CN111602087A

CN111602087A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer and compound

Info

Publication number: CN111602087A
Application number: CN201980008459.7A
Authority: CN
Inventors: 冈田敬; 村上嘉崇; 面手真人; 广瀬阳一
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2018-04-19
Filing date: 2019-03-12
Publication date: 2020-08-28
Anticipated expiration: 2039-03-12
Also published as: CN111602087B; TWI810273B; JPWO2019202884A1; TW201943845A; WO2019202884A1; JP7036200B2

Abstract

The liquid crystal aligning agent contains a polymer (P) having: structural unit U1, derived from a compound represented by formula (1); and a structural unit U2 that is derived from a compound having a partial structure represented by formula (2), formula (3), formula (4), or formula (5) and is different from structural unit U1. G¹The group is a group having a cyclic structure exhibiting crosslinkability, a group having an aromatic condensed polycyclic structure, or a group having a nitrogen-containing heterocyclic structure. E¹A group having a polymerizable carbon-carbon unsaturated bond, a carbon atom of the polymerizable carbon-carbon unsaturated bond and G¹Having a cyclic structure, an aromatic condensed polycyclic structure orThe ring of the nitrogen-containing heterocyclic structure is bonded via a single bond or-COO-, etc. (E)¹)_i‑(G¹)_j…(1)

Description

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

CROSS-REFERENCE TO RELATED APPLICATIONS

The application is based on Japanese application No. 2018-80881 filed on 19/4/2018, and the description content of the application is incorporated in the application.

Technical Field

The present disclosure 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 various applications represented by display devices such as televisions, personal computers, and smart phones. These liquid crystal elements include a liquid crystal alignment film having a function of aligning liquid crystal molecules in a certain direction. In general, the liquid crystal alignment film is formed on the substrate by applying, preferably heating, a liquid crystal alignment agent obtained by dissolving a polymer component in an organic solvent to the substrate. As a polymer component of a liquid crystal aligning agent, polyamic acid or soluble polyimide is widely used in terms of excellent mechanical strength, liquid crystal alignment properties, and affinity for liquid crystal (for example, see patent document 1 or patent document 2).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2012/176822

Patent document 2: japanese patent laid-open No. 2017-138575

Disclosure of Invention

Problems to be solved by the invention

If the alignment regulating force of the liquid crystal molecules by the liquid crystal alignment film is weak, when the liquid crystal cell is operated for a long time, the initial alignment direction is deviated from the initial direction of the liquid crystal cell production, and burning called Alternating Current (AC) afterimage may occur. In particular, when a liquid crystal alignment film is obtained by photo-alignment treatment, the alignment regulating force of liquid crystal molecules is insufficient compared to that in rubbing treatment, and AC afterimages tend to be easily generated. In order to meet the recent demand for further higher performance of liquid crystal devices, it is desired that the liquid crystal devices have excellent electrical characteristics (high voltage holding ratio), which are basic characteristics of liquid crystal devices, in addition to sufficiently reducing AC residual images.

The present disclosure has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal aligning agent which can obtain a liquid crystal device exhibiting a high voltage holding ratio and reduced AC image sticking.

Means for solving the problems

The following methods are provided in accordance with the present disclosure.

[1] A liquid crystal aligning agent comprising a polymer (P) having: a structural unit U1 derived from a compound represented by the following formula (1); and a structural unit U2 which is a structural unit derived from a compound having a partial structure represented by the following formula (2), formula (3), formula (4) or formula (5), and which is different from the structural unit U1:

(E¹)_i-(G¹)_j…(1)

(in the formula (1), G¹A group having a cyclic structure exhibiting crosslinkability, a group having an aromatic condensed polycyclic structure, or a group having a nitrogen-containing heterocyclic structure; e¹At least one carbon atom forming a polymerizable carbon-carbon unsaturated bond and G as a group having a polymerizable carbon-carbon unsaturated bond¹The ring having a cyclic structure, an aromatic condensed polycyclic structure or a nitrogen-containing heterocyclic structure exhibiting crosslinkability is bonded by a single bond or via a group of-COO-, -CONR⁵⁰-、**-CH₂-CONR⁵⁰-, -O-or phenylene (wherein,"" indicates a bond to a carbon atom forming a polymerizable carbon-carbon unsaturated bond); r⁵⁰Is a hydrogen atom, or represents R⁵⁰A ring structure formed by bonding with other groups; one of i and j is 1 and the other is 2, or i ═ j ═ 1)

[ solution 1]

(in the formula (2), R¹Is a monovalent organic group having 1 or more carbon atoms, R²And R³Each independently is a hydrogen atom or a methyl group; in the formula (3), R⁴Is a monovalent organic group having 1 or more carbon atoms, R⁵Is hydrogen atom or C1 or more monovalent organic group, R⁶And R⁷Each independently is a hydrogen atom or a methyl group; in the formula (4), R⁸Is a monovalent organic group having 1 or more carbon atoms, R¹¹Is hydrogen atom or C1 or more monovalent organic group, R⁹And R¹⁰Each independently is a hydrogen atom or a methyl group; x¹⁰And X¹¹One of them is a single bond and the other is a methylene group; in the formula (5), R¹²Is a monovalent organic group having 1 or more carbon atoms, R¹³And R¹⁴Each independently a hydrogen atom or a methyl group).

[2] A liquid crystal alignment film formed by using the liquid crystal aligning agent of [1 ].

[3] A liquid crystal cell comprising the liquid crystal alignment film of [2 ].

[4] A polymer body having: structural unit U1 derived from a compound represented by the formula (1); and a structural unit U2 that is derived from a compound having a partial structure represented by the formula (2), the formula (3), the formula (4), or the formula (5), and that is different from the structural unit U1.

[5] A compound represented by the following formula (6),

[ solution 2]

(in the formula (6), B¹Is a monovalent group represented by the following formula (7), formula (8), formula (9) or formula (10), D¹Is a divalent group represented by the following formula (11), X¹And X²Independently represents a single bond, -CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO-, -O-CH₂-、-CH₂-O-or alkanediyl having 1 to 3 carbon atoms, A¹And A²Each independently being substituted or unsubstituted phenylene, cyclohexylene or naphthylene, R¹⁸Is alkyl, alkoxy, fluoroalkyl, fluoroalkoxy or-R with 2-20 carbon atoms¹⁹-Y¹(wherein, R¹⁹Is an alkanediyl group having 2 to 20 carbon atoms, Y¹Is a trialkylsilyl group); m is an integer of 0 to 2, and n is an integer of 1 to 3; in the case where m is 2, a plurality of A¹、X¹Each independently has the definition; in case n is 2 or 3, a plurality of R¹⁸Each independently having the definition

[ solution 3]

(in the formula (7), R²And R³Are each as defined for formula (2); in the formula (8), R⁵、R⁶And R⁷Are each as defined for formula (3); in the formula (9), R⁹、R¹⁰、R¹¹、X¹⁰And X¹¹Are each as defined for formula (4); in the formula (10), R¹³And R¹⁴Are each as defined for formula (5); "+" indicates a bond)

[ solution 4]

(in formula (11), A³、A⁴And A⁵Each independently being a substituted or unsubstituted phenylene or cyclohexylene group, L¹And L²Each independently represents a single bond, an alkanediyl group having 1 to 5 carbon atoms or a group wherein at least one methylene group of the alkanediyl group is substituted with "-O-" (whereinOxygen atoms not being continuous), X³And X⁴Independently of each other-CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO-or-O-, R¹⁶And R¹⁷Each independently is a hydrogen atom, a methyl group, a halogen atom or a cyano group; k and r are each independently 0 or 1; "*¹' and²"represents a bond; wherein, includes¹And B¹The condition of bonding, and²and B¹In the case of a bond).

ADVANTAGEOUS EFFECTS OF INVENTION

According to the liquid crystal aligning agent containing the polymer (P), a liquid crystal element which shows a high voltage holding ratio and in which AC afterimage is reduced can be obtained.

Detailed Description

Liquid crystal aligning agent

The liquid crystal aligning agent of the present disclosure contains a polymer (P) having: structural unit U1 derived from a compound represented by the formula (1); and a structural unit U2 that is derived from a compound having a partial structure represented by the formula (2), the formula (3), the formula (4), or the formula (5), and is different from the structural unit U1. Hereinafter, the components contained in the liquid crystal aligning agent of the present disclosure and other components optionally blended as necessary will be described.

In the present specification, the term "hydrocarbon group" is intended to include chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group having no cyclic structure in the main chain and consisting of only a chain structure. Wherein the unsaturated moiety may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. The alicyclic hydrocarbon group is not necessarily composed of only the structure of the alicyclic hydrocarbon, and includes a hydrocarbon group having a chain structure in a part thereof. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. In addition, the structure may not necessarily be composed of only an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in a part thereof.

< Polymer (P) >)

With respect to structural unit U1

In the formula (1), in G¹In the case of a group having a cyclic structure exhibiting crosslinkability, the cyclic structure is preferably a group capable of forming a covalent bond between the same or different molecules by heat or light. As G¹Specific examples of the group having a cyclic structure exhibiting crosslinkability include groups having a cyclic ether structure, a cyclic (thio) carbonate structure, a lactone structure, a lactam structure, or an oxazoline structure. The cyclic ether structure is preferably an oxetanyl group (1, 2-oxirane structure) or an oxetanyl group (1, 3-epoxypropane structure), and is more preferably an oxetanyl group in view of high reactivity by heat or light.

As G¹As a preferred example of the group having a cyclic structure exhibiting crosslinkability, there can be mentioned the groups represented by the following formulae (2-A-1) to (2-A-6).

[ solution 5]

(formula (2-A-1) to (2-A-6) wherein R⁵¹～R⁵⁶Each independently is a monovalent substituent; r1, r3, r5, r7, r9 and r11 are respectively and independently integers of 0-2, and r2, r4, r6, r8 and r10 are respectively and independently integers of 1-5; "+" indicates with E¹The bond of carbon atom(s) to form a polymerizable carbon-carbon unsaturated bond in (1)

In the formulae (2-A-1) to (2-A-6), R is⁵¹～R⁵⁶Specific examples of (3) include: methyl group, ethyl group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), and the like. r1, r3, r5, r7, r9 and r11 are preferably 0 or 1, and more preferably 0.

Examples of the aromatic condensed polycyclic structure include: aromatic hydrocarbon rings such as naphthalene ring, anthracene ring, and fluorene ring; and an aromatic heterocyclic ring such as a naphthoquinone ring, an anthraquinone ring, a quinoline ring, a quinazoline ring, a benzimidazole ring, or an indole ring, or a structure in which a substituent is introduced into the ring portion of these rings. Examples of the substituent include: methyl group, ethyl group, halogen atom, carboxyl group, protected carboxyl group, amino group, protected amino group and the like. Among these, the aromatic condensed polycyclic structure is preferably a structure having a naphthalene ring, a fluorene ring, an anthracene ring, a naphthoquinone ring, or an anthraquinone ring, and more preferably a structure having a naphthalene ring or an anthracene ring.

The nitrogen-containing heterocyclic structure may be a monocyclic ring or a condensed ring, and examples thereof include: and nitrogen-containing heterocycles such as pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, 1H-pyrrolo [2,3-b ] pyridine, purine, quinoline, isoquinoline, naphthyridine, phenazine, quinoxaline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine, morpholine, hexamethyleneimine, oxazole, isoxazole, 4, 5-dihydrooxazole, 4, 5-dihydrobenzoxazole, dihydromaleimide, and benzomaleimide, and structures in which a substituent is introduced into the nitrogen-containing heterocycle. Examples of the substituent include: alkyl groups and alkoxy groups having 1 to 5 carbon atoms.

