KR20220072741A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal device - Google Patents

Abstract

(Project) It is providing the liquid crystal aligning agent from which liquid-crystal orientation is favorable, voltage retention is high, and the liquid crystal element excellent in reliability can be obtained.
(Solution) Liquid-crystal alignment of the polymer [P] having in the main chain at least one partial structure (A) selected from the group consisting of a partial structure represented by Formula (1-1) and a partial structure represented by Formula (1-2) included in the
In the formula, B ¹ is a substituted or unsubstituted aromatic ring. R ¹ is -C(R ¹⁰ )(R ¹¹ )- with respect to a nitrogen atom constituting the condensed ring in Formula (1-1) or a carbon atom constituting the condensed ring in Formula (1-2); 2 bonded to -O-, -S-, -CO-, -COO-, -NR ⁴ -, -CO-NR ⁴ -, -NR ⁴ -CO-O- or -NR ⁴ -CO-NR ⁵ - It is an organic group of R ² is a monovalent organic group. R ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.

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 DEVICE}

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

BACKGROUND ART Liquid crystal elements are applied to a wide range of applications from relatively large display devices such as liquid crystal televisions and information displays to small display devices such as smart phones. The performance of a liquid crystal element is determined by various characteristics, such as the orientation of a liquid crystal, the magnitude|size of a pretilt angle, and voltage retention. In order to improve the performance of a liquid crystal element, improvement of the liquid crystal aligning film for aligning a liquid crystal in a fixed direction other than improvement of a liquid crystal material is conventionally performed (for example, refer patent document 1 and patent document 2).

In Patent Document 1, polyamic acid obtained by using bis(5-aminobenzoimidazole)benzene as a diamine in a liquid crystal aligning agent containing polyamic acid, which is a reaction product of tetracarboxylic dianhydride and diamine, and a derivative thereof. Making it contain in a liquid crystal aligning agent is indicated. Moreover, making a liquid crystal aligning agent contain the polyimide obtained using 5-amino-2- (4-aminophenyl) benzoimidazole as diamine by patent document 2 is indicated.

Japanese Laid-Open Patent Publication No. 2010-54872 Japanese Laid-Open Patent Publication No. 2015-106156

In recent years, along with the high-definition liquid crystal element, the requirements for quality are becoming stricter. In order to satisfy such a request|requirement, it is calculated|required by a liquid crystal element to further improve the liquid-crystal orientation and voltage retention. Moreover, as a characteristic of a liquid crystal element, it is calculated|required that it shows high voltage retention even when used over a long period of time, and that it is excellent in reliability.

This invention is made|formed in view of the said subject, Comprising: Liquid-crystal orientation is favorable, a voltage retention is high, and its main object is to provide the liquid crystal aligning agent from which the liquid crystal element excellent in reliability can be obtained.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject, and discovered that the said subject could be solved by using the polymer which has in the principal chain the condensed ring structure which the aromatic ring and the imidazole ring condensed, and came to complete this invention. Specifically, the present invention provides the following means.

<1> Contains a polymer [P] having in the main chain at least one partial structure (A) selected from the group consisting of a partial structure represented by the following formula (1-1) and a partial structure represented by the following formula (1-2) The liquid crystal aligning agent which does.

(In Formulas (1-1) and (1-2), B ¹ is a substituted or unsubstituted aromatic ring, and the nitrogen-containing heterocycle and condensed ring in Formulas (1-1) and (1-2) R ¹ is -C(R ¹⁰ ) with respect to the nitrogen atom constituting the condensed ring in the formula (1-1) or the carbon atom constituting the condensed ring in the formula (1-2). (R ¹¹ )-, -O-, -S-, -CO-, -COO-, -NR ⁴ -, -CO-NR ⁴ -, -NR ⁴ -CO-O- or -NR ⁴ -CO-NR It is a divalent organic group bonded by ^5- . R ¹⁰ and R ¹¹ are each independently a hydrogen atom or an alkyl group. R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent organic group. R ² is a monovalent organic group. R ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. "*" represents a bond.)

<2> A liquid crystal aligning film formed using the liquid crystal aligning agent of <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, liquid-crystal orientation is favorable, voltage retention is high, and the liquid crystal element excellent in reliability can be obtained.

(Form for implementing the invention)

《Liquid crystal aligning agent》

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. An "aromatic ring" is a meaning including an aromatic hydrocarbon ring and an aromatic heterocyclic ring. An "organic group" refers to a group having a hydrocarbon group having 1 or more carbon atoms.

The liquid crystal aligning agent of this indication is a polymer which has in a principal chain the partial structure (A) which is at least 1 sort(s) chosen from the group which consists of the partial structure represented by following formula (1-1), and following formula (1-2) [P].

(In Formulas (1-1) and (1-2), B ¹ is a substituted or unsubstituted aromatic ring, and the nitrogen-containing heterocycle and condensed ring in Formulas (1-1) and (1-2) R ¹ is -C(R ¹⁰ ) with respect to the nitrogen atom constituting the condensed ring in the formula (1-1) or the carbon atom constituting the condensed ring in the formula (1-2). (R ¹¹ )-, -O-, -S-, -CO-, -COO-, -NR ⁴ -, -CO-NR ⁴ -, -NR ⁴ -CO-O- or -NR ⁴ -CO-NR It is a divalent organic group bonded by ^5- . R ¹⁰ and R ¹¹ are each independently a hydrogen atom or an alkyl group. R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent organic group. R ² is a monovalent organic group. R ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. "*" represents a bond.)

<Polymer [P]>

・About partial structure (A)

In the formulas (1-1) and (1-2), R ¹ is -C(R ¹⁰ )(R ¹¹ ) with respect to the condensed ring in the formulas (1-1) and (1-2). )-, -O-, -S-, -CO-, -COO-, -NR ⁴ -, -CO-NR ⁴ -, -NR ⁴ -CO-O- or -NR ⁴ -CO-NR ⁵ -( Hereinafter, it should just couple|bond by "connecting group L"). Moreover, when R< ¹ > is couple|bonded with -COO- with respect to the nitrogen atom which comprises the condensed ring in Formula (1-1), or the carbon atom which comprises the condensed ring in Formula (1-2), -COO - may couple|bond with either -CO- or -O- with respect to a nitrogen atom or a carbon atom in a condensed ring. Similarly, R ¹ is -CO-NR ⁴ - or -NR ⁴ with respect to the nitrogen atom constituting the condensed ring in Formula (1-1) or the carbon atom constituting the condensed ring in Formula (1-2). When bonding with -CO-O-, -CO-NR ⁴ - and -NR ⁴ -CO-O- may be bonded with -NR ⁴ - with respect to a nitrogen atom or a carbon atom in the condensed ring, -CO- Or you may couple|bond with -O-. As R< ¹ >, the divalent group which consists of a chain structure, and the divalent group which has a cyclic structure is mentioned, for example.

In the linking group L, R ¹⁰ and R ¹¹ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom (ie, when -C(R ¹⁰ )(R ¹¹ )- is a methylene group). . The monovalent organic group of R ⁴ and R ⁵ is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent leaving group (hereinafter also simply referred to as a “leaving group”) which is released by heat or light. When R ⁴ and R ⁵ are 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.

