogen-containing non-aromatic heterocyclic groups adjacent to each other not doing it.)

Specific examples of the specific diamine (B2) include metaxylylenediamine, pentamethylenediamine, hexamethylenediamine and the like as aliphatic diamine; As the alicyclic diamine, 4,4'-methylenebis(cyclohexylamine) or the like; As aromatic diamines, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 4-aminophenyl-4-aminobenzoate, 4, 4'-diaminobenzanilide, 1,3-bis(4-aminophenyl)urea, 1,3-bis(4-aminophenethyl)urea, 1,3-bis(4-aminobenzyl)urea, 1, 5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,6-bis(4-aminophenoxy) C)hexane, bis[2-(4-aminophenyl)ethyl]hexane diacid, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 2,2-bis[4 -(4-aminophenoxy)phenyl]propane, 4,4'-[4,4'-propane-1,3-diylbis(piperidin-1,4-diyl)]dianiline, diethylene glycol bis (4-aminophenyl)ether, 1,4-bis(4-aminophenoxy)benzene, the above formulas (DA-1) to (DA-15) and (DA-17) to (DA-20) a compound represented by each of the following formulas (DC-1) to a compound represented by each of the formulas (DC-7); Examples of the diaminoorganosiloxane include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and the like.

As specific diamine (B2), among these, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenylethane, 4,4'- diaminodiphenyl ether, 1,2-bis(4) -Aminophenoxy)ethane, 4,4'-[4,4'-propane-1,3-diylbis(piperidin-1,4-diyl)]dianiline, bis[2-(4-aminophenyl) It is preferable to use at least 1 sort(s) chosen from the group which consists of ) ethyl] hexane diacid, diethylene glycol bis(4-aminophenyl) ether, hexamethylenediamine, and the compound represented by said formula (DC-5).

It is preferable that the polymer [B] is at least 1 sort(s) chosen from the group which consists of a polyamic acid, a polyamic acid ester, and a polyimide at a point with high affinity with the polymer [A]. In particular, when the polymer [B] has the partial structure and the partial structure Y represented by the formula (2) in the main chain, the accumulated charge can be quickly relieved while increasing the solubility of the polymer [B], and the AC residual image It is suitable in that it can sufficiently reduce the

When the polymer [B] is polyamic acid, the polyamic acid (hereinafter also referred to as “polyamic acid [B]”) is a diamine compound containing tetracarboxylic dianhydride, specific diamines (B1) and specific diamines (B2). It can be obtained by reacting The polyamic acid [B], the polyamic acid ester, and the polyimide that are the polymer [B] can be produced in the same manner as in the polymer [A].

As tetracarboxylic dianhydride used for the synthesis|combination of polymer [B], the illustration of the tetracarboxylic dianhydride used for synthesis|combination of polymer [A], and description of a preferable example can be cited. That is, the tetracarboxylic dianhydride used in the synthesis of polyamic acid [B] preferably contains at least one compound selected from the group consisting of aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride, , it is more preferable to include alicyclic tetracarboxylic dianhydride. The use ratio of alicyclic tetracarboxylic dianhydride is preferably 20 mol% or more, more preferably 40 mol% or more, with respect to the total amount of tetracarboxylic dianhydride used for the synthesis of polyamic acid [B], It is more preferable that it is 50 mol% or more.

In addition, in the synthesis of polyamic acid [B], polyamic acid ester, and polyimide, which are polymer [B], as a diamine compound, a compound different from the specific diamine (B1) and the specific diamine (B2) (hereinafter referred to as “other diamine (B)”) ') may be additionally used. Examples of the other diamine (B) include p-phenylenediamine, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 4,4-diamino-2,2'-dimethylbiphenyl, 3,5-dia and mino-N,N-bis(pyridin-3-ylmethyl)benzamide. Synthesis WHEREIN: It is preferable that it is 20 mol% or less, and, as for the usage-amount of another diamine (B), it is more preferable that it is 10 mol% or less with respect to the total amount of the diamine compound used for the synthesis|combination of a polymer [B].

Synthesis of polymer [B] WHEREIN: The diamine compound used for the synthesis|combination of polymer [B] from the point that the usage-amount of a specific diamine (B1) can relieve|moderate a residual electric charge rapidly and can fully aim at reduction of a DC residual image. It is preferable that it is 5 mol% or more with respect to the total amount, It is more preferable that it is 10 mol% or more, It is more preferable that it is 15 mol% or more. In addition, the usage-amount of specific diamine (B1) is 95 mol with respect to the total amount of the diamine compound used for the synthesis|combination of polymer [B] from a viewpoint of suppressing AC afterimage and a viewpoint of ensuring the solubility of polymer [B]. % or less, more preferably 80 mol% or less, and still more preferably 70 mol% or less.