At G¹In the case of a monovalent group having a nitrogen-containing heterocyclic structure, the group G is¹Preferred specific examples of (3) include: a group obtained by removing a hydrogen atom bonded to a nitrogen atom of pyrrole, imidazole, carbazole, purine, indole, morpholine, benzimidazole, dihydromaleimide or benzomaleimide; a group obtained by removing at least one hydrogen atom bonded to a carbon atom of pyridine, pyrimidine, pyrazine, acridine, phenazine, quinoline, isoquinoline, naphthyridine, isoxazole, 4, 5-dihydrooxazole or benzoxazole.

In the formula (1), with respect to E¹At least one carbon atom forming the polymerizable carbon-carbon unsaturated bond and a ring in a cyclic structure, an aromatic condensed polycyclic structure or a nitrogen-containing heterocyclic structure exhibiting crosslinkability are bonded via a single bond, -COO-, -CONR⁵⁰-、**-CH₂-CONR⁵⁰-, -O-or phenylene. Specifically, E¹Preferably any one of the groups represented by the following formulae (e-1) to (e-11).

[ solution 6]

(formula (e-1) to (e-11) wherein R²⁰～R³⁴、R³⁶～R⁴⁰、R⁴²、R⁴³And R⁴⁵～R⁴⁹Each independently is a hydrogen atom or a methyl group; r³⁵、R⁴¹And R⁴⁴Each independently represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms; ". x 3" indicates the relation with G¹A bond of the ring, ". sup.4" represents a bond with R⁵⁰Key of (2)

As R³⁵、R⁴¹、R⁴⁴Specific examples of the monovalent organic group include: a C1-30 monovalent hydrocarbon group having at least one methylene group represented by the formula-O-, -CO-, -COO-or-NR⁶⁰- (wherein, R)⁶⁰R is a hydrogen atom or a monovalent hydrocarbon group (hereinafter, the same) substituted group (hereinafter, also referred to as "group α"), a monovalent hydrocarbon group having 1 to 30 carbon atoms, a group α in which at least one hydrogen atom is substituted with a halogen atom, or the like³⁶、R⁴²Preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Among them, E is a group of compounds having a high degree of freedom in selection of monomers, in terms of further improving the voltage holding ratio of the liquid crystal device obtained, further reducing the AC residual image, and¹the preferred examples are any of the groups represented by the formulae (e-1) to (e-4), and the more preferred examples are any of the groups represented by the formulae (e-1) to (e-3).

Preferably, i and j are both 1.

As a specific example of the compound represented by the formula (1), G¹Examples of the compound having a group having a cyclic structure exhibiting crosslinkability (hereinafter, also referred to as "compound (G-1)") include compounds represented by the following formulae (1-1-1) to (1-1-18), compounds represented by the following formulae (1-3-11), and the like; as G¹Examples of the compound having a group having an aromatic condensed polycyclic structure (hereinafter, also referred to as "compound (G-2)") include compounds represented by the following formulae (1-2-1) to (1-2-19)The compounds shown below and the like; as G¹Examples of the compound having a group having a nitrogen-containing heterocyclic structure (hereinafter, also referred to as "compound (G-3)") include compounds represented by the following formulae (1-3-1) to (1-3-18), formula (1-1-10), formula (1-1-11), formula (1-2-8), and formula (1-2-9). Further, the polymer (P) may have a structural unit derived from one of these compounds, or may have a structural unit derived from two or more compounds.

[ solution 7]

[ solution 8]

[ solution 9]

(wherein R is a hydrogen atom or a methyl group)

The polymer (P) may have, as the structural unit U1, only one of the structural unit derived from the compound (G-1), the structural unit derived from the compound (G-2) and the structural unit derived from the compound (G-3), or two or more of these may be present as the structural unit U1. The polymer (P) may have a structural unit derived from the compound (G-1), a structural unit derived from the compound (G-2) or a structural unit derived from the compound (G-3).

From the viewpoint of sufficiently obtaining the effect of improving the voltage holding ratio and the effect of reducing the AC image retention, the content ratio of the structural unit U1 in the polymer (P) is preferably 1 mol% or more, more preferably 3 mol% to 60 mol%, and still more preferably 4 mol% to 50 mol% with respect to the total amount of the monomer-derived structural units in the polymer (P).

With respect to structural unit U2

In the formulae (2) to (5), with respect to R⁵And R¹¹As specific examples of the monovalent organic group (c), R of the formula (e-6) can be applied³⁵And R of the formula (e-8)⁴¹Description of the monovalent organic group of (1).

As R¹、R⁴、R⁸And R¹²Examples of the monovalent organic group include: a monovalent hydrocarbon group having 1 to 30 carbon atoms, at least one methylene group of the hydrocarbon group being substituted by-O-, -CO-, -COO-or-NR⁶⁰A substituted group α, a monovalent hydrocarbon group having 1 to 30 carbon atoms or a group α in which at least one hydrogen atom is substituted with a halogen atom, a monovalent group having a photo-alignment group, a group having a crosslinking group, or the like.

In the aspect in which the orientation of the liquid crystal is controlled by applying anisotropy to an organic film formed using the polymer (P) by irradiating the film with polarized or unpolarized radiation, at least a part of the structural unit U2 included in the polymer (P) is preferably a photo-alignment group. In this case, the polymer (P) has R¹、R⁴Or R⁸A structural unit which is a monovalent group having a photo-alignment group is the structural unit U2.

The photo-alignment group is preferably a functional group capable of imparting anisotropy to a film by a photo-isomerization reaction, a photo-dimerization reaction, a photo-Fries rearrangement (photo-Fries rearrangement) reaction, or a photo-decomposition reaction by light irradiation. Specific examples of the photo-alignment group include: an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a cinnamic acid-containing group containing cinnamic acid or a derivative thereof (cinnamic acid structure) as a basic skeleton, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, a cyclobutane-containing structure containing cyclobutane or a derivative thereof as a basic skeleton, and the like. Among these, the photo-alignment group is preferably a group containing a cinnamic acid structure in terms of high sensitivity to light or easy introduction into a polymer side chain.

The polymer (P) preferably has, as the structural unit U2, a structural unit derived from a compound represented by the following formula (6) (hereinafter, also referred to as "specific monomer").

[ solution 10]

[ solution 11]

[ solution 12]

(in formula (11), A³、A⁴And A⁵Each independently being a substituted or unsubstituted phenylene or cyclohexylene group, L¹And L²Independently represents a single bond, an alkanediyl group having 1 to 5 carbon atoms or a group wherein at least one methylene group of the alkanediyl group is substituted with "-O-" (wherein oxygen atoms are not continuous), X³And X⁴Independently of each other-CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO-or-O-, R¹⁶And R¹⁷Each independently is a hydrogen atom, a methyl group, a halogen atom or a cyano group; k and r are each independently 0 or 1; "*¹' and²"represents a bond; wherein, includes¹And B¹The condition of bonding, and²and B¹In the case of a bond).

In the above formula (6), B is a group capable of easily performing a polymerization reaction and obtaining a polymer having a sufficiently large molecular weight¹The group represented by the formula (7), the formula (8) or the formula (9) is preferable, and the group represented by the formula (7) or the formula (8) is particularly preferable. The formula (9) includes the following formulae (9-1) and (9-2).

[ solution 13]

(formula (9-1) and formula (9-2) wherein R⁹、R¹⁰、R¹¹、X¹⁰And X¹¹Are each as defined for formula (4); "+" indicates a bond)

In terms of the effect of improving the voltage holding ratio of the liquid crystal element obtained, X¹And X²Preferably a single bond, -CO-O-, -O-CO-, -O-, or an alkanediyl group having 1 to 3 carbon atoms, more preferably a single bond, -CO-O-or-O-CO-. In A¹And A²When the substituent is present, examples of the substituent include: methyl group, ethyl group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.). As R¹⁶And R¹⁷Specific examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom and iodineAn atom. R¹⁶And R¹⁷Preferably a hydrogen atom.

In terms of further reducing the AC afterimage of the obtained liquid crystal element, m is preferably 1 or 2. In this case, "-A" in the formula (6) is used in order to further improve the improvement effect of the electric characteristics and the AC image sticking characteristics of the liquid crystal element²-X²-(A¹-X¹) m- "is preferably any of the groups represented by the following formulae (a-1) to (a-9). Among these, the groups represented by the following formulae (a-1) to (a-3) and (a-6) to (a-8) are more preferable, the groups represented by the following formulae (a-1), (a-7) and (a-8) are still more preferable, and the groups represented by the following formulae (a-1) and (a-8) are particularly preferable.

[ solution 14]

(wherein⁵"represents and R¹⁸Bond of bond, "")⁶"denotes a group with B¹Bond key of bond

R¹⁸Alkyl, alkoxy, fluoroalkyl, fluoroalkoxy and-R of¹⁹-Y¹The polymer may be linear or branched, and is preferably linear. In terms of further improving the effects of improving the voltage holding ratio of the liquid crystal element and reducing the AC image sticking, R is¹⁸Preferably fluoroalkyl, fluoroalkoxy or-R¹⁹-Y¹More preferably fluoroalkyl group or fluoroalkoxy group, and particularly preferably "-R⁶¹-Y²"wherein R is⁶¹Is alkanediyl, Y²Is perfluoroalkyl, R⁶¹And Y²The total number of carbon atoms of (2) or more). n is preferably 1 or 2. At R¹⁸In the case of alkyl, alkoxy, fluoroalkyl or fluoroalkoxy, R¹⁸The number of carbon atoms of (b) is preferably 3 or more, more preferably 4 or more.

The compound represented by the formula (6) is preferably a compound represented by the following formula (b-1) in terms of further improving the electric characteristics of the obtained liquid crystal element and the improvement effect of reducing AC image stickingThe radicals shown in the figure. Further, R in the formula (b-1)⁸⁰-(CF₂)_a1-(CH₂)_a2-X⁵- "corresponds to R of formula (6)¹⁸。

[ solution 15]

(in the formula (b-1), A⁶、A⁷And A⁸Each independently being substituted or unsubstituted 1, 4-cyclohexylene or 1, 4-phenylene, X⁵Is a single bond or an oxygen atom, R⁸⁰Is fluoromethyl or methyl, a1 is an integer of 0-2, a2 is an integer of 1-20, a3 is 0 or 1; wherein, in R⁸⁰In the case of methyl, a1 ═ 0; "+" indicates a bond)

In the formula (b-1), A is a group that can further improve the effect of reducing AC image sticking and the voltage holding ratio⁶Preference is given to substituted or unsubstituted 1, 4-cyclohexylene, particular preference to 1, 4-cyclohexylene.

In the case where a3 is 0, A⁸Preferably 1, 4-cyclohexylene, in which case a3 is 1⁸Preferably 1, 4-phenylene, more preferably A⁷Is 1, 4-cyclohexylene, A⁸Is 1, 4-phenylene.

As A⁶～A⁸Examples of the substituent which may be contained include: methyl group, ethyl group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.). a1 is preferably 0 or 1. a2 is preferably 2 or more. In terms of ease of synthesis or obtaining, a3 is preferably 1; in terms of high improvement effect of the afterimage characteristics, a3 is preferably 2. In terms of further improving the electric characteristics of the liquid crystal element and the improvement effect of reducing the AC afterimage, R is⁸⁰Preferably trifluoromethyl.

