CN116731727A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer and compound - Google Patents

Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer and compound Download PDF

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Publication number
CN116731727A
CN116731727A CN202310149268.0A CN202310149268A CN116731727A CN 116731727 A CN116731727 A CN 116731727A CN 202310149268 A CN202310149268 A CN 202310149268A CN 116731727 A CN116731727 A CN 116731727A
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liquid crystal
polymer
compound
nitrogen
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安池伸夫
西村达哉
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JSR Corp
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JSR Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
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    • C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
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    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
    • C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
    • C07C225/28—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of non-condensed quinone rings
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    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
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    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/34—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
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    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
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    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
    • C07D279/24—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with hydrocarbon radicals, substituted by amino radicals, attached to the ring nitrogen atom
    • C07D279/26—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with hydrocarbon radicals, substituted by amino radicals, attached to the ring nitrogen atom without other substituents attached to the ring system
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C—CHEMISTRY; METALLURGY
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents

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Abstract

The invention provides a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal element, a polymer and a compound, which show good coating property and can obtain a liquid crystal element which is not easy to generate residual image caused by accumulation of residual charges. A liquid crystal aligning agent satisfying at least one of the requirements (I) and (II). Essential condition (I): a compound containing a partial structure (A) and a partial structure (B) in the same molecule; essential condition (II): a compound containing a partial structure (A) and a partial structure (B) in different molecules; partial structure (a): at least one selected from the group consisting of a specific substituted heterocyclic structure, a quinone structure, and a tetracyanoquinodimethane structure; partial structure (B): at least one selected from the group consisting of a partial structure represented by the following formula (b 1) and a phenothiazine structure. * -X 1 ‑B 1 ‑X 2 ‑* (b1)。

Description

Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer and compound
Technical Field
The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal element, a polymer and a compound.
Background
Liquid crystal elements are used in a wide range of applications from relatively large display devices such as liquid crystal televisions and information displays (information display) to small display devices such as smartphones. The performance of a liquid crystal element is determined by various characteristics such as the alignment property, the magnitude of the pretilt angle, and the voltage holding ratio of the liquid crystal. In order to improve the performance of liquid crystal elements, conventionally, a liquid crystal alignment film for aligning liquid crystals in a certain direction has been improved.
When a voltage is applied to a liquid crystal element to accumulate charges in the liquid crystal cell, there is a concern that the display quality of the liquid crystal element is degraded in the form of a Direct Current (DC) afterimage that is visually recognized by a viewer. Therefore, one of the characteristics required for the liquid crystal alignment film is that the accumulation of residual charges is small.
Accordingly, various techniques for suppressing accumulation of residual charges in a liquid crystal cell and improving display quality of a liquid crystal element have been proposed (for example, refer to patent document 1 or patent document 2). Patent document 1 discloses that the accumulated charge is reduced by containing a polyamic acid obtained by reacting a diamine compound containing a nitrogen-containing diamine, such as N4, N4' -bis (4-aminophenyl) -benzidine, with a tetracarboxylic dianhydride. Patent document 2 discloses a liquid crystal alignment film in which a liquid crystal alignment agent is made to contain a polymer obtained from a diamine having a structure in which a carbazole structure and a benzene ring are bonded through an amino group, thereby obtaining a rapid relaxation of accumulated charges.
[ Prior Art literature ]
[ patent literature ]
Patent document 1 japanese patent laid-open publication No. 2008-107811
[ patent document 2] International publication No. 2018/110354
Disclosure of Invention
[ problem to be solved by the invention ]
In recent years, liquid crystal display devices having a large screen size or a high definition have been widely used. In these applications, higher display uniformity and fewer afterimages are further required than in the past. Therefore, it is required that the liquid crystal alignment film can be formed using a liquid crystal alignment agent that exhibits excellent coatability (printability) and that the accumulation of residual charges is small. On the other hand, in the conventional method of reducing residual charges accumulated in a liquid crystal element by introducing a tertiary amine or a nitrogen-containing aromatic heterocycle into a liquid crystal alignment film, the following may occur: the functional groups (for example, carboxyl groups) of the polymer component interact with the nitrogen-containing compound to reduce the solubility, and it is difficult to cope with high coatability in recent years.
In addition, with the recent increase in the use of liquid crystal devices in general, development of liquid crystal elements which are less likely to cause afterimages has been demanded. In order to suppress the occurrence of an afterimage and achieve a high quality of a liquid crystal element, it is required that charges are not easily accumulated in the liquid crystal cell and the accumulated charges can be promptly relaxed.
The purpose of the present invention is to provide a liquid crystal aligning agent which has good coating property and can obtain a liquid crystal element which is not easy to generate residual image caused by accumulation of residual charges.
[ means of solving the problems ]
The present inventors have made diligent studies and as a result, have found that the above problems can be solved by introducing a specific structural unit into a liquid crystal alignment film, and have completed the present invention. Specifically, the following means can be provided by the present invention.
< 1 > a liquid crystal aligning agent satisfying at least one of the following requirements (I) and (II).
Essential condition (I): a compound having the following partial structure (A) and partial structure (B) in the same molecule;
essential condition (II): a compound comprising the following partial structure (A) and partial structure (B) in different molecules;
partial structure (a): at least one selected from the group consisting of a substituted heterocyclic structure, a quinone structure, and a tetracyanoquinodimethane structure, wherein one or more hydrogen atoms bonded to the nitrogen-containing aromatic heterocyclic ring are substituted with an electron withdrawing group that does not detach upon heating at a temperature of 230 ℃ or lower;
partial structure (B): at least one selected from the group consisting of a partial structure represented by the following formula (b 1) and a phenothiazine structure;
[ chemical 1]
*-X 1 -B 1 -X 2 -* (b1)
(in the formula (b 1), X 1 、B 1 X is X 2 Satisfies the following [ i ]]Or [ ii ]]The method comprises the steps of carrying out a first treatment on the surface of the "x" means a bond;
[i]X 1 is an aromatic ring group; b (B) 1 is-NY 3 -or an aromatic heterocyclic group; x is X 2 Y and Y 3 Is X 2 Is an aromatic ring group and Y 3 Is a hydrogen atom or a monovalent organic group, or represents X 2 And Y is equal to 3 Are combined with each other and X 2 Y and Y 3 The bonded nitrogen atoms together form a nitrogen-containing fused ring structure; wherein the nitrogen-containing condensed ring structure has an aromatic ring, B 1 Is bonded to an aromatic ring in the nitrogen-containing fused ring structure;
[ii]B 1 is-NY 3 -；Y 3 Is a hydrogen atom or a monovalent organic group; x is X 1 X is X 2 Representing combinations with each other and X 1 X is X 2 The bonded nitrogen atoms together form a nitrogen-containing fused ring structure; wherein the nitrogen-containing condensed ring structure has a plurality of aromatic rings, B 1 Wherein the nitrogen atom of the ring members connects two aromatic rings in the nitrogen-containing fused ring structure
The liquid crystal aligning agent according to < 2 > or < 1 > contains at least one polymer (P) selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, wherein the polymer (P) contains a structural unit derived from a diamine compound having the partial structure (B).
< 3 > the liquid crystal aligning agent according to < 1 > or < 2 > comprises at least one polymer (P) selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, wherein the polymer (P) comprises the following structural Unit (UA) and structural Unit (UB) in the same molecule or comprises the following structural Unit (UA) and structural Unit (UB) in different molecules.
Structural Unit (UA): a structural unit derived from at least one selected from the group consisting of a diamine compound (DA-1) having a substituted heterocyclic structure in which one or more hydrogen atoms bonded to a nitrogen-containing aromatic heterocyclic ring are substituted with an electron-withdrawing group that does not come off by heating at a temperature of 230 ℃ or lower, and a diamine compound (DA-2) having a quinone structure;
structural Unit (UB): a structural unit derived from at least one selected from the group consisting of a diamine compound (DB-1) and a diamine compound (DB-2), the diamine compound (DB-1) having a partial structure represented by the formula (b 1), the diamine compound (DB-2) having a phenothiazine structure;
the liquid crystal aligning agent according to < 4 > to < 3 > wherein the diamine compound (DA-1) is a compound represented by the following formula (a 1-1).
[ chemical 2]
(in the formula (a 1-1), A 1 A group having a substituted heterocyclic structure in which one or more hydrogen atoms bonded to the nitrogen-containing aromatic heterocyclic ring are substituted with an electron-withdrawing group which is not detached by heating at a temperature of 230 ℃ or lower; r is R 1 Is a single bond or a (n1+1) valent linking group; ar (Ar) 1 Is an aromatic ring group; n1 is 1 or 2)
The liquid crystal aligning agent according to < 5 > or < 3 > or < 4 > wherein the diamine compound (DA-2) is at least one selected from the group consisting of a compound represented by the following formula (a 2-1) and a compound represented by the following formula (a 2-2).
[ chemical 3]
(in the formula (a 2-1), A 2 Is a radical having a quinone structure; r is R 2 Is a single bond or a (n2+1) valent linking group; ar (Ar) 2 Is an aromatic ring group; n2 is 1 or 2;
in the formula (a 2-2), A 3 Is a radical having a quinone structure; r is R 3 R is R 4 Each independently a single bond or a divalent organic group; ar (Ar) 3 Ar and Ar 4 Each independently an aromatic ring radical)
A liquid crystal aligning agent according to any one of < 3 > to < 5 > wherein the diamine compound (DB-2) is a compound represented by the following formula (b 2-1).
[ chemical 4]
(in the formula (b 2-1), A 4 Is a group having a phenothiazine structure; r is R 5 Is a single bond or a (n3+1) valent linking group; ar (Ar) 5 Is an aromatic ring group; n3 is 1 or 2)
The liquid crystal aligning agent according to any one of < 7 > to < 2 > to < 6 >, wherein the polymer (P) further comprises a structural Unit (UC) derived from a diamine compound having a partial structure represented by the following formula (2).
[ chemical 5]
(in the formula (2), X 5 X is X 6 Each independently an aromatic ring group; r is R 7 R is R 8 Each independently is a single bond, an alkanediyl group having 1 to 10 carbon atoms or a substituted alkanediyl group having 1 to 10 carbon atoms; y is Y 5 Y and Y 6 Each independently is 4 -NR 9 -CO-or 4 -CO-NR 9 -；R 9 Is a hydrogen atom or a monovalent organic group; "* 4 "means and Z 5 Is a bond of (a); z is Z 5 Is a single bond or a divalent organic group; m is 0 or 1; in the case where m is 0, R 7 、R 8 Or both of them are alkanediyl or substituted alkanediyl having 1 to 10 carbon atoms; "x" means a bond
The liquid crystal aligning agent according to < 8 > above, which comprises the compound having the partial structure (A) (except for the polymer) and the polymer (P).
The liquid crystal aligning agent according to any one of < 1 > to < 8 > wherein the electron withdrawing group is at least one selected from the group consisting of a halogen atom, a cyano group, a halogenated alkyl group and an acyl group.
A liquid crystal aligning agent according to any one of < 1 > to < 9 > further comprising a polymer (Q) having no one of the partial structures (A) and (B).
The liquid crystal aligning agent according to < 11 > or < 10 >, wherein the polymer (Q) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and addition polymer.
A liquid crystal alignment film of < 12 > which is formed using the liquid crystal alignment agent according to any one of < 1 > to < 11 >.
< 13 > a liquid crystal element comprising the liquid crystal alignment film according to the < 12 > above.
< 14 > a polymer which is a polyamic acid, polyamic acid ester or polyimide and which contains the following structural Unit (UA) and structural Unit (UB) in the same molecule.
Structural Unit (UA): a structural unit derived from at least one selected from the group consisting of a diamine compound (DA-1) having a substituted heterocyclic structure in which one or more hydrogen atoms bonded to a nitrogen-containing aromatic heterocyclic ring are substituted with an electron-withdrawing group that does not come off by heating at a temperature of 230 ℃ or lower, and a diamine compound (DA-2) having a quinone structure;
structural Unit (UB): a structural unit derived from at least one selected from the group consisting of a diamine compound (DB-1) and a diamine compound (DB-2), wherein the diamine compound (DB-1) has a partial structure represented by the following formula (b 1), and the diamine compound (DB-2) has a phenothiazine structure;
[ chemical 6]
*-X 1 -B 1 -X 2 -* (b1)
(in the formula (b 1), X 1 、B 1 X is X 2 Satisfies the following [ i ] ]Or [ ii ]]；
[i]X 1 Is an aromatic ring group; b (B) 1 is-NY 3 -or an aromatic heterocyclic group; x is X 2 Y and Y 3 Is X 2 Is an aromatic ring group and Y 3 Is a hydrogen atom or a monovalent organic group, or represents X 2 And Y is equal to 3 Are combined with each other and X 2 Y and Y 3 The bonded nitrogen atoms together form a nitrogen-containing fused ring structure; wherein the nitrogen-containing condensed ring structure has an aromatic ring, B 1 Is bonded to an aromatic ring in the nitrogen-containing fused ring structure;
[ii]B 1 is-NY 3 -；Y 3 Is a hydrogen atom or a monovalent organic group; x is X 1 X is X 2 Representing combinations with each other and X 1 X is X 2 The bonded nitrogen atoms together form a nitrogen-containing fused ring structure; wherein the saidThe nitrogen-containing condensed ring structure has a plurality of aromatic rings, B 1 The nitrogen atom of (a) connects two aromatic rings in the nitrogen-containing fused ring structure;
"x" means a bond
< 15 > a compound represented by the following formula (a 1-1).
[ chemical 7]
(in the formula (a 1-1), A 1 A group having a substituted heterocyclic structure in which one or more hydrogen atoms bonded to the nitrogen-containing aromatic heterocyclic ring are substituted with at least one member selected from the group consisting of a halogen atom, a cyano group, a halogenated alkyl group and an acyl group; r is R 1 Is a single bond or a (n1+1) valent linking group; ar (Ar) 1 Is an aromatic ring group; n1 is 1 or 2)
< 16 > a compound represented by the following formula (a 2-2).
[ chemical 8]
H 2 N-Ar 3 -R 3 -A 3 -R 4 -Ar 4 -NH 2 (a2-2)
(in the formula (a 2-2), A 3 Is a radical having a quinone structure; r is R 3 R is R 4 Each independently a single bond or a divalent organic group; ar (Ar) 3 Ar and Ar 4 Each independently an aromatic ring radical)
< 17 > a compound represented by the following formula (b 2-1).
[ chemical 9]
(in the formula (b 2-1), A 4 Is a group having a phenothiazine structure; r is R 5 Is a single bond or a (n3+1) valent saturated chain hydrocarbon group; ar (Ar) 5 Is an aromatic ring group; n3 is 1 or 2)
[ Effect of the invention ]
According to the liquid crystal aligning agent of the present invention, a liquid crystal element which has excellent coatability and little accumulation of residual charges and is less likely to generate afterimage (DC afterimage) can be obtained.
Drawings
FIG. 1 is a schematic diagram showing a compound (DA-1) 1 H-NMR spectrum.
FIG. 2 is a schematic diagram showing the compound (DA-9) 1 H-NMR spectrum.
Detailed Description
Liquid Crystal alignment agent
Hereinafter, each component contained in the liquid crystal aligning agent of the present disclosure and other components optionally blended will be described.
In the present specification, the term "hydrocarbon group" means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The term "chain hydrocarbon group" means a straight chain hydrocarbon group and a branched hydrocarbon group having no cyclic structure in the main chain and only chain structures. Wherein, the chain hydrocarbon group can be saturated or unsaturated. The term "alicyclic hydrocarbon group" means a hydrocarbon group having a structure containing only alicyclic hydrocarbon as a ring structure and containing no aromatic ring structure. The alicyclic hydrocarbon group does not need to have a structure containing only alicyclic hydrocarbon, and includes a group having a chain structure in a part thereof. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. The aromatic hydrocarbon group need not contain only an aromatic ring structure, but may contain a chain structure or an alicyclic hydrocarbon structure in a part thereof. The term "aromatic ring" is intended to include aromatic hydrocarbon rings and aromatic heterocyclic rings. The term "organic group" refers to an atomic group obtained by removing any hydrogen atom from a compound containing carbon (i.e., an organic compound).
The "backbone" of a polymer refers to the portion of the polymer that contains the longest chain of atoms. The "backbone" portion may be allowed to include a ring structure. For example, by "having a specific structure in the main chain" is meant that the specific structure forms part of the main chain. By "side chain" is meant a portion branching from the "backbone" of the polymer. The term "tetracarboxylic acid derivative" is intended to include tetracarboxylic acid dianhydrides, tetracarboxylic acid diesters, and tetracarboxylic acid diester dihalides.
The liquid crystal aligning agent of the present disclosure is a composition that satisfies at least one of the following requirements (I) and (II).
Essential condition (I): the compound contains a partial structure (A) and a partial structure (B) in the same molecule.