It is preferable that the usage-amount of specific diamine (B2) is 5 mol% or more with respect to the total amount of the diamine compound used for the synthesis|combination of polymer [B] at the point which can make the solubility of polymer [B] high, and 10 mol % or more is more preferable, and it is still more preferable that it is 15 mol% or more. Moreover, it is preferable that the usage-amount of a specific diamine (B2) is 90 mol% or less with respect to the whole quantity of the diamine compound used for the synthesis|combination of a polymer [B] from a viewpoint of fully aiming reduction of DC residual image, and it is 80 mol% It is more preferable that it is less than or equal, and it is still more preferable that it is 70 mol% or less.

In addition, about the various conditions in the synthesis|combining method of each polymer, such as polyamic acid [B], description of the above-mentioned polymer [A] can be invoked.

When the solution viscosity of the polymer [A] and polymer [B] used for preparation of a liquid crystal aligning agent sets it as a solution with a density|concentration of 10 mass %, it is preferable that it is what has a solution viscosity of 10-800 mPa*s, and 15-500 mPa It is more preferable to have a solution viscosity of s. In addition, the solution viscosity (mPa·s) is a polymer solution having a concentration of 10% by mass prepared using a good polymer solvent (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.), It is the value measured in 25 degreeC using the E-type rotational viscometer.

For each of the polymer [A] and the polymer [B], the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. Moreover, the molecular weight distribution (Mw/Mn) represented by ratio of Mw and the number average molecular weight (Mn) of polystyrene conversion measured by GPC becomes like this. Preferably it is 7 or less, More preferably, it is 5 or less.

Liquid crystal aligning agent WHEREIN: It is preferable that content of a polymer [A] is 1 mass % or more with respect to the whole quantity of the polymer component contained in a liquid crystal aligning agent from a viewpoint of fully aiming at reduction of an AC residual image, and it is 2 mass % It is more preferable that it is more than it, It is still more preferable that it is 5 mass % or more, It is still more preferable that it is 10 mass % or more. Moreover, it is preferable that content of a polymer [A] is 90 mass % or less with respect to the whole quantity of the polymer component contained in a liquid crystal aligning agent from a viewpoint of reducing a DC afterimage by relaxation of a residual electric charge, and it is 80 mass % or less It is more preferable, and it is still more preferable that it is 70 mass % or less.

It is preferable that content of a polymer [B] is 10 mass % or more with respect to the whole quantity of the polymer component contained in a liquid crystal aligning agent, It is more preferable that it is 20 mass % or more, It is more preferable that it is 30 mass % or more. Moreover, it is preferable that content of a polymer [B] is 99 mass % or less with respect to the whole quantity of the polymer component contained in a liquid crystal aligning agent, It is more preferable that it is 98 mass % or less, It is still more preferable that it is 95 mass % or less, It is still more preferable that it is 90 mass % or less.

<Other ingredients>

A liquid crystal aligning agent may contain the component (it is also called "other components" hereafter) different from a polymer [A] and a polymer [B] as needed other than a polymer [A] and a polymer [B].

(Other polymers)

The liquid crystal aligning agent of this indication may contain the polymer (henceforth "other polymer") different from a polymer [A] and a polymer [B] as a polymer component. The main skeleton of the other polymer is not particularly limited. Examples of other polymers include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyenamine, polyurea, polyamide, polyamideimide, polybenzoxazole precursor, polybenzoxazole. , a cellulose derivative, polyacetal, (meth)acrylic polymer, styrene polymer, maleimide polymer, or styrene-maleimide polymer. In the case of using together with the polymer [A] and the polymer [B], the affinity with the liquid crystal is high, and from the viewpoint of increasing the reliability of the liquid crystal element, the other polymers are from the group consisting of polyamic acid, polyamic acid ester and polyimide. It is preferable that it is at least 1 type selected from.

When making a liquid crystal aligning agent contain another polymer, it is a liquid crystal aligning agent. WHEREIN: As for content of another polymer, 30 mass % or less is preferable with respect to the total amount of a polymer [A], a polymer [B], and another polymer. and 20 mass % or less is more preferable, 10 mass % or less is still more preferable, and 5 mass % or less is still more preferable.

(solvent)

The liquid crystal aligning agent of this indication is prepared as a liquid composition in which a polymer [A], a polymer [B], and the other component used as needed preferably disperse|distribute or melt|dissolve in a suitable solvent.