With respect to said formula (11), A³、A⁴And A⁵Substituents which may be present said A¹And A²Description of the substituents of (1).

The obtained liquid crystal element has higher effect of improving the voltage holding ratioIn summary, X³And X⁴preferably-CO-O-, -O-CO-, -O-, or an alkanediyl group having 1 to 3 carbon atoms, and more preferably-CO-O-or-O-CO-.

At the point²And B¹In the case of the bond, L is a bond that can further improve the effect of reducing the AC residual image¹Preferably a single bond, particularly preferably L¹Is a single bond and k is 0, or L¹Is a single bond and X³is-CO-O-or-O-CO-. For the same reason, in¹And B¹In the case of a bond, when r is 1, L is preferably L²Is a single bond, particularly preferably L²Is a single bond and X⁴is-CO-O-or-O-CO-.

Specific examples of the specific monomer include compounds represented by the following formulae (6-1) to (6-41). Of these, the specific monomer may preferably be used as ". alpha. in the formula (11)²And B¹A bound compound. The polymer (P) may have only one structural unit derived from a specific monomer as the structural unit U1, or may have two or more structural units derived from a specific monomer as the structural unit U1.

[ solution 16]

[ solution 17]

[ solution 18]

[ solution 19]

(formula (6-1) to (6-41) wherein B¹The same as said formula (6); r⁶⁴Has 2 to 20 carbon atomsAlkylene or oxyalkylene, b1 is an integer of 2 to 20, b2 is 1 or 2)

The method for synthesizing the specific monomer is not particularly limited, and can be synthesized by appropriately combining conventional methods of organic chemistry depending on the molecular structure of the desired compound. For example, B¹The compound which is the group represented by the formula (7) can be obtained by the following method: reacting hydroxyl-containing maleimide (4-hydroxyphenylmaleimide, 4-hydroxycyclohexylmaleimide, 3-hydroxyphenylmaleimide, 4-hydroxy-2-methylphenylmaleimide, 4-hydroxy-3-methylphenylmaleimide, etc.) with a corresponding group "R¹⁸-A²-X²-(A¹-X¹) m- "with a cinnamic acid derivative. In addition, B¹The compound which is the group represented by the formula (8) can be obtained, for example, by the following method: let' R¹⁸-A²-X²-(A¹-X¹)m-D¹-NH₂The amine compound represented by the formula is reacted with maleic anhydride. B is¹The compound which is the group represented by the formula (9) can be obtained, for example, by the following method: let' R¹⁸-A²-X²-(A¹-X¹)m-D¹-NH₂Reaction of amine Compound represented by the formula with itaconic anhydride, B¹The compound which is a group represented by the formula (10) can be produced, for example, by reacting B¹A compound B which is a group represented by the formula (9)¹Is obtained by partial reduction of the ketone in (1). The method for synthesizing the specific monomer is not limited to the above method.

The polymer (P) may include only a structural unit having a photo-alignment group (hereinafter, also referred to as "structural unit U2A") as the structural unit U2, but may include a structural unit having no photo-alignment group (hereinafter, also referred to as "structural unit U2B") in addition to the structural unit U2A. The structural unit U2B is not particularly limited, and examples thereof include: n-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (4-glycidyloxyphenyl) maleimide, N-glycidylmaleimide, 3- (2, 5-dioxo-3-pyrrolin-1-yl) benzoic acid, 4- (2, 5-dioxo-3-pyrrolin-1-yl) benzoic acid, methyl 4- (2, 5-dioxo-3-pyrrolin-1-yl) benzoate, N-methylitaconimide, N- (m-methoxyphenyl) itaconimide, and open rings thereof.

The content ratio of the structural unit U2 in the polymer (P) (the total amount thereof in the case of having the structural unit U2A and the structural unit U2B) is preferably 1 mol% or more, more preferably 3 mol% to 60 mol%, and still more preferably 4 mol% to 40 mol% with respect to the total amount of the structural units derived from monomers in the polymer (P).

The content ratio of the structural unit U2A is preferably 1 mol% or more, more preferably 3 mol% to 50 mol%, and still more preferably 4 mol% to 30 mol% with respect to the total amount of the monomer-derived structural units of the polymer (P), from the viewpoint of sufficiently obtaining the effect of reducing the AC afterimage.

The liquid crystal aligning agent of the present disclosure may improve electrical characteristics and AC image sticking characteristics by including a polymer having the structural unit U1 and the structural unit U2, and in order to further improve the improvement effect of the characteristics, the polymer (P) may have structural units other than the structural unit U1 and the structural unit U2. The polymer (P) preferably has at least one of the following (x1) and (x2) in a side chain as another structural unit, and particularly preferably has both (x1) and (x2) in a side chain.

(x1) functional group of at least one of oxetanyl group and oxetanyl group (excluding the oxetanyl group and the oxetanyl group of the structural unit U1) (hereinafter, also referred to as "functional group (x 1)")

(x2) a functional group which reacts with at least one of the oxetanyl group and the oxetanyl group by heating (hereinafter, also referred to as "functional group (x 2)")

(regarding the functional group (x1))

The case where the polymer (P) has the functional group (x1) is preferable in that a liquid crystal alignment film exhibiting high liquid crystal alignment properties can be obtained even when the firing temperature at the time of forming the alignment film is lowered. Among oxetanyl groups and oxetanyl groups (hereinafter, also simply referred to as "epoxy groups") as the functional group (x1), an oxetanyl group is preferable in view of high reactivity.

(regarding the functional group (x2))

The polymer (P) preferably has a functional group (x2) in terms of more sufficiently exhibiting a reduction in AC image retention and a high voltage holding ratio. Examples of the functional group (x2) include: carboxyl group, hydroxyl group, isocyanate group, amino group, groups obtained by protecting these groups with a protecting group, alkoxymethyl group, and the like. Among them, the functional group (x2) is preferably at least one selected from the group consisting of a carboxyl group, a protected carboxyl group (hereinafter, also referred to as "protected carboxyl group"), an amino group, and a protected amino group (hereinafter, also referred to as "protected amino group"), in view of enabling the storage stability of the obtained liquid crystal aligning agent to be better and enabling the reactivity with an oxetane ring and an oxirane ring to be high by heating. Further, the amino group includes a primary amino group, a secondary amino group and a tertiary amino group.

The protected carboxyl group is not particularly limited as long as it is released by heat to produce a carboxyl group. Preferred specific examples of the protected carboxyl group include a structure represented by the following formula (12), an acetal ester structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, and the like.

[ solution 20]

(in the formula (12), R³¹,R³²And R³³Each independently an alkyl group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R³¹And R³²Are bonded to each other and R³¹And R³²The bonded carbon atoms together form a C4-20 divalent alicyclic hydrocarbon group or cyclic ether group, and R³³Is alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms or aryl group having 6 to 20 carbon atoms; "+" indicates a bond)

The protected amino group is not particularly limited as long as it is thermally dissociated to produce a primary amino group. Examples of the protecting group include: urethane-based protecting groups, amide-based protecting groups, imide-based protecting groups, sulfonamide-based protecting groups, and the like. Among these, tert-Butoxycarbonyl (BOC) is particularly preferable in terms of high releasability by heat and in terms of minimizing the amount of a compound derived from the removed protecting group remaining in the film.

In terms of the electrical characteristics of the obtained liquid crystal element and the high degree of freedom in selecting monomers, the functional group (x1) and the functional group (x2) are preferably introduced into the polymer (P) by at least one selected from the group consisting of styrene compounds and (meth) acrylic compounds. In the present specification, the term "(meth) acrylic compound" refers to a compound having only one (meth) acrylic group in one molecule, and is distinguished from maleimide compounds and itaconimide compounds.

When the other structural unit has a structural unit derived from a compound having a functional group (x1) (hereinafter, also referred to as "compound E1"), the compound E1 preferably has a partial structure represented by the following formula (13) as a group having an epoxy group. R in the following formula (13)⁷⁰Preferably, the number of carbon atoms is 2 or more.

*-R⁷⁰-G²…(13)

(in the formula (13), R⁷⁰Is an alkanediyl group having 1 to 20 carbon atoms or a group having-O-, -COO-or-OCO-in the carbon-carbon bond of the alkanediyl group, G²Is an oxetanyl, oxetanyl or 3, 4-epoxycyclohexyl group; "+" indicates a bond)

The compound E1 and the compound having a functional group (x2) (hereinafter, also referred to as "compound E2") are not particularly limited as long as they can be polymerized with the monomer forming the structural unit U1 and the monomer forming the structural unit U2, but are preferably at least one selected from the group consisting of the above-mentioned formulae (E-1), (E-3) to (E-7) and (E-10), and more preferably at least one selected from the group consisting of the above-mentioned formulae (E-3) and (E-5) to (E-7), in terms of ease of polymerization and high degree of freedom in selection of the monomers.

Specific examples of the compound E1 include styrene compounds such as: 3- (glycidyloxymethyl) styrene, 4-glycidyl-alpha-methylstyrene, etc.,

examples of the (meth) acrylic compounds include: glycidyl (meth) acrylate, glycidyl α -ethylacrylate, glycidyl α -n-propylacrylate, glycidyl α -n-butylacrylate, 3, 4-epoxybutyl (meth) acrylate, 3, 4-epoxybutyl α -ethylacrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 6, 7-epoxyheptyl α -ethylacrylate, 4-hydroxybutyl glycidyl acrylate, and (3-ethyloxetan-3-yl) methyl (meth) acrylate. One of these compounds E1 may be used alone, or two or more thereof may be used in combination.

Specific examples of the compound E2 include styrene compounds such as: 3-vinylbenzoic acid, 4-vinylbenzoic acid, compounds represented by the following formulae (m1-1) to (m1-4), and the like,

examples of the (meth) acrylic acid compound include: carboxyl group-containing compounds such as (meth) acrylic acid, α -ethylacrylic acid, maleic acid, fumaric acid, vinylbenzoic acid, crotonic acid, citraconic acid, mesaconic acid, itaconic acid, 3-maleimidobenzoic acid, and 3-maleimidopropionic acid; protected carbonyl group-containing compounds represented by the following formulae (m2-1) to (m 2-12); amino group-containing compounds represented by the following formulae (m1-5) to (m 1-7); and protected amino group-containing compounds represented by the following formulae (m1-8) and (m1-9), respectively. Further, when the polymer (P) is synthesized, the compound E2 may be used singly or in combination of two or more of these.

[ solution 21]

[ solution 22]

(in the formula, R¹⁵Is a hydrogen atom or a methyl group)

In the polymer (P), the content ratio of the structural unit derived from the compound E1 is preferably 2 mol% or more, more preferably 5 mol% to 70 mol%, and still more preferably 10 mol% to 60 mol%, relative to the total amount of the structural units derived from the monomers contained in the polymer (P).

The content ratio of the structural unit derived from the compound E2 is preferably 2 mol% or more, more preferably 3 mol% to 60 mol%, and still more preferably 5 mol% to 50 mol% with respect to the total amount of the structural units derived from the monomers contained in the polymer (P).

The polymer (P) may have, as another structural unit, a structural unit derived from a monomer having neither the functional group (x1) nor the functional group (x 2). Examples of the monomer include: (meth) acrylic compounds such as alkyl (meth) acrylate, cycloalkyl (meth) acrylate, benzyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; aromatic vinyl compounds such as styrene, methylstyrene and divinylbenzene; conjugated diene compounds such as 1, 3-butadiene and 2-methyl-1, 3-butadiene; maleic anhydride, and the like. The content ratio of the monomer-derived structural unit to the total amount of the monomer-derived structural units in the polymer (P) is preferably 20 mol% or less, more preferably 10 mol% or less, and still more preferably 3 mol% or less.