Essential condition (II): the compound contains a partial structure (A) and a partial structure (B) in different molecules.
Here, the partial structure (a) is at least one selected from the group consisting of a substituted heterocyclic structure, a quinone structure, and a tetracyanoquinodimethane structure, each of which is substituted with an electron withdrawing group (wherein, the group is a group which does not detach by heating at 230 ℃ or lower) by one or more hydrogen atoms bonded to a nitrogen-containing aromatic heterocyclic ring. The partial structure (B) is at least one selected from the group consisting of a partial structure represented by the following formula (B1) and a phenothiazine structure.
[ chemical 10]
*-X 1 -B 1 -X 2 -* (b1)
(in the formula (b 1), X 1 、B 1 X is X 2 Satisfies the following [ i ]]Or [ ii ]]The method comprises the steps of carrying out a first treatment on the surface of the "x" means a bond;
[i]X 1 is an aromatic ring group; b (B) 1 is-NY 3 -or an aromatic heterocyclic group; x is X 2 Y and Y 3 Is X 2 Is an aromatic ring group and Y 3 Is a hydrogen atom or a monovalent organic group, or represents X 2 And Y is equal to 3 Are combined with each other and X 2 Y and Y 3 The bonded nitrogen atoms together form a nitrogen-containing fused ring structure; wherein the nitrogen-containing condensed ring structure has an aromatic ring, B 1 Is bonded to an aromatic ring in the nitrogen-containing fused ring structure;
[ii]B 1 is-NY 3 -；Y 3 Is a hydrogen atom or a monovalent organic group; x is X 1 X is X 2 Representing combinations with each other and X 1 X is X 2 The bonded nitrogen atoms together form a nitrogen-containing fused ring structure; wherein the nitrogen-containing condensed ring structure has a plurality of aromatic rings, B 1 Wherein the nitrogen atom of the ring members connects two aromatic rings in the nitrogen-containing fused ring structure
In the case where the liquid crystal aligning agent of the present disclosure satisfies the requirement (I), the compound containing the partial structure (a) and the partial structure (B) in the same molecule may be a polymer component or an additive component (i.e., a compound different from the polymer). In addition, when the liquid crystal aligning agent of the present disclosure satisfies the requirement (II), the compound having the partial structure (a) and the compound having the partial structure (B) may be each a polymer component or an additive component.
In terms of the coating property of the liquid crystal aligning agent and the high improvement effect of the reduction of afterimage in the liquid crystal element, the liquid crystal aligning agent of the present disclosure preferably contains at least one polymer (P) selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, the polymer (P) containing a structural unit derived from a diamine compound having a partial structure (B). Preferred modes of the liquid crystal aligning agent of the present disclosure include the following modes [ 1 ] and [ 2 ].
The polymer (P) of the form [ 1 ] contains the following structural Unit (UA) and structural Unit (UB) in the same molecule, or the structural Unit (UA) and structural Unit (UB) in different molecules.
Structural Unit (UA): a structural unit derived from at least one selected from the group consisting of a diamine compound (DA-1) having a substituted heterocyclic structure in which one or more hydrogen atoms bonded to a nitrogen-containing aromatic heterocyclic ring are substituted with an electron-withdrawing group that does not come off by heating at a temperature of 230 ℃ or lower, and a diamine compound (DA-2) having a quinone structure;
structural Unit (UB): a structural unit derived from at least one selected from the group consisting of a diamine compound (DB-1) and a diamine compound (DB-2), the diamine compound (DB-1) having a partial structure represented by the formula (b 1), the diamine compound (DB-2) having a phenothiazine structure;
Form [ 2 ] contains a compound having a partial structure (A) (excluding a polymer) and a polymer (P) as a polymer having a partial structure (B).
The mode of [ 1 ] is a first liquid crystal aligning agent, the mode of [ 2 ] is a second liquid crystal aligning agent, and each liquid crystal aligning agent will be described below.
< first liquid Crystal alignment agent >
The first liquid crystal aligning agent contains, as the polymer (P), at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and contains a specific structural Unit (UA) and structural Unit (UB)) in the same molecule or in different molecules. The polymer (P) and other components optionally blended in the first liquid crystal aligning agent of the present disclosure will be described in detail below. In this specification, as far as the components are not mentioned specifically, one kind may be used alone, or two or more kinds may be used in combination.
< Polymer (P) >)
The polymer (P) is a polymer having a structural unit derived from a tetracarboxylic acid derivative and a structural unit derived from a diamine compound in the same molecule. The polymer (P) contains the structural Unit (UA) and the structural Unit (UB) as structural units derived from the diamine compound in the same molecule, or contains the structural Unit (UA) and the structural Unit (UB) as structural units derived from the diamine compound in different molecules.
Specific examples of the liquid crystal aligning agent containing the polymer (P) include the following modes (I) and (II).
(I) The polymer (P1) has a structural Unit (UA) and a structural Unit (UB) in the same molecule.
(II) A Polymer (PA) having a structural Unit (UA) and a Polymer (PB) having a structural Unit (UB) (wherein the polymer is different from the Polymer (PA)).
Among these, the form of the polymer (P1) containing (I) is preferable in terms of sufficiently obtaining the effect of reducing DC residual image while minimizing the structural components of the liquid crystal aligning agent. The diamine compound (DA-1), the diamine compound (DA-2), the diamine compound (DB-1) and the diamine compound (DB-2) are different from each other. First, the structural Unit (UA) and the structural Unit (UB) are described below.
[ concerning structural Units (UA) ]
The structural Unit (UA) is derived from at least one selected from the group consisting of a diamine compound (DA-1) having a substituted heterocyclic structure in which one or more hydrogen atoms bonded to a nitrogen-containing aromatic heterocyclic ring are substituted with an electron-withdrawing group (hereinafter, also referred to as an "electron-withdrawing group F1") that does not undergo detachment by heating at a temperature of 230 ℃ or lower, and a diamine compound (DA-2) having a quinone structure. The diamine compound (DA-1) and the diamine compound (DA-2) are each a compound which exhibits electron acceptance when used in combination with at least one selected from the group consisting of the diamine compound (DB-1) and the diamine compound (DB-2).
Diamine compound (DA-1)
The substituted heterocyclic structure of the diamine compound (DA-1) has a structure in which an electron withdrawing group F1 is bonded to a nitrogen-containing aromatic heterocycle. The nitrogen-containing aromatic heterocycle to which the electron withdrawing group F1 is bonded may be a single ring or a condensed ring. Specific examples of the nitrogen-containing aromatic heterocycle include: pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, quinoline ring, isoquinoline ring, benzimidazole ring, indazole ring, acridine ring, and the like. Among these, the nitrogen-containing aromatic heterocycle to which the electron withdrawing group F1 is bonded is preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring, more preferably an imidazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring, and still more preferably an imidazole ring.
The electron withdrawing group F1 is not particularly limited as long as it is an electron withdrawing group that does not come off by heating at a temperature of 230 ℃ or lower. The electron withdrawing group F1 is, for example, a group which is not detached even by heating at 100 ℃ or higher. Among them, the electron withdrawing group F1 is preferably at least one selected from the group consisting of a halogen atom, a cyano group, a halogenated alkyl group, and an acyl group. Here, examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Examples of the halogenated alkyl group include a group in which one or more hydrogen atoms of a linear or branched alkyl group having 1 to 10 carbon atoms are substituted with a halogen atom. Among these, the halogenated alkyl group is preferably a group having 1 to 6 carbon atoms, more preferably a group having 1 to 3 carbon atoms, still more preferably a perfluoroalkyl group having 1 to 3 carbon atoms, and particularly preferably a trifluoromethyl group. The acyl group is preferably a structure having a monovalent hydrocarbon group having 1 to 6 carbon atoms bonded to a carbonyl group. In the acyl group, the hydrocarbon group bonded to the carbonyl group is more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group or an ethyl group.
In the substituted heterocyclic structure of the diamine compound (DA-1), the number of electron-withdrawing groups F1 bonded to the nitrogen-containing aromatic heterocyclic ring is not particularly limited. The number of electron withdrawing groups F1 bonded to each nitrogen-containing aromatic heterocycle is, for example, one to four, preferably one to three, more preferably one or two.
In the above, the electron withdrawing group F1 is preferably at least one selected from the group consisting of a halogen atom, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, and an acyl group, more preferably a cyano group or an acyl group, and particularly preferably a cyano group, in order to further enhance the effect of reducing DC residual images.
The diamine compound (DA-1) may have only one substituted heterocyclic structure, or may have two or more. The number of the substituted heterocyclic structures of the diamine compound (DA-1) is preferably one to three, more preferably one or two, from the viewpoint of improving the solubility of the polymer (P) and securing the coatability of the liquid crystal aligning agent.
The diamine compound (DA-1) is preferably a compound represented by the following formula (a 1-1).
[ chemical 11]
(in the formula (a 1-1), A 1 A group having a substituted heterocyclic structure in which one or more hydrogen atoms bonded to the nitrogen-containing aromatic heterocyclic ring are substituted with an electron-withdrawing group which is not detached by heating at a temperature of 230 ℃ or lower; r is R 1 Is a single bond or a (n1+1) valent linking group; ar (Ar) 1 Is an aromatic ring group; n1 is 1 or 2)
In the formula (a 1-1), the A is 1 Specific examples and preferred examples of the substituted heterocyclic structure, the nitrogen-containing aromatic heterocyclic ring and the electron-withdrawing group F1 are applicable to the description.
In the case where n1 is 1, R is 1 Examples of the (n1+1) valent linking group include: -O-, -CO- 1 -O-CO-、* 1 -CO-O-、* 1 -NR 11 -CO-、* 1 -CO-NR 11 -, an alkanediyl group having 1 to 4 carbon atoms any methylene group of an alkanediyl group having 2 to 4 carbon atoms is replaced by-O-; -CO-, -CO-O-, or-NR 11 -CO-substituted divalent radical (R 11 Is hydrogen atom or alkyl group with 1-3 carbon atoms, " 1 "means and Ar 1 Bond of (c) and the like.
In the case where n1 is 2, R is 1 Examples of the (n1+1) valent linking group include: a trivalent saturated chain hydrocarbon group having 1 to 4 carbon atoms trivalent saturated chain hydrocarbon group with 2-4 carbon atoms any methylene group is present through-O- -CO-, -CO-O-, or-NR 11 -CO-substituted trivalent radical, 1 -N(-R 12 -) 2 (R 11 ". Times. 1 "has the same meaning as described, R 12 Is an alkanediyl group having 1 to 4 carbon atoms or an alkanediyl group having 2 to 4 carbon atoms, wherein any methylene group is represented by-O-; -CO-, -CO-O-, or-NR 11 -a divalent group substituted by CO-or the like).
In terms of further improving the reduction effect of the DC residual image, R in the above 1 Preferably a (n1+1) valent linking group, more preferably by an alkanediyl group, to A 1 A nitrogen-containing aromatic heterocyclic group. In addition, at R 1 To be combined with A by alkanediyl 1 In the case of the nitrogen-containing aromatic heterocyclic-bonded group, R 1 Can be combined with Ar through alkanediyl 1 The bonding is carried out, or through-O-, -CO-, -CO-O-or-NR 11 -CO-and Ar 1 And (5) bonding.
Ar 1 The aromatic ring group represented is one obtained by removing p (wherein, in R 1 In the case of a single bond, p is the value (n1+2), R 1 If not a single bond, p is a number of 3) any hydrogen atomIs a base of (2). Examples of the aromatic ring contained in the aromatic ring group include: aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring; nitrogen-containing aromatic heterocyclic rings such as pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, quinoline ring, isoquinoline ring and benzimidazole ring. Among these, ar 1 The aromatic ring of the represented aromatic ring group is preferably a benzene ring, naphthalene ring, pyridine ring or pyrimidine ring, and more preferably a benzene ring. Ar (Ar) 1 The aromatic ring group represented may have a substituent in the aromatic ring moiety in addition to the two primary amino groups. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms, a halogen atom, and the like.
In Ar 1 The aromatic ring group represented has two primary amino groups bonded to the aromatic ring. The bonding position of these primary amino groups is not particularly limited. For example, in Ar 1 When the aromatic ring group represented has a benzene ring, the bonding position of the two primary amino groups may be relative to other groups (R 1 ) But in the 2, 4-position, 2, 5-position or 3, 5-position.
Specific examples of the diamine compound (DA-1) include compounds represented by the following formulae (d-1-1) to (d-1-16).
[ chemical 12]
[ chemical 13]
[ chemical 14]
In the case where the polymer (P) contains structural units derived from the diamine compound (DA-1), the proportion of the structural units derived from the diamine compound (DA-1) is preferably 2 mol% or more, more preferably 5 mol% or more, relative to all the structural units derived from the diamine compound constituting the polymer (P). The proportion of the structural unit derived from the diamine compound (DA-1) is preferably 95 mol% or less, more preferably 90 mol% or less, based on all the structural units derived from the diamine compound constituting the polymer (P).
In addition, in the case where the first liquid crystal aligning agent contains two or more polymers (P), the proportion of the structural units derived from the diamine compound (DA-1) means the proportion of all the structural units derived from the diamine compound (DA-1) contained in the two or more polymers (P) relative to all the structural units derived from the diamine compound constituting the two or more polymers (P). For example, in the case where the first liquid crystal aligning agent contains the first polymer and the second polymer as the polymer (P), the proportion of the structural units derived from the diamine compound (DA-1) represents the proportion of the total amount of the structural units derived from the diamine compound (DA-1) constituting the first polymer and the structural units derived from the diamine compound (DA-1) constituting the second polymer relative to the total amount of all the structural units derived from the diamine compound constituting the first polymer and all the structural units derived from the diamine compound constituting the second polymer (the same applies to the structural units below).
Diamine compound (DA-2)
The diamine compound (DA-2) is a compound having a quinone structure in the main chain or side chain. Specifically, the diamine compound (DA-2) is preferably at least one selected from the group consisting of a compound represented by the following formula (a 2-1) and a compound represented by the following formula (a 2-2).
[ 15]
H 2 N-Ar 3 -R 3 -A 3 -R 4 -Ar 4 -NH 2 (a2-2)
(in the formula (a 2-1), A 2 Is a radical having a quinone structure; r is R 2 Is a single bond or a (n2+1) valent linking group; ar (Ar) 2 Is an aromatic ring group;n2 is 1 or 2;
in the formula (a 2-2), A 3 Is a radical having a quinone structure; r is R 3 R is R 4 Each independently a single bond or a divalent organic group; ar (Ar) 3 Ar and Ar 4 Each independently an aromatic ring radical)
Examples of the quinone structure of the diamine compound (DA-2) include a benzoquinone structure and a naphthoquinone structure. Of these, the quinone structure of the diamine compound (DA-2) is preferably a benzoquinone structure.
In the formula (a 2-1), A 2 The group represented by the following formula (r-1) is preferable.
[ 16]
(in the formula (R-1), R 21 、R 22 R is R 23 Each independently represents a hydrogen atom, a C1-3 alkyl group or a C1-3 alkoxy group; r is R 24 R is R 25 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; a is 0 or 1; "x" means a bond
In the formula (R-1), R 21 、R 22 R is R 23 Preferably a hydrogen atom, methyl or methoxy. R is R 24 R is R 25 Preferably a hydrogen atom or a methyl group.
In the case where n2 is 1, R is 2 A (n2+1) valent linking group represented by the formula, examples thereof include alkanediyl having 1 to 3 carbon atoms containing-O-, between carbon-carbon bonds of the alkanediyl group-CO-, -CO-O-, or-NR 14 Divalent radicals of carbon number 2 to 4 of-CO- (R 14 A hydrogen atom or an alkyl group having 1 to 3 carbon atoms). In the case where n2 is 2, R is 2 Examples of the (n2+1) valent linking group include a trivalent saturated chain hydrocarbon group having 1 to 4 carbon atoms and a trivalent saturated chain hydrocarbon group having 1 to 4 carbon atoms.
With respect to Ar 2 Specific examples and preferred examples of the aromatic ring group represented by the formula (a 1-1) may be used Ar 1 Is described in (2). n2 is preferably 1.
In the formula (a 2-2), A 2 Preferably a group represented by the following formula (r-2).
[ chemical 17]
(in the formula (R-2), R 26 R is R 27 Each independently represents a hydrogen atom, a C1-3 alkyl group or a C1-3 alkoxy group; r is R 28 R is R 29 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; a1 and a2 are each independently 0 or 1; "x" means a bond
In the formula (R-2), R 26 R is R 27 Preferably a hydrogen atom, methyl or methoxy. R is R 28 R is R 29 Preferably a hydrogen atom or a methyl group. In view of ease of synthesis of the compound represented by the formula (a 2-2), a1 and a2 are preferably 1.