As the solvent, an organic solvent is preferably used. Specific examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, Phenol, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol, 1- Hexanol, 2-hexanol, propane-1,2-diol, 3-methoxy-1-butanol, ethylene glycol monomethyl ether, methyl lactate, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, aceto Methyl acetate, ethyl acetoacetate, ethyl propionate, methyl methoxypropionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl 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, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutylate, diisopentyl ether, ethylene carbonate, propylene carbonate, propylene glycol monomethyl Ether (PGME), diethylene glycol diethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol diacetate, cyclopentanone, cyclohexanone, etc. are mentioned.

As another component contained in a liquid crystal aligning agent, antioxidant, a metal chelate compound, a hardening accelerator, surfactant, a filler, a dispersing agent, a photosensitizer, etc. are mentioned other than the above, for example. The blending ratio of other components can be appropriately selected according to each compound within a range that does not impair the effects of the present disclosure.

Although the solid content concentration (ratio which the total mass of components other than the solvent of a liquid crystal aligning agent occupies to the total mass of a liquid crystal aligning agent) in a liquid crystal aligning agent considers a viscosity, volatility, etc., and is suitably selected, Preferably it is 1-10 It is the range of mass %. The film thickness of a coating film can fully be ensured that solid content concentration is 1 mass % or more, and the liquid crystal aligning film which shows favorable liquid-crystal orientation is easy to be obtained. On the other hand, when the solid content concentration is 10% by mass or less, the coating film can have an appropriate thickness, and a liquid crystal aligning film showing good liquid crystal alignment property is easily obtained, and the viscosity of the liquid crystal aligning agent becomes appropriate and applicability can be made favorable tends to

«Liquid crystal alignment film and liquid crystal element»

The liquid crystal aligning film of this indication is manufactured with the liquid crystal aligning agent prepared as mentioned above. Moreover, the liquid crystal element of this indication is equipped with the liquid crystal aligning film formed using the liquid crystal aligning agent demonstrated above. The driving method of the liquid crystal in the liquid crystal element is not particularly limited, and for example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type ( It can be applied to various modes such as Optically Compensated Bend) type and PSA (Polymer Sustained Alignment) type. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, the substrate used differs depending on the desired operation mode. Steps 2 and 3 are common to each operation mode.

<Step 1: Formation of a coating film>

First, a liquid crystal aligning agent is apply|coated on a board|substrate, Preferably a coating film is formed on a board|substrate by heating an application surface. As a board|substrate, For example, glass, such as float glass and soda glass; A transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate or poly(alicyclic olefin) can be used. Examples of the transparent conductive film formed on one surface of the substrate include an NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG Corporation in the United States), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), and the like. can be heard When manufacturing a TN-type, STN-type, or VA-type liquid crystal element, two substrates on which a patterned transparent conductive film is formed are used. On the other hand, when manufacturing an IPS type or FFS type liquid crystal element, the board|substrate on which the electrode patterned in comb-tooth shape is formed, and the counter board|substrate on which the electrode is not formed are used.

The coating method of the liquid crystal aligning agent to a board|substrate is not specifically limited, For example, a spin coating method, a printing method (for example, an offset printing method, a flexographic printing method, etc.), an inkjet method, a slit coating method, a bar coater method , an extrusion die method, a direct gravure coater method, a chamber doctor coater method, an offset gravure coater method, an impregnation coater method, an MB coater method, or the like.

After apply|coating a liquid crystal aligning agent, for purposes, such as liquid flow prevention of the apply|coated liquid crystal aligning agent, Preferably, preliminary heating (prebaking) is performed. Pre-baking temperature becomes like this. Preferably it is 30-200 degreeC, and pre-baking time becomes like this. Preferably it is 0.25 to 10 minutes. After that, the solvent is completely removed and, if necessary, a calcination (post-baking) step is performed for the purpose of thermally imidizing the amic acid structure present in the polymer. The baking temperature (post-baking temperature) at this time becomes like this. Preferably it is 80-280 degreeC, More preferably, it is 80-250 degreeC. Post-baking time becomes like this. Preferably it is 5 to 200 minutes. The film thickness of the film to be formed is preferably 0.001 to 1 µm.

<Step 2: Orientation treatment>

When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal element, the process (orientation process) which provides liquid-crystal orientation ability is performed with respect to the coating film formed in the said process 1. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. It is preferable to use the rubbing process which rubs the surface of the coating film formed on the board|substrate with cotton etc. as an orientation process, or the photo-alignment process which irradiates light to a coating film and provides liquid-crystal orientation ability. When manufacturing the liquid crystal element of a vertical alignment type, you may use the coating film formed in the said process 1 as it is as a liquid crystal aligning film, and in order to further improve liquid-crystal orientation ability, you may orientation-process with respect to the said coating film.