(Synthesis of Polymer (P))

The method for synthesizing the polymer (P) is not particularly limited, and can be obtained, for example, by radical polymerization of the monomer in an organic solvent in the presence of a polymerization initiator. The polymerization initiator to be used is preferably an azo compound such as 2,2' -azobis (isobutyronitrile), 2' -azobis (2, 4-dimethylvaleronitrile), or 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile). The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of all monomers used in the reaction. Examples of the organic solvent to be used include: alcohols, ethers, ketones, amides, esters, hydrocarbon compounds, and the like.

In the polymerization reaction, the reaction temperature is preferably 30 to 120 ℃ and the reaction time is preferably 1 to 36 hours. The amount (a) of the organic solvent used is preferably 0.1 to 60% by mass of the total amount (b) of the monomers used in the reaction relative to the total amount (a + b) of the reaction solution. The reaction solution in which the polymer is dissolved can be prepared by separating the polymer (P) contained in the reaction solution and then feeding the separated polymer (P) to the liquid crystal aligning agent by a conventional separation method such as a method of drying a precipitate obtained by injecting the reaction solution into a large amount of a poor solvent under reduced pressure or a method of distilling the reaction solution under reduced pressure using an evaporator. The polymer (P) can be synthesized, for example, by living radical polymerization using a reversible addition fragmentation chain transfer (RAFT) reagent.

The weight average molecular weight (Mw) of the polymer (P) in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) is preferably 1,000 to 300,000, more preferably 2,000 to 100,000. 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 polymer (P) used in the preparation of the liquid crystal aligning agent may be only one kind, or two or more kinds may be combined.

In order to sufficiently obtain the effect of improving the electric characteristics and the low image sticking characteristics of the liquid crystal element, the content ratio of the polymer (P) in the liquid crystal aligning agent is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, relative to the total amount of the polymer components contained in the liquid crystal aligning agent. The upper limit of the content ratio of the polymer (P) is not particularly limited, and is preferably 90% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less with respect to all polymers contained in the liquid crystal aligning agent, in order to sufficiently obtain the effect of improving various properties (for example, liquid crystal alignment properties, electrical properties, and the like) by using a polymer different from the polymer (P) in combination, and to achieve cost reduction.

< other ingredients >

The liquid crystal aligning agent of the present disclosure may also contain other components than the polymer (P) as necessary. The other components are not particularly limited as long as the effects of the present disclosure are not impaired, and examples thereof include the following components.

(Polymer (Q))

The liquid crystal aligning agent of the present disclosure preferably contains at least one polymer (hereinafter, also referred to as "polymer (Q)") selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, in addition to the polymer (P). In this case, the polymer (P) is biased to exist in the upper layer, and thus the effect of improving the electrical characteristics and the AC afterimage characteristics by the polymer (P) can be achieved by the smallest possible amount of the polymer (P), which is preferable in view of the above. In view of the above, it is preferable that the polymer (P) is a polymer having a halogen atom or a silicon atom and the polymer (Q) is a combination of polymers having no halogen atom or silicon atom, since phase separation can be easily caused.

The polymer (Q) can be synthesized by a conventional method. For example, the polyamic acid can be obtained by reacting tetracarboxylic dianhydride with diamine. In the present specification, the term "tetracarboxylic acid derivative" is intended to include tetracarboxylic acid dianhydrides, tetracarboxylic acid diesters, and tetracarboxylic acid diester dihalides.

The tetracarboxylic dianhydride used for the polymerization is not particularly limited, and various tetracarboxylic dianhydrides can be used. Specific examples of these include: aliphatic tetracarboxylic acid dianhydrides such as butane tetracarboxylic acid dianhydride and ethylenediamine tetraacetic acid dianhydride; 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-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, cyclopentanetetracarboxylic dianhydride, Alicyclic tetracarboxylic dianhydrides such as cyclohexanetetracarboxylic dianhydride; and aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 4' - (hexafluoroisopropylidene) diphthalic anhydride, p-phenylenebis (trimellitic acid monoester anhydride), ethyleneglycol bis (trimellitic acid anhydride), and 1, 3-propanediol bis (trimellitic acid anhydride), and in addition, tetracarboxylic dianhydrides described in japanese patent application laid-open No. 2010-97188 may be used. Further, the tetracarboxylic dianhydride may be used alone or in combination of two or more.

Examples of the diamine used in the polymerization include: aliphatic diamines such as ethylenediamine and tetramethylenediamine; alicyclic diamines such as p-cyclohexanediamine and 4,4' -methylenebis (cyclohexylamine); hexadecyloxydiaminobenzene, cholestanyloxydiaminobenzene, cholestanyl diaminobenzoate, cholestyryl diaminobenzoate, lanostanyl diaminobenzoate, 3, 6-bis (4-aminobenzoyloxy) cholestane, 3, 6-bis (4-aminophenoxy) cholestane, 1-bis (4- ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 2, 5-diamino-N, N-diallylaniline, the following formulae (2-1) to (2-3)

[ solution 23]

Side chain type aromatic diamines such as the compounds represented by the above formulae; p-phenylenediamine, 4' -diaminodiphenylmethane, 4' -diaminodiphenylamine, 4-aminophenyl-4 ' -aminobenzoate, 4' -diaminoazobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, 4' -diaminobiphenyl-3-carboxylic acid, 1, 5-bis (4-aminophenoxy) pentane, bis [2- (4-aminophenyl) ethyl ] adipic acid, bis (4-aminophenyl) amine, N-bis (4-aminophenyl) methylamine, N ' -bis (4-aminophenyl) -benzidine, 2' -dimethyl-4, 4' -diaminobiphenyl, N ' -diaminodiphenyl, N, 4' -diaminodiphenyl, N ' -diaminodiphenyl, non-side-chain aromatic diamines such as 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 4 '-diaminodiphenyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 4' - (phenylenediisopropylidene) dianiline, 1, 4-bis (4-aminophenoxy) benzene, 4- (4-aminophenoxycarbonyl) -1- (4-aminophenyl) piperidine, and 4,4'- [4,4' -propane-1, 3-diylbis (piperidine-1, 4-diyl) ] diphenylamine; diaminoorganosiloxanes such as 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane, and diamines described in Japanese patent application laid-open No. 2010-97188 may be used. Further, one kind of diamine may be used alone, or two or more kinds may be used in combination.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature in this case is preferably-20 ℃ to 150 ℃ and the reaction time is preferably 0.1 hour to 24 hours. Examples of the organic solvent used in the reaction include: aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and the like. The amount of the organic solvent used is preferably such that the total amount of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 50 mass% relative to the total amount of the reaction solution.

In the case where the polymer (Q) is a polyamic acid ester, the polyamic acid ester can be obtained, for example, by the following method or the like: a method of reacting the obtained polyamic acid with an esterifying agent (for example, methanol or ethanol, N-dimethylformamide diethyl acetal, or the like), a method of reacting a tetracarboxylic acid diester with a diamine compound in the presence of an appropriate dehydration catalyst, and a method of reacting a tetracarboxylic acid diester dihalide with a diamine in the presence of an appropriate base.

In the case where the polymer (Q) is a polyimide, the polyimide can be obtained, for example, by subjecting the obtained polyamic acid to dehydrative ring closure and imidization. The imidization ratio of the polyimide is preferably 20% to 95%, more preferably 30% to 90%. The imidization ratio is a ratio of the number of imide ring structures of the polyimide to the total of the number of amic acid structures and the number of imide ring structures, expressed as a percentage.

The polymer (Q) preferably has a weight average molecular weight (Mw) of 1,000 to 500,000, more preferably 2,000 to 300,000, in terms of polystyrene, as measured by GPC. The molecular weight distribution (Mw/Mn) is preferably 7 or less, more preferably 5 or less. The polymer (Q) contained in the liquid crystal aligning agent may be one kind alone, or two or more kinds may be combined.

In the case of using the polymer (P) and the polymer (Q) as the polymer components of the liquid crystal aligning agent, the blending ratio of the polymer (P) is preferably 1 part by mass or more with respect to 100 parts by mass of the polymer (Q) used in the preparation of the liquid crystal aligning agent, from the viewpoint of sufficiently obtaining the improvement effect of the AC afterimage characteristic and the electrical characteristic. More preferably 2 to 50 parts by mass, and still more preferably 5 to 30 parts by mass. The polymer (P) and the polymer (Q) may be used singly or in combination of two or more.

(solvent)

The liquid crystal aligning agent of the present disclosure is prepared in the form of a solution composition in which a polymer component and optionally a component are dissolved in an organic solvent. Examples of the organic solvent include: aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and the like. The solvent component may be one of these solvents, or may be a mixed solvent of two or more of these solvents.

Examples of the solvent component of the liquid crystal aligning agent include a solvent having high polymer solubility and leveling property (hereinafter, also referred to as "first solvent"), a solvent having good wet spreadability (hereinafter, also referred to as "second solvent"), and a mixed solvent thereof.

Specific examples of the solvent include: n-methyl-2-pyrrolidone, γ -butyrolactone, γ -butyrolactam, N-dimethylformamide, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, diisobutyl ketone, ethylene carbonate, propylene carbonate, N-ethyl-2-pyrrolidone, N- (N-pentyl) -2-pyrrolidone, N- (tert-butyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 3-butoxy-N, N-dimethylpropionamide, 3-methoxy-N, N-dimethylpropionamide, and the like;

examples of the second solvent include: ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diacetone alcohol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, cyclopentanone, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, isopentyl isobutyrate, propylene glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol monobutyl ether, diisoamyl ether, and the like. One of these solvents may be used alone, or two or more of them may be used in combination.

When the solvent component of the liquid crystal aligning agent is a mixed solvent of the first solvent and the second solvent, the content ratio of the first solvent is preferably 10% by mass or more, and more preferably 15% by mass to 85% by mass, relative to the total amount of the solvent components.

Other components contained in the liquid crystal aligning agent include, for example: a polymer other than the polymer (P) and the polymer (Q), a low-molecular compound having at least one epoxy group in the molecule and having a molecular weight of 1000 or less (for example, ethylene glycol diglycidyl ether, N ' -tetraglycidyl-m-xylylenediamine, N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, etc.), a functional silane compound, a polyfunctional (meth) acrylate, an antioxidant, a metal chelate compound, a hardening accelerator, a surfactant, a filler, a dispersant, a photosensitizer, etc. The blending ratio of the other components may be appropriately selected depending on each compound within a range not impairing the effect of the present disclosure.

The concentration of the solid component in the 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) may be appropriately selected in consideration of viscosity, volatility and the like, and is preferably in the range of 1 to 10 mass%. When the solid content concentration is less than 1% by mass, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10 mass%, the film thickness of the coating film is too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent tends to increase to lower the coatability.

Liquid crystal alignment film and liquid crystal cell

The liquid crystal alignment film of the present disclosure is formed of the liquid crystal aligning 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 aligning agent described above. The operation mode of the liquid crystal In the liquid crystal element is not particularly limited, and can be applied to various modes such as a Twisted Nematic (TN) mode, a Super Twisted Nematic (STN) mode, a Vertical Alignment (VA) mode (including a Vertical Alignment-Multi-domain Vertical Alignment (VA-MVA) mode, a Vertical Alignment-Patterned Vertical Alignment (VA-PVA) mode, and the like), an In-Plane Switching (IPS) mode, an edge Field Switching (FFS) mode, an Optically Compensated Bend (Optically Compensated Bend, OCB) mode, a Polymer Stabilized Alignment (PSA) mode, and the like. The liquid crystal element can be manufactured by a method including, for example, the following steps 1 to 3. In step 1, the substrate used is different depending on the desired operation mode. The step 2 and the step 3 are commonly used in each operation mode.