In the formula (a 2-2), R is 3 R is R 4 The divalent organic radical represented by the formula, alkyldiyl having 1 to 12 carbon atoms more than one methylene group of an alkanediyl group having 2 to 12 carbon atoms is reacted with a catalyst through-O-; -CO-, -CO-O-, or-NR 16 -CO-(R 16 A divalent group substituted with a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). From the viewpoint of obtaining a liquid crystal alignment film exhibiting good liquid crystal alignment properties, R 3 R is R 4 The alkanediyl group of the divalent organic group represented is preferably linear. R is R 3 R is R 4 The divalent organic group represented is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 6, and still more preferably a carbon number of 1 to 3.
Ar 3 Ar and Ar 4 The aromatic ring group represented is a group obtained by removing two arbitrary hydrogen atoms from the ring portion of an aromatic ring. As the aromatic ring of the aromatic ring group, ar in the formula (a 1-1) is exemplified 1 Aromatic hydrocarbon rings and nitrogen-containing aromatic heterocyclic rings exemplified in the description of (a). Ar (Ar) 2 The aromatic ring is preferably a benzene ring, naphthalene ring, pyridine ring or pyrimidine ring, and more preferably a benzene ring. In addition, ar 3 Ar and Ar 4 The aromatic ring group represented may have a substituent in the aromatic ring moiety in addition to the primary amino group. As the substituent, there may be mentioned a C1-to-C3, a halogen atom, etc.
Specific examples of the diamine compound (DA-2) include compounds represented by the following formulae (d-2-1) to (d-2-9).
[ chemical 18]
The diamine compound (DA-2) may be used in combination with at least one selected from the group consisting of the diamine compound (DB-1) and the diamine compound (DB-2) to enhance the effect of relaxing the residual charges and the effect of reducing the accumulation of charges, and is preferably a compound having a quinone structure in the main chain, more preferably a compound represented by the formula (a 2-2). Specifically, the compounds represented by the respective formulae (d-2-1) to (d-2-3) and (d-2-7) can be preferably used.
In the case where the polymer (P) contains structural units derived from the diamine compound (DA-2), the proportion of the structural units derived from the diamine compound (DA-2) is preferably 2 mol% or more, more preferably 5 mol% or more, relative to all the structural units derived from the diamine compound constituting the polymer (P). The proportion of the structural unit derived from the diamine compound (DA-2) is preferably 95 mol% or less, more preferably 90 mol% or less, based on all the structural units derived from the diamine compound constituting the polymer (P).
The proportion of the structural Unit (UA) in the polymer (P) is preferably 5 mol% or more, more preferably 10 mol% or more, with respect to all the structural units derived from the diamine compound constituting the polymer (P). The proportion of the structural Unit (UA) is preferably 95 mol% or less, more preferably 90 mol% or less, based on all the structural units derived from the diamine compound constituting the polymer (P).
[ concerning the structural Unit (UB) ]
The structural Unit (UB) is derived from at least one selected from the group consisting of a diamine compound (DB-1) and a diamine compound (DB-2), wherein the diamine compound (DB-1) has a partial structure represented by the formula (b 1), and the diamine compound (DB-2) has a phenothiazine structure. The diamine compound (DB-1) and the diamine compound (DB-2) are each a compound that exhibits electron donating properties when used in combination with at least one selected from the group consisting of the diamine compound (DA-1) and the diamine compound (DA-2). The diamine compound (DB-1) is a compound having no phenothiazine structure, and in this respect, the diamine compound (DB-1) is different from the diamine compound (DB-2).
Diamine compound (DB-1)
In the formula (b 1), X is 1 X is X 2 Examples of the aromatic ring group 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 among these, a nitrogen-containing aromatic heterocyclic group is preferable. X is X 1 X is X 2 The aromatic ring group represented may have a substituent at the ring portion. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, and the like.
Regarding X 1 、X 2 Specific examples of the divalent aromatic hydrocarbon group include a group obtained by removing any two hydrogen atoms bonded to carbon atoms constituting a ring of a benzene ring, a naphthalene ring or an anthracene ring; examples of the divalent nitrogen-containing aromatic heterocyclic group include a group in which any two hydrogen atoms bonded to carbon atoms constituting a pyridine ring, pyrimidine ring, pyridazine ring or pyrazine ring are removed; examples of the divalent oxygen-containing aromatic heterocyclic group include a group obtained by removing any two hydrogen atoms bonded to carbon atoms constituting a ring of a furan ring; examples of the divalent sulfur-containing aromatic heterocyclic group include a group in which any two hydrogen atoms bonded to carbon atoms constituting a ring of a thiophene ring are removed. From the viewpoint of achieving high density of the liquid crystal alignment film, X 1 X is X 2 The aromatic ring group represented is preferably a divalent aromatic hydrocarbon group or a divalent nitrogen-containing aromatic heterocyclic group, more preferably a divalent aromatic hydrocarbon group, and further preferably a phenylene group.
At B 1 In the case of an aromatic heterocyclic group, examples of the aromatic heterocyclic group include X 1 、X 2 In the description of (2)Examples of the divalent aromatic heterocyclic group are illustrated. Among these, B is a component capable of improving the effect of relaxing the accumulated charges 1 The aromatic heterocyclic group represented is preferably a group in which any two hydrogen atoms bonded to carbon atoms constituting the ring of the pyrrole ring, furan ring or thiophene ring are removed.
At B 1 is-NY 3 In the case of Y 3 The monovalent organic group represented is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms or a group which is thermally desorbed to generate a hydrogen atom (hereinafter, also referred to as a "thermally releasable group"). In Y 3 In the case of a monovalent hydrocarbon group, the monovalent hydrocarbon group is preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, more preferably an alkyl group having 1 to 3 carbon atoms.
In Y 3 In the case of a thermally releasable group, Y is 3 Examples include: urethane-based heat-releasable groups, amide-based heat-releasable groups, imide-based heat-releasable groups, sulfonamide-based heat-releasable groups, and the like. Among these, urethane-based heat-releasable groups are preferable in terms of high heat-releasable properties. Specific examples thereof include: t-butoxycarbonyl, benzyloxycarbonyl, 1-dimethyl-2-haloethyloxycarbonyl, allyloxycarbonyl, 2- (trimethylsilyl) ethoxycarbonyl, 9-fluorenylmethyloxycarbonyl and the like. Among these, tert-butoxycarbonyl (Boc group) is particularly preferred in terms of excellent heat-based releasability and reduced residual amount of the deprotected moiety in the film.
Wherein Y is 3 Preferably a hydrogen atom, a C1-3 alkyl group or a thermally releasable group, more preferably a hydrogen atom, a C1-3 alkyl group or a t-butoxycarbonyl group.
At X 1 、B 1 X is X 2 Satisfy the [ i ]]And X is 2 Y and Y 3 Representing combinations with each other and X 2 Y and Y 3 In the case of a nitrogen-containing condensed ring structure formed by bonded nitrogen atoms together, examples of the condensed ring structure include: indoline structure, isoindoline structure, indole structure, 1,2,3, 4-tetrahydroquinoline structure, 1, 2-dihydroquinoline structure, 1, 2-dihydroisoquinoline structure, carbazole structure, and the like. In addition, inX 2 Y and Y 3 In the case of combining with each other to form a nitrogen-containing condensed ring structure, B 1 The nitrogen atom of (a) is bonded to the aromatic ring in the nitrogen-containing condensed ring structure by a single bond.
At X 1 、B 1 X is X 2 Satisfy said [ ii ]]In the case of (1), when X 1 X is X 2 Representing combinations with each other and X 1 X is X 2 When the bonded nitrogen atoms together form a nitrogen-containing condensed ring structure, the nitrogen-containing condensed ring structure is preferably a carbazole structure. Specific examples of the carbazole structure include a structure in which any two hydrogen atoms are removed from a ring portion of a 9H-carbazole ring or an N-substituted carbazole ring. Examples of the N-substituted carbazole ring include 9-methyl carbazole and 9-ethyl carbazole.
As a preferred specific example of the partial structure represented by the formula (b 1), X 1 、B 1 X is X 2 Satisfy the [ i ]]In the case of (a), the partial structures represented by the following formulae (3-1) to (3-10) may be exemplified; at X 1 、B 1 X is X 2 Satisfy said [ ii ]]In the case of (2), the partial structure represented by the following formula (3-11) may be mentioned. In order to obtain a liquid crystal element in which the accumulation of residual charges is small and DC residual images are less likely to occur, the polymer (P) preferably has a partial structure represented by the formula (b 1) in the main chain of the polymer (P).
[ chemical 19]
(in the formulae (3-1) to (3-11), Y 3 Y and Y 4 Each independently a hydrogen atom or a monovalent organic group; "x" means a bond
The diamine compound (DB-1) may have only one partial structure represented by the formula (b 1), or may have two or more. In addition, when the diamine compound (DB-1) has two or more partial structures represented by the formula (b 1), the number of partial structures represented by the formula (b 1) in the diamine compound (DB-1) represents the total number thereof. From the viewpoint of ensuring the solubility of the polymer (P), the total number of the partial structures represented by the formula (b 1) per molecule of the diamine compound (DB-1) is preferably one or two. The diamine compound (DB-1) is preferably an aromatic diamine, and among them, an aromatic diamine having a structure capable of introducing a partial structure represented by the formula (b 1) into the main chain of the polymer (P) is preferable.
The term "aromatic diamine" refers to a diamine in which two primary amino groups are bonded to the same aromatic ring or different aromatic rings in the molecule. In the aromatic diamine, the aromatic ring to which the two primary amino groups are bonded may be a single ring or a condensed ring. In the case where the primary amino group of the aromatic diamine is bonded to the condensed ring, the primary amino group of the aromatic diamine may be bonded to the aromatic ring constituting the condensed ring, and the single ring sharing one side with the aromatic ring to which the primary amino group is bonded may be an aromatic ring or an aliphatic ring.
Specific examples of the diamine compound (DB-1) include compounds represented by the following formulae (d-3-1) to (d-3-22).
[ chemical 20]
[ chemical 21]
[ chemical 22]
In the case where the polymer (P) contains structural units derived from the diamine compound (DB-1), the proportion of the structural units derived from the diamine compound (DB-1) is preferably 2 mol% or more, more preferably 5 mol% or more, relative to all the structural units derived from the diamine compound constituting the polymer (P). The proportion of the structural unit derived from the diamine compound (DB-1) is preferably 90 mol% or less, more preferably 80 mol% or less, relative to all the structural units derived from the diamine compound constituting the polymer (P).
Diamine compound (DB-2)
The diamine compound (DB-2) is a compound having a phenothiazine structure. The diamine compound (DB-2) is preferably a compound capable of introducing a phenothiazine structure into the side chains of the polymer (P), and specifically, a compound represented by the following formula (b 2-1) can be preferably used.
[ chemical 23]
(in the formula (b 2-1), A 4 Is a group having a phenothiazine structure; r is R 5 Is a single bond or a (n3+1) valent linking group; ar (Ar) 5 Is an aromatic ring group; n3 is 1 or 2)
In the formula (b 2-1), A 4 Preferably, the group is one obtained by removing a hydrogen atom bonded to a carbon atom or a nitrogen atom constituting a ring having a structure represented by the following formula (r-3).
[ chemical 24]
(in the formula (R-3), R 31 R is R 32 Each independently represents an alkyl group having 1 to 3 carbon atoms; b1 and b2 are each independently an integer of 0 to 4; when b1 is 2 or more, a plurality of R 31 The same or different; when b2 is 2 or more, a plurality of R 32 The same or different)
In the case where n3 in the formula (b 2-1) is 1, R is 5 Examples of the (n3+1) valent linking group include: -O-, -CO- 3 -O-CO-、* 3 -CO-O-、* 3 -NR 17 -CO-、* 3 -CO-NR 17 -, an alkanediyl group having 1 to 4 carbon atoms any methylene group in the alkanediyl group having 2 to 4 carbon atoms is reacted with a catalyst through-O-; -CO-, -CO-O-, or-NR 17 -CO-substituted divalent radical (R 17 Is hydrogen atom or alkyl group with 1-3 carbon atoms, " 3 "means and Ar 5 Bond of (c) and the like.
In the case where n3 is 2, R is 5 Examples of the (n3+1) valent linking group include: a trivalent saturated chain hydrocarbon group having 1 to 4 carbon atoms any methylene in the trivalent saturated chain hydrocarbon group with 2-4 carbon atoms is treated by-O-; -CO-, -CO-O-, or-NR 17 -CO-substituted trivalent radical, 3 -N(-R 17 -) 2 (R 17 ". Times. 3 "the same meaning as described), and the like.
In terms of high reduction effect of DC afterimage, R 5 The (n3+1) valent linking group is preferable, and more preferable is a group bonded to a nitrogen atom in the formula (r-3) (i.e., a nitrogen atom constituting a ring portion of the phenothiazine ring) through an alkanediyl group.
With respect to Ar 3 Specific examples and preferred examples of the aromatic ring group represented by the formula (a 1-1) may be used Ar 1 Is described in (2). n3 is preferably 1.
Specific examples of the diamine compound (DB-2) include compounds represented by the following formulae (d-4-1) to (d-4-6).
[ chemical 25]
In the case where the polymer (P) contains structural units derived from the diamine compound (DB-2), the proportion of the structural units derived from the diamine compound (DB-2) is preferably 2 mol% or more, more preferably 5 mol% or more, relative to all the structural units derived from the diamine compound constituting the polymer (P). The proportion of the structural unit derived from the diamine compound (DB-2) is preferably 90 mol% or less, more preferably 80 mol% or less, relative to all the structural units derived from the diamine compound constituting the polymer (P).
The proportion of the structural Unit (UB) in the polymer (P) is preferably 2 mol% or more, more preferably 5 mol% or more, relative to all the structural units derived from the diamine compound constituting the polymer (P). The proportion of the structural Unit (UB) is preferably 90 mol% or less, more preferably 85 mol% or less, relative to all the structural units derived from the diamine compound constituting the polymer (P).
In order to sufficiently improve the capability of reducing residual charges accumulated by applying a direct current voltage and sufficiently obtain the effect of reducing DC residual images in the obtained liquid crystal alignment film, the ratio of the structural Units (UA) to the structural Units (UB) contained in the polymer (P) is preferably set to a ratio of 0.05 mol to 9.0 mol relative to 1 mol of the structural Units (UA). From the viewpoint of the above, the ratio of the structural Unit (UB) to 1 mol of the structural Unit (UA) is more preferably 0.10 mol to 5.0 mol, and still more preferably 0.12 mol to 3.5 mol.
[ other structural units ]
The polymer (P) may further contain a structural unit (hereinafter, also referred to as "other structural unit") different from the structural Unit (UA) and the structural Unit (UB) as a structural unit derived from the diamine compound. The other structural unit may be present in the polymer (P1), the Polymer (PA) or the Polymer (PB), or may be present in two or more thereof.
Structural Unit (UC)
The polymer (P) preferably further comprises a structural Unit (UC) derived from a diamine compound having a partial structure represented by the following formula (2). The polymer (P) further contains a structural Unit (UC), thereby further improving the effect of reducing DC afterimage.
[ chemical 26]
(in the formula (2), X 5 X is X 6 Each independently a divalent aromatic ring radical; r is R 7 R is R 8 Each independently is a single bond, an alkanediyl group having 1 to 10 carbon atoms or a substituted alkanediyl group having 1 to 10 carbon atoms; y is Y 5 Y and Y 6 Each independently is 4 -NR 9 -CO-or 4 -CO-NR 9 -；R 9 Is a hydrogen atom or a monovalent organic group; "* 4 "means and Z 5 Is a bond of (a); z is Z 5 Is a single bond or a divalent organic group; m is 0 or 1; at the position ofIn the case where m is 0, R 7 、R 8 Or both of them are alkanediyl or substituted alkanediyl having 1 to 10 carbon atoms; "x" means a bond
In formula (2), X 5 X is X 6 The divalent aromatic ring group of (2) is preferably an aromatic hydrocarbon group. As X 5 、X 6 Specifically, the examples include groups obtained by removing any two hydrogen atoms bonded to carbon atoms constituting the ring of an aromatic hydrocarbon ring such as a benzene ring, naphthalene ring and anthracene ring. From the viewpoint of achieving high density of the liquid crystal alignment film, X 5 X is X 6 The aromatic ring is preferably unsubstituted. Wherein X is 5 X is X 6 Phenylene is preferred, and 1, 4-phenylene is particularly preferred.
At R 7 R is R 8 In the case of a substituted or unsubstituted alkanediyl group having 1 to 10 carbon atoms, R is preferably selected from the group consisting of 7 R is R 8 Preferably straight. At R 7 R is R 8 In the case of an alkanediyl group, examples of the substituent include: halogen atom, hydroxyl group, amino group, cyano group, alkoxy group, protected hydroxyl group, protected amino group, and the like. R is R 7 R is R 8 Preferably one or both of them is a substituted or unsubstituted alkanediyl having from 1 to 10 carbon atoms, more preferably R 7 R is R 8 Both of which are substituted or unsubstituted alkanediyl groups having 1 to 10 carbon atoms.