In R ⁴ and R ⁵ , the leaving group is preferably a monovalent group (hereinafter, also referred to as a “thermal leaving group”) which is removed by heat and substituted with a hydrogen atom. Specific examples of the thermal leaving group include groups generally used as protecting groups for amino groups, and examples thereof include carbamate protecting groups, amide protecting groups, imide protecting groups, and sulfonamide protecting groups. Among these, a carbamate-type protecting group is preferable at the point with high desorption property by heat|fever. Specific examples of R ⁴ and R ⁵ in the case where R ⁴ and R ⁵ are a leaving group include a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, and an allyloxy group. A carbonyl group, 2-(trimethylsilyl)ethoxycarbonyl group, etc. are mentioned. Among these, a tert-butoxycarbonyl group (Boc group) is particularly preferable from the viewpoints of excellent thermal detachability and the ability to reduce the amount remaining in the film of the detached structure.

Among them, R ⁴ and R ⁵ are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a thermal leaving group, and more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or tert-butoxycarbonyl group.

The point that the voltage retention ratio (VHR) of the liquid crystal element can be increased, the point that a reliable liquid crystal element with little decrease in the voltage retention ratio even when driven for a long period of time can be obtained, and the point that a liquid crystal element showing good liquid crystal alignment property can be obtained In R ¹ , it is preferable to have a chain hydrocarbon structure having 1 or more carbon atoms in the main chain. Specifically, R ¹ is a divalent chain hydrocarbon group having 1 or more carbon atoms, or -O-, -S-, -CO-, - on the condition that arbitrary methylene groups of a chain hydrocarbon group having 2 or more carbon atoms are not adjacent to each other. It is preferable that it is a divalent group substituted with COO-, -NR ⁴ -, -CO-NR ⁴ -, -NR ⁴ -CO-O-, or -NR ⁴ -CO-NR ⁵ -. ^In addition, about the specific example and preferable example of ^R4 and R5, the above description can be referred to (the same hereafter).

When R ¹ is a divalent chain hydrocarbon group, the chain hydrocarbon group may be linear or branched. R An alkanediyl group is preferable and, as for the chain hydrocarbon group in ¹ , a linear alkanediyl group is more preferable. When R ¹ is a divalent chain hydrocarbon group, the carbon number of the chain hydrocarbon group is preferably 2 or more, and 3 or more This is more preferable. In addition, from the viewpoint of achieving both improvement of film strength (and improvement of rubbing resistance) and improvement of voltage retention of the liquid crystal element, when R ¹ is a chain hydrocarbon group, the carbon number of R ¹ is 20 or less. It is preferable, 15 or less are more preferable, and 10 or less are still more preferable.

R ¹ is any methylene group that the chain hydrocarbon group has -O-, -S-, -CO-, -COO-, -NR ⁴ -, -CO-NR ⁴ -, -NR ⁴ -CO-O- or - In the case of a divalent group substituted with NR ⁴ -CO-NR ⁵ -, the above description is incorporated for specific examples and preferred examples of the chain hydrocarbon group.

In the partial structure represented by Formula (1-1), R ¹ is -C(R ¹⁰ )(R ¹¹ )-, -CO- from the viewpoint of obtaining a liquid crystal element having good liquid crystal orientation, high reliability and high VHR. , -COO-, -NR ⁴ -, -CO-NR ⁴ -, -NR ⁴ -CO-O- or -NR ⁴ -CO-NR ⁵ - is preferably a divalent organic group bonded to, -C(R It is more preferable that it is a divalent organic group couple|bonded with ¹⁰ )( ^R11 )-.

From the viewpoint of achieving high VHR of the liquid crystal element, high reliability, and quantification of liquid crystal orientation, R ¹ is, among others, a hydrocarbon group bonded to the condensed ring in Formulas (1-1) and (1-2). It is preferable that it is a divalent organic group. Specifically, R ¹ is a divalent chain hydrocarbon group having 1 or more carbon atoms, or -O-, -S-, -CO-, -COO-, -NR ⁴ - , -CO-NR ⁴ -, -NR ⁴ -CO-O- or -NR ⁴ -CO-NR ⁵ - is preferably a divalent organic group.

In said formula (1-2), as R< ² >, a C1-C10 monovalent|monohydric hydrocarbon group and a leaving group are mentioned. According to the structure in which R2 in the partial structure represented by said Formula ( ^1-2 ) is an organic group, compared with the case where ^R2 is a hydrogen atom, it is suitable at the point which can implement|achieve favorable liquid-crystal orientation and high voltage retention. For specific examples and preferred examples of the leaving group represented by R ² , the description of the leaving group represented by R ⁴ and R ⁵ is incorporated. Viewing angle characteristics of a liquid crystal element by setting it as a liquid crystal element showing a low pretilt angle (hereinafter also referred to as "low pretilt angle characteristic") of, for example, 1 degree or less in a point of view of obtaining a liquid crystal element showing good liquid crystal alignment and a rubbing alignment film From the viewpoint ^of improving

With respect to R ³ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

^A benzene ring or a pyridine ring is preferable and, as for the aromatic ring in B1, a viewpoint of achieving high VHR-ization of a liquid crystal element, high reliability-ization, and liquid-crystal orientation quantification, and a benzene ring is more preferable.

From a viewpoint of obtaining the liquid crystal element which shows favorable liquid-crystal orientation and low pretilt angle characteristic, partial structure (A) is a partial structure represented by said Formula (1-1), or R< ² > in said Formula (1-2) The partial structure which is a C1-C10 monovalent|monohydric hydrocarbon group or a leaving group is preferable, and it is more preferable that it is a partial structure represented by said Formula (1-1).

When B ¹ in the formulas (1-1) and (1-2) is a substituted or unsubstituted benzene ring, the partial structure (A) is, specifically, the following formulas (1-1A) and (1-A) 2A).

(In formulas (1-1A) and (1-2A), R ^1a is a divalent chain hydrocarbon group having 1 or more carbon atoms, or arbitrary methylene groups of a chain hydrocarbon group having 2 or more carbon atoms are not adjacent to each other - 2 substituted with O-, -S-, -CO-, -COO-, -NR ⁴ -, -CO-NR ⁴ -, -NR ⁴ -CO-O- or -NR ⁴ -CO-NR ⁵ - m is an integer of 0 to 3, and from the viewpoint of improving the liquid crystal orientation of the obtained liquid crystal element, 0 to ² are preferable, 0 or 1 is more preferable, and 0 is still more preferable. and R ³ has the same meaning as in the formulas (1-1) and (1-2). When m is 2 or 3, a plurality of R ³ in the formula is the same or different from each other. " indicates that it is a bond.)

The method for producing the polymer [P] is not particularly limited as long as the partial structure (A) can be introduced into the main chain. Since it is easy to introduce|transduce the partial structure (A) into a main chain, it is preferable that the polymer [P] is manufactured by the method of superposing|polymerizing using the monomer which has a partial structure (A). The monomer having a partial structure (A) is a diamine compound having a partial structure (A) from the viewpoint of being able to form a liquid crystal aligning film having high affinity with liquid crystal and high mechanical strength, and a high degree of freedom in the selection of the monomer ( Hereinafter also referred to as "specific diamine") is preferred.

Here, the "main chain" of a polymer refers to the part of the "stem" which consists of the chain of the longest atom in a polymer. In addition, it is permissible for the part of this "stem" to contain a ring structure. That is, "having a partial structure (A) in the main chain" means that the partial structure (A) constitutes a part of the main chain. The "side chain" of a polymer means the part branched from the "stem" of a polymer.