< step 1: formation of coating film

First, a liquid crystal aligning agent is applied to a substrate, and preferably, the coated surface is heated, thereby forming a coating film on the substrate. As the substrate, for example, a transparent substrate including the following materials can be used: float glass, soda glass, and the like; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin). The transparent conductive film provided on one surface of the substrate may use: containing tin oxide (SnO)₂) A film of (Nesa) (registered trademark of PPG Corp., USA) containing indium oxide-tin oxide (In)₂O₃-SnO₂) Indium Tin Oxide (ITO) film, and the like. In the case of manufacturing a TN-type, STN-type, or VA-type liquid crystal cell, 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 element, a substrate provided with electrodes patterned into a comb-tooth shape and an opposing substrate provided with no electrodes are used. The liquid crystal aligning agent is preferably applied to the substrate by offset printing, flexography, gravure, or gravure,Spin coating, roll coater or ink jet printing.

After the liquid crystal aligning agent is applied, it is preferable to perform preliminary heating (pre-baking) for the purpose of preventing dripping 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, a calcination (post-baking) step is performed for the purpose of completely removing the solvent and, if necessary, thermally imidizing the amic acid structure present in the polymer. The calcination temperature (post-baking temperature) in this case is preferably 80 to 250 ℃, more preferably 80 to 200 ℃. The post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 μm.

< step 2: orientation treatment

In the case of producing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal cell, a treatment (alignment treatment) is performed to impart liquid crystal alignment ability to the coating film formed in the above-described step 1. Thereby, the coating film is provided with the alignment ability of the liquid crystal molecules, and becomes a liquid crystal alignment film. As the orientation treatment, there can be mentioned: rubbing treatment for rubbing a coating film in a certain direction by a roller around which a cloth containing fibers such as nylon (nylon), rayon (rayon), or cotton (cotton) is wound to impart liquid crystal aligning ability to the coating film, photo-aligning treatment for irradiating a coating film formed on a substrate with light to impart liquid crystal aligning ability to the coating film, and the like. Among these, photo-alignment treatment is preferable. In the case of producing a vertical alignment type liquid crystal cell, the coating film formed in the step 1 may be used as it is as a liquid crystal alignment film, but an alignment treatment may be applied to the coating film in order to further improve the liquid crystal alignment ability.

Light irradiation for photo-alignment can be performed by the following method or the like: a method of irradiating a coating film after the post-baking step, a method of irradiating a coating film after the pre-baking step and before the post-baking step, and a method of irradiating a coating film during heating of a coating film in at least any one of the pre-baking step and the post-baking step. As the radiation irradiated to the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150nm to 800nm can be used. Preferably, the ultraviolet light contains light having a wavelength of 200nm to 400 nm. When the radiation is polarized light, the radiation may be linearly polarized light or partially polarized light. When the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or from a combination of these directions. The irradiation direction in the case of unpolarized radiation is an oblique direction.

Examples of the light source used include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and an excimer laser. The irradiation dose of the radiation is preferably 400J/m²～50,000J/m²More preferably 1,000J/m²～20,000J/m². After the light irradiation for imparting alignment ability, the substrate surface may be cleaned 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 the substrate may be heated.

< step 3: construction of liquid Crystal cell

Two substrates on which liquid crystal alignment films are formed in this manner are prepared, and liquid crystal is disposed between the two substrates disposed to face each other, thereby manufacturing a liquid crystal cell. In the production of a liquid crystal cell, for example, the following methods can be mentioned: a method of arranging two substrates in opposition to each other with a gap therebetween so that liquid crystal alignment films oppose each other, bonding peripheral portions of the two substrates together with a sealant, and injecting/filling liquid crystal into a cell gap surrounded by the surfaces of the substrates and the sealant to seal the injection hole; a method using a One Drop Filling (ODF) method. For the sealant, for example, an epoxy resin containing a hardener and alumina balls as spacers (spacers) can be used. The liquid crystal includes nematic liquid crystal and smectic liquid crystal, and among them, nematic liquid crystal is preferable. In the PSA mode, after the liquid crystal cell is constructed, a process of irradiating the liquid crystal cell with light while applying a voltage between conductive films provided on a pair of substrates is performed.

Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell as necessary to produce a liquid crystal cell. Examples of the polarizing plate include: a polarizing plate obtained by sandwiching a polarizing film called an "H film" obtained by stretching and orienting polyvinyl alcohol and absorbing iodine while absorbing it, or a polarizing plate including the H film itself, with a cellulose acetate protective film.

The liquid crystal element of the present disclosure can be effectively applied to various applications, for example, various display devices such as a clock, a portable game, a word processor, a notebook Personal computer, a car navigation system, a camcorder, a Personal Digital Assistant (PDA), a digital camera, a mobile phone, a smartphone, various monitors, a liquid crystal television, an information display, a light adjusting film, a retardation film, and the like.

Examples

The present disclosure is not limited to the following examples.

In the following examples, the weight average molecular weight (Mw), the number average molecular weight (Mn) and the molecular weight distribution (Mw/Mn) of the polymer were measured by the following methods.

< weight average molecular weight, number average molecular weight and molecular weight distribution >

Mw and Mn were measured by Gel Permeation Chromatography (GPC) under the following conditions. The molecular weight distribution (Mw/Mn) was calculated from the Mw and Mn thus obtained.

The device comprises the following steps: showa electrician (thigh) "GPC-101"

GPC column: "GPC-KF-801", "GPC-KF-802", "GPC-KF-803", and "GPC-KF-804" manufactured by Shimadzu GLC (SHIMADZU GLC)

Mobile phase: tetrahydrofuran (THF), or N, N-dimethylformamide solution containing lithium bromide and phosphoric acid

Temperature of the pipe column: 40 deg.C

Flow rate: 1.0 mL/min

Sample concentration: 1.0% by mass

Sample injection amount: 100 μ L

A detector: differential refractometer

Standard substance: monodisperse polystyrene

The structural formulae of the compounds used in the following examples are shown below.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

[ solution 24]

[ solution 25]

< Synthesis of monomer >

Synthetic example 1: synthesis of Compound (MI-01) ]

Compound (MI-01) was synthesized according to the following scheme 1.

[ solution 26]

Synthesis of Compound (MI-01)

In a 100mL eggplant type flask equipped with a stirrer were added 14.0g of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid, 20g of thionyl chloride, and 0.01g of N, N-dimethylformamide, and stirred at 80 ℃ for 1 hour. Thereafter, excess thionyl chloride was removed by a diaphragm pump, and 100g of tetrahydrofuran was added to prepare a solution a.

In a 500mL three-necked flask equipped with a stirrer were again added 5.67g of 4-hydroxyphenylmaleimide, 200g of tetrahydrofuran, and 12.1g of triethylamine, and ice-bath was performed. Solution a was added dropwise thereto and stirred at room temperature for 3 hours. The reaction solution was reprecipitated with 800mL of water, and the obtained white solid was dried under vacuum, whereby 14.3g of compound (MI-01) was obtained.

[ Synthesis example 2: synthesis of Compound (MI-02) ]

Compound (MI-02) was synthesized according to the following scheme 2.

[ solution 27]

Synthesis of Compound (M-2-1)

In a 1000mL three-necked flask equipped with a stirrer, 11.5g of 4-amino-cyclohexanol was introduced, and 150g of tetrahydrofuran was added and ice-cooled. A solution containing 9.81g of maleic anhydride and 150g of tetrahydrofuran was added dropwise thereto, and stirred at room temperature for 3 hours. Thereafter, the precipitated white solid was recovered by filtration. The white solid was vacuum-dried, whereby 20.2g of compound (M-2-1) was obtained.

Synthesis of Compound (M-2-2) (4-Hydroxycyclohexylmaleimide)

In a 500mL three-necked flask equipped with a stirrer, 17.1g of the compound (M-2-1), 10.9g of zinc (II) chloride and 250g of toluene were added, and the mixture was heated and stirred at 80 ℃. A solution containing 23.2g of bis (trimethylsilyl) amine and 100g of toluene was added dropwise thereto, and stirred at 80 ℃ for 5 hours. Then, 300g of ethyl acetate was added to the reaction solution, and liquid separation washing with 1mol/L hydrochloric acid, 1 liquid separation washing with an aqueous sodium bicarbonate solution, and 3 liquid separation washing with water were performed 2 times. Thereafter, the organic layer was concentrated using a rotary evaporator (rota evaporator). The obtained white solid was put into a mixed solvent of THF/ethanol/water, and the white solid precipitated in the middle was recovered by filtration. The white solid was vacuum-dried, whereby 7.99g of compound (M-2-2) was obtained.

Synthesis of Compound (MI-02)

14.0g of a compound (MI-02) was obtained in the same manner as in Synthesis example 1, except that 4-hydroxycyclohexylmaleimide was used in place of 4-hydroxyphenylmaleimide in Synthesis example 1.

[ Synthesis example 3: synthesis of Compound (MI-03) ]

Compound (MI-03) was synthesized according to scheme 3 below.

[ solution 28]

Synthesis of Compound (M-3-1)

In a 2000mL three-necked flask equipped with a stirrer, 11.5g of N-Boc-4-hydroxyaniline (N-BOC-4-hydroxyyaniline) and 23.3g of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bis (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid were taken, and 1000g of methylene chloride was added and ice-cooled. To this solution, 1.21g of N, N-dimethylaminopyridine and 11.5g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride were added in this order, and after stirring at room temperature for 8 hours, the mixture was washed with 500g of distilled water for 4 times of liquid separation. Thereafter, the organic layer was slowly concentrated by a rotary evaporator until the content was 100g, and a white solid precipitated in the course of the concentration was collected by filtration. The white solid was vacuum-dried, whereby 31.6g of compound (M-3-1) was obtained.

Synthesis of Compound (M-3-2)

30.3g of the compound (M-3-1) and 33.8g of trifluoroacetic acid were put in a 300mL round bottom flask equipped with a stirrer, 50g of methylene chloride was added thereto, and the mixture was stirred at room temperature for 1 hour. Thereafter, the mixture was neutralized with a saturated aqueous sodium bicarbonate solution, and then subjected to 4 times of liquid separation washing with 50g of distilled water. Thereafter, the organic layer was slowly concentrated by a rotary evaporator until the content was 50g, and a white solid precipitated in the course of the concentration was collected by filtration. The white solid was vacuum-dried, whereby 24.8g of compound (M-3-2) was obtained.

Synthesis of Compound (MI-03)

In a 2000mL three-necked flask equipped with a stirrer, 24.7g of the compound (M-3-2) was placed, and 200g of tetrahydrofuran was added thereto and ice-cooled. A solution containing 4.34g of maleic anhydride and 200g of tetrahydrofuran was added dropwise thereto, and stirred at room temperature for 3 hours. Thereafter, the precipitated solid was recovered by filtration. The yellow solid was vacuum-dried, whereby 28.9g of the compound (MI-03) was obtained.

[ Synthesis example 4: synthesis of Compound (MI-04) ]

Compound (MI-04) was synthesized according to the following scheme 4.