Light irradiation for photo-alignment is a method of irradiating the coating film after the post-baking process, a method of irradiating the coating film before the post-baking process as after the pre-baking process, heating the coating film in at least any of the pre-baking process and the post-baking process It can carry out by the method of irradiating with respect to a coating film, etc. in the middle. As radiation irradiated to the coating film, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used. Preferably, it is an ultraviolet-ray containing light of a wavelength of 200-400 nm. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. When the radiation to be used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. In the case of non-polarized radiation, the irradiation direction is set to an oblique direction.

As a light source to be used, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. are mentioned, for example. The radiation dose is preferably 200 to 30,000 J/m 2 , more preferably 500 to 10,000 J/m 2 . After light irradiation for imparting orientation ability, the substrate surface is treated with, for example, water or an organic solvent (eg, methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.) Alternatively, a process for washing using a mixture thereof or a process for heating the substrate may be performed.

<Step 3: Construction of a liquid crystal cell>

A liquid crystal cell is manufactured by preparing two board|substrates with a liquid crystal aligning film as mentioned above, and arrange|positioning a liquid crystal between the board|substrates of 2 sheets opposingly arranged. In order to manufacture a liquid crystal cell, for example, two board|substrates are opposingly arrange|positioned through a gap so that a liquid crystal aligning film may oppose, the periphery of two board|substrates is joined with a sealing compound, In the cell gap surrounded by the board|substrate surface and a sealing agent, A method of sealing an injection hole by injecting and filling a liquid crystal, a method by an ODF method, etc. are mentioned. As a sealing agent, the epoxy resin etc. containing the aluminum oxide sphere as a hardening|curing agent and a spacer can be used, for example. As a liquid crystal, although either a positive type and a negative type may be used, Preferably it is a negative type. As a negative liquid crystal, the Merck company "MLC-6608", "MLC-6609", "MLC-6610", "MLC-7026-100" etc. are mentioned, for example. In particular, when a negative liquid crystal is used in the liquid crystal element of the IPS type and the FFS type, it is preferable from the viewpoint that the transmission loss at the upper portion of the electrode can be reduced and the contrast can be improved. Moreover, as a liquid crystal, a nematic liquid crystal and a smectic liquid crystal are mentioned, Among these, a nematic liquid crystal is preferable.

When manufacturing a liquid crystal display device, then, a polarizing plate is bonded to the outer surface of a liquid crystal cell, and a liquid crystal display element is obtained. As a polarizing plate, the polarizing plate which sandwiched the polarizing film called "H film" which absorbed iodine while stretching orienting polyvinyl alcohol, with a cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned.

The liquid crystal element of the present invention can be effectively applied to various uses. Specifically, for example, a watch, a portable game machine, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, a smartphone, various types of monitors, LCD TVs, information displays, etc. , a dimming device, retardation film, and the like.

(Example)

EXAMPLES Hereinafter, although embodiment is described in more detail based on an Example, this invention is not interpreted limitedly by a following Example.

In the following examples, the imidation ratio of the polyimide in the polymer solution was measured by the following method. The required amounts of the raw material compound and the polymer used in the following examples were ensured by repeating the synthesis on the synthesis scale shown in the following synthesis examples as needed.

[Imidation rate of polyimide]

The polyimide solution was poured into pure water, and the obtained precipitate was dried under reduced pressure sufficiently at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidation ratio [%] was determined by the following formula (1).

Imidization ratio [%] = (1-(β1/(β2×α)))×100 … (One)

(In formula (1), β1 is the proton-derived peak area of the NH group appearing around 10 ppm of chemical shift, β2 is the peak area derived from other protons, and α is the NH group in the polymer precursor (polyamic acid). It is the ratio of the number of other protons to one proton of

The abbreviations of the monomers used in the Examples are as follows.

(tetracarboxylic acid dianhydride)

-Compound (c-1) to compound (c-5): a compound represented by each of the following formulas (c-1) to (c-5)

(diamine compound)

-Compound (DA-1) to compound (DA-14): a compound represented by each of the above formulas (DA-1) to (DA-14)

・Compound (DB-1) to compound (DB-20): a compound represented by each of the above formulas (DB-1) to (DB-20)

-Compound (d-1) to compound (d-5): a compound represented by each of the following formulas (d-1) to (d-5)

-Compound (b-1) to compound (b-11): a compound represented by each of the following formulas (b-1) to (b-11)

<Synthesis of polymer>

1. Synthesis of polyamic acid

[Synthesis Example 1]

100 mol parts of compound (c-2) as tetracarboxylic dianhydride and 100 mol parts of compound (DA-1) as diamine compound were dissolved in N-methyl-2-pyrrolidone (NMP), followed by reaction at room temperature for 6 hours. , a solution containing 15% by mass of polyamic acid (this is called "polymer (PAA-1)") was obtained.