Y 5 Y and Y 6 Is an amide bond () 4 -NR 9 -CO-or 4 -CO-NR 9 -)。R 9 The monovalent organic group represented is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms or a thermally releasable group. At R 9 In the case of a monovalent hydrocarbon group, the monovalent hydrocarbon group is preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, more preferably an alkyl group having 1 to 3 carbon atoms.
At R 9 In the case of a thermally releasable group, R is 9 Y in the formula (b 1) is exemplified 3 Exemplified by thermally releasable groups of (a). R is excellent in heat-based releasability and can reduce the amount of residual part in the film after deprotection 9 The indicated thermally releasable group is particularly preferably t-butoxycarbonyl (Boc group).
Wherein R is 9 Preferably a hydrogen atom, a C1-3 alkyl group or a thermally releasable group, more preferably a hydrogen atom, a C1-3 alkyl group or a t-butoxycarbonyl group.
Z 5 Is a single bond or a divalent organic group. Z is a component capable of improving voltage holding characteristics and liquid crystal alignment of a liquid crystal element 5 Divalent organic radicals are preferred. Examples of the divalent organic group include a divalent hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon group having-O-, -S-or-NR between carbon-carbon bonds of the hydrocarbon group 9 - (wherein R 9 And Y is equal to 5 Y and Y 6 R in (a) 9 The same meaning), and the like. In addition, Z 5 By hydrocarbon radicals with Y 5 Y and Y 6 Is bonded to the substrate.
In terms of improving the solubility of the polymer (P), Z among these 5 The divalent organic group represented is preferably a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a hydrocarbon group having-O-, -S-or-NR between carbon-carbon bonds of the chain hydrocarbon group 9 The divalent group is particularly preferably an alkanediyl group having 1 to 20 carbon atoms or a cycloalkylene group having 4 to 12 carbon atoms. Z is Z 5 The carbon number of (2) is preferably 1 to 12, more preferably 1 to 10.m is 0 or 1, preferably 1.
The diamine compound (hereinafter also referred to as "diamine compound (C)") providing the structural Unit (UC) is preferably an aromatic diamine, and among them, an aromatic diamine having a structure capable of introducing a part of the structure represented by the formula (2) into the main chain of the polymer (P) is preferable.
Specific examples of the diamine compound (C) include compounds represented by the following formulae (d-5-1) to (d-5-24).
[ chemical 27]
[ chemical 28]
[ chemical 29]
(wherein "Boc" represents a t-butoxycarbonyl group)
When the polymer (P) contains the structural Unit (UC), the proportion of the structural Unit (UC) is preferably 2 mol% or more, more preferably 5 mol% or more, relative to all the structural units derived from the diamine compound constituting the polymer (P). The proportion of the structural Unit (UC) is preferably 50 mol% or less, more preferably 40 mol% or less, relative to all the structural units derived from the diamine compound constituting the polymer (P).
In terms of improving the DC residual image characteristic, the structural Unit (UC) is preferably introduced into the same polymer together with the structural Unit (UA) and the structural Unit (UB). That is, the liquid crystal aligning agent of the present disclosure preferably contains, as the polymer (P), a polymer having a structural Unit (UA), a structural Unit (UB), and a structural Unit (UC) in one molecule.
The polymer (P) may contain, as other structural units, structural Units (UD) not having the partial structure represented by the formula (2). The diamine compound constituting the structural Unit (UD) may be: aliphatic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. The aliphatic diamine may be a chain diamine or an alicyclic diamine.
Specific examples of these diamine compounds include chain diamines such as meta-xylylenediamine (meta-xylylenediamine) and hexamethylenediamine; examples of the alicyclic diamine include 1, 4-diaminocyclohexane and 4,4' -methylenebis (cyclohexylamine); as the aromatic diamine, p-phenylenediamine, 4' -diaminodiphenylmethane, 4' -diaminodiphenylethane, 4-aminophenyl-4-aminobenzoate, 4' -diaminoazobenzene, 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' - (pentamethylene dioxy) bis (3-aminopyridine), N ' -bis (5-amino-2-pyridyl) -N, N ' -di (tert-butoxycarbonyl) ethylenediamine, bis [2- (4-aminophenyl) ethyl ] adipic acid, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl amine, 4' -diaminodiphenyl ethyl urea, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis (4-aminophenyl) hexafluoropropane 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 4' - (phenylenediisopropylidene) diphenylamine, 2, 6-diaminopyridine, 2, 4-diaminopyrimidine, 3, 6-diaminoacridine, N4, main chain diamines such as N4 '-bis (4-aminophenyl) -N4, N4' -dimethylbenzidine and N, N '-bis (5-aminopyridin-2-yl) -N, N' -di (t-butoxycarbonyl) ethylenediamine;
Hexadecyloxy-2, 4-diaminobenzene, octadecyloxy-2, 5-diaminobenzene, cholestanoyloxy-3, 5-diaminobenzene, cholestanoyloxy-2, 4-diaminobenzene, cholestanoyl 3, 5-diaminobenzoate, lanostanyl 3, 5-diaminobenzoate, 3, 6-bis (4-aminobenzoyloxy) cholestane, 3, 6-bis (4-aminophenoxy) cholestane, 4- (4' -trifluoromethoxybenzoyloxy) cyclohexyl-3, 5-diaminobenzoate, 1-bis (4- ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 3, 5-diaminobenzoate=5-cholestan-3-yl diamine of the formula (E), and the like;
[ chemical 30]
(in the formula (E-1), X I X is X II Each independently is a single bond, -O-, -COO-, or-OCO- (wherein "x" represents a bond to the diaminophenyl side); r is R I An alkanediyl group having 1 to 3 carbon atoms; r is R II Is a single bond or an alkanediyl group having 1 to 3 carbon atoms; r is R III Alkyl, alkoxy, fluoroalkyl or fluoroalkoxy having 1 to 20 carbon atoms; a is 0 or 1; b is an integer of 0 to 3; c is an integer of 0 to 2; d is 0 or 1; wherein 1+.a+b+c+.3)
Examples of the diaminoorganosiloxane include 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane and the like.
Examples of the compound represented by the formula (E-1) include compounds represented by the following formulae (E-1-1) to (E-1-4).
[ 31]
When the polymer (P) contains the structural Unit (UD), the proportion of the structural Unit (UD) is preferably 65 mol% or less, more preferably 55 mol% or less, with respect to all the structural units derived from the diamine compound constituting the polymer (P).
[ structural units derived from tetracarboxylic acid derivatives ]
The structural unit (hereinafter, also referred to as "structural unit (TA)") derived from the tetracarboxylic acid derivative contained in the polymer (P) is not particularly limited as long as it is a compound capable of condensing with a diamine compound to obtain a polymer. Examples of the monomers for providing the structural unit (TA) include: aliphatic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, and derivatives thereof. The aliphatic tetracarboxylic dianhydride includes a chain tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride.
Specific examples thereof include 1,2,3, 4-butane tetracarboxylic dianhydride, ethylenediamine tetraacetic dianhydride, and the like, as the chain tetracarboxylic dianhydride; examples of the alicyclic tetracarboxylic dianhydride include 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic dianhydride, 5- (2, 5-dioxotetrahydrofuran-3-yl) -3a,4,5,9 b-tetrahydronaphtho [1,2-c ] furan-1, 3-dione, 5- (2, 5-dioxotetrahydrofuran-3-yl) -8-methyl-3 a,4,5,9 b-tetrahydronaphtho [1,2-c ] furan-1, 3-dione, 2,4,6, 8-tetracarboxylic bicyclo [3.3.0] octane-2:4, 6:8-dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, and 3,5, 6-tricarboxyl-2-carboxymethyl norbornane-2:3, 5:6-dianhydride; examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4'- (hexafluoroisopropylidene) diphthalic anhydride, ethylene glycol bistrimellitic anhydride, 4' -carbonyldiphthalic anhydride, and 3,3', 4' -biphenyltetracarboxylic dianhydride.
In terms of making it possible to obtain a liquid crystal alignment film which is excellent in coatability and printability (particularly, inkjet coatability) of the obtained liquid crystal alignment agent and which exhibits excellent liquid crystal alignment properties, the tetracarboxylic acid derivative which provides the structural unit (TA) is preferably one containing an aliphatic tetracarboxylic dianhydride or a derivative thereof, and more preferably one containing an alicyclic tetracarboxylic dianhydride or a derivative thereof. In the polymer (P), the proportion of the structural unit derived from the alicyclic tetracarboxylic dianhydride or its derivative is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 50 mol% or more, with respect to all the structural units derived from the tetracarboxylic acid derivative constituting the polymer (P).
[ Synthesis of Compounds ]
The method for producing the diamine compound (DA-1), the diamine compound (DA-2), the diamine compound (DB-1) and the diamine compound (DB-2) is not particularly limited, and they can be produced by appropriately combining conventional methods of organic chemistry. As an example thereof, the following method can be mentioned: first, a dinitro intermediate having a nitro group in place of a primary amino group is synthesized in a target diamine compound, and then the nitro group of the obtained dinitro intermediate is aminated using an appropriate reduction system.
The method of synthesizing the dinitro intermediate may be appropriately selected depending on the molecular structure of the target diamine compound. For example, the compound represented by the formula (a 1-1) can be synthesized by the following method or the like: make it have a number corresponding to A 1 Secondary amine compound of the structure of (A) and "Y 1 -R 1 -Ar 1 -(NO 2 ) 2 "dinitro compound (Y) 1 A method of reacting a functional group (for example, a halogen atom, a carboxyl group, a halocarbonyl group, etc.) which is reactive with an amino group; make it have a number corresponding to A 1 Secondary amine compounds of the structure of (2)And has a "Y 1 -R 1 -Y 2 "Compound of partial structure represented by (Y) 2 Protected carboxyl) and an intermediate obtained by the reaction with a compound having a structure corresponding to Ar 1 A process for reacting a primary amino dinitro compound; make it have a number corresponding to A 1 -R 1 Hydroxyl compound having a structure corresponding to Ar 1 A process for reacting a dinitro compound having a halogen atom. The method of synthesizing the diamine compound is not limited to the above.
[ Synthesis of Polymer (P) ]
The polymer (P) can be obtained by a method comprising a step of polymerizing a monomer comprising a tetracarboxylic acid derivative and a diamine compound.
Polyamic acid
In the case where the polymer (P) is a polyamic acid, the polyamic acid (hereinafter, also referred to as "polyamic acid (P)") can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound and, if necessary, a molecular weight modifier.
In the synthesis reaction of the polyamide acid (P), the ratio of the tetracarboxylic dianhydride to the diamine compound is preferably a ratio of 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride to 1 equivalent of the amino group of the diamine compound. Examples of the molecular weight regulator include: acid monoanhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, and the like; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. The ratio of the molecular weight regulator is preferably 20 parts by mass or less based on 100 parts by mass of the total of the tetracarboxylic dianhydride and the diamine compound used.
In the synthesis reaction of the polyamic acid (P), the reaction temperature is preferably from-20℃to 150℃and the reaction time is preferably from 0.1 to 24 hours. Examples of the organic solvent used for the reaction include: aprotic polar solvents, phenol solvents, alcohol solvents, ketone solvents, ester solvents, ether solvents, halogenated hydrocarbons, and the like. Among these, it is preferable to use one or more selected from the group consisting of N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, γ -butyrolactone, tetramethylurea, hexamethylphosphoric triamide, m-cresol, xylenol and halogenated phenol as a reaction solvent, or a mixture of one or more of them with other organic solvents (for example, butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount of the organic solvent to be used is preferably an amount such that the total amount of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 50% by mass based on the total amount of the reaction solution.
In the case of obtaining a polymer solution in which the polyamic acid (P) is dissolved by the polymerization, the polymer solution may be directly supplied to the preparation of the liquid crystal aligning agent, or the polyamic acid (P) contained in the polymer solution may be separated and supplied to the preparation of the liquid crystal aligning agent.
Polyamic acid ester
In the case where the polymer (P) is a polyamic acid ester, the polyamic acid ester can be obtained, for example, by the following method or the like: [I] a method of reacting polyamic acid (P) with an esterifying agent; [ II ] a method of reacting a tetracarboxylic diester with a diamine compound; [ III ] A method for reacting a tetracarboxylic acid diester dihalide with a diamine compound. The polyamic acid ester may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester can be directly used for preparing the liquid crystal aligning agent. In addition, the method comprises the following steps. The polyamic acid ester contained in the reaction solution may also be separated, and the separated polyamic acid ester may be used for the preparation of a liquid crystal aligning agent.
Polyimide (II)
In the case where the polymer (P) is polyimide, the polyimide (hereinafter, also referred to as "polyimide (P)") can be obtained, for example, by dehydrating and ring-closing the polyamic acid (P) and imidizing the same. The polyimide (P) may be a full imide compound obtained by dehydrating and ring-closing all the amic acid structure of the polyamic acid (P) which is a precursor thereof, or may be a partial imide compound obtained by dehydrating and ring-closing only a part of the amic acid structure and simultaneously combining the amic acid structure and the imide ring structure. The polyimide (P) preferably has an imidization ratio of 20% to 99%, more preferably 30% to 90%. The imidization rate is a ratio of the number of imide ring structures to the total of the number of amic acid structures and the number of imide ring structures of the polyimide expressed as a percentage. Here, a part of the imide ring may be an isonimide ring.
The dehydration ring closure of the polyamic acid (P) is preferably performed by the following method: the polyamic acid (P) is dissolved in an organic solvent, and a dehydrating agent and a dehydrating ring-closing catalyst are added to the solution, and optionally heated. In the above method, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles based on 1 mole of the amic acid structure of the polyamic acid (P). As the dehydration ring-closing catalyst, for example, it is possible to use: tertiary amines such as pyridine, collidine, lutidine, triethylamine, etc. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 moles based on 1 mole of the dehydrating agent to be used.
Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents used for synthesizing the polyamic acid (P). The reaction temperature of the dehydration ring-closure reaction is preferably 0℃to 180 ℃. The reaction time is preferably 1.0 to 120 hours. In addition, the reaction solution containing polyimide (P) can be directly used for the preparation of a liquid crystal aligning agent. Alternatively, the polyimide (P) may be separated from the reaction solution, and the separated polyimide (P) may be used for the preparation of a liquid crystal aligning agent. Polyimide (P) can also be obtained by dehydration ring closure of polyamic acid ester.
When a solution having a concentration of 10% by mass is prepared, the solution viscosity of the polymer (P) is preferably 10 mPas to 800 mPas, more preferably 15 mPas to 500 mPas. The solution viscosity (mpa·s) is a value measured at 25 ℃ using an E-type rotational viscometer on a polymer solution having a concentration of 10 mass% prepared using a good solvent (for example, γ -butyrolactone, N-methyl-2-pyrrolidone, etc.) for the polymer (P).
The weight average molecular weight (Mw) of the polymer (P) in terms of polystyrene as measured by gel permeation chromatography (gel permeation chromatography, GPC) is preferably 1,000 ～ 500,000, more preferably 2,000 ～ 300,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 7 or less, more preferably 5 or less.
The content of the polymer (P) in the liquid crystal aligning agent is preferably 20 mass% or more, more preferably 30 mass% or more, and still more preferably 40 mass% or more, based on the total amount of solid components contained in the liquid crystal aligning agent (i.e., the total mass of components other than the solvent of the liquid crystal aligning agent).
< other Components >)
The first liquid crystal aligning agent may contain a component (hereinafter, also referred to as "other component") different from the polymer (P) as required in addition to the polymer (P).
Polymer (Q)
The first liquid crystal aligning agent may further contain a polymer (Q) having no one of the partial structures (a) and (B). 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, polyalkene amine, polyurea, polyamide, polyamideimide, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, addition polymer (e.g., (meth) acrylic polymer, styrene polymer, maleimide polymer, styrene-maleimide copolymer), and the like. Among these, the polymer (Q) is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and addition polymer.
When the first liquid crystal aligning agent is made to contain the polymer (Q), the content ratio of the polymer (Q) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, relative to 100 parts by mass of the total amount of the polymer (P) and the polymer (Q) contained in the first liquid crystal aligning agent. The content ratio of the polymer (Q) is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, based on 100 parts by mass of the total amount of the polymer (P) and the polymer (Q) contained in the first liquid crystal aligning agent.
Solvent(s)
The first liquid crystal aligning agent is preferably prepared as a liquid composition in which the polymer (P) and other components used as needed are dispersed or dissolved in an appropriate solvent.
As the solvent, an organic solvent can be 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, gamma-butyrolactone, gamma-butyrolactam, 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, methyl acetoacetate, ethyl propionate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-N-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-N-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene glycol monomethyl ether (propylene glycol monomethyl ether, PGME), diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate, PGMEA), propylene glycol dimethyl ether, cyclohexanone, and the like. As the solvent, one kind or two or more kinds may be used singly or in combination.