[ solution 29]

Synthesis of Compound (MI-04)

In a 500mL eggplant-shaped flask equipped with a stirrer, 6.53g of monomethyl maleate, 25g of thionyl chloride, and 0.01g of N, N-dimethylformamide were added, and the mixture was stirred at 60 ℃ for 2 hours. Thereafter, excess thionyl chloride was removed by a diaphragm pump, and 50g of tetrahydrofuran was added to prepare a solution a.

A1000 mL three-necked flask equipped with a stirrer was charged with 26.8g of the compound (M-3-2), 500g of tetrahydrofuran and 13.2g of triethylamine again, and subjected to ice-bath. Solution a was added dropwise thereto and stirred at room temperature for 8 hours. The reaction solution was reprecipitated with 1200mL of water, and the obtained white solid was dried under vacuum to obtain 25.4g of compound (MI-04).

[ Synthesis example 5: synthesis of Compound (MI-05) ]

19.1g of compound (MI-05) was obtained in the same manner as in Synthesis example 1-3, except that compound (M-3-2) was used as a raw material and itaconic anhydride was used instead of maleic anhydride in Synthesis example 3.

[ Synthesis example 6: synthesis of Compound (MI-06) ]

14.4g of a compound (MI-06) was obtained in the same manner as in Synthesis example 1, except that 4-hydroxy-2-methylphenylmaleimide was used in place of 4-hydroxyphenylmaleimide in Synthesis example 1. Furthermore, in the synthesis of M-2-1 in Synthesis example 2, 4-hydroxy-2-methylphenylmaleimide was synthesized using 2-methyl-4-hydroxyaniline instead of 4-hydroxycyclohexylamine.

[ Synthesis example 7: synthesis of Compound (MI-07) ]

14.5g of a compound (MI-07) was obtained in the same manner as in Synthesis example 1, except that 4-hydroxy-3-methylphenylmaleimide was used in place of 4-hydroxyphenylmaleimide in Synthesis example 1. Furthermore, in the synthesis of the compound (M-2-1) of Synthesis example 2, 4-hydroxy-3-methylphenylmaleimide was synthesized using 3-methyl-4-hydroxyaniline instead of 4-hydroxycyclohexylamine.

[ Synthesis example 8: synthesis of Compound (MI-08) ]

Compound (MI-08) was synthesized according to scheme 8 below.

[ solution 30]

Synthesis of 4-hydroxy- α -methyl cinnamic acid (Compound (M-8-1))

In a 200mL three-necked flask equipped with a stirrer, 9.74g of 4-hydroxybenzaldehyde, 25g of propionic anhydride, and 15.2g of sodium propionate were mixed and stirred at 145 ℃ for 16 hours under a nitrogen atmosphere. After the reaction, the reaction mixture was cooled in an ice bath, and 100ml of water was added thereto and stirred for 3 hours to precipitate a solid, which was then filtered. The obtained solid was added to a 10% aqueous sodium hydroxide solution and stirred at 0 ℃ for 30 minutes. After insoluble matter was filtered, hydrochloric acid was added to the filtrate to make the filtrate acidic, and the resulting solid was filtered. The solid was dissolved in 200ml of ethyl acetate and washed with water 3 times. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 8.73g of 4-hydroxy- α -methyl cinnamic acid (compound (M-8-1)).

Synthesis of Compound (M-8-2)

4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carboxylic acid was reacted with 4-hydroxy- α -methyl cinnamic acid by the same method as in Synthesis example 1 to obtain 15.0g of compound (M-8-2).

Synthesis of Compound (MI-08)

14.6g of compound (MI-08) was obtained by the same method as in Synthesis example 1, except that compound (M-8-2) was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1.

[ Synthesis example 9: synthesis of Compound (MI-09) ]

Compound (MI-09) was synthesized according to scheme 9 below.

[ solution 31]

14.5g of compound (MI-09) was obtained by the same procedure as in Synthesis example 1, except that compound (M-9-1) was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1. Compound (M-9-1) was synthesized in the same manner as in Synthesis example 8, except that 2-methyl-4-hydroxycinnamic acid was used in place of 4-hydroxy-. alpha. -methyl cinnamic acid.

[ Synthesis example 10: synthesis of Compound (MI-10)

Compound (MI-10) was synthesized according to scheme 10 below.

[ solution 32]

14.5g of compound (MI-10) was obtained in the same manner as in Synthesis example 1, except that compound (M-10-1) was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1. Compound (M-10-1) was synthesized in the same manner as in Synthesis example 8, except that 3-methyl-4-hydroxycinnamic acid was used in place of 4-hydroxy-. alpha. -methyl cinnamic acid.

[ Synthesis example 11: synthesis of Compound (MI-11) ]

Compound (MI-11) was synthesized according to scheme 11 below.

[ solution 33]

14.4g of compound (MI-11) was obtained by the same method as in Synthesis example 1, except that (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) thio) phenyl) acrylate was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1.

Further, (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) thio) phenyl) acrylic acid was synthesized using 4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carboxylic acid and 4-mercaptocinnamic acid by the same method as in the above scheme 8. 4-mercaptocinnamic acid can be synthesized by the method described in Japanese patent No. 2646314.

[ Synthesis example 12: synthesis of Compound (MI-12)

13.4g of compound (MI-12) was obtained in the same manner as in Synthesis example 1, except that (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid was used in place of (E) -3- (4- ((4 '-pentyl- [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1.

[ Synthesis example 13: synthesis of Compound (MI-13) ]

Compound (MI-13) was synthesized according to scheme 13 below.

[ chemical 34]

12.3g of compound (MI-13) was obtained in the same manner as in Synthesis example 1, except that (E) -3- (4- ((4- (4,4, 4-trifluorobutyl) cyclohexyl) benzoyl) oxy) phenyl) acrylic acid was used in place of (E) -3- (4- ((4'- (4,4,4, 4-trifluorobutyl) - [1,1' -bis (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1. Further, (E) -3- (4- ((4- (4- (4,4, 4-trifluorobutyl) cyclohexyl) benzoyl) oxy) phenyl) acrylate was synthesized using 4- (4- (4,4, 4-trifluorobutyl) cyclohexyl) benzoic acid and coumaric acid and by the same method as described in scheme 8.

Synthesis example 14: synthesis of Compound (MI-14)

15.7g of compound (MI-14) was obtained by the same method as in Synthesis example 1, except that (E) -3- (4- ((4- (3- (trimethylsilyl) propoxy) cyclohexyl) benzoyl) oxy) phenyl) acrylic acid was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bis (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1.

[ Synthesis example 15: synthesis of Compound (MI-15)

Compound (MI-15) was synthesized according to scheme 15 below.

[ solution 35]

Synthesis of Compound (M-15-1)

A300 mL three-necked flask was charged with 6.36g of potassium tert-butoxide, and nitrogen gas was purged. Then, 28.3g of 4,4, 4-trifluorobutyltriphenylphosphonium iodide dissolved in 180ml of tetrahydrofuran was added dropwise thereto, and the reaction was carried out at room temperature for 1 hour. Then, 10.4g of 4- (1, 4-dioxaspiro [4.5] decan-8-yl) cyclohexanone was added thereto, and the reaction was carried out at room temperature for 72 hours. The solvent was distilled off by a rotary evaporator, and then extracted with diethyl ether, and purified by a silica gel column using hexane/ethyl acetate as a developing solvent. The solvent was removed by means of a rotary evaporator to obtain 8.1g of compound (M-15-1).

Synthesis of Compound (M-15-2)

In a 500mL three-necked flask, 7.7g of the compound (M-15-1) was placed, and nitrogen gas was purged. Then, 225ml of methanol and 1.23g of palladium-activated carbon (Pd 10%) were added, and the inside of the flask was replaced with hydrogen gas to install a balloon (balloon) filled with hydrogen gas. After stirring vigorously at room temperature for 12 hours, filtration was carried out using celite, and the residue was washed with dichloromethane. The filtrate was subjected to 3 times of liquid-separation washing with water, and the solvent was removed using a rotary evaporator, thereby obtaining 7.5g of compound (M-15-2).

Synthesis of Compound (M-15-3)

In a 200mL three-necked flask, 7.5g of the compound (M-15-2) was placed, and nitrogen gas was purged. Then, 30ml of acetone and 15ml of water were added, and then 23.4ml of trifluoroacetic acid was added dropwise, followed by reaction at room temperature for 16 hours. The solvent was removed by a rotary evaporator, and the ethyl acetate extract was purified by a silica gel column (hexane/ethyl acetate). After the solvent was removed by a rotary evaporator, vacuum drying was performed, whereby 4.6g of compound (M-15-3) was obtained.

Synthesis of Compound (M-15-4)

A100 mL three-necked flask was charged with 0.44g of magnesium, and purged with nitrogen. Then, 10ml of dehydrated tetrahydrofuran was added thereto, and the mixture was cooled in an ice bath. 0.15ml of iodinated benzene dissolved in 4ml of dehydrated tetrahydrofuran was slowly added dropwise, reacted at room temperature for 30 minutes, and reacted at 70 ℃ for 30 minutes. After the mixture was returned to room temperature and cooled in an ice bath, 4.6g of the compound (M-15-3) dissolved in 20ml of dehydrated tetrahydrofuran was slowly added dropwise. The reaction mixture was returned to room temperature and the solution reacted for 5 hours was poured into a saturated aqueous solution of ammonium chloride. The organic layer was collected, washed with a saturated aqueous solution of ammonium chloride for 2 times, and then purified by a silica gel column using hexane/ethyl acetate as a developing solvent. The solvent was removed by means of a rotary evaporator to obtain 4.1g of compound (M-15-4).

Synthesis of Compound (M-15-5)

In a 100mL three-necked flask, 4.1g of the compound (M-15-4) was placed and nitrogen substitution was performed. Then, 2.5ml of acetic acid, 0.25g of palladium-activated carbon (Pd 10%), and 20ml of tetrahydrofuran were added, replaced with a hydrogen atmosphere, and stirred at room temperature for 6 hours. The reaction solution was filtered with celite, and washed with tetrahydrofuran. The filtrate was concentrated using a rotary evaporator, and ethyl acetate was added thereto and stirred at 0 ℃ for 1 hour. The precipitated solid was filtered and vacuum-dried, whereby 3.4g of the compound (M-15-5) was obtained.

Synthesis of Compound (M-15-6)

In a 100mL three-necked flask, 3.4g of the compound (M-15-5) and 0.03g of iron (III) chloride were placed, and nitrogen gas was purged. Subsequently, 5.5g of a 15% aqueous solution of hydrobromic acid was added, and then 7.4g of a 10% aqueous solution of sodium hypochlorite was added dropwise thereto, and stirred at room temperature for 2 hours. The organic layer was recovered, and washed with a 5% aqueous solution of sodium hydrogencarbonate and distilled water in this order. After the solvent was removed by a rotary evaporator, vacuum drying was performed, whereby 2.5g of compound (M-15-6) was obtained.

Synthesis of Compound (M-15-7)

A100 mL three-necked flask was charged with 0.43g of acrylic acid and 2.02g of potassium tert-butoxide, and purged with nitrogen. Then, 12ml of water was added and stirred at room temperature for 10 minutes, after which 1.35g of palladium acetate and 2.5g of the compound (M-15-6) were added and stirred at 100 ℃ for 24 hours. After returning to room temperature, an aqueous hydrochloric acid solution was added dropwise until the pH was 1. Thereafter, the extract was extracted with dichloromethane, and washed with brine (brine), an aqueous sodium sulfate solution, and water in this order. Purification was performed by flash column chromatography (flash column chromatography), and the solvent was removed by a rotary evaporator and vacuum-dried, whereby 2.1g of the compound (M-15-7) was obtained.