Specific diamine should just be a monomer which has a partial structure (A) and two primary amino groups, and is not specifically limited about the structure of another part. As a preferable specific example of specific diamine, the compound represented by the compound represented by a following formula (2-1), and a following formula (2-2) are mentioned. It is preferable that the polymer [P] has a structural unit derived from at least 1 sort(s) selected from the group which consists of a compound represented by a following formula (2-1), and a compound represented by a following formula (2-2).

(In formulas (2-1) and (2-2), A ¹ is a single bond, a divalent alicyclic group, a divalent aromatic cyclic group, a divalent group represented by the following formula (3-1), or a It is a divalent group represented by 3-2) B ¹ , R ¹ , R ² and R ³ have the same meanings as in the formulas (1-1) and (1-2) above, with the proviso that A ¹ is a single bond. In the case of , R ¹ is bonded to the primary amino group in the formula with a carbon atom constituting the hydrocarbon group.)

(In Formulas (3-1) and (3-2), B ² is a substituted or unsubstituted aromatic ring, and the nitrogen-containing heterocycle and condensed ring in Formulas (3-1) and (3-2) R ⁶ is a monovalent organic group. R ⁷ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. (2-1) or (2-2) represents a bond with the primary amino group. "*" represents a bond.)

In the formulas (2-1) and (2-2), as the divalent alicyclic group of A ¹ , two A group from which a hydrogen atom has been removed is exemplified. When A ¹ is a divalent alicyclic group, a substituent may be introduced into the ring portion of the alicyclic hydrocarbon ring. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom.

Examples of the divalent aromatic ring group for A ¹ include a divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group. The divalent aromatic ring group of A ¹ is preferably a divalent aromatic hydrocarbon group or a divalent nitrogen-containing aromatic heterocyclic group. A ¹ may have a substituent in the aromatic ring moiety. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom.

As a specific example when A ¹ is a divalent aromatic ring group, as a divalent aromatic hydrocarbon group, two arbitrary hydrogen atoms bonded to carbon atoms constituting the benzene ring, biphenyl ring, naphthalene ring or anthracene ring ring are removed. the group made; Examples of the divalent nitrogen-containing aromatic heterocyclic group include groups obtained by removing two arbitrary hydrogen atoms bonded to carbon atoms constituting the pyridine ring, pyrimidine ring, pyridazine ring or pyrazine ring ring.

It is preferable that it is a substituted or unsubstituted phenylene group, a biphenylene group, or a pyridinediyl group, and, as for the divalent aromatic ring group of A1 from ^a viewpoint of attaining densification of a liquid crystal aligning film, it is more preferable that it is a substituted or unsubstituted phenylene group. do.

A benzene ring or a pyridine ring is preferable, and, as for the aromatic ring of B< ¹ >, a benzene ring is more preferable from a viewpoint of achieving high VHR-ization of a liquid crystal element, high reliability-ization, and liquid-crystal orientation improvement.

In the formulas (3-1) and (3-2), for specific examples and preferred examples of R ⁶ , R ⁷ , R ² , R in the formulas (2-1) and (2-2) Each of the descriptions of ³ is incorporated herein by reference. About ^the specific example and preferable example of B2, description of ^B1 in said Formula (2-1) and Formula (2-2) is incorporated.

In the above formulas (2-1) and (2-2), the position of the primary amino group bonded to the condensed ring structure in which the aromatic ring and the imidazole ring are condensed (hereinafter also referred to as “specific condensed ring structure”) is not particularly limited. does not When a specific condensed-ring structure is a benzimidazole structure, as for the bonding position of the primary amino group in a benzimidazole structure, 5-position or 6th-position is preferable. Moreover, the specific diamine used for the synthesis|combination of polymer [P] may contain the positional isomer from which the position of the primary amino group couple|bonded with the specific condensed-ring structure differs.

From the viewpoint of obtaining a highly reliable liquid crystal element with little decrease in voltage retention (VHR) even when driven for a long period of time, and from the viewpoint of obtaining a liquid crystal element showing good liquid crystal orientation, A ¹ is a divalent alicyclic group, a divalent aromatic ring group, It is preferably a divalent group represented by the formula (3-1) or a divalent group represented by the formula (3-2), and a divalent aromatic ring group, a divalent group represented by the formula (3-1) or the formula ( It is more preferable that it is a divalent group represented by 3-2).

It is preferable that specific diamine is at least 1 sort(s) chosen from the group which consists of the compound which is especially represented by a compound represented by a following formula (2-1A), and a following formula (2-2A).

(In formulas (2-1A) and (2-2A), A ^1a is a single bond, a divalent alicyclic group, a divalent aromatic cyclic group, a divalent group represented by the following formula (3-1A), or a It is a divalent group represented by 3-2A).R ^1a and m have the same meaning as the formulas (1-1A) and (1-2A) above. R ² and R ³ are the formulas (1-1) And it has the same meaning as in Formula (1-2).)

(In Formulas (3-1A) and (3-2A), r is an integer of 0 to 3. R ⁶ and R ⁷ have the same meaning as in Formulas (3-1) and (3-2) When r is 2 or 3, a plurality of R ⁷ in the formula are the same or different groups from each other. indicates that it is a bond of . "*" indicates that it is a bond.)

Specific diamine is at least 1 selected from the group consisting of a compound represented by Formula (2-1A) and a compound in which R ² is a monovalent hydrocarbon group or leaving group having 1 to 10 carbon atoms in Formula (2-2A) among the above. Species are preferable, and the compound represented by said Formula (2-1A) is more preferable. In the compound represented by the formula (2-1A), in the formula (2-1A), A ^1a is a divalent group represented by the formula (3-1A), a phenylene group, a biphenylene group, or a pyridinediyl group It is preferable, and it is more preferable that it is a divalent group represented by said Formula (3-1A).

As a specific example of specific diamine, the compound etc. which are represented by each of following formula (4-1) - (4-34) are mentioned.

In the polymer [P], the content ratio of the structural unit derived from the monomer having the partial structure (A) (hereinafter also referred to as “structural unit (A)”) expresses good liquid crystal orientation and low pretilt angle characteristics, Moreover, from a viewpoint of obtaining the liquid crystal element which shows high VHR and high reliability, it is preferable that it is 2 mol part or more with respect to 100 mol part of the total amount of the monomeric unit which polymer [P] has. The content of the structural unit (A) is more preferably 5 mol parts or more, still more preferably 7 mol parts or more, with respect to 100 mol parts of the total amount of monomer units in the polymer [P]. The content of the structural unit (A) may be appropriately set depending on the main chain of the polymer [P], but is, for example, 50 mol parts or less with respect to 100 mol parts of the total amount of the monomer units in the polymer [P]. In addition, the number of structural units (A) which the polymer [P] has may be one, and 2 or more types may be sufficient as them.

・About polymer [P]

The main chain of the polymer [P] is not particularly limited. The polymer [P] is at least selected from the group consisting of polyamic acids, polyamic acid esters, and polyimides, in terms of being able to form a liquid crystal aligning film with high affinity and mechanical strength with a liquid crystal and high reliability. It is preferable that it is 1 type.

(polyamic acid)

When the polymer [P] is polyamic acid, the polyamic acid (hereinafter also referred to as "polyamic acid [P]") can be obtained by reacting tetracarboxylic dianhydride with a diamine compound containing a specific diamine.