[Synthesis Examples 2-17, 23-46]

The same operation as in Synthesis Example 1 was performed except that the types and amounts of tetracarboxylic dianhydride and diamine compounds used were changed as shown in Tables 1 and 2 below, and polyamic acids (polymers (PAA-2) to (PAA) -41)) was obtained. In addition, in Table 1 and Table 2, the compounding quantity of tetracarboxylic dianhydride shows the ratio (mol%) with respect to the total amount of tetracarboxylic dianhydride used for the synthesis|combination of each polymer. The compounding quantity of a diamine compound shows a ratio (mol%) to the whole quantity of the diamine compound used for the synthesis|combination of each polymer.

2. Synthesis of polyimide

[Synthesis Example 18]

90 mol parts of compound (c-1) and 10 mol parts of compound (c-5) as tetracarboxylic dianhydride and 100 mol parts of compound (DA-2) as a diamine compound were dissolved in NMP and reacted at room temperature for 6 hours to obtain poly A solution containing 15% by mass of amic acid was obtained. Next, NMP was added to the obtained polyamic acid solution, it was set as the solution with a polyamic acid concentration of 10 mass %, pyridine and acetic anhydride were added, and dehydration ring closure reaction was performed at 60 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP to obtain a solution containing 15% by mass of a polyimide having an imidation rate of about 80% (this is referred to as "polymer (PI-1)").

[Synthesis Examples 19 to 22]

The same operation as in Synthesis Example 18 was performed except that the types and amounts of tetracarboxylic dianhydride and diamine compounds used were changed as shown in Table 1 below, and polyimides (polymers (PI-2) to (PI-5) ) was obtained.

[Example 1]

1. Preparation of liquid crystal aligning agent

The solution of the polymer (PAA-1) obtained in Synthesis Example 1 and the solution of the polymer (PAA-36) obtained in Synthesis Example 41 were diluted with NMP and butylcellosolve (BC), and the solid content concentration was 4.0 mass % and the solvent composition ratio obtained the solution used as NMP:BC=80:20 (mass ratio). A liquid crystal aligning agent (R-1) was prepared by filtering this solution with the filter with a hole diameter of 0.2 micrometer.

2. Preparation of FFS-type liquid crystal cell using rubbing method

A glass substrate having a flat electrode (bottom electrode), an insulating layer and a comb-toothed electrode (top electrode) laminated on one side in this order (referred to as a first substrate), and a glass substrate without an electrode (referred to as a second substrate) ) was prepared. Next, the liquid crystal aligning agent (R-1) was apply|coated to each of the single side|surface of the electrode formation surface of a 1st board|substrate, and a 2nd board|substrate using a spinner, and it heated (prebaked) for 3 minutes with a 110 degreeC hotplate. . Then, drying (post-baking) was performed for 30 minutes in 230 degreeC oven which replaced the inside of the furnace with nitrogen, and the coating film with an average film thickness of 0.08 micrometer was formed. Next, the coating film surface was rubbed with a rubbing machine having a roll wound with rayon cloth at a roll rotation speed of 1000 rpm, a stage moving speed of 3 cm/sec, and a bushy foot press-in length of 0.3 mm. Then, a pair of board|substrates which have a liquid crystal aligning film were obtained by performing ultrasonic cleaning for 1 minute in ultrapure water, and drying for 10 minutes in 100 degreeC clean oven then.

Then, with respect to a pair of board|substrates which have a liquid crystal aligning film, the liquid crystal injection port was left at the edge of the surface on which the liquid crystal aligning film was formed, and the aluminum oxide sphere containing epoxy resin adhesive agent with a diameter of 3.5 micrometers was screen-printed. Then, the board|substrates were superimposed on each other and pressed, and the adhesive agent was thermosetted at 150 degreeC over 1 hour. Next, after filling the gap between a pair of board|substrates with negative liquid crystal (Merck Corporation make, MLC-6608) from the liquid crystal injection port, the liquid crystal injection port was sealed with the epoxy adhesive. Furthermore, in order to remove the flow orientation at the time of liquid crystal injection, after heating this at 120 degreeC, it cooled slowly to room temperature, and the liquid crystal cell was manufactured. In addition, when a pair of board|substrates were overlapped with each other, it was made so that the rubbing method of each board|substrate became antiparallel.