Examples of the other components blended in the first liquid crystal aligning agent include, in addition to the above, the following: crosslinking agents, antioxidants, metal chelate compounds, hardening accelerators, surfactants, fillers, dispersants, photosensitizers, and the like. The blending ratio of the other components may be appropriately selected depending on the respective compounds within a range that does not impair the effects of the present disclosure.
The solid content concentration of the first liquid crystal aligning agent (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. The solid content concentration of the liquid crystal aligning agent is preferably in the range of 1 to 10 mass%. When the solid content concentration is 1 mass% or more, the film thickness of the coating film can be sufficiently ensured, and a liquid crystal alignment film exhibiting more excellent liquid crystal alignment properties can be obtained, which is preferable in terms of this point. On the other hand, if the solid content concentration is 10 mass% or less, the following tends to be true: the coating film can be formed to a proper thickness, so that a liquid crystal alignment film exhibiting good liquid crystal alignment properties can be easily obtained, and the viscosity of the liquid crystal alignment agent can be properly adjusted, thereby improving the coatability.
< second liquid Crystal alignment agent >
The second liquid crystal aligning agent contains a polymer (P) and a compound having a partial structure (a) (wherein the polymer is other than the polymer; hereinafter also referred to as "compound (MA)"), and the polymer (P) is a polymer containing a structural unit derived from a diamine compound having a partial structure (B). In the following description, the portions overlapping with the first liquid crystal aligning agent will be omitted, and the description of the first liquid crystal aligning agent will be referred to.
< Polymer (P) >)
The polymer (P) contained in the second liquid crystal aligning agent is a polymer having a structural unit derived from a tetracarboxylic acid derivative and a structural unit derived from a diamine compound in one molecule, and contains the structural Unit (UB) as a structural unit derived from a diamine compound. Specific examples and preferred examples of the structural Unit (UB) and the ratio of the structural Unit (UB) in the polymer (P) can be described in the first liquid crystal aligning agent.
The polymer (P) may also contain a structural unit different from the structural Unit (UB) as a structural unit derived from a diamine compound. The structural unit may be the same as the structural unit described as another structural unit in the description of the first liquid crystal aligning agent. The polymer (P) contained in the second liquid crystal aligning agent may contain both the structural Unit (UB) and the structural Unit (UA). In terms of easy adjustment of the content of the structural Unit (UA) in the liquid crystal aligning agent, the polymer (P) contained in the second liquid crystal aligning agent preferably does not contain the structural Unit (UA).
In the second liquid crystal aligning agent, the content of the polymer (P) is preferably 20 mass% or more, more preferably 30 mass% or more, and still more preferably 40 mass% or more, based on the total amount of solid components contained in the liquid crystal aligning agent. The content of the polymer (P) is preferably 99 mass% or less, more preferably 98 mass% or less, based on the total amount of solid components contained in the liquid crystal aligning agent.
< Compound (MA) >)
The compound (MA) has, as the partial structure (a), at least one selected from the group consisting of a substituted heterocyclic structure substituted with an electron withdrawing group F1, a quinone structure, and a tetracyanoquinodimethane structure. Specific examples and preferred examples of the substituted heterocyclic structure of the compound (MA) include those described as specific examples and preferred examples of the substituted heterocyclic structure of the diamine compound (DA-1).
Specific examples and preferred examples of the quinone structure of the compound (MA) include the structures similar to those described as specific examples and preferred examples of the quinone structure of the diamine compound (DA-2). From the viewpoint of enhancing the interaction with the partial structure (B), the quinone structure possessed by the compound (MA) is preferably a secondary amino group (-NH-) or a tertiary amino group bonded to a ring. The number of secondary amino groups and tertiary amino groups bonded to the ring of the quinone structure (the total amount thereof in the case of having two or more kinds) is preferably one or two.
The tetracyanoquinodimethane structure of the compound (MA) may have a substituent on a ring portion. As the substituent, there may be mentioned: alkyl groups having 1 to 3 carbon atoms, alkoxy groups having 1 to 3 carbon atoms, halogen atoms, and the like.
Specific examples of the compound (MA) include compounds represented by the following formulae (d-6-1) to (d-6-3) as a compound having a substituted heterocyclic structure substituted with an electron-withdrawing group F1; examples of the compound having a quinone structure include compounds represented by the following formulae (d-6-4) to (d-6-7); examples of the compound having a tetracyanoquinodimethane structure include compounds represented by the following formulae (d-6-8) to (d-6-14).
[ chemical 32]
In the second liquid crystal aligning agent, the content of the compound (MA) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 5 parts by mass or more, based on 100 parts by mass of the total amount of the polymer components contained in the liquid crystal aligning agent. The content of the compound (MA) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and still more preferably 20 parts by mass or less, based on 100 parts by mass of the total amount of the polymer components contained in the liquid crystal aligning agent.
The second liquid crystal aligning agent may further contain a component different from the polymer (P) and the compound (MA), if necessary. Specific examples, preferable examples, content ratios, and the like of the components described above can be applied to descriptions of other components in the first liquid crystal aligning agent.
Liquid crystal alignment film and liquid crystal element
The liquid crystal alignment film of the present disclosure can be manufactured by the liquid crystal alignment agent prepared as described. In addition, the liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The driving method of the liquid crystal In the liquid crystal element is not particularly limited, and is applicable to various modes such as a Twisted Nematic (TN) mode, a super Twisted Nematic (Super Twisted Nematic, STN) mode, a vertical alignment (Vertical Alignment, VA) mode (including a vertical alignment-Multi-domain vertical alignment (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) mode, a vertical alignment-pattern vertical alignment (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) mode, an In-Plane Switching (IPS) mode, a fringe field Switching (Fringe Field Switching, FFS) mode, an optically compensated bend (Optically Compensated Bend, OCB) mode, and a polymer stable alignment (Polymer Sustained Alignment, PSA) mode. The liquid crystal element can be manufactured by a method including the following steps 1 to 3, for example. In step 1, the substrate is used in accordance with a desired operation mode. Step 2 and step 3 are common to each operation mode.
< procedure 1: formation of coating film >
First, a liquid crystal aligning agent is coated on a substrate, and the coated surface is preferably heated to form a coating film on the substrate. As the substrate, for example, there can be used: float glass, sodium glass, and the like; transparent substrates comprising plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly (alicyclic olefin). As the transparent conductive film provided on one surface of the substrate, a film containing tin oxide (SnO 2 ) Nesa (Nesa) film (registered trademark of PPG company, U.S.) containing indium oxide-tin oxide (In 2 O 3 -SnO 2 ) Indium Tin Oxide (ITO) films, and the like. In the case of manufacturing a TN-type, STN-type, or VA-type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, in the case of manufacturing an IPS type or FFS type liquid crystal device, a substrate provided with electrodes patterned into a comb-teeth type and an opposing substrate provided with no electrodes are used.
The method of applying the liquid crystal aligning agent to the substrate is not particularly limited. The liquid crystal aligning agent can be applied to the substrate by, for example, a spin coating method, a printing method (for example, an offset printing method, a flexographic printing method, or the like), an inkjet method, a slit coating method, a bar coater method, an extrusion die (extrusion die) method, a direct gravure coater (direct gravure coater) method, a cavity blade coater (chamber doctor coater) method, an offset gravure coater (offset gravure coater) method, a dip coater method, or an MB coater method.
After the liquid crystal aligning agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing sagging of the applied liquid crystal aligning agent, and the like. The pre-baking temperature is preferably 30-200 ℃, and the pre-baking time is preferably 0.25-10 minutes. Thereafter, 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 existing in the polymer. The calcination temperature (post-baking temperature) at this time is preferably 80 to 280 ℃, more preferably 80 to 250 ℃. The post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the formed film is preferably 0.001 μm to 1 μm.
< procedure 2: orientation process >
In the case of manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal device, a process (alignment process) for imparting liquid crystal alignment ability to the coating film formed in the step 1 is performed. Thus, the liquid crystal molecules are imparted with orientation ability to the coating film to form a liquid crystal orientation film. As the alignment treatment, a rubbing treatment of wiping the surface of a coating film formed on a substrate with cotton, nylon, or the like, or a photo-alignment treatment of irradiating the coating film with light to impart liquid crystal alignment ability thereto is preferably used. In the case of manufacturing a vertical alignment type liquid crystal element, the coating film formed in the step 1 may be used as a liquid crystal alignment film as it is, or the coating film may be subjected to an alignment treatment in order to further improve the liquid crystal alignment ability. A liquid crystal alignment film suitable for a liquid crystal element of a vertical alignment type can also be preferably used for a liquid crystal element of a PSA type.
The light irradiation for photo-alignment may be performed by the following method or the like: a method of irradiating the coating film after the post-baking step; a method of irradiating the coating film after the pre-baking step and before the post-baking step; a method of irradiating the coating film during heating of the coating film in at least either one of the pre-baking step and the post-baking step. As the radiation irradiated to the coating film, for example, there can be used: ultraviolet and visible rays including light having a wavelength of 150nm to 800 nm. Preferably ultraviolet rays containing light having a wavelength of 200nm to 400 nm. In the case where the radiation is polarized, the radiation may be linearly polarized or partially polarized. In the case where the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed in a direction perpendicular to the substrate surface, in an oblique direction, or in a combination of these directions. The irradiation direction in the case of unpolarized radiation is set to be an oblique direction.
Examples of the light source to be used include: low pressure mercury lamps, high pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and the like. The irradiation amount of the radiation is preferably 200J/m 2 ～30,000J/m 2 More preferably 500J/m 2 ～10,000J/m 2 . After the light irradiation for imparting orientation ability, a treatment of cleaning the substrate surface with, for example, water, an organic solvent (for example, methanol, isopropanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, or the like) or a mixture thereof, or a treatment of heating the substrate may be performed.
< procedure 3: construction of liquid Crystal cell
Two substrates having a liquid crystal alignment film formed thereon are prepared, and a liquid crystal cell is manufactured by disposing liquid crystal between the two substrates disposed in opposition to each other. In manufacturing a liquid crystal cell, for example, the following methods are listed: the liquid crystal display device is manufactured by a method of disposing two substrates facing each other with a gap therebetween, bonding the peripheral portions of the two substrates with a sealant, injecting and filling liquid crystal into a cell gap surrounded by the substrate surface and the sealant, and sealing the injection hole, and a method of using a One Drop Fill (ODF) method. As the sealant, for example, an epoxy resin containing a hardener and alumina balls as spacers, or the like can be used. The liquid crystal includes nematic liquid crystal (nematic liquid crystal) and smectic liquid crystal (smectic liquid crystal), and among them, nematic liquid crystal is preferable.
In PSA mode, the following process is performed: a polymerizable compound (for example, a polyfunctional (meth) acrylate compound or the like) is filled in the cell gap together with the liquid crystal, and after the liquid crystal cell is constructed, the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films provided on the pair of substrates. In the production of a PSA-type liquid crystal element, the polymerizable compound is used in an amount of, for example, 0.01 to 3 parts by mass, preferably 0.05 to 1 part by mass, based on 100 parts by mass of the total liquid crystal.
In the case of manufacturing a liquid crystal display device, a polarizing plate is then bonded to the outer surface of the liquid crystal cell. As the polarizing plate, there may be mentioned: a polarizing plate in which a polarizing film called an "H film" in which polyvinyl alcohol is stretched and oriented and iodine is absorbed while being sandwiched by a cellulose acetate protective film, or a polarizing plate including an H film itself.
The liquid crystal element of the present disclosure can be effectively applied to various uses. Specifically, the present invention can be used as various display devices or light control devices such as a timepiece, a portable game machine, a word processor (word processor), a notebook personal computer, a car navigation system (car navigation system), a video camera (cam camera), a personal digital assistant (Personal Digital Assistant, PDA), a digital camera (digital camera), a mobile phone, a smart phone, various monitors, a liquid crystal television, an information display, and a phase difference film.
Examples (example)
Hereinafter, embodiments will be described in more detail based on examples, but the present invention is not limited by the following examples.
In the following examples, the imidization rate of polyimide in a polymer solution, and the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured by the following methods. The required amounts of the raw material compounds and polymers used in the examples below were ensured by repeating the synthesis at the synthesis scale shown in the synthesis examples below, if necessary.
[ imidization Rate of polyimide ]
Adding polyimide solution into pure water, drying the obtained precipitate at room temperature under reduced pressure, dissolving in deuterated dimethyl sulfoxide, and performing hydrogen spectrum nuclear magnetic resonance at room temperature with tetramethylsilane as reference material 1 H-nuclear magnetic resonance， 1 H-NMR) determination. According to the obtained 1 H-NMR spectrum, the imidization rate [%]。
Imidization ratio [%]＝(1-(A 1 /(A 2 ×α)))×100…(I)
(in the formula (I), A 1 To be chemically displacedPeak area of protons originating from NH groups occurring around 10ppm, a 2 For peak area derived from other protons, α is the number ratio of other protons to one proton of NH groups in the precursor of the polymer (polyamic acid)
[ weight average molecular weight (Mw) and number average molecular weight (Mn) ]
Mw and Mn are polystyrene equivalent values obtained by GPC measurement under the following conditions.
And (3) pipe column: manufactured by Tosoh (Stro), TSKgelGRCXLII
Solvent: tetrahydrofuran (THF)
Temperature: 40 DEG C
Pressure: 68kgf/cm 2
The abbreviations of the compounds are described below. In the following, the compound represented by the formula (X) may be simply referred to as "compound (X)".
(tetracarboxylic dianhydride)
[ 33]
(diamine compound)
[ chemical 34]
[ 35]
[ 36]
[ 37]
[ 38]
[ 39]
[ 40]
[ chemical 41]
(monomer containing carbon-carbon unsaturated bond)
[ chemical 42]
[ chemical 43]
(additive)
[ 44]
[ 45]
(solvent)
NMP: n-methyl-2-pyrrolidone (NMP)
NEP: n-ethyl-2-pyrrolidone (N-ethyl-2-pyrrosidone, NEP)
GBL: gamma-Butyrolactone (GBL)
BC: butyl Cellosolve (Butyl Cellosolve, BC)
DGDE: diethylene glycol diethyl ether (Diethylene Glycol Diethyl Ether, DGDE) DIBK: diisobutyl ketone (Diisobutyl ketone, DIBK)
(synthetic solvent)
DMF: n, N-dimethylformamide (N, N-Dimethyl formamide, DMF)
THF: tetrahydrofuran (THF)
DMAc: dimethylacetamide (Dimethyl acetamide, DMAc)
< Synthesis of Compounds >
Synthesis example 1-1 Synthesis of Compound (DA-1)
4, 5-dicyanoimidazole (12.7 mmol) and potassium carbonate (15.3 mmol) were added to DMF (15 mL) and stirred under nitrogen at room temperature for 30 min. Then, 3, 5-dinitrobenzyl chloride (15.2 mmol) was added to the stirred reaction solution, and the mixture was stirred at room temperature under nitrogen for 6 hours. After the reaction, ethyl acetate was added thereto, and the mixture was washed with water. The organic phase was concentrated under reduced pressure and dried, whereby a compound represented by the following formula (DA-1-1) was obtained in a yield of 95%.
Next, the intermediate (DA-1-1) (15.2 mmol), zinc powder (303 mmol) and ammonium chloride (152 mmol) were added to a mixed solvent of THF (30 mL) and ethanol (6 mL), and the mixture was stirred under nitrogen at 0 ℃. Then, pure water (432 mmol) was added dropwise thereto, and stirring was continued at 0℃for 1 hour. Thereafter, the mixture was stirred at room temperature under nitrogen for 5 hours. After the reaction, the reaction solution was filtered through celite, ethyl acetate was added, and the mixture was washed with water. The organic phase was concentrated under reduced pressure, whereby compound (DA-1) was obtained as a yellow solid in 70% yield. Hydrogen spectrum nuclear magnetic resonance of compound (DA-1) 1 H-nuclear magnetic resonance， 1 H-NMR) Spectroscopy (dimethyl sulfoxide (dimethyl sulfoxide, DMSO) -d 6 400 MHz) is shown in fig. 1.
Atmospheric pressure ionization electrospray (Atmospheric Pressure Ionization-eleotospray, API-ES) m/z:239.1 (calculation [ M+H ]] + (calc.for[M+H] + )：239.10)
[ chemical 46]
Synthesis example 1-2 Synthesis of Compound (DA-2)
4, 5-dicyanoimidazole (12.7 mmol) and triethylamine (15.3 mmol) were added to THF (15 mL) and stirred under nitrogen at 0deg.C for 10 min. Then, 3, 5-dinitrobenzoyl chloride (12.7 mmol) dissolved in 10mL of THF was added dropwise to the stirred reaction solution, and stirring was continued at 0℃for 1 hour. Thereafter, the mixture was stirred at room temperature under nitrogen for 5 hours. After the reaction, ethyl acetate was added thereto, and the mixture was washed with water. The organic phase was concentrated under reduced pressure and dried, whereby a compound represented by the following formula (DA-2-1) was obtained in a yield of 90%.