(tetracarboxylic acid dianhydride)

As tetracarboxylic dianhydride used for the synthesis|combination of polyamic acid [P], aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. Specific examples thereof include 1,2,3,4-butanetetracarboxylic dianhydride, ethylenediamine tetraacetic 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 et al., 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-2 anhydride; As aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycol bisanhydrotrimellitate, 4,4'-(hexafluoroiso propylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 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 of polyamic acid [P] is highly soluble, and a liquid crystal aligning film exhibiting good liquid crystal alignment and electrical properties can be obtained, so aliphatic tetracarboxylic dianhydride and alicyclic tetracarbon It is preferable that at least 1 sort(s) chosen from the group which consists of acid dianhydrides is included, and it is more preferable that alicyclic tetracarboxylic dianhydride is included. The proportion of alicyclic tetracarboxylic dianhydride used 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 [P], It is more preferable that it is 50 mol% or more.

(diamine compound)

A specific diamine may be sufficient as the diamine compound used for the synthesis|combination of polyamic acid [P], The diamine (henceforth "other diamine") which does not have a partial structure (A) may be included with a specific diamine. Examples of other diamines include aliphatic diamine, alicyclic diamine, aromatic diamine, and diaminoorganosiloxane.

Specific examples of other diamines include metaxylylenediamine, hexamethylenediamine, and the like as aliphatic diamines; Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and the like; As aromatic diamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4-aminophenyl-4-aminobenzoate, 4,4'-diamino Azobenzene, 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, 6,6'-(pentamethylenedioxy)bis(3-aminopyridine), N,N'-di(5-amino-2-pyridyl) )-N,N'-di(tert-butoxycarbonyl)ethylenediamine, bis[2-(4-aminophenyl)ethyl]hexane diacid, 4,4'-diaminodiphenyl ether, 4,4' -diaminodiphenylamine, 4,4'-diaminodiphenethylurea, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoro lopropane, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-(phenylenediisopropylidene)bisaniline, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-dia Minocarbazole, 3,6-diaminoacridine, a monomer containing a diphenylamine structure, the following formula (D-1)

(In formula (D-1), R ¹¹ and R ¹² are each independently an alkanediyl group. R ¹³ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a protecting group. n1 is an integer of 1 to 3 When n1 is 2 or 3, a plurality of R ¹² are the same or different groups, and a plurality of R ¹³ are the same or different from each other.)

Main chain type diamines, such as a compound represented by;

Hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, chole Steryloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3 ,5-diaminobenzoic acid cholesteryl, 3,5-diaminobenzoic acid lanostanyl, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane , 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 3,5-diaminobenzoic acid = 5ξ-cholestan-3-yl, the following formula (E-1)

(In formula (E-1), X ^I and X ^II are each independently a single bond, -O-, *-COO-, or *-OCO- (where "*" is a bond with the diaminophenyl group side) R ^I is an alkanediyl group having 1 to 3 carbon atoms R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms R ^III is an alkyl group or alkoxy group having 1 to 20 carbon atoms , a fluoroalkyl group, or a fluoroalkoxy group. a is 0 or 1. b is an integer from 0 to 3. c is an integer from 0 to 2. d is 0 or 1. provided that 1≤a+b+c≤ is 3.)

side-chain diamines such as compounds represented by

Examples of the diaminoorganosiloxane include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and the like.

As a compound represented by said Formula (D-1), the compound etc. which are represented by each of following formula (D-1-1) - Formula (D-1-3) are mentioned, for example. As a compound represented by said Formula (E-1), the compound etc. which are represented by each of following formula (E-1-1) - Formula (E-1-4) are mentioned, for example. As other diamine, 1 type can be used individually or in combination of 2 or more type. In addition, in the formula, "Boc" represents a tert-butoxycarbonyl group (hereinafter the same).

In the synthesis of polyamic acid [P], the use ratio of a specific diamine is, from the viewpoint of obtaining a liquid crystal device that exhibits good liquid crystal orientation and low pretilt angle characteristics, and exhibits high VHR and high reliability, polyamic acid [P] ], it is preferable that it is 5 mol% or more with respect to the total amount of the diamine compound used for synthesis|combination, It is more preferable that it is 10 mol% or more, It is still more preferable that it is 15 mol% or more. As specific diamine, you may use individually by 1 type, and may use it in combination of 2 or more type.

(Synthesis of polyamic acid)

Polyamic acid [P] 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 [P], the ratio of using tetracarboxylic dianhydride and the diamine compound is such that the ratio of the acid anhydride groups of tetracarboxylic dianhydride to 0.2 to 2 equivalents with respect to 1 equivalent of the amino group of the diamine compound is desirable. 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, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. and the like. 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 [P] 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 an aprotic polar solvent, a phenol solvent, an alcohol solvent, a ketone solvent, an ester solvent, an ether solvent, a halogenated hydrocarbon, and a hydrocarbon. Among these, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphotriamide, At least one selected from the group consisting of m-cresol, xylenol and halogenated phenol is used as the reaction solvent, or at least one of these and another organic solvent (eg, butyl cellosolve, diethylene glycol diethyl It is preferred to use mixtures with ethers, etc.). It is preferable that the usage-amount of an organic solvent sets it as the quantity used as 0.1-50 mass % with respect to the total amount of the total amount of tetracarboxylic dianhydride and diamine.

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

・Polyamic acid ester

When the polymer [P] is a polyamic acid ester, the polyamic acid ester (hereinafter also referred to as “polyamic acid ester [P]”) is, for example, [I] a method of reacting polyamic acid [P] with an esterifying agent; [II] a method of reacting a tetracarboxylic acid diester with a diamine compound containing a specific diamine, [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine compound containing a specific diamine, etc. can The polyamic acid ester [P] may have only a amic acid ester structure, or may be a partial esterified product in which the amic acid structure and the amic acid ester structure coexist. The reaction solution formed by dissolving polyamic acid ester [P] may be used for preparation of a liquid crystal aligning agent as it is, and after isolating polyamic acid ester [P] contained in a reaction solution, you may provide for preparation of a liquid crystal aligning agent.

・Polyimide

When the polymer [P] is a polyimide, the polyimide (hereinafter also referred to as “polyimide [P]”) can be obtained, for example, by imidizing the polyamic acid [P] synthesized as described above by dehydration and ring closure. have. The polyimide [P] may be a complete imidide in which all of the amic acid structure of the polyamic acid [P], which is its precursor, has been cyclized by dehydration, or only a part of the amic acid structure is cyclized by dehydration so that the amic acid structure and the imide ring structure coexist. Partial imide storage is fine. It is preferable that the imidation ratio is 20 to 99 %, and, as for polyimide [P], 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, an isoimide ring may be sufficient as a part of an imide ring.

The dehydration ring closure of the polyamic acid [P] is preferably performed by dissolving the polyamic acid [P] in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating as 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 [P]. 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 [P]. 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 polyimide [P] may be used for preparation of a liquid crystal aligning agent as it is, and after isolating polyimide [P], you may provide for preparation of a liquid crystal aligning agent.

The solution viscosity of the polymer [P] preferably has a solution viscosity of 10 to 800 mPa·s, more preferably 15 to 500 mPa·s when a solution having a concentration of 10% by mass is used. . In addition, the solution viscosity (mPa·s) is a concentration of 10% by mass prepared using a positive solvent (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer [P]. It is the value measured in 25 degreeC about the polymer solution of using E-type rotational viscometer.