3. Evaluation of inkjet applicability (evaluation of solubility)

As a substrate on which a liquid crystal aligning agent is applied, a glass substrate with a transparent electrode made of ITO is heated on a hot plate at 200° C. for 1 minute, followed by ultraviolet/ozone cleaning to reduce the contact angle of water on the transparent electrode surface to 10° or less immediately after used that The liquid crystal aligning agent (R-1) prepared in said 1. was apply|coated on the transparent electrode surface of the said glass substrate with a transparent electrode using the inkjet applicator (Shibaura Mechatronics Co., Ltd. product). The application conditions at this time were 2,500 times/(nozzle/min), and the discharge amount was 250 mg/10 seconds, and 2 reciprocating (total 4 times) application was set. After application|coating and leaving still for 1 minute, the coating film with an average film thickness of 0.1 micrometer was formed by heating at 80 degreeC. About the obtained coating film, under the interference fringe measuring lamp (sodium lamp) irradiation, the nonuniformity and the number of splashes were visually observed. The case where both the points of unevenness and splashing are 0 is called "good (◎)", the case where all the points of unevenness and splashing are 1 or more and less than 3 is "good (○)", and when all the points of unevenness and splashing are 3 or more was evaluated as "defect (x)". Moreover, when inkjet applicability|paintability is favorable, it can be said that the polymer used for preparation of the liquid crystal aligning agent has favorable solubility. As a result, the inkjet applicability|paintability of the liquid crystal aligning agent of this Example was "excellent."

4. Evaluation of AC Afterimage Characteristics

For the FFS-type liquid crystal cell manufactured in 2. above, after driving at an alternating voltage of 10V for 72 hours, using a device in which a polarizer and an analyzer are disposed between the light source and the light quantity detector, the minimum relative expressed by the following formula (2) The transmittance (%) was measured.

Minimum relative transmittance (%) = (β-B0)/(B100-B0) × 100 … (2)

(In formula (2), B0 is the amount of light transmitted from the blank under the cross nicol. B100 is the amount of light transmitted from the blank to the para nicol. β is the liquid crystal cell between the polarizer and the analyzer under the cross nicol. It is the minimum amount of light transmitted through the

The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal cell, and in the FFS type liquid crystal cell, the smaller the black level in the dark state, the better the contrast characteristic and the better the AC afterimage characteristic. A thing with a minimum relative transmittance of less than 0.3 % was made into "good (circle)", a thing of 0.3 % or more and less than 2.0 % was made into "good|favorableness (circle)", and a thing of 2.0 % or more made "defect (x)". As a result, in this Example, it was evaluation of "excellence".

5. Evaluation of electrical properties

After leaving the FFS-type liquid crystal cell manufactured in 2 above still in an oven at 60 ° C., the voltage retention rate (VHR) was measured at 1 V and 1670 msec using a VHR measuring device “VHR-1” manufactured by Toyo Technica. . As evaluation criteria, when the VHR is 80% or more, "good (◎)", when less than 80% and 70% or more, "good (○)", when less than 70% or more than 60%, "possible (Δ)", 60% In the case of less than, it was set as "impossibility (x)". As a result, the evaluation of VHR of this Example was "excellent".

6. Evaluation of reliability after light irradiation

The reliability of the FFS-type liquid crystal cell manufactured in said 2. was evaluated. Evaluation was performed as follows. First, after applying the voltage of 1V to a liquid crystal cell for 60 microseconds, the voltage retention ratio (VHR1) 1670 milliseconds after application cancellation|release was measured. Next, after irradiating CCFL (backlight) to a liquid crystal cell at 60 degreeC for 1 week, it left still in room temperature and it cooled naturally to room temperature. After cooling, after applying the voltage of 1V to the liquid crystal cell for 60 microseconds, the voltage retention ratio (VHR2) 1670 milliseconds after application cancellation|release was measured. In addition, the VHR measuring apparatus "VHR-1" by Toyo Technica was used as a measuring apparatus. The rate of change (?VHR) in VHR at this time was calculated by the difference between VHR1 and VHR2 (?VHR=VHR1-VHR2), and reliability was evaluated by ?VHR. When the ΔVHR was less than 10%, “good (◎)”, when it was 10% or more and less than 15%, “good (○)”, when it was 15% or more and less than 20%, “possible (Δ)”, 20% or more This case was judged as "impossible (x)". As a result, in this Example, reliability was "excellent".

7. Evaluation of DC afterimage characteristics

With respect to the liquid crystal cell manufactured in step 2 above, drive at AC 2.5V to set the luminance difference between any two pixels to 0, then apply DC 1V to only one pixel while driving at 2.5V AC to 20 The charge was accumulated by applying for a minute. When the application of DC 1V was completed and the operation was returned only to AC 2.5V, a difference in luminance occurred between the two pixels due to the accumulated electric charge. By observing the change with time of this luminance difference, the relaxation time of the process in which a residual DC value attenuates was computed. When the relaxation time was less than 10 seconds, "good (◎)", when the relaxation time was 10 seconds or more and less than 20 seconds, "good (○)", when the relaxation time was 20 seconds or more, "bad (x)" was judged as As a result, in this Example, it was evaluation of "excellence".