Synthesis of Compound (MI-15)

1.7g of compound (MI-15) was obtained by the same method as in Synthesis example 1-1, except that compound (M-15-7) was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1-1.

Synthesis example 16: synthesis of Compound (MI-16) ]

Compound (MI-16) was synthesized according to scheme 16 below.

[ solution 36]

Synthesis of Compound (M-16-1)

In a 500mL three-necked flask, 22.4g of 4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carboxylic acid was placed and purged with nitrogen. Then, 200mL of THF was added and stirring was performed at 0 ℃. After 3.3g of sodium borohydride was added thereto, 12.1g of boron trifluoride diethyl ether was slowly added dropwise and reacted for 18 hours. After completion of the reaction, the reaction mixture was transferred to a 2L beaker, neutralized with hydrochloric acid, and 1.5L of water was added thereto. The precipitated solid was filtered and then vacuum-dried, whereby 20.6g of compound (M-16-1) was obtained.

Synthesis of Compound (M-16-2)

In a 1L three-necked flask, 20.6g of the compound (M-16-1), 0.819g of N, N-dimethyl-4-aminopyridine, 200mL of dichloromethane, 13.6g of triethylamine were added, and the mixture was cooled to 0 ℃. A solution of 14.1g of p-toluenesulfonyl chloride dissolved in 100mL of dichloromethane was slowly added dropwise thereto, and then the reaction was carried out for 20 hours. After completion of the reaction, 100mL of dichloromethane was added, the reaction solution was subjected to 3 times of liquid separation with 500mL of water, the organic layer was dried with magnesium sulfate, and then magnesium sulfate was removed by filtration. Then, the solvent of the filtrate was distilled off by using a rotary evaporator and the resulting solid was dried in vacuum, whereby 29.3g of compound (M-16-2) was obtained.

Synthesis of Compound (M-16-3)

To a 1L three-necked flask, 29.3g of the compound (M-16-2), 7.82g of 4-hydroxybenzaldehyde, 13.3g of potassium carbonate, and 200mL of N, N-dimethylformamide were added, and reacted at 100 ℃ for 5 hours. After completion of the reaction, 500mL of ethyl acetate was added, liquid separation was performed 3 times using 500mL of water, and then the organic layer was dried over magnesium sulfate. Then, magnesium sulfate was removed by filtration. Then, magnesium sulfate was filtered by filtration, and the solvent of the filtrate was distilled off by a rotary evaporator and the resulting solid was dried in vacuum, thereby obtaining 23.4g of compound (M-16-3).

Synthesis of Compound (M-16-4)

In a 1L eggplant-shaped flask, 23.4g of the compound (M-16-3), 11.9g of malonic acid, 300mL of pyridine, and 7.29g of piperidine were added, and the mixture was reacted under reflux for 8 hours. Thereafter, the reaction mixture was cooled to room temperature, 300mL of ethanol was added, and the solid was collected by filtration. The obtained solid was washed with ethanol and then dried under vacuum, whereby 18.1g of compound (M-16-4) was obtained.

Synthesis of Compound (MI-16)

17.8g of compound (MI-16) was obtained by the same method as in Synthesis example 1-1, except that compound (M-16-4) was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bis (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1-1.

[ Synthesis example 17: synthesis of Compound (MI-17)

Compound (MI-17) was synthesized according to scheme 17 below.

[ solution 37]

12.6g of compound (MI-17) was obtained in the same manner as in Synthesis example 1, except that (E) -3- (4- ((4- (4,4, 4-trifluorobutoxy) benzoyl) oxy) phenyl) acrylate was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bis (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1.

[ Synthesis example 18: synthesis of Compound (MI-18) ]

Compound (MI-18) was synthesized according to scheme 18 below.

[ solution 38]

Synthesis of Compound (M-18-1)

82g of methyl 4-hydroxybenzoate, 166g of potassium carbonate and 400mL of N, N-dimethylacetamide were put into a 1L eggplant-shaped flask, and stirred at room temperature for 1 hour, and then 95g of 4,4, 4-trifluoro-1-iodobutane was added thereto, and the mixture was reacted at room temperature for 5 hours with stirring. After the reaction, reprecipitation was performed with water. Then, 32g of sodium hydroxide and 400mL of water were added to the precipitate, and the mixture was refluxed for 4 hours to conduct hydrolysis reaction. After the reaction was completed, neutralization was performed with hydrochloric acid, and the resulting precipitate was recrystallized with ethanol, whereby 80g of compound (M-18-1) was obtained.

Synthesis of Compound (MI-18-2)

In a reaction vessel, 46.4g of the compound (M-18-1) was taken, and 200mL of thionyl chloride and 0.2mL of N, N-dimethylformamide were added thereto, and stirred at 80 ℃ for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, and tetrahydrofuran was added to prepare a solution a. Next, 30g of 4-hydroxybenzoic acid, 55g of potassium carbonate, 2.4g of tetrabutylammonium, 200mL of tetrahydrofuran, and 400mL of water were put into a 2L three-necked flask different from the flask described above. The aqueous solution was cooled in an ice bath, and solution a was slowly added dropwise, followed by reaction with stirring for 2 hours. After completion of the reaction, hydrochloric acid was added to the reaction mixture to neutralize the mixture, the mixture was extracted with ethyl acetate, and then the extract was dried over magnesium sulfate, concentrated, and recrystallized from ethanol to obtain 39g of compound (M-18-2) as white crystals.

Synthesis of Compound (M-18-3)

33g of the compound (M-18-3) was obtained in the same manner as in the compound (M-18-2) except that the compound (M-18-2) was used in place of the compound (M-18-1) and 4-hydroxycinnamic acid was used in place of 4-hydroxybenzoic acid.

Synthesis of Compound (MI-18)

15.4g of compound (MI-18) was obtained by the same method as in Synthesis example 1-1, except that compound (MI-18-3) was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1-1.

[ Synthesis example 19: synthesis of Compound (MI-19)

Compound (MI-19) was synthesized according to scheme 19 below.

[ solution 39]

16.1g of compound (MI-19) was obtained by the same method as in Synthesis example 1, except that compound (M-19-3) was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1. Furthermore, in Synthesis example 18, compounds (M-19-1) to (MI-19-3) were synthesized using 1,1,1,2, 2-pentafluoro-4-iodobutane in place of 4,4, 4-trifluoro-1-iodobutane.

[ Synthesis example 20: synthesis of Compound (MI-20) ]

16.1g of compound (MI-20) was obtained by the same method as in Synthesis example 1, except that (E) -4- ((3- (4- ((4- (4,4, 4-trifluorobutoxy) benzoyl) oxy) phenyl) acryloyl) oxy) benzoic acid was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bis (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1.

Synthesis example 21: synthesis of Compound (MI-21)

Compound (MI-21) was synthesized according to scheme 21 below.

[ solution 40]

15.8g of compound (MI-21) was obtained by the same method as in Synthesis example 1, except that compound (MI-21-3) was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1. Further, in Synthesis example 22, compounds (M-21-1) to (M-21-3) were synthesized in the same manner except that the starting material was replaced with 3-fluoro-4-hydroxybenzoic acid instead of 4-hydroxy-2, 3,5, 6-tetrafluorophenylbenzoic acid.

[ Synthesis example 22: synthesis of Compound (MI-22)

Compound (MI-22) was synthesized according to scheme 22 below.

[ solution 41]

Synthesis of Compound (M-22-1)

In a 1000mL three-necked flask equipped with a stirrer, 21.0g of 4-hydroxy-2, 3,5, 6-tetrafluorophenylbenzoic acid, 53.0g of 4,4, 4-trifluoro-1-iodobutane, 83.2g of potassium carbonate, and 500mL of dimethylacetamide were added, and heated at 90 ℃ for 10 hours under a nitrogen atmosphere. After the reaction, the mixture was poured into 500mL of water, and extracted 3 times with 300mL of ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. To the obtained crude product were added 100mL of THF, 100mL of ethanol, and 50mL of water, and further 9.2g of lithium hydroxide monohydrate, and the mixture was stirred at room temperature for 5 hours. After the reaction, the mixture was made acidic with 1-part hydrochloric acid, and then extracted 3 times with 100mL of ethyl acetate. After anhydrous sodium sulfate was added to the organic layer and dried, the solvent was distilled off under reduced pressure and recrystallized from ethyl acetate/hexane to obtain 25.0g of compound (M-22-1).

Synthesis of Compound (M-22-2)

Synthesis example 18 was carried out in the same manner as in the above example except for using the compound (M-22-1) in place of the compound (M-18-2), thereby obtaining 22.1g of the compound (M-22-2).

Synthesis of Compound (M-21-3)

Synthesis example 18 was carried out in the same manner as in the above example except for using the compound (M-22-2) in place of the compound (M-18-1) to obtain 17.1g of the compound (M-22-3).

Synthesis of Compound (MI-22)

17.2g of compound (MI-22) was obtained by the same method as in Synthesis example 1, except that compound (M-22-3) was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1.

[ Synthesis example 23: synthesis of Compound (MI-23)

Compound (MI-23) was synthesized according to scheme 23 below.

[ solution 42]

Synthesis of Compound (M-23-1)

In a 500mL three-necked flask equipped with a stirrer were added 16.8g of methyl 3, 4-dihydroxybenzoate, 53.0g of 4,4, 4-trifluoro-1-iodobutane, 83.2g of potassium carbonate, and 500mL of dimethylacetamide, and heated at 90 ℃ for 10 hours under a nitrogen atmosphere. After the reaction, the reaction mixture was poured into 500mL of water, and the precipitate was filtered. The filtered solid was added to 10% aqueous sodium hydroxide solution and stirred at room temperature for 5 hours. After the reaction, the reaction mixture was made acidic with 1-part hydrochloric acid, and the resulting precipitate was filtered and dried by a vacuum drier to obtain 28.0g of compound (M-23-1).

Synthesis of Compound (M-23-2)

Synthesis example 18 was carried out in the same manner as in the above example except for using the compound (M-23-1) in place of the compound (M-18-2), thereby obtaining 23.4g of the compound (M-23-2).

Synthesis of Compound (M-23-3)

Synthesis example 18 was carried out in the same manner as in the above example except for using the compound (M-23-2) in place of the compound (M-18-1) to obtain 17.3g of the compound (M-23-2).

Synthesis of Compound (MI-23)

17.2g of compound (MI-23) was obtained by the same procedure as in Synthesis example 1, except that compound (MI-23-3) was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1.

[ Synthesis example 24: synthesis of Compound (MI-24)

Compound (MI-24) was synthesized according to scheme 24 below.

[ solution 43]

Synthesis of Compound (M-24-1)

In a 500mL eggplant-shaped flask equipped with a stirrer, 10.0g of 4'- (4,4, 4-trifluorobutyl) - [1,1' -bis (cyclohexane) ] -4-carboxylic acid, 37g of thionyl chloride and 0.02g of N, N-dimethylformamide were added, and the mixture was stirred at 60 ℃ for 2 hours. Thereafter, excess thionyl chloride was removed by a diaphragm pump, and 250g of tetrahydrofuran was added to prepare a solution a.