The weight average molecular weight (Mw) of the polymer [P] 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. In addition, at the time of preparation of a liquid crystal aligning agent, as polymer [P], you may use individually by 1 type, and may use it in combination of 2 or more type.

<Other ingredients>

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

・Polymer [Q]

The liquid crystal aligning agent of this indication may further contain the polymer (henceforth "polymer [Q]") which does not have a partial structure (A) as a polymer component. The main skeleton of the polymer [Q] is not particularly limited. Examples of the polymer [Q] include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyenamine, polyurea, polyamide, polyamideimide, polybenzoxazole precursor, polybenzoxa. A sol, a cellulose derivative, polyacetal, a (meth)acrylic-type polymer, a styrene-type polymer, a maleimide-type polymer, a styrene-maleimide-type copolymer, etc. are mentioned. From the viewpoint of obtaining a highly reliable liquid crystal device, the polymer [Q] is a structural unit derived from, among these, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, and a monomer having a polymerizable unsaturated carbon-carbon bond. At least one selected from the group consisting of polymers including Examples of the polymer containing a structural unit derived from a monomer having a polymerizable unsaturated carbon-carbon bond include a (meth)acrylic polymer, a styrene polymer, a maleimide polymer, and a styrene-maleimide copolymer.

When making a liquid crystal aligning agent contain a polymer [Q], 1 mass % or more is preferable with respect to the total amount of a polymer [P] and a polymer [Q], and, as for the content rate of a polymer [Q], 2 mass % or more is more desirable. Moreover, 95 mass % or less is preferable with respect to the total amount of polymer [P] and polymer [Q], and, as for the content rate of polymer [Q], 90 mass % or less is more preferable. As polymer [Q], 1 type can be used individually or in combination of 2 or more type.

·solvent

The liquid crystal aligning agent of this indication is prepared as a liquid composition in which a polymer [P] 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 a solvent, 1 type can be used individually or in mixture of 2 or more types.

As another component contained in a liquid crystal aligning agent, a crosslinking 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 it is suitable at the point which can obtain the liquid crystal aligning film which shows more favorable liquid-crystal orientation. On the other hand, if solid content concentration is 10 mass % or less, a coating film can be made into suitable thickness, and the liquid crystal aligning film which shows favorable liquid-crystal orientation is easy to be obtained, and the viscosity of a liquid crystal aligning agent becomes moderate, and applicability|paintability 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. is available. In the case of manufacturing the TN type, STN type, VA type or PSA type liquid crystal element, two substrates on which the 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. Application of the liquid crystal aligning agent to a substrate is, for example, a spin coating method, a printing method (eg, an offset printing method, a flexographic printing method, etc.), an inkjet method, a slit coating method, a bar coater method, and extrusion. It can be carried out by a 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 thermal imidization of the amic acid structure present in the polymer. The firing temperature (post-baking temperature) at this time is preferably 80 to 280°C, more preferably 80 to 250°C. Post-baking time becomes like this. Preferably it is 5 to 200 minutes. The film thickness of the film formed becomes like this. Preferably it is 0.001-1 micrometer.

<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, nylon, etc. as an orientation treatment, 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. The liquid crystal aligning film suitable for the liquid crystal element of a vertical alignment type can be used suitably also for a PSA type liquid crystal element.

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, linearly polarized light or partially polarized light may be sufficient. 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 made into 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 washed with, for example, water, an organic solvent (eg, methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.) ) or a mixture thereof may be used for cleaning or heating the substrate.

<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, a nematic liquid crystal and a smectic liquid crystal are mentioned, Among these, a nematic liquid crystal is preferable.

In the PSA mode, a polymerizable compound (for example, a polyfunctional (meth)acrylate compound, etc.) is filled in the cell gap together with the liquid crystal, and after the liquid crystal cell is constructed, a voltage between the conductive films of a pair of substrates A process of irradiating light to the liquid crystal cell in a state in which is applied is performed. At the time of manufacture of the liquid crystal element of PSA type, the usage ratio of a polymeric compound is 0.01-3 mass parts with respect to a total of 100 mass parts of a liquid crystal, Preferably it is 0.05-1 mass part.

When manufacturing a liquid crystal display device, a polarizing plate is bonded together on the outer surface of a liquid crystal cell then. As a polarizing plate, the polarizing plate which sandwiched the polarizing film called "H film" which absorbed iodine while extending|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 this indication can be effectively applied to various uses. Specifically, for example, various display devices such as watches, portable game consoles, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smart phones, various monitors, liquid crystal TVs, and information displays; , a dimming device, retardation film, and the like.

(Example)

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 weight average molecular weight (Mw) and number average molecular weight (Mn) of the styrene-maleimide copolymer, and the imidation ratio of the polyimide in the polymer solution were measured by the following methods. 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.

[Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn)]

Mw and Mn are polystyrene conversion values measured by GPC in the following conditions.

Column: TSKgel GRCXLII manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40℃

Pressure: 68kgf/cm2

[Imidation rate of polyimide]

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

Imidization ratio [%] = (1-(A ¹ /(A ² ×α))) × 100 … (One)

(In formula (1), A ¹ is the peak area derived from protons of the NH group appearing in the vicinity of 10 ppm of the chemical shift, A ² is the peak area derived from other protons, and α is the polymer precursor (polyamic acid) It is the ratio of the number of other protons to one proton of the NH group.)

The abbreviation of a compound is as follows. In addition, below, the compound represented by Formula (X) may be simply represented as "compound (X)."

(tetracarboxylic acid dianhydride)

(diamine compound)

In addition, in the compounds (DA-1) to (DA-6) used in the following examples, the compound (compound represented by the above formula) having a primary amino group at the 5-position of benzimidazole is a compound of benzimidazole. Positional isomers having a primary amino group at the 6-position are included.

(etc)

<Synthesis of polymer>

1. Synthesis of polyamic acid

[Synthesis Example 1]

100 parts by mole of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 100 parts by mole of 4,4'-diamino-1,2-diphenylethane as diamine compound N-methyl-2 - It melt|dissolved in pyrrolidone (NMP), it reacted at room temperature for 6 hours, and obtained the solution containing 15 mass % of polyamic acids (this is called polymer (PA-1)).

[Synthesis Examples 2-28]

Polyamic acids (polymers (PA-2) to (PA) -28)) was obtained.

2. Synthesis of polyimide

[Synthesis Example 29]

100 mol parts of 1,3-dimethylcyclobutane-1,2:3,4-tetracarboxylic dianhydride as tetracarboxylic dianhydride, 20 mol parts of compound (DA-4) and 80 mol of compound (DB-7) as diamine compound The part was melt|dissolved in NMP, it reacted at room temperature for 6 hours, and the solution containing 15 mass % of polyamic acids 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 new NMP to obtain a solution containing 15% by mass of a polyimide having an imidation ratio of about 80% (this is called a polymer (PI-1)).

[Synthesis Examples 30 to 35]

The same operation as in Synthesis Example 29 was performed except that the types and amounts of the tetracarboxylic dianhydride and diamine compounds to be used were changed as shown in Table 3, and polyimides (polymers (PI-2) to (PI-7) )) was obtained.

3. Synthesis of polyorganosiloxane

[Synthesis Example 36]

In a 1000 mL three-necked flask, 100.0 g of 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane (compound represented by the above formula (s-1)), 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine It injected|threw-in and mixed at room temperature. Next, 100 g of deionized water was dripped from the dropping funnel over 30 minutes, and then, the reaction was performed at 80°C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by mass aqueous ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure. Methyl isobutyl ketone was added in an appropriate amount, and the 50 mass % solution of the polymer (ESSQ-1) which is polyorganosiloxane which has an epoxy group was obtained.