Next, the intermediate (DA-2-1) (11.4 mmol) and 5% Pd/C (0.73 g) were added to a mixed solvent of THF (12 mL) and ethanol (12 mL), and stirred under nitrogen at 0℃for 10 minutes. Then, hydrazine monohydrate (68.6 mmol) was added dropwise to the stirred reaction solution, and stirring was continued at 0℃for 30 minutes. Thereafter, stirring was carried out under nitrogen at 66℃for 6 hours. After the reaction, the reaction solution was filtered through celite, ethyl acetate was added, and the mixture was washed with water. The organic phase was concentrated under reduced pressure, whereby compound (DA-2) was obtained in 85% yield.
[ 47]
Synthesis examples 1 to 3 Synthesis of Compound (DA-3)
4, 5-dicyanoimidazole (12.7 mmol) and potassium carbonate (25.4 mmol) were added to DMF (25 mL) and stirred under nitrogen at room temperature for 30 min. Then, ethyl 3-bromopropionate (15.2 mmol) was added to the stirred reaction solution, and stirred under nitrogen at 100℃for 6 hours. After the reaction, ethyl acetate was added thereto, and the mixture was washed with water. The organic phase was concentrated under reduced pressure and dried, whereby a compound represented by the following formula (DA-3-1) was obtained in 80% yield.
The intermediate (DA-3-1) (10.2 mmol) was added to 1mol/L aqueous hydrochloric acid (20 mL) and stirred at reflux for 8 hours. Thereafter, the solution was concentrated, washed with ethanol and dried, whereby a compound represented by the following formula (DA-3-2) was obtained in 80% yield.
Intermediate (DA-3-2) (8.1 mmol) was added to thionyl chloride (81.3 mmol). Stirring was carried out under nitrogen at room temperature while DMF (0.08 mmol) was added. Thereafter, the mixture was stirred under reflux for 1.5 hours. After completion of the reaction, the reaction mixture was concentrated, and the residue was dissolved in THF (10 mL). The solution was designated as solution A. 3, 5-dinitroaniline (8.1 mmol) and triethylamine (16.3 mmol) were dissolved in THF (10 mL) and stirred under nitrogen at 0deg.C for 10 minutes. To the solution was added dropwise the solution a, and stirring was continued at 0 ℃ for 1 hour. Thereafter, the mixture was stirred at room temperature under nitrogen for 3 hours. After the reaction, ethyl acetate was added thereto, and the mixture was washed with water. The organic phase was concentrated under reduced pressure and dried, whereby a compound represented by the following formula (DA-3-3) was obtained in a yield of 85%.
The intermediate (DA-3-3) (6.9 mmol) and 5% Pd/C (0.44 g) were added to a mixed solvent of THF (8 mL) and ethanol (8 mL) and stirred under nitrogen at 0deg.C for 10 minutes. Then, hydrazine monohydrate (41.5 mmol) was added dropwise to the stirred reaction solution, and stirring was continued at 0℃for 30 minutes. Thereafter, the mixture was stirred at room temperature under nitrogen for 6 hours. After the reaction, the reaction solution was filtered through celite, ethyl acetate was added, and the mixture was washed with water. The organic phase was concentrated under reduced pressure, whereby compound (DA-3) was obtained in 80% yield.
[ 48]
Synthesis examples 1 to 4 Synthesis of Compound (DA-4)
Compound (DA-4) was synthesized in the same manner as in Synthesis example 1-1, except that 4, 5-dicyanoimidazole was changed to 2,4, 5-tribromoimidazole in the first stage of the synthesis scheme of Synthesis example 1-1.
Synthesis examples 1 to 5 Synthesis of Compound (DA-5)
Compound (DA-5) was synthesized in the same manner as in Synthesis example 1-1, except that 3, 5-dinitrobenzyl chloride was changed to 2, 4-dinitrobenzyl chloride in the first stage of the synthesis scheme in Synthesis example 1-1.
Synthesis examples 1 to 6 Synthesis of Compound (DA-6)
The compound (DA-6-1) (12.3 mmol) was added to DMAc (20 mL) and stirred under nitrogen at 0deg.C for 10 min. Then, sodium t-butoxide (18.5 mmol) was added to the stirred reaction solution in several portions, and stirring was continued at 0℃for 30 minutes. Thereafter, 2, 4-dinitrofluorobenzene (13.5 mmol) dissolved in DMAc (5 mL) was added to the stirred reaction solution and stirred under nitrogen at 0℃for 6 hours. After the completion of the reaction, water was added, followed by ethyl acetate for liquid-separation washing. The organic phase was concentrated under reduced pressure and dried, whereby a compound represented by the following formula (DA-6-2) was obtained in a yield of 90%.
The intermediate (DA-6-2) (11.1 mmol) and 5% Pd/C (0.71 g) were added to a mixed solvent of THF (12 mL) and ethanol (12 mL) and stirred under nitrogen at 0deg.C for 10 minutes. Then, hydrazine monohydrate (66.4 mmol) was added dropwise to the stirred reaction solution, and stirring was continued at 0℃for 30 minutes. Thereafter, stirring was carried out under nitrogen at 66℃for 6 hours. After the reaction, the reaction solution was filtered through celite, ethyl acetate was added, and the mixture was washed with water. The organic phase was concentrated under reduced pressure, whereby compound (DA-6) was obtained in 90% yield. Furthermore, the compound (DA-6-1) was synthesized according to the well-known literature (Bioorganic and medicinal chemistry communication (Bioorganic & Medicinal Chemistry Letters) (2019), 29 (9), 1138-1142).
[ 49]
Synthesis examples 1 to 7 Synthesis of Compound (DA-7)
Compound (DA-7) was synthesized in the same manner as in Synthesis example 1-1, except that 4, 5-dicyanoimidazole was changed to 4-acetylimidazole in the first stage of the synthesis scheme of Synthesis example 1-1.
Synthesis examples 1 to 8 Synthesis of Compound (DA-8)
In the first stage of the synthesis scheme of Synthesis example 1-1, compound (DA-8) was synthesized in the same manner as in Synthesis example 1-1, except that 4, 5-dicyanoimidazole was changed to 4, 5-bis (trifluoromethyl) imidazole and 3, 5-dinitrobenzyl chloride was changed to 2, 4-dinitrobenzyl chloride.
Synthesis examples 1 to 9 Synthesis of Compound (DA-9)
2, 5-dimethoxy-1, 4-benzoquinone (17.8 mmol) was added to ethanol (25 mL) and stirred at room temperature under nitrogen. 2- (4-aminophenyl) ethylamine (36.0 mmol) dissolved in ethanol (15 mL) was added dropwise to the reaction solution, and the mixture was stirred at room temperature under nitrogen for 5 hours. After completion of the reaction, the precipitated solid was separated by filtration, and the solid was washed with ethanol and then dried, whereby a compound (DA-9) which was a bluish solid was obtained in a yield of 95%. The compound (DA-9) 1 H-NMR spectrum (DMSO-d) 6 400 MHz) is shown in fig. 2.
API-ES m/z:377.2 (calculation [ M+H ]] + (calc.for[M+H] + )：377.20)
[ 50]
Synthesis examples 1 to 10 Synthesis of Compound (DA-10)
Synthesis examples 1 to 9 were repeated in the same manner as in Synthesis examples 1 to 9 except that 2- (4-aminophenyl) ethylamine was changed to 4-aminobenzylamine, to obtain Compound (DA-10).
Synthesis examples 1 to 11 Synthesis of Compound (DA-11)
3- (4-nitrophenyl) propionic acid (15.0 mmol) was added to thionyl chloride (150.0 mmol). Stirring was carried out under nitrogen at room temperature while DMF (0.15 mmol) was added. Thereafter, the mixture was stirred under reflux for 1.5 hours. After completion of the reaction, the reaction mixture was concentrated, and the residue was dissolved in THF (20 mL). The solution was designated as solution B. Ethylenediamine (30.0 mmol) and triethylamine (60.0 mmol) were dissolved in THF (30 mL) and stirred under nitrogen at 0 ℃ for 10 minutes. To the solution was added dropwise the solution B, and stirring was continued at 0 ℃ for 1 hour. Thereafter, the mixture was stirred at room temperature under nitrogen for 3 hours. After the reaction, ethyl acetate was added thereto, and the mixture was washed with water. The organic phase was concentrated under reduced pressure and dried, whereby a compound represented by the following formula (DA-11-1) was obtained in a yield of 70%.
The intermediate (DA-11-1) (10.5 mmol) and 5% Pd/C (0.67 g) were added to ethanol (25 mL) and the reaction vessel was purged with nitrogen. Then, the reaction vessel was replaced with hydrogen gas, and stirred at room temperature for 12 hours. After completion of the reaction, THF was added to the reaction solution, followed by filtration through celite, and the filtrate was concentrated under reduced pressure, whereby the compound represented by the following formula (DA-11-2) was obtained in a yield of 90%.
In the third stage of the following synthesis scheme, compound (DA-11) was obtained by synthesizing in the same manner as in Synthesis examples 1 to 9, except that 2- (4-aminophenyl) ethylamine was changed to intermediate (DA-11-2) and the solvent was changed from ethanol to THF.
[ 51]
Synthesis examples 1 to 12 Synthesis of Compound (DA-12)
2-amino-5-nitrobenzyl amine (10.0 mmol) and 5% Pt/C (1.56 g) were added to ethanol (40 mL) and the reaction vessel was purged with nitrogen. Then, the reaction vessel was replaced with hydrogen gas, and stirred at room temperature for 12 hours. After completion of the reaction, THF was added to the reaction solution, followed by filtration through celite, and the filtrate was concentrated under reduced pressure, whereby the compound represented by the following formula (DA-12-1) was obtained in a yield of 90%.
2, 5-dimethoxy-1, 4-benzoquinone (18.0 mmol) was added to ethanol (35 mL) and stirred at room temperature under nitrogen. Intermediate (DA-12-1) (9.0 mmol) dissolved in ethanol (15 mL) was added dropwise to the reaction solution and stirred at room temperature under nitrogen for 3 hours. After the completion of the reaction, the solvent was removed, and the residue was purified by silica gel column chromatography (elution in a mixed solvent of ethyl acetate and hexane), whereby compound (DA-12) was obtained.
[ 52]
Synthesis examples 1 to 13 Synthesis of Compound (DA-13)
In the second stage of the synthesis scheme of Synthesis examples 1 to 12, compound (DA-13) was synthesized in the same manner as in Synthesis examples 1 to 12 except that 2, 5-dimethoxy-1, 4-benzoquinone was changed to 2, 3-dimethylbenzoquinone.
Synthesis examples 1 to 14 Synthesis of Compound (DA-14)
The reaction vessel was purged with nitrogen by adding the following formula (DA-14-1) (21.0 mmol) and 5% Pd/C (1.34 g) to ethanol (50 mL). Then, the reaction vessel was replaced with hydrogen gas, and stirred at room temperature for 12 hours. After completion of the reaction, THF was added to the reaction solution, followed by filtration through celite, and the filtrate was concentrated under reduced pressure, whereby the compound represented by the following formula (DA-14-2) was obtained in a yield of 90%.
The reaction in the second stage of the synthesis scheme described below was performed in the same manner as in Synthesis examples 1 to 12 except that the intermediate (DA-12-1) was changed to the intermediate (DA-14-2) in the second stage of the synthesis scheme in Synthesis examples 1 to 12, and Compound (DA-14) was obtained. The compound represented by the following formula (DA-14-1) was synthesized according to a known literature (journal of Oriental chemistry (Oriental Journal of Chemistry) (2013), 29 (1), 17-22).
[ 53]
Synthesis examples 1 to 15 Synthesis of Compound (DB-23)
Phenothiazine (10.0 mmol) and 3, 5-dinitrobenzyl chloride (10.0 mmol) were added to THF (30 mL) and stirred under nitrogen at room temperature for 10 min. Then, sodium hydroxide (13.0 mmol) dissolved in pure water (15 mL) was added to the stirred reaction solution, and stirred at room temperature under nitrogen for 6 hours. After the reaction, ethyl acetate was added thereto, and the mixture was washed with water. The organic phase was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (elution in a mixed solvent of ethyl acetate and hexane), whereby the following formula (DB-23-1) was obtained in a yield of 70%.
Next, intermediate (DB-23-1) (7.0 mmol), zinc powder (140 mmol) and ammonium chloride (70.0 mmol) were added to a mixed solvent of THF (30 mL) and ethanol (5 mL), and stirred under nitrogen at 0 ℃. Then, pure water (200 mmol) was added dropwise thereto, and stirring was continued at 0℃for 1 hour. Thereafter, the mixture was stirred at room temperature under nitrogen for 5 hours. After the reaction, the reaction solution was filtered through celite, ethyl acetate was added, and the mixture was washed with water. The organic phase was concentrated under reduced pressure, whereby compound (DB-23) was obtained in 90% yield. Compound (DB-23) 1 H-NMR spectrum (DMSO-d) 6 400MHz, ppm) are as follows.
δ=7.05 (m, 4H), 6.87 (t, j=7.6 hz, 2H), 6.74 (d, j=8.8 hz, 2H), 5.72 (s, 2H), 5.68 (s, 1H), 4.77 (s, 2H), 4.72 (s, 4H). API-ES m/z:320.1 (calculation [ M+H ]] + (calc.for[M+H] + )：320.12)
[ 54]
Synthesis of Compound (DB-24) of Synthesis examples 1-16
3, 5-dinitroaniline (15.0 mmol) and triethylamine (18.0 mmol) were added to THF (20 mL) and stirred under nitrogen at 0deg.C for 10 min. Subsequently, 3-bromopropionyl chloride (15.0 mmol) dissolved in THF (10 mL) was added dropwise, and stirring was continued at 0℃for 1 hour. Thereafter, the mixture was stirred at room temperature under nitrogen for 3 hours. After the reaction, ethyl acetate was added thereto, and the mixture was washed with water. The organic phase was concentrated under reduced pressure and dried, whereby a compound represented by the following formula (DB-24-1) was obtained in a yield of 90%.
The synthesis was performed in the same manner as in Synthesis examples 1 to 15 except that the reaction in the second and third stages of the synthesis schemes described below was changed to the intermediate (DB-24-1) in the synthesis schemes of Synthesis examples 1 to 15, and Compound (DB-24) was obtained.
[ 55]
Synthesis examples 1 to 17 Synthesis of Compound (DB-25)
2, 4-dinitrophenol (10.0 mmol) and potassium carbonate (20.0 mmol) were added to DMF (20 mL) and stirred at room temperature under nitrogen for 10 minutes. Subsequently, 1, 2-dibromoethane (20.0 mmol) dissolved in DMF (5 mL) was added to the stirred reaction solution. Thereafter, the mixture was stirred under nitrogen at 100℃for 6 hours. After the reaction, ethyl acetate was added thereto, and the mixture was washed with water. The organic phase was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (elution in a mixed solvent of ethyl acetate and hexane), whereby the following formula (DB-25-1) was obtained in 80% yield.
The reaction in the second stage of the synthesis scheme described below was performed in the same manner as in synthesis examples 1 to 15 except that 3, 5-dinitrobenzyl chloride was changed to intermediate (DB-25-1) in the first stage of the synthesis scheme in synthesis examples 1 to 15, to obtain intermediate (DB-25-2).
Intermediate (DB-25-2) (5.0 mmol) and 5% Pd/C (0.32 g) were added to a mixed solvent of THF (8 mL) and ethanol (8 mL) and stirred under nitrogen at 0deg.C for 10 min. Then, hydrazine monohydrate (30.0 mmol) was added dropwise to the stirred reaction solution, and stirring was continued at 0℃for 30 minutes. Thereafter, stirring was carried out under nitrogen at 66℃for 6 hours. After the reaction, the reaction solution was filtered through celite, ethyl acetate was added, and the mixture was washed with water. The organic phase was concentrated under reduced pressure, whereby compound (DB-25) was obtained in 80% yield.
[ 56]
Synthesis examples 1 to 18 Synthesis of Compound (DB-26)
2-methoxyphenothiazine (10.0 mmol) and sodium hydroxide (20.0 mmol) were added to DMSO (20 mL) and stirred under nitrogen at room temperature for 15 min. Then, methyl iodide (100 mmol) was added dropwise. Thereafter, the mixture was stirred at 65℃for 9 hours. After the reaction, ethyl acetate was added thereto, and the mixture was washed with water. The organic phase was concentrated under reduced pressure and dried, whereby a compound represented by the following formula (DB-26-1) was obtained in a yield of 90%.