8. Evaluation of rubbing resistance

The liquid crystal aligning agent (R-1) prepared in said 1. was apply|coated using the spinner on a glass substrate, and it heated (prebaking) for 3 minutes on a 110 degreeC hotplate. Thereafter, drying (post-baking) was performed for 30 minutes in an oven at 230° C. in which the inside of the furnace was substituted with nitrogen to form a coating film having an average film thickness of 0.08 µm, and the haze value of the coating film was measured using a hazemeter. . Next, with respect to this coating film, the rubbing process was performed 5 times with a roll rotation speed of 1000 rpm, a stage moving speed of 3 cm/sec, and a bushy foot press-in length of 0.3 mm with the rubbing machine which has a roll wound with cotton cloth. Then, the haze value of the liquid crystal aligning film was measured using the haze meter, and the difference (haze change value) with the haze value before a rubbing process was calculated by following Numerical formula (3).

Haze change value (%) = [Haze value (%) of film after rubbing treatment] - [Haze value (%) of film before rubbing treatment] ... (3)

About the rubbing tolerance of a liquid crystal aligning film, when haze change value was less than 0.8, "good (circle)", when haze change value was 0.8 or more and less than 1.5 "good (○)", haze change value was 1.5 or more was evaluated as "defect (x)". When the haze change value is less than 1.5 (more preferably less than 0.8), the film strength is sufficiently high and it can be said that the rubbing resistance is excellent. As a result, in this Example, the rubbing resistance was "excellent".

[Examples 2 to 21 and Comparative Examples 1 to 8]

Except having changed the composition of a liquid crystal aligning agent like following Table 3, it carried out similarly to Example 1, and prepared the liquid crystal aligning agent. Moreover, using the obtained liquid crystal aligning agent, it carried out similarly to Example 1, the FFS-type liquid crystal cell was manufactured by the rubbing method, and various evaluation was performed. Those results are shown in Table 4 below. In Table 3, compounding quantity shows the compounding quantity (mass part) in solid content of each polymer with respect to the whole quantity of the polymer component used for preparation of a liquid crystal aligning agent.

[Examples 22 and 23]

Except for changing the composition of the liquid crystal aligning agent as shown in Table 3 below and using the photo-alignment method instead of the rubbing method for the liquid crystal aligning film, the liquid crystal aligning agent was prepared in the same manner as in Example 1, and the FFS-type liquid crystal cell manufactured, and various evaluations were performed. A result is shown in Table 4. Formation of the liquid crystal aligning film by the photo-alignment method was performed in the following procedure.

(Formation of liquid crystal aligning film by photo-alignment method)

A liquid crystal aligning agent is sprayed on each surface of a glass substrate in which a flat electrode (bottom electrode), an insulating layer, and a comb-toothed electrode (top electrode) are laminated on one side in this order, and a counter glass substrate on which an electrode is not formed. was applied and heated (pre-baked) for 1 minute on a hot plate at 80°C. Then, drying (post-baking) was performed for 30 minutes in 230 degreeC oven which substituted the inside of the furnace with nitrogen, and the coating film with an average film thickness of 0.1 micrometer was formed. The obtained coating film was subjected to photo-alignment treatment by irradiating 1,000 J/m 2 of ultraviolet rays containing a linearly polarized 254 nm bright line from the normal line direction to the substrate using a Hg-Xe lamp. In addition, this irradiation amount is the value measured using the photometer measured with wavelength 254nm reference|standard. Next, the coating film to which the photo-alignment process was given was heated in a 230 degreeC clean oven for 30 minutes, heat processing was performed, and the liquid crystal aligning film was formed.

Moreover, by carrying out a series of said operation by respectively changing the ultraviolet irradiation amount after post-baking in the range of 100-10,000 J/m<2>, three or more liquid crystal cells with different ultraviolet irradiation amounts were manufactured, and the exposure amount which showed the most favorable orientation characteristic Using the liquid crystal cell of (optimum exposure amount), it carried out similarly to Example 1, and performed various evaluation.

As shown in Table 4, in Examples 1-23, compared with Comparative Examples 1-8, the balance of various characteristics of inkjet applicability|paintability, AC afterimage characteristic, VHR, reliability, DC afterimage characteristic, and rubbing tolerance was maintained. In particular, Examples 1-6, 8, 9, 11, and 14-22 were excellent in any characteristic evaluation of "double-circle". On the other hand, in Comparative Examples 1-8, the characteristic of at least any one of inkjet applicability|paintability, AC residual image characteristic, reliability, DC residual image characteristic, and rubbing tolerance was evaluation of "x".