In a 500 mL three-necked flask, 3.10 g of compound (c-1) (20 mol% with respect to the amount of epoxy groups contained in the polymer (ESSQ-1)) and 3.24 g of compound (c-2) (the epoxy contained in the polymer (ESSQ-1)) 10 mol%), tetrabutylammonium bromide 1.00g, polymer (ESSQ-1) containing solution 20.0g, and methylisobutylketone 290.0g were added, and it stirred at 90 degreeC for 18 hours. After cooling to room temperature, the liquid separation washing operation was repeated 10 times with distilled water. After that, the organic layer is recovered, and the concentration and NMP dilution are repeated twice with a rotary evaporator, and then adjusted so that the solid content concentration is 10% by mass using NMP, and polyorganosiloxane (a polymer (PSQ- The NMP solution of 1) was obtained.

4. Synthesis of styrene-maleimide-based copolymer

[Synthesis Example 37]

In a 100 mL two-neck flask under nitrogen, 5.00 g of compound (M-1), 1.05 g of compound (M-2), 4.80 g of compound (M-3) and 2.26 g of compound (M-4) as polymerization monomers; 0.39 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator, 0.39 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and N-methyl as a solvent 52.5 ml of -2-pyrrolidone (NMP) was added, and polymerization was carried out at 70°C for 6 hours. After reprecipitation in methanol, the precipitate was filtered and vacuum dried at room temperature for 8 hours to obtain a styrene-maleimide-based copolymer (this is referred to as polymer (MI-1)). The weight average molecular weight (Mw) measured in polystyrene conversion by GPC was 30000, and molecular weight distribution (Mw/Mn) was 2.

[Synthesis Example 38]

In a 100 mL two-neck flask under nitrogen, as a polymerization monomer, 10 mole parts of compound (M-5), 10 mole parts of compound (M-6), 30 mole parts of compound (M-7), 10 mole parts of compound (M-8), compound 20 mol parts of (M-9), 20 mol parts of compound (M-10), 2 mol parts of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator, and 50 ml of tetrahydrofuran as a solvent In addition, it superposed|polymerized at 70 degreeC for 6 hours. After reprecipitation in methanol, the precipitate was filtered and vacuum dried at room temperature for 8 hours to obtain a styrene-maleimide-based copolymer (this is referred to as polymer (MI-2)). The weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 92700, and molecular weight distribution (Mw/Mn) was 4.78.

<Preparation and evaluation of liquid crystal aligning agent>

[Example 1: Rubbing FFS type liquid crystal display device]

1. Preparation of liquid crystal aligning agent

The solution of the polymer (PA-4) obtained in Synthesis Example 4 was diluted with NMP and butylcellosolve (BC), the solvent composition was NMP/BC=80/20 (mass ratio), and the solid content concentration was 3.5 mass % solution. A liquid crystal aligning agent (AL-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 (referred to as a first substrate) in which a flat electrode (bottom electrode), an insulating layer, and a comb-tooth electrode (top electrode) are laminated on one side in this order, and a glass substrate without an electrode (referred to as a second substrate) ) was prepared. Next, the liquid crystal aligning agent (AL-1) was apply|coated with the spinner to each of the single side|surface of the electrode formation surface of a 1st board|substrate, and a 2nd board|substrate, and it heated (prebaked) for 3 minutes on a 110 degreeC hotplate. Then, drying (post-baking) was performed for 30 minutes in the 230 degreeC oven which replaced the inside of the furnace with nitrogen, and the coating film with an average film thickness of 0.08 micrometers 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 epoxy resin adhesive which left the liquid crystal injection hole in the edge of the surface on which the liquid crystal aligning film was formed, and put the aluminum oxide sphere of diameter 3.5 micrometers was screen-printed and apply|coated. 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 a 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 liquid crystal orientation

The liquid crystal cell manufactured in said 2. was left still on the high-brightness backlight of 27,000 cd/m<2> for 500 hours, and the liquid-crystal orientation was evaluated by the retardation change rate in before and behind irradiation of a backlight. First, about the liquid crystal cell manufactured in said 2., retardation was measured by the Optoscience company Axoscan, and the change rate alpha of retardation before and behind backlight irradiation was computed by following Numerical formula (z-1). It can be said that the liquid-crystal orientation is favorable, so that change rate (alpha) is small. The case where the rate of change α was 1% or less was considered "good (○)", the case where it was larger than 1% and 2% or less was "possible (Δ)", and the case where it was larger than 2% was called "poor (x)".

α=Δθ/θ1 … (z-1)

(In formula (z-1), Δθ represents the retardation difference before and after irradiation, and θ1 represents the retardation value before irradiation.)

As a result, evaluation of the liquid-crystal orientation of this Example was evaluation of "possibility ((triangle|delta))".

4. Evaluation of low pre-tilt angle characteristics

About the liquid crystal cell manufactured in said 2., nonpatent literature "T. J. Scheffer et. al. J. Appl. Phys. vo.19, p.2013 (1980)", the value of the inclination angle of liquid crystal molecules from the substrate surface was measured by the crystal rotation method using He-Ne laser light, and this was called the pretilt angle. . When the measured value of the pretilt angle was less than 0.75 degrees, it was "good (○)", when it was 0.75 degrees or more and 1.0 degrees or less, it was "possible (Δ)", and when it was larger than 1.0 degrees, it was called "bad (x)". As a result, the evaluation of the low pre-tilt angle characteristic of this Example was "possible (Δ)" (refer to the item of "Low tilt" in Table 4).

5. Assessment of Initial VHR

After leaving still the liquid crystal cell manufactured in said 2. in 60 degreeC oven, the voltage retention (VHR) was measured on 1V and 1670 msec conditions using the Toyo Technica company VHR measuring apparatus "VHR-1". As evaluation criteria, when VHR is higher than 70%, it was set as "good (○)", when 70% or less and 60% or more, "possible (Δ)", and when less than 60%, "bad (x)" was set. As a result, evaluation of the initial stage VHR of this Example was "good (circle)".

6. Assessment of VHR Reliability

About the liquid crystal cell manufactured in said 2., the reliability with respect to voltage retention 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 Toyo Technica company VHR measuring apparatus "VHR-1" was used as a measuring apparatus. The rate of change of VHR (?VHR) at this time was calculated from the difference between VHR1 and VHR2 (?VHR=VHR1-VHR2), and VHR reliability was evaluated by ?VHR. The case where ΔVHR was less than 15% was judged as "good (○)", the case where it was 15% or more and 20% or less was judged as "possible (Δ)", and the case where it was larger than 20% was judged as "poor (x)". As a result, in this Example, VHR reliability was "good (circle)".

7. Evaluation of film strength (rubbing resistance)

The liquid crystal aligning agent (AL-1) prepared in said 1. was apply|coated using the spinner on a glass substrate, and it heated (prebaked) 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. When the haze value of the film before the rubbing treatment is Hz1 (%) and the haze value of the film after the rubbing treatment is Hz2 (%), the haze change value is expressed by the following formula (z-2).