The intermediate (DB-26-1) (9.0 mmol) was added to dichloromethane (18 mL) and stirred under nitrogen at 0deg.C for 15 min. Then, boron tribromide (1M methylene chloride solution, 13.5 mL) was added dropwise. Thereafter, stirring was continued for another 10 hours after the temperature was raised to room temperature under nitrogen at 0℃for 2 hours. After the completion of the reaction, water was added thereto, followed by neutralization with a saturated aqueous sodium hydrogencarbonate solution, and liquid separation extraction was performed with methylene chloride. The organic phase was concentrated under reduced pressure and dried, whereby a compound represented by the following formula (DB-26-2) was obtained in a yield of 95%.
Intermediate (DB-26-2) (8.6 mmol) and potassium carbonate (17.1 mmol) were added to DMF (15 mL) and stirred at room temperature under nitrogen for 30 min. Then, intermediate (DB-26-1) (8.6 mmol) dissolved in DMF (5 mL) was added to the stirred reaction solution and stirred under nitrogen at 100deg.C for 6 hours. After the reaction, ethyl acetate was added thereto, and the mixture was washed with water. The organic phase was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (elution in a mixed solvent of ethyl acetate and hexane), whereby a compound represented by the following formula (DB-26-3) was obtained in 80% yield.
An intermediate (DB-26) was obtained by the same method as in Synthesis examples 1-17, except that the intermediate (DB-25-2) was changed to the intermediate (DB-26-3) in the third stage of the synthesis process of Synthesis examples 1-17, with respect to the reaction in the fourth stage of the following synthesis process
[ 57]
Synthesis examples 1 to 19 Synthesis of Compound (DB-27)
In the third stage of the synthesis scheme of Synthesis examples 1-18, compound (DB-27) was synthesized in the same manner as in Synthesis examples 1-18 except that the intermediate (DB-25-1) was changed to 2, 4-dinitrofluorobenzene.
Synthesis examples 1 to 20 Synthesis of Compound (DB-28)
Compound (DB-28) was synthesized in the same manner as in Synthesis examples 1-6 except that in the first stage of the synthesis scheme of Synthesis examples 1-6, compound (DA-6-1) was changed to phenothiazine.
< Synthesis of Polymer >
1. Synthesis of Polyamic acid
Synthesis examples 2 to 1
100 parts by mol of the compound (c-1) as tetracarboxylic dianhydride, 60 parts by mol of the compound (DA-1) as a diamine compound, 10 parts by mol of the compound (DB-20) and 30 parts by mol of the compound (b-13) were dissolved in N-methyl-2-pyrrolidone (NMP), and reacted at room temperature for 6 hours to obtain a solution containing 15% by mass of polyamic acid (which was referred to as polymer (PAA-1)).
Synthesis examples 2-2 to 2-34, synthesis examples 2-38 to 2-41
The same procedure as in Synthesis example 2-1 was conducted except that the types and amounts of the tetracarboxylic dianhydride and diamine compound used were changed as shown in Table 1 or Table 2, and a solution containing polyamide acid (polymer (PAA-2) to polymer (PAA-38)) was obtained.
2. Synthesis of polyimide
Synthesis examples 2 to 35
30 parts by mol of the compound (b-14) and 70 parts by mol of the compound (b-15) which are diamine compounds were dissolved in N-methyl-2-pyrrolidone (NMP), 50 parts by mol of the compound (c-1) and 50 parts by mol of the compound (c-4) which are tetracarboxylic dianhydrides were added, and reacted at 40℃for 24 hours, whereby a solution containing 20% by mass of polyamic acid was obtained.
Then, NMP was added to the polymer solution obtained to prepare a solution having a polyamic acid concentration of 10 mass%, pyridine and acetic anhydride were added thereto, and a dehydration ring-closure reaction was performed at 90℃for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with new NMP, thereby obtaining a solution containing polyimide having an imidization ratio of about 60% by mass of 15% (this was referred to as polymer (PI-1)).
Synthesis examples 2 to 36, synthesis examples 2 to 37, synthesis examples 2 to 42 and Synthesis examples 2 to 43
The same operations as in Synthesis examples 2 to 35 were carried out except that the types and amounts of the tetracarboxylic dianhydride and diamine compound used were changed as shown in Table 1 or Table 2, and solutions containing polyimides (Polymer (PI-2) to Polymer (PI-5)) were obtained.
TABLE 1
TABLE 2
3. Synthesis of styrene-maleimide-based copolymer [ Synthesis example 3-1]
5.00g of compound (M-1), 1.05g of compound (M-2), 4.80g of compound (M-3) and 2.26g of compound (M-4), 0.39g of 2,2' -azobis (2, 4-dimethylvaleronitrile) as a radical polymerization initiator, 0.39g of 2, 4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 52.5mL of N-methyl-2-pyrrolidone (NMP) as a solvent were put into a 100mL two-necked flask under nitrogen atmosphere, and polymerized at 70℃for 6 hours. After reprecipitation in methanol, the precipitate was filtered and dried under vacuum at room temperature for 8 hours, whereby a styrene-maleimide-based copolymer (which was designated as polymer (MI-1)) was obtained. The weight average molecular weight Mw measured by GPC and in terms of polystyrene was 30000 and the molecular weight distribution Mw/Mn was 2.
Synthesis example 3-2
10 parts by mole of compound (M-5), 10 parts by mole of compound (M-6), 30 parts by mole of compound (M-7), 10 parts by mole of compound (M-8), 20 parts by mole of compound (M-9) and 20 parts by mole of compound (M-10), 2 parts by mole of 2,2' -azobis (2, 4-dimethylvaleronitrile) as a radical polymerization initiator, and 50mL of tetrahydrofuran as a solvent were put into a 100mL two-necked flask under nitrogen, and polymerized at 70℃for 6 hours. After reprecipitation in methanol, the precipitate was filtered and dried under vacuum at room temperature for 8 hours, whereby a styrene-maleimide-based copolymer (which was designated as polymer (MI-2)) was obtained. The weight average molecular weight Mw measured by GPC and in terms of polystyrene was 92700, and the molecular weight distribution Mw/Mn was 4.78.
Preparation and evaluation of liquid Crystal alignment agent
Example 1: light FFS type liquid Crystal display element
1. Preparation of liquid Crystal alignment agent
In the solution containing the polymer (PAA-1) obtained in Synthesis example 2-1, to be the polymer (PAA-1) in terms of solid content conversion: polymer (PAA-35) =60: 40 (mass ratio) the solution containing the polymer (PAA-35) obtained in Synthesis examples 2 to 38 was added and diluted with NMP, GBL and BC, thereby producing a solvent composition ratio of NMP: GBL: bc=45: 30:25 (mass ratio), a solution having a solid content concentration of 3.5 mass%. The solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent (AL-1).
2. FFS type liquid crystal cell fabrication using photo-alignment
A glass substrate (first substrate) having a flat electrode (bottom electrode), an insulating layer, and a comb-shaped electrode (top electrode) laminated in this order on one surface, and a glass substrate (second substrate) having no electrode were prepared. Then, a liquid crystal alignment agent (AL-1) was applied to the electrode formation surface of the first substrate and one surface of the second substrate by a rotator, and heated (prebaked) by a hot plate at 80℃for 1 minute. Thereafter, the film was dried (post-baking) in an oven at 230℃in which nitrogen gas was substituted for the inside of the oven for 30 minutes to form a coating film having an average film thickness of 0.1. Mu.m. For the obtained coating film, ultraviolet ray 4,000J/m containing a linearly polarized 254nm bright line was irradiated from the substrate normal direction using an Hg-Xe lamp 2 And photo-alignment treatment is performed. The irradiation amount is a value measured using a light meter measuring with a wavelength of 254nm as a reference. Then, the photo-alignment-treated coating film was heated in a clean oven at 230 ℃ for 30 minutes to perform heat treatment, thereby forming a liquid crystal alignment film.
Next, an epoxy adhesive containing alumina balls having a diameter of 3.5 μm was applied to one of a pair of substrates on which a liquid crystal alignment film was formed by screen printing. Thereafter, the substrates were overlapped and pressed so that the projection directions of the polarization axes on the substrate surface at the time of light irradiation became antiparallel, and the adhesive was thermally cured at 150 ℃ for 1 hour. Then, a negative type liquid crystal (MLC-6608, manufactured by Merck) was filled between a pair of substrates through a liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive, thereby obtaining an optical FFS type liquid crystal cell. Further, in order to remove the flow alignment at the time of liquid crystal injection, the liquid crystal was heated at 120℃and then cooled to room temperature gradually. In addition, the ultraviolet irradiation amount after post baking was set at 100J/m 2 ～10,000J/m 2 Is changed within the range of (2) to perform the series of operations, thereby producing ultraviolet radiation Three or more liquid crystal cells having different amounts were evaluated by using a liquid crystal cell having an exposure amount (optimum exposure amount) that exhibited the best alignment characteristics.
3. Evaluation
(1) DC afterimage characteristics at room temperature
The liquid crystal cell manufactured in the step 2 was placed under an atmosphere of 1 air pressure at 25 ℃. An alternating rectangular wave (alternating (Alternating Current, AC)) having a frequency of 30Hz was used to drive the light source at a relative transmittance of 100%, and the luminance difference between any two pixels was set to 0, and then at 5000cd/m 2 AC driving is performed under the backlight irradiation of (a), and simultaneously, a Direct Current (DC) 0.5V is applied to only a single pixel for 60 minutes to accumulate electric charges. When the application of DC 0.5V is completed and the AC-only drive with the relative transmittance of 50% is resumed, a luminance difference (Δl1) is generated between the two pixels due to the accumulated charges. The time from the end of the application of DC 0.5V to the time when the luminance difference Δl1 becomes 36.8% or less of the initial value was set as the residual image erasing time, by observing the change with time of the luminance difference Δl1. Further, since the charge stored in the liquid crystal cell is relaxed faster as the time is shorter, the afterimage tends to disappear, and the DC afterimage characteristic is said to be better. For evaluation, the case where the image sticking elimination time was less than 10 minutes was "very good (excellent)", the case where it was 10 minutes or more and less than 20 minutes was "good (o)", the case where it was 20 minutes or more and less than 30 minutes was "delta"), and the case where it was 30 minutes or more was "bad (x)". As a result, in this example, the evaluation was "very good (very good)".
(2) DC afterimage characteristics at 60 DEG C
The liquid crystal cell manufactured in the step 2 was placed under an atmosphere of 1 air pressure at 60 ℃. After driving with an alternating current rectangular wave (AC) having a frequency of 30Hz at a relative transmittance of 100% and setting the luminance difference between any two pixels to 0, the luminance difference was set at 5000cd/m 2 AC driving is performed under the backlight irradiation of (a) while Direct Current (DC) 0.1V is applied for 60 minutes only to a single pixel to accumulate electric charges. When the application of DC 0.1V is completed and the drive is resumed to the AC-only drive with the relative transmittance of 50%, the accumulated charge causes a bright state between the two pixelsThe difference in degree (it is set to Δl2). In addition, as a general trend, charges are more likely to accumulate in the liquid crystal cell at a high temperature than at room temperature. Therefore, in order to compare the charge accumulation easiness of the liquid crystal cell between samples under more severe conditions, the charge accumulation easiness of the liquid crystal cell is evaluated by a method reflecting the initial accumulated charge amount under a high-temperature environment (short-term afterimage evaluation). The smaller the luminance difference Δl2, the less likely the liquid crystal cell is to accumulate charge, which can be said to be better. The value obtained by dividing the luminance difference Δl2 by the average value of the luminance of two pixels is set to "very good (excellent)", 1% or more and less than 2% is set to "good (o)", 2% or more and less than 3% is set to "ok (Δ)", and 3% or more is set to "bad (x)". As a result, in this example, the evaluation was "very good (very good)".
(3) Evaluation of liquid Crystal alignment
In the liquid crystal cell manufactured in the above 2, the presence or absence of an abnormal region (domain) in the change of brightness when a voltage of 5V is applied/released (ON/OFF) was observed with a microscope at a magnification of 50 times. Regarding the evaluation, the case where no abnormal region was observed was regarded as "good", and the case where an abnormal region was observed was regarded as "bad". As a result, in this example, the evaluation was "good".
(4) Evaluation of inkjet coatability
As a substrate coated with a liquid crystal aligning agent, a substrate was used in which a glass substrate having a transparent electrode including an ITO film was heated on a hot plate at 200 ℃ for 1 minute, and then subjected to ultraviolet/ozone cleaning so that the contact angle of water on the surface of the transparent electrode became 10 ° or less. The liquid crystal aligning agent (AL-1) prepared in the above-mentioned item 1 was applied onto the transparent electrode surface of the glass substrate with the transparent electrode using an inkjet coater (manufactured by the company of zhpu electro-mechanical (Shibaura Mechatronics)). The coating conditions at this time were set as follows: two round trips (four total) of application were performed at 2,500 times/(nozzle/min) and a discharge amount of 250mg/10 seconds. After the coating, the mixture was allowed to stand for 1 minute, and then heated at 80℃to thereby form a coating film having an average film thickness of 0.1. Mu.m. With respect to the obtained coating film, the number of irregularities and depressions was visually observed under irradiation of an interference fringe measurement lamp (sodium lamp). The case where the uneven and recessed portion combination was 0 was evaluated as "excellent", the case where the uneven and recessed portion combination was 1 or more and less than 3 was evaluated as "good" (o), and the case where the uneven and recessed portion combination was 3 or more was evaluated as "poor" (x). In addition, if the solubility of the polymer is good, the inkjet coatability tends to be improved. As a result, the inkjet coatability of the liquid crystal aligning agent of the example was evaluated as "excellent (excellent)".
Examples 2 to 10, 13 to 19, 21 to 35 and comparative examples 1 to 4
A liquid crystal aligning agent was prepared in the same manner as in example 1, except that the composition of the liquid crystal aligning agent was changed as shown in table 3. Using the obtained liquid crystal aligning agent, an optical FFS type liquid crystal cell was produced in the same manner as in example 1, and various evaluations were performed. The results are shown in Table 4.
Example 11: friction FFS type liquid Crystal display element
1. Preparation of liquid Crystal alignment agent
In the solution containing the polymer (PAA-11) obtained in Synthesis examples 2 to 11, to be the polymer (PAA-11) in terms of solid content conversion: polymer (PAA-38) =60: 40 The solution containing the polymer (PAA-38) obtained in Synthesis examples 2 to 41 was added so as to give a total of 100 parts by mass of the polymer (PAA-11) and the polymer (PAA-38) and 10 parts by mass of the additive (AD-1). The resulting mixture was diluted with NMP, NEP and BC to obtain NMP having a solid content concentration of 4.0 mass% and a solvent composition ratio of NMP: NEP: bc=25: 55:20 (mass ratio) solution. The solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent (AL-11).
2. Manufacturing of FFS type liquid crystal cell using rubbing method
A first substrate and a second substrate similar to those of example 1 were prepared. Then, a liquid crystal alignment agent (AL-11) was applied to the electrode formation surface of the first substrate and the one surface of the second substrate by a rotator, and heated (prebaked) by a hot plate at 110℃for 3 minutes. Thereafter, the film was dried (post-baking) in an oven at 230℃in which nitrogen gas was substituted for the inside of the oven for 30 minutes to form a coating film having an average film thickness of 0.08. Mu.m. Then, the surface of the coating film was subjected to a rubbing treatment at a roller rotation speed of 1000rpm, a stage moving speed of 3 cm/sec and a Mao Yaru length of 0.3mm by using a rubbing machine having a roller around which a rayon cloth was wound. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then, drying was performed in a clean oven at 100 ℃ for 10 minutes, thereby obtaining a pair of substrates having liquid crystal alignment films.
Then, a pair of substrates having a liquid crystal alignment film was coated with an epoxy adhesive containing alumina spheres having a diameter of 3.5 μm by screen printing while leaving a liquid crystal injection port at the edge of the surface on which the liquid crystal alignment film was formed. Thereafter, the substrates were laminated and pressure-bonded, and the adhesive was thermally cured at 150 ℃ for 1 hour. Then, a negative type liquid crystal (manufactured by Merck) was filled into a gap between a pair of substrates through a liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, the liquid crystal was heated at 120 ℃ and then cooled down to room temperature gradually, thereby manufacturing a liquid crystal cell (rubbing FFS type liquid crystal cell). When a pair of substrates is stacked, the rubbing directions of the substrates are antiparallel.
3. Evaluation
Using the liquid crystal aligning agent prepared in the above 1 and the liquid crystal cell prepared in the above 2, various evaluations were performed in the same manner as in example 1. The evaluation results are shown in table 4.
Example 12, example 20 and example 36
A liquid crystal aligning agent was prepared in the same manner as in example 11, except that the composition of the liquid crystal aligning agent was changed as shown in table 3. Further, using the obtained liquid crystal aligning agent, a rubbing FFS type liquid crystal cell was produced in the same manner as in example 11, and various evaluations were performed. The evaluation results are shown in table 4.