According to the liquid crystal aligning agent containing a polymer [A] and a polymer [B] from the above result, it became clear that the residual image of a liquid crystal display element can be decreased and the liquid crystal aligning film with high dynamic strength can be manufactured. Moreover, the polymer [A] and polymer [B] had favorable solubility and it became clear that the liquid crystal aligning agent excellent in applicability|paintability can be obtained.

Claims (7)

A polymer [A] having the following structural unit (U1) and not having the following structural unit (U2);
Polymer [B] having the following structural unit (U2) and the following structural unit (U3)
containing, a liquid crystal aligning agent.
Structural unit (U1): Structural unit derived from diamine which has a partial structure represented by following formula (1)
Structural unit (U2): Structural unit derived from diamine which has a partial structure represented by following formula (2)
Structural unit (U3): a structural unit derived from a diamine having the following partial structure Y
Partial structure Y: In the structure represented by -(CH ₂ ) _n - (where n is an integer of 1 to 20), -(CH ₂ ) _n+1 - in the structure represented by -, any methylene group is -O-, -S-, -COO-, -NR ⁷ -, -NR ⁷ -CO-, -NR ⁷ -COO-, -NR ⁷ -CO-NR ⁸ -, or a structure substituted with a nitrogen-containing non-aromatic heterocyclic group (provided that R ⁷ and R ⁸ are each independently a hydrogen atom or a monovalent organic group; when n is 2 or more, -O-, -S-, -COO-, -NR ⁷ -, -NR ⁷ -CO-, -NR ⁷ -COO-, -NR ⁷ -CO-NR ⁸ - and nitrogen-containing non-aromatic heterocyclic groups are not adjacent to each other), -O-, -S-, -COO-, -NR ⁷ -CO-, -NR ⁷ -COO-, or -NR ⁷ -CO-NR ⁸ -

(In formula (1), X ¹ and X ² are each independently a divalent aromatic ring group; however, in the aromatic ring of X ¹ , the bonding position of R ¹ and the bonding position of the group bonding to “*” A substituent is not bonded to a position different from that, and to the aromatic ring of X ² , a substituent is not bonded to a position different from the bonding position of R ² and the bonding position of a group bonding to "*"; ¹ and R ² are each independently a single bond, an alkanediyl group having 1 to 10 carbon atoms, or a substituted alkanediyl group having 1 to 10 carbon atoms; Y ¹ and Y ² are each independently * ¹ -NR ³ -CO- or * ¹ -CO-NR ³ -; R ³ is a hydrogen atom or a monovalent organic group; “* ¹ ” represents a bond with Z ¹ ; Z ¹ is a single bond or a divalent organic group; ; m is 0 or 1; when m is 0, at least one of R ¹ and R ² is an alkanediyl group having 1 to 10 carbon atoms or a substituted alkanediyl group; “*” indicates a bond)

(in formula (2), A ¹ and A ² are each independently a divalent aromatic ring group; B ¹ is -NR ⁴ - or a divalent aromatic heterocyclic group; when B ¹ is a divalent aromatic heterocyclic group, R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group, and when B ¹ is -NR ⁴ -, R ⁴ , R ⁵ and R ⁶ are (i) or (ii) below;
(i) R ⁴ is a hydrogen atom or a monovalent organic group; R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group, or R ⁵ and R ⁶ together represent a ring structure constituted by A ¹ , -NR ⁴ - and A ² together;
(ii) R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent organic group, or R ⁴ and R ⁵ represent a ring structure formed by combining with A ¹ and a nitrogen atom; R ⁶ is a hydrogen atom or a monovalent organic group;
"*" indicates that it is a bonding hand) According to claim 1,
The said polymer [A] and the said polymer [B] are at least 1 sort(s) chosen from the group which consists of a polyamic acid, polyamic acid ester, and a polyimide, Liquid crystal aligning agent. The method of claim 1,
At least one of said R< ¹ > and said R< ² > is a C1-C10 alkanediyl group or a substituted alkanediyl group, The liquid crystal aligning agent. The method of claim 1,
The liquid crystal aligning agent whose diamine which has a partial structure represented by said Formula (1) is a compound represented by a following formula (DA).

(In Formula (DA), R ¹ , R ² , Y ¹ , Y ² , Z ¹ and m have the same meaning as in Formula (1) above) The method of claim 1,
The liquid crystal aligning agent in which the said polymer [B] contains 5-95 mass % of the said structural unit (U2) with respect to the whole quantity of the diamine unit which the said polymer [B] has. The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-5. A liquid crystal element provided with the liquid crystal aligning film of Claim 6.