Haze change value (%) = Hz2-Hz1 ... (z-2)

The case where the haze change value in a liquid crystal aligning film was less than 1.0 was evaluated as "favorable (○)" and the case where it was 1.0 or more and 1.5 or less was "possible ((triangle|delta))", and the case larger than 1.5 was evaluated as "defect (x)." If the haze change value is 1.5 or less (more preferably less than 1.0), the film strength is sufficiently high and the rubbing resistance is high, that is, it can be said that the mechanical properties of the film are good. As a result, in this Example, it was evaluation of the film|membrane strength "good|favorableness (circle)".

[Examples 2 to 16 and Comparative Examples 1 to 4]

Except having changed the composition of the liquid crystal aligning agent like Table 4, 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. Their results are shown in Table 4. In addition, in Examples 5-7, 9-13 and 15, and Comparative Example 3, two types of polymers were used as a polymer component. In Table 4, the numerical value of the polymer column shows the compounding ratio (mass part) in solid content of each polymer with respect to 100 mass parts of whole amounts of the polymer component used for preparation of a liquid crystal aligning agent.

As shown in Table 4, Examples 1-16 using the liquid crystal aligning agent containing a polymer [P] compared with Comparative Examples 1-4 using the liquid crystal aligning agent which does not contain a polymer [P], liquid-crystal orientation, The initial VHR and VHR reliability were balanced, and it was a favorable result. Moreover, Examples 1-16 were favorable also about the low pre-tilt angle characteristic and the mechanical characteristic of a film|membrane.

[Example 17: Optical FFS type liquid crystal display element]

1. Preparation of liquid crystal aligning agent

A solution containing 60 parts by mass of the polymer (PA-11) obtained in Synthesis Example 11 and a solution containing 40 parts by mass of the polymer (PA-24) obtained in Synthesis Example 24 were mixed, diluted with NMP and BC, and solvent composition This NMP/BC=80/20 (mass ratio) and solid content concentration set it as the solution which is 3.5 mass %. A liquid crystal aligning agent (AL-17) 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 photo-alignment method

The 1st board|substrate and 2nd board|substrate similar to Example 1 were prepared. Next, a liquid crystal aligning agent (AL-17) is apply|coated with a spinner to each of the one board|substrate surface of the electrode formation surface of a 1st board|substrate and a 2nd board|substrate, and it heats on an 80 degreeC hotplate for 1 minute (prebaking). did. 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 an 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 heat-processed by heating in 230 degreeC clean oven for 30 minutes, and the liquid crystal aligning film was formed.

Next, about one board|substrate among a pair of board|substrates in which the liquid crystal aligning film was formed, the epoxy resin adhesive which put the aluminum oxide sphere of diameter 3.5 micrometers in the outer edge of the surface which has a liquid crystal aligning film was apply|coated by screen printing. Then, the board|substrates were superimposed and pressed together so that the projection direction of the polarization axis|shaft to the board|substrate surface at the time of light irradiation might be antiparallel, and the adhesive agent was thermosetted at 150 degreeC over 1 hour. Next, after filling a negative liquid crystal (Merck Corporation make, MLC-6608) between a pair of board|substrates from a liquid crystal injection port, the liquid crystal injection port was sealed with the epoxy adhesive, and the liquid crystal cell was obtained. Moreover, 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. In addition, by carrying out a series of operations by changing the ultraviolet irradiation amount after post-baking in the range of 100 to 10,000 J/m 2 , three or more liquid crystal cells with different ultraviolet irradiation amounts are manufactured, and the exposure amount showing the best alignment characteristics The liquid crystal cell of (optimum exposure amount) was used for the following evaluation.

3. Evaluation

About the liquid crystal cell manufactured by said 2., the method similar to Example 1 evaluated the liquid-crystal orientation, initial stage VHR, and VHR reliability. Moreover, it carried out similarly to Example 1, and evaluated film strength using the liquid crystal aligning agent (AL-17). Table 5 shows the evaluation results.

[Examples 18-20]

Except having changed the composition of the liquid crystal aligning agent like Table 5, it carried out similarly to Example 17, and prepared the liquid crystal aligning agent. Moreover, using the obtained liquid crystal aligning agent, it carried out similarly to Example 17, the FFS-type liquid crystal cell was manufactured by the photo-alignment method, and various evaluation was performed. Their results are shown in Table 5. In Table 5, the numerical value of the polymer column shows the compounding ratio (mass part) in solid content of each polymer with respect to 100 mass parts of whole amounts of the polymer component used for preparation of a liquid crystal aligning agent.

As shown in Table 5, in Examples 17-20 using the liquid crystal aligning agent containing a polymer [P], liquid-crystal orientation, initial stage VHR, and VHR reliability were all favorable evaluation. In addition, Examples 17 to 20 had good film mechanical properties.

[Example 21: Optical VA type liquid crystal display element]

1. Preparation of liquid crystal aligning agent

A solution containing 30 parts by mass of the polymer (MI-1) obtained in Synthesis Example 37 and 70 parts by mass of the polymer (PA-24) obtained in Synthesis Example 24 was mixed, diluted with NMP and BC, and the solvent composition was NMP/ BC=80/20 (mass ratio) and solid content concentration set it as the solution which is 3.5 mass %. A liquid crystal aligning agent (AL-21) was prepared by filtering this solution with the filter with a hole diameter of 0.2 micrometer.

2. Preparation of optical VA type liquid crystal cell

On the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film, the liquid crystal aligning agent (AL-21) prepared above was apply|coated with the spinner, and prebaking was performed for 1 minute on an 80 degreeC hotplate. Then, it heated at 230 degreeC for 1 hour in the oven which replaced the inside of the furnace with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. Next, the surface of this coating film was irradiated with 1,000 J/m of polarized ultraviolet light containing a bright line of 313 nm using an Hg-Xe lamp and a Glan Taylor prism from a direction inclined by 40° from the substrate normal to impart liquid crystal alignment ability. . The same operation was repeated and a pair (two sheets) of board|substrates which have a liquid crystal aligning film were created.

After applying an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 3.5 µm to the outer periphery of the surface having a liquid crystal aligning film in the substrate by screen printing, the liquid crystal aligning film surfaces of a pair of substrates are opposed to each other, and each substrate was pressed so that the projection direction of the optical axis of the ultraviolet rays to the substrate surface was antiparallel, and the adhesive was thermosetted at 150°C for 1 hour. Next, after filling the gap between the board|substrates from a liquid crystal injection port with negative liquid crystal (Merck Corporation make, MLC-6608), 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 130 degreeC, it cooled slowly to room temperature.

3. Evaluation

About the liquid crystal cell manufactured by said 2., the method similar to Example 1 evaluated the liquid-crystal orientation, initial stage VHR, and VHR reliability. Table 6 shows the evaluation results.

[Comparative Example 5]

Except having changed the composition of the liquid crystal aligning agent like Table 6, it carried out similarly to Example 21, and prepared the liquid crystal aligning agent. Moreover, using the obtained liquid crystal aligning agent, it carried out similarly to Example 21, the optical VA type liquid crystal cell was manufactured, and various evaluation was performed. Their results are shown in Table 6. In Table 6, the numerical value of the polymer column shows the compounding ratio (mass part) in solid content of each polymer with respect to 100 mass parts of whole amounts of the polymer component used for preparation of a liquid crystal aligning agent.

As shown in Table 6, in Example 21 using the liquid crystal aligning agent containing a polymer [P], liquid-crystal orientation, initial stage VHR, and VHR reliability were all favorable evaluation. On the other hand, as for the comparative example 5 using the liquid crystal aligning agent which does not contain a polymer [P], initial stage VHR "possible" and VHR reliability were evaluation of "poor".