Comparative examples 1A to 4A
A rubbing FFS type liquid crystal cell was produced in the same manner as in example 11, except that AR-1 to AR-4 shown in Table 3 were used as a liquid crystal aligning agent, and various evaluations were performed. As a result, the results of comparative examples 1A to 4A were equivalent to those of comparative examples 1 to 4 (optical FFS type liquid crystal display devices).
TABLE 3
TABLE 4
Example 37: light vertical liquid Crystal display element
1. Preparation of liquid Crystal alignment agent
To the solution containing the polymer (PAA-1) obtained in Synthesis example 2-1, the polymer (MI-1) obtained in Synthesis example 3-1 was added so that the polymer (MI-1) became 5 parts by mass based on 95 parts by mass of the polymer (PAA-1) in terms of solid content conversion, and diluted with NMP, GBL, DGDE and DIBK, whereby a solid content concentration of 3.5% by mass and a solvent composition ratio of NMP were obtained: GBL: DGDE: dibk=20: 30:40:10 (mass ratio) solution. The solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent (AL-37).
2. Manufacture of optically homeotropic liquid crystal cell (UV 2A)
The liquid crystal aligning agent (AL-37) prepared in the above 1 was coated on the transparent electrode surface of the glass substrate with the transparent electrode containing the ITO film using a rotator, and pre-baked using a hot plate at 80℃for 1 minute. Thereafter, the resulting film was heated at 230℃for 1 hour in an oven in which nitrogen gas was substituted for the inside of the oven to form a coating film having a film thickness of 0.1. Mu.m. Then, for the coated film surface, polarized ultraviolet rays 1,000J/m containing bright lines of 313nm were irradiated from a direction inclined by 40 ° with respect to the substrate normal line using an Hg-Xe lamp and a Glan-Taylor prism (glan-taylor prism) 2 And imparts liquid crystal alignment capability. Repeating the same operation to make a pair of(two) substrates having a liquid crystal alignment film.
An epoxy adhesive containing alumina balls having a diameter of 3.5 μm was applied to the outer periphery of the surface of one of the substrates having a liquid crystal alignment film by screen printing, and then the surfaces of the liquid crystal alignment films of the pair of substrates were brought into contact with each other, and the adhesive was thermally cured at 150 ℃ for 1 hour so that the projection directions of the ultraviolet light axes of the substrates on the substrate surfaces became antiparallel. Then, a negative type liquid crystal (MLC-6608 manufactured by Merck) was filled into the gap between the substrates through the liquid crystal inlet, and then the liquid crystal inlet was sealed with an epoxy adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, the liquid crystal was heated at 130 ℃ and then cooled to room temperature gradually.
3. Evaluation
Using the liquid crystal aligning agent prepared in the above 1 and the liquid crystal cell prepared in the above 2, various evaluations were performed in the same manner as in example 1. The evaluation results are shown in table 6.
Comparative example 5
A liquid crystal aligning agent was prepared in the same manner as in example 37, except that the composition of the liquid crystal aligning agent was changed as shown in table 5. Using the obtained liquid crystal aligning agent, a light-vertical liquid crystal cell was produced in the same manner as in example 37, and various evaluations were performed. The evaluation results are shown in table 6.
TABLE 5
TABLE 6
Example 38: PSA type liquid Crystal display element
1. Preparation of liquid Crystal alignment agent
To the solution containing the polymer (PI-2) obtained in synthesis examples 2 to 36, the polymer (MI-2) obtained in synthesis example 3 to 2 was added so that the polymer (MI-2) was 5 parts by mass based on 95 parts by mass of the polymer (PI-2) in terms of solid matter conversion, and the mixture was diluted with NMP and BC to prepare a solution having a solvent composition of NMP/bc=50/50 (mass ratio) and a solid matter concentration of 3.5 mass%. The solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal aligning agent (AL-38).
Manufacture of PSA-type liquid Crystal cell
(1) Preparation of liquid Crystal composition
To 10g of nematic liquid crystal (MLC-6608, manufactured by Merck (Merck)) was added 5 mass% of a liquid crystalline compound represented by the following formula (L1-1) and 0.3 mass% of a photopolymerizable compound represented by the following formula (L2-1) and mixed, thereby obtaining a liquid crystal composition LC1.
[ 58]
(2) Manufacture of liquid crystal cell
The liquid crystal alignment agent (AL-38) thus prepared was applied onto the transparent electrode surface of a glass substrate having a transparent electrode comprising an ITO film using a rotator, prebaked for 1 minute by a hot plate at 80℃and then heated in an oven replaced with nitrogen gas at 200℃for 1 hour to remove the solvent, thereby forming a coating film (liquid crystal alignment film) having a film thickness of 0.08. Mu.m. The coating film was subjected to a rubbing treatment at a roll rotation speed of 400rpm, a stage moving speed of 3 cm/sec and a Mao Yaru length of 0.1mm by using a rubbing machine having a roll around which a rayon cloth was wound. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then, drying was performed in a clean oven at 100 ℃ for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. The operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film. The rubbing treatment is a weak rubbing treatment for the purpose of controlling collapse of the liquid crystal and performing alignment division by a simple method.
An epoxy adhesive containing alumina balls having a diameter of 3.5 μm was applied to the outer periphery of the surface of one of the substrates having a liquid crystal alignment film by screen printing, and then the liquid crystal alignment film surfaces of the pair of substrates were opposed to each other and overlapped and pressure-bonded, and the adhesive was thermally cured by heating at 150℃for 1 hour. Then, after filling the gap between the substrates with the liquid crystal composition LC1 from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy adhesive, and further, in order to remove the flow orientation at the time of liquid crystal injection, the liquid crystal was heated at 150 ℃ for 10 minutes and then cooled down to room temperature gradually.
Then, with respect to the obtained liquid crystal cell, 50,000J/m was applied to an alternating current of 10V having a frequency of 60Hz between the counter electrodes to drive the liquid crystal, using an ultraviolet irradiation device using a metal halide lamp as a light source 2 Is irradiated with ultraviolet rays. The irradiation amount is a value measured using a light meter measuring with a wavelength of 365nm as a reference. Thereby, a PSA-type liquid crystal cell was produced.
3. Evaluation
Using the liquid crystal aligning agent prepared in the above 1 and the liquid crystal cell prepared in the above 2, various evaluations were performed in the same manner as in example 1. The evaluation results are shown in table 8.
Comparative example 6
A liquid crystal aligning agent was prepared in the same manner as in example 38, except that the composition of the liquid crystal aligning agent was changed as shown in table 7. Using the obtained liquid crystal aligning agent, PSA-type liquid crystal cells were produced in the same way as in example 38, and various evaluations were performed. The evaluation results are shown in table 8.
TABLE 7
TABLE 8
As shown in tables 4, 6 and 8, examples 1 to 38 using the liquid crystal aligning agent containing the polymer (P) exhibited excellent liquid crystal alignment properties in comparison with comparative examples 1 to 6 using the liquid crystal aligning agent containing no polymer (P), and were excellent in DC afterimage characteristics at room temperature (i.e., relaxation characteristics of accumulated charges) and DC afterimage characteristics at 60 ℃. The liquid crystal aligning agents of examples 1 to 38 were also excellent in inkjet coatability.
From the above results, it is clear that: the liquid crystal aligning agent containing the polymer (P) has good coating property, and can obtain a liquid crystal element which has excellent liquid crystal alignment property and is not easy to accumulate residual charges and can alleviate residual charges rapidly.

Claims (17)

1. A liquid crystal aligning agent satisfying at least one of the following requirements (I) and (II);
Essential condition (I): a compound having the following partial structure (A) and partial structure (B) in the same molecule;
essential condition (II): a compound comprising the following partial structure (A) and partial structure (B) in different molecules;
partial structure (a): at least one selected from the group consisting of a substituted heterocyclic structure, a quinone structure, and a tetracyanoquinodimethane structure, wherein one or more hydrogen atoms bonded to the nitrogen-containing aromatic heterocyclic ring are substituted with an electron withdrawing group that does not detach upon heating at a temperature of 230 ℃ or lower;
partial structure (B): at least one selected from the group consisting of a partial structure represented by the following formula (b 1) and a phenothiazine structure;
*-X 1 -B 1 -X 2 -* (b1)
in the formula (b 1), X 1 、B 1 X is X 2 Satisfies the following [ i ]]Or [ ii ]]The method comprises the steps of carrying out a first treatment on the surface of the "x" means a bond;
[i]X 1 is an aromatic ring group; b (B) 1 is-NY 3 -or an aromatic heterocyclic group; x is X 2 Y and Y 3 Is X 2 Is an aromatic ring group and Y 3 Is a hydrogen atom or a monovalent organic group, or represents X 2 And Y is equal to 3 Are combined with each other and X 2 Y and Y 3 The bonded nitrogen atoms together form a nitrogen-containing fused ring structure; wherein the nitrogen-containing condensed ring structure has an aromatic ring, B 1 Is bonded to an aromatic ring in the nitrogen-containing fused ring structure;
[ii]B 1 is-NY 3 -；Y 3 Is a hydrogen atom or a monovalent organic group; x is X 1 X is X 2 Representing combinations with each other and X 1 X is X 2 The bonded nitrogen atoms together form a nitrogen-containing fused ring structure; wherein the nitrogen-containing condensed ring structure has a plurality of aromatic rings, B 1 The nitrogen atom of (a) connects two aromatic rings in the nitrogen-containing fused ring structure.
2. The liquid crystal aligning agent according to claim 1, comprising at least one polymer (P) selected from the group consisting of polyamic acid, polyamic acid ester and polyimide,
the polymer (P) contains structural units derived from a diamine compound having the partial structure (B).
3. The liquid crystal aligning agent according to claim 1, comprising at least one polymer (P) selected from the group consisting of polyamic acid, polyamic acid ester and polyimide,
the polymer (P) comprises the following structural Units (UA) and structural Units (UB) in the same molecule, or comprises the following structural Units (UA) and structural Units (UB) in different molecules;
structural Unit (UA): a structural unit derived from at least one selected from the group consisting of a diamine compound (DA-1) having a substituted heterocyclic structure in which one or more hydrogen atoms bonded to a nitrogen-containing aromatic heterocyclic ring are substituted with an electron-withdrawing group that does not come off by heating at a temperature of 230 ℃ or lower, and a diamine compound (DA-2) having a quinone structure;
Structural Unit (UB): structural units derived from at least one selected from the group consisting of a diamine compound (DB-1) having a partial structure represented by the formula (b 1) and a diamine compound (DB-2) having a phenothiazine structure.
4. The liquid crystal aligning agent according to claim 3, wherein the diamine compound (DA-1) is a compound represented by the following formula (a 1-1);
in the formula (a 1-1), A 1 A group having a substituted heterocyclic structure in which one or more hydrogen atoms bonded to the nitrogen-containing aromatic heterocyclic ring are substituted with an electron-withdrawing group which is not detached by heating at a temperature of 230 ℃ or lower; r is R 1 Is a single bond or a (n1+1) valent linking group; ar (Ar) 1 Is an aromatic ring group; n1 is 1 or 2.
5. The liquid crystal aligning agent according to claim 3, wherein the diamine compound (DA-2) is at least one selected from the group consisting of a compound represented by the following formula (a 2-1) and a compound represented by the following formula (a 2-2);
in the formula (a 2-1), A 2 Is a radical having a quinone structure; r is R 2 Is a single bond or a (n2+1) valent linking group; ar (Ar) 2 Is an aromatic ring group; n2 is 1 or 2;
in the formula (a 2-2), A 3 Is a radical having a quinone structure; r is R 3 R is R 4 Each independently a single bond or a divalent organic group; ar (Ar) 3 Ar and Ar 4 Each independently is an aromatic ring group.
6. The liquid crystal aligning agent according to claim 3, wherein the diamine compound (DB-2) is a compound represented by the following formula (b 2-1);
in the formula (b 2-1), A 4 Is a group having a phenothiazine structure; r is R 5 Is a single bond or a (n3+1) valent linking group; ar (Ar) 5 Is an aromatic ring group; n3 is 1 or 2.
7. The liquid crystal aligning agent according to claim 3, wherein the polymer (P) further comprises a structural Unit (UC) derived from a diamine compound having a partial structure represented by the following formula (2);
in the formula (2), X 5 X is X 6 Each independently an aromatic ring group; r is R 7 R is R 8 Each independently is a single bond, an alkanediyl group having 1 to 10 carbon atoms or a substituted alkanediyl group having 1 to 10 carbon atoms; y is Y 5 Y and Y 6 Each independently is 4 -NR 9 -CO-or 4 -CO-NR 9 -；R 9 Is a hydrogen atom or a monovalent organic group; "* 4 "means and Z 5 Is a bond of (a); z is Z 5 Is a single bond or a divalent organic group; m is 0 or 1; in the case where m is 0, R 7 、R 8 Or both of them are alkanediyl or substituted alkanediyl having 1 to 10 carbon atoms; "×" indicates a bond.
8. The liquid crystal aligning agent according to claim 2, comprising a compound having the partial structure (a) and the polymer (P), wherein the compound having the partial structure (a) does not contain a polymer.
9. The liquid crystal aligning agent according to claim 1, wherein the electron withdrawing group is at least one selected from the group consisting of a halogen atom, a cyano group, a halogenated alkyl group and an acyl group.
10. The liquid crystal aligning agent according to claim 1, further comprising a polymer (Q) having no one of the partial structure (a) and the partial structure (B).
11. The liquid crystal aligning agent according to claim 10, wherein the polymer (Q) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and addition polymer.
12. A liquid crystal alignment film formed using the liquid crystal alignment agent according to any one of claims 1 to 11.
13. A liquid crystal element comprising the liquid crystal alignment film according to claim 12.
14. A polymer which is a polyamic acid, polyamic acid ester or polyimide and comprises the following structural Units (UA) and structural Units (UB) in the same molecule;
structural Unit (UA): a structural unit derived from at least one selected from the group consisting of a diamine compound (DA-1) having a substituted heterocyclic structure in which one or more hydrogen atoms bonded to a nitrogen-containing aromatic heterocyclic ring are substituted with an electron-withdrawing group that does not come off by heating at a temperature of 230 ℃ or lower, and a diamine compound (DA-2) having a quinone structure;
Structural Unit (UB): a structural unit derived from at least one selected from the group consisting of a diamine compound (DB-1) and a diamine compound (DB-2), wherein the diamine compound (DB-1) has a partial structure represented by the following formula (b 1), and the diamine compound (DB-2) has a phenothiazine structure;
*-X 1 -B 1 -X 2 -* (b1)
in the formula (b 1), X 1 、B 1 X is X 2 Satisfies the following [ i ]]Or [ ii ]]；
[i]X 1 Is an aromatic ring group; b (B) 1 is-NY 3 -or an aromatic heterocyclic group; x is X 2 Y and Y 3 Is X 2 Is an aromatic ring radicalAnd Y is 3 Is a hydrogen atom or a monovalent organic group, or represents X 2 And Y is equal to 3 Are combined with each other and X 2 Y and Y 3 The bonded nitrogen atoms together form a nitrogen-containing fused ring structure; wherein the nitrogen-containing condensed ring structure has an aromatic ring, B 1 Is bonded to an aromatic ring in the nitrogen-containing fused ring structure;
[ii]B 1 is-NY 3 -；Y 3 Is a hydrogen atom or a monovalent organic group; x is X 1 X is X 2 Representing combinations with each other and X 1 X is X 2 The bonded nitrogen atoms together form a nitrogen-containing fused ring structure; wherein the nitrogen-containing condensed ring structure has a plurality of aromatic rings, B 1 The nitrogen atom of (a) connects two aromatic rings in the nitrogen-containing fused ring structure;
"×" indicates a bond.
15. A compound represented by the following formula (a 1-1);
in the formula (a 1-1), A 1 A group having a substituted heterocyclic structure in which one or more hydrogen atoms bonded to the nitrogen-containing aromatic heterocyclic ring are substituted with at least one member selected from the group consisting of a halogen atom, a cyano group, a halogenated alkyl group and an acyl group; r is R 1 Is a single bond or a (n1+1) valent linking group; ar (Ar) 1 Is an aromatic ring group; n1 is 1 or 2.
16. A compound represented by the following formula (a 2-2);
H 2 N-Ar 3 -R 3 -A 3 -R 4 -Ar 4 -NH 2 (a2-2)
in the formula (a 2-2), A 3 Is a radical having a quinone structure; r is R 3 R is R 4 Each independently a single bond or a divalent organic group; ar (Ar) 3 Ar and Ar 4 Each independently is an aromatic ring group.
17. A compound represented by the following formula (b 2-1);
in the formula (b 2-1), A 4 Is a group having a phenothiazine structure; r is R 5 Is a single bond or a (n3+1) valent saturated chain hydrocarbon group; ar (Ar) 5 Is an aromatic ring group; n3 is 1 or 2.
CN202310149268.0A 2022-03-08 2023-02-22 Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer and compound Pending CN116731727A (en)

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