[Example 22: PSA type liquid crystal display device]

1. Preparation of liquid crystal aligning agent

A solution containing 5 parts by mass of the polymer (PSQ-1) obtained in Synthesis Example 36 and a solution containing 95 parts by mass of the polymer (PI-6) obtained in Synthesis Example 34 are mixed, diluted with NMP and BC, and solvent composition This NMP/BC=50/50 (mass ratio) and solid content concentration set it as the solution which is 3.5 mass %. A liquid crystal aligning agent (AL-22) was prepared by filtering this solution with the filter with a hole diameter of 0.2 micrometer.

2. Preparation of liquid crystal composition

With respect to 10 g of nematic liquid crystal (Merck Corporation make, MLC-6608), 0.3 mass of the photopolymerizable compound represented by 5 mass % of the liquid crystalline compound represented by a following formula (L1-1) and a following formula (L2-1) % was added and mixed to obtain liquid crystal composition LC1.

3. Preparation of PSA type liquid crystal cell

After applying the liquid crystal aligning agent (AL-22) prepared above using a spinner on the transparent electrode plate of the glass substrate with a transparent electrode which consists of an ITO film|membrane, prebaking on a hotplate at 80 degreeC for 1 minute, nitrogen By heating at 200°C for 1 hour in an oven substituted with , and removing the solvent, a 0.08 µm-thick coating film (liquid crystal aligning film) was formed. This coating film was rubbed with a rubbing machine having a roll wound with rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm/sec, and a bushy foot press-in length of 0.1 mm. Then, the board|substrate which has a liquid crystal aligning film was obtained by performing ultrasonic cleaning for 1 minute in ultrapure water, and drying for 10 minutes in 100 degreeC clean oven then. This operation was repeated and a pair (two sheets) of board|substrates which have a liquid crystal aligning film were obtained. In addition, this rubbing process is a weak rubbing process performed for the purpose of controlling collapse of a liquid crystal and performing orientation division|segmentation by a simple method.

An epoxy resin adhesive having an aluminum oxide sphere having a diameter of 3.5 µm is applied to the outer periphery of the surface having a liquid crystal aligning film in the substrate by screen printing, and then the liquid crystal aligning film surfaces of a pair of substrates are opposed to each other and overlapped The adhesive was thermally cured by pressing and heating at 150°C for 1 hour. Next, after filling the gap between the liquid crystal injection port and the substrate with the liquid crystal composition LC1 from the liquid crystal injection port, the liquid crystal injection port is sealed with an epoxy adhesive, and further heated at 150° C. for 10 minutes to remove the flow orientation during liquid crystal injection, and then at room temperature annealed until

Next, with respect to the obtained liquid crystal cell, an alternating current of 10 V with a frequency of 60 Hz is applied between the electrodes, and in a state in which the liquid crystal is driven, using an ultraviolet irradiation device using a metal halide lamp as a light source, an irradiation amount of ultraviolet rays of 50,000 J/m 2 investigated with In addition, this irradiation amount is the value measured using the photometer measured with wavelength 365nm reference|standard. Thereby, the PSA type liquid crystal cell was manufactured.

4. Evaluation

About the liquid crystal cell manufactured by said 3., the method similar to Example 1 evaluated the liquid-crystal orientation, initial stage VHR, and VHR reliability. Table 7 shows the evaluation results.

[Example 23 and Comparative Example 6]

Except having changed the composition of the liquid crystal aligning agent like Table 7, it carried out similarly to Example 22, and prepared the liquid crystal aligning agent. Moreover, using the obtained liquid crystal aligning agent, it carried out similarly to Example 22, the PSA type liquid crystal cell was manufactured, and various evaluation was performed. Table 7 shows the evaluation results. In Table 7, the numerical value of the polymer column shows the compounding ratio (mass part) in solid content of each polymer with respect to 100 mass parts of whole amounts of the polymer component used for preparation of a liquid crystal aligning agent.

As shown in Table 7, Examples 22 and 23 using the liquid crystal aligning agent containing a polymer [P] were evaluation with favorable liquid-crystal orientation, initial stage VHR, and VHR reliability all. On the other hand, in the comparative example 6 using the liquid crystal aligning agent which does not contain a polymer [P], initial stage VHR was "possible", and VHR reliability was evaluation of "poor".

From the above result, according to the liquid crystal aligning agent containing polymer [P], the liquid-crystal orientation was favorable, voltage retention was high, and it became clear that the liquid crystal element excellent in reliability could be obtained.

Claims (8)

Liquid crystal containing a polymer [P] having in the main chain at least one partial structure (A) selected from the group consisting of a partial structure represented by the following formula (1-1) and a partial structure represented by the following formula (1-2) aligning agent.

(In Formulas (1-1) and (1-2), B ¹ is a substituted or unsubstituted aromatic ring, and the nitrogen-containing heterocycle and condensed ring in Formulas (1-1) and (1-2) forming a structure; R ¹ is -C(R ¹⁰ ) with respect to a nitrogen atom constituting the condensed ring in Formula (1-1) or a carbon atom constituting the condensed ring in Formula (1-2) (R ¹¹ )-, -O-, -S-, -CO-, -COO-, -NR ⁴ -, -CO-NR ⁴ -, -NR ⁴ -CO-O- or -NR ⁴ -CO-NR ⁵ - is a divalent organic group bonded to; R ¹⁰ and R ¹¹ are each independently a hydrogen atom or an alkyl group; R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent organic group; R ² is a monovalent organic group; R ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; "*" represents a bond) According to claim 1,
The said polymer [P] has a structural unit derived from at least 1 sort(s) selected from the group which consists of a compound represented by a following formula (2-1), and a compound represented by a following formula (2-2), The liquid crystal aligning agent.

(In formulas (2-1) and (2-2), A ¹ is a single bond, a divalent alicyclic group, a divalent aromatic cyclic group, a divalent group represented by the following formula (3-1), or a 3-2) is a divalent group represented by: B ¹ , R ¹ , R ² and R ³ have the same meanings as in Formulas (1-1) and (1-2), provided that A ¹ is a single bond In the case of , R ¹ is bonded to the primary amino group in the formula with a carbon atom constituting the hydrocarbon group)

(In Formulas (3-1) and (3-2), B ² is a substituted or unsubstituted aromatic ring, and the nitrogen-containing heterocycle and condensed ring in Formulas (3-1) and (3-2) A structure is formed; R ⁶ is a monovalent organic group; R ⁷ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; "*1" is a formula (2-1) or (2-2) represents a bond with the primary amino group; "*" represents a bond) According to claim 1,
Said R< ¹ > has a C1 or more chain hydrocarbon structure in a principal chain, The liquid crystal aligning agent. According to claim 1,
The said polymer [P] is at least 1 sort(s) chosen from the group which consists of polyamic acid, polyamic acid ester, and a polyimide, Liquid crystal aligning agent. 5. The method of claim 4,
The said polymer [P] has a structural unit derived from alicyclic tetracarboxylic dianhydride, The liquid crystal aligning agent. According to claim 1,
The liquid crystal aligning agent which further contains the polymer [Q] which does not have the said partial structure (A). The liquid crystal aligning film formed with the liquid crystal aligning agent in any one of Claims 1-6. A liquid crystal element provided with the liquid crystal aligning film of Claim 7.