A1000 mL three-necked flask equipped with a stirrer was charged with 6.8g of hydroquinone, 140g of tetrahydrofuran, and 4.9g of pyridine again, and subjected to ice-bath. Solution a was added dropwise thereto and stirred at room temperature for 8 hours. The reaction solution was reprecipitated with 2500mL of water, and the obtained white solid was dried under vacuum. Extraction was performed with ethyl acetate, and purification was performed with a silica gel column using hexane/ethyl acetate as a developing solvent. After the solvent was removed by a rotary evaporator, vacuum drying was performed, whereby 3.8g of compound (M-24-1) was obtained.

Synthesis of Compound (MI-24)

1.77g of (E) -3- (4- (2, 5-dioxo-2, 5-dihydro-1H-pyrrol-1-yl) phenyl) acrylic acid, 8.7g of thionyl chloride and 0.01g of N, N-dimethylformamide were added, and the mixture was stirred at 60 ℃ for 2 hours. Thereafter, excess thionyl chloride was removed by a diaphragm pump, and 50g of tetrahydrofuran was added to prepare a solution B.

In a 100mL three-necked flask equipped with a stirrer were again added 3.0g of the compound (M-24-1), 25g of tetrahydrofuran and 1.2g of pyridine, and ice-bath was performed. Solution B was added dropwise thereto and stirred at room temperature for 8 hours. The reaction solution was reprecipitated with 1000mL of water, and the obtained white solid was dried under vacuum, whereby 3.7g of compound (MI-24) was obtained.

[ Synthesis example 25]

Compound (MI-25) was synthesized according to scheme 25 below.

[ solution 44]

Synthesis of Compound (M-25-1)

Synthesis example 18 was carried out in the same manner as in the above example except for using methyl 6-hydroxy-2-naphthoate in place of methyl 4-hydroxybenzoate to obtain 30.1g of a compound (M-25-1).

Synthesis of Compound (M-25-2)

Synthesis example 18 was carried out in the same manner as in the above example except for using the compound (M-25-1) in place of the compound (M-18-2), thereby obtaining 15.0g of the compound (M-25-2).

Synthesis of Compound (MI-25)

13.5g of compound (MI-25) was obtained by the same method as in Synthesis example 1, except that compound (M-25-2) was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid in Synthesis example 1.

[ Synthesis example 26: synthesis of Compound (MI-26) ]

14.2g of a compound (MI-26) was obtained in the same manner as in Synthesis example 1, except that 3-hydroxyphenylmaleimide was used in place of 4-hydroxyphenylmaleimide in Synthesis example 1.

[ Synthesis example 27: synthesis of Compound (MI-27) ]

Compound (MI-27) was synthesized according to scheme 27 below.

[ solution 45]

Synthesis of Compound (M-27-1)

In a 2000mL three-necked flask equipped with a stirrer, 6.90g of (4-aminophenyl) ethanol was taken, and 200g of tetrahydrofuran was added and ice-cooled. A solution containing 5.11g of maleic anhydride and 200g of tetrahydrofuran was added dropwise thereto, and stirred at room temperature for 3 hours. Thereafter, the precipitated solid was recovered by filtration. The solid was vacuum-dried, whereby 11.5g of compound (M-27-1) was obtained.

Synthesis of Compound (M-27-2)

In a 500mL three-necked flask equipped with a stirrer, 10.9g of the compound (M-27-1), 9.38g of zinc (II) chloride and 250g of toluene were added, and the mixture was heated and stirred at 80 ℃. A solution containing 14.8g of bis (trimethylsilyl) amine and 100g of toluene was added dropwise thereto, and stirred at 80 ℃ for 5 hours. Then, 300g of ethyl acetate was added to the reaction solution, and liquid separation washing with 1mol/L hydrochloric acid, 1 time of liquid separation washing with an aqueous sodium hydrogencarbonate solution, and 1 time of liquid separation washing with a saturated saline solution were performed 2 times. Thereafter, the organic layer was slowly concentrated by a rotary evaporator until the content was 50g, and a white solid precipitated in the course of the concentration was collected by filtration. The white solid was vacuum-dried, whereby 5.86g of compound (M-27-2) was obtained.

Synthesis of Compound (MI-27)

In a 100mL eggplant type flask equipped with a stirrer were added 9.37g of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid, 25g of thionyl chloride, 0.02g of N, N-dimethylformamide, and stirred at 80 ℃ for 1 hour. Thereafter, excess thionyl chloride was removed by a diaphragm pump to obtain a compound (M-27-3). 100g of tetrahydrofuran was added thereto to prepare a solution A.

In a 500mL three-necked flask equipped with a stirrer were again added 4.34g of the compound (M-27-2), 200g of tetrahydrofuran and 2.58g of triethylamine, and an ice bath was made. Solution a was added dropwise thereto and stirred at room temperature for 3 hours. The reaction solution was reprecipitated with 800mL of water, and the obtained white solid was dried under vacuum, whereby 8.78g of compound (MI-27) was obtained.

[ Synthesis example 28: synthesis of Compound (MI-28)

Compound (MI-28) was synthesized according to scheme 28 below.

[ solution 46]

24.1g of compound (MI-28) was obtained in the same manner as in the synthesis of compound (MI-27) of Synthesis example 27, except that 1- [4- (hydroxymethyl) phenyl ] pyrrole-2, 5-dione was used as a starting material in place of compound (M-27-3) and compound (M-27-2) in the synthesis of compound (MI-27) of Synthesis example 27.

Synthesis example 29: synthesis of Compound (MI-29) ]

Compound (MI-29) was synthesized according to scheme 29 below.

[ solution 47]

Synthesis of Compound (M-29-1)

In a 2000mL three-necked flask equipped with a stirrer, 15.1g of 4- (4-aminophenyl) propan-1-ol and 1000g of tetrahydrofuran were taken, and 15.2g of triethylamine was added to make an ice bath. A solution containing 26.1g of tert-butyl dicarbonate and 100g of tetrahydrofuran was added dropwise thereto, and stirred at room temperature for 10 hours, after which 300g of ethyl acetate was added to the reaction solution, and 4 times of liquid-separation washing was performed with 200g of distilled water. Thereafter, the organic layer was slowly concentrated by a rotary evaporator until the content was 100g, and a white solid precipitated in the course of the concentration was collected by filtration. The white solid was vacuum-dried, whereby 23.6g of compound (M-29-1) was obtained.

Synthesis of Compounds (M-29-2) to (M-29-4)

Synthesis example 3 was repeated in the same manner with the exception that compound (M-29-1) was used instead of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid and N-Boc-4-hydroxyaniline as raw materials in Synthesis example 3 to obtain 30.0g of compound (M-29-4).

Synthesis of Compound (MI-29)

In a 2000mL three-necked flask equipped with a stirrer, 30.0g of the compound (M-29-4), 8.79g of zinc (II) chloride, and 250g of toluene were added, and the mixture was heated and stirred at 80 ℃. A solution containing 13.8g of bis (trimethylsilyl) amine and 100g of toluene was added dropwise thereto, and stirred at 80 ℃ for 5 hours. Then, 300g of ethyl acetate was added to the reaction solution, and liquid separation washing with 1mol/L hydrochloric acid, 1 time of liquid separation washing with an aqueous sodium hydrogencarbonate solution, and 1 time of liquid separation washing with a saturated saline solution were performed 2 times. Thereafter, the organic layer was slowly concentrated by a rotary evaporator until the content was 50g, and a white solid precipitated in the course of the concentration was collected by filtration. The white solid was vacuum-dried, whereby 9.18g of the compound (MI-29) was obtained.

[ Synthesis example 30: synthesis of Compound (MI-30)

Compound (MI-30) was synthesized according to scheme 30 below.

[ solution 48]

Synthesis of Compound (M-30-1)

In a 500mL three-necked flask equipped with a stirrer, 20.9g of N-Boc-4-hydroxyaniline, 15.0g of 2-bromoethanol, 20.7g of potassium carbonate, and 250mL of N, N-dimethylformamide were added, and reacted at 60 ℃ for 4 hours. After the reaction, the reaction solution was poured into 1500mL of distilled water, and the precipitated solid was collected by filtration. Thereafter, the solid was vacuum-dried, whereby 24.8g of the compound (M-30-1) was obtained.

Synthesis of Compound (MI-30)

32.0g of compound (MI-30) was obtained in the same manner as in Synthesis example 29, except that compound (M-30-1) was used as a starting material in place of compound (M-29-1) in the syntheses of compounds (M-29-1) to (M-29-4) and (MI-29) in Synthesis example 29.

[ Synthesis example 31: synthesis of Compound (MI-31) ]

In synthesis example 27, 14.4g of compound (MI-31) was obtained by a similar method to synthesis example 27, except that (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid was used in place of (E) -3- (4- ((4'- (4,4, 4-trifluorobutyl) - [1,1' -bi (cyclohexane) ] -4-carbonyl) oxy) phenyl) acrylic acid as a raw material.

Comparative example Synthesis examples 1 and 2

Compound (MI-32) was synthesized according to the method described in Japanese patent No. 4296821, and Compound (MI-33) was synthesized according to the method described in Japanese patent No. 3055062.

[ Synthesis example 32: synthesis of Compound (MI-34) ]

Compound (MI-34) was obtained in the same manner as Compound (MI-15) except that methacrylic acid was used instead of acrylic acid in Synthesis example 15 (see scheme 32 below).

[ solution 49]

Synthetic example 33: synthesis of Compound (MI-35) ]

Compound (MI-35) was obtained by the same method as Compound (MI-15) except that in Synthesis example 15, 4-hydroxy-3-methylphenylmaleimide was used in place of 4-hydroxyphenylmaleimide (see scheme 33 below).

[ solution 50]

[ Synthesis example 34: synthesis of Compound (MI-36)

Compound (MI-36) was obtained in the same manner as Compound (MI-15) except that in Synthesis example 15, methacrylic acid was used in place of acrylic acid, and 4-hydroxy-3-methylphenylmaleimide was used in place of 4-hydroxyphenylmaleimide.

[ Synthesis example 35: synthesis of Compound (MI-37)

Compound (MI-37) was obtained in the same manner as in compound (MI-34) except that pentyltriphenylphosphonium iodide was used in place of 4,4, 4-trifluorobutyltriphenylphosphonium iodide in the synthesis of compound (MI-34) (see scheme 35 below).

[ solution 51]

[ Synthesis example 36: synthesis of Compound (MI-38)

Compound (MI-38) was obtained in the same manner as compound (MI-35) except that pentyltriphenylphosphonium iodide was used in place of 4,4, 4-trifluorobutyltriphenylphosphonium iodide in the synthesis of compound (MI-35).

[ Synthesis example 37: synthesis of Compound (MI-39) ]

Compound (MI-39) was obtained in the same manner as compound (MI-36) except that pentyltriphenylphosphonium iodide was used in place of 4,4, 4-trifluorobutyltriphenylphosphonium iodide in the synthesis of compound (MI-36).

[ Synthesis example 38: synthesis of Compound (MI-40) ]

Compound (MI-40) was obtained in the same manner as Compound (MI-37) except that 2- (trifluoromethyl) acrylic acid was used in place of methacrylic acid in the synthesis of Compound (MI-37).

[ Synthesis example 39: synthesis of Compound (MI-41)

Compound (MI-41) was obtained in the same manner as compound (MI-15) except that 4-hydroxy-3-methoxyphenylmaleimide was used in place of 4-hydroxyphenylmaleimide in Synthesis example 15. Furthermore, 4-hydroxy-3-methoxyphenylmaleimide was synthesized by using 4-hydroxy-3-methoxyaniline in place of 4-hydroxycyclohexylamine in the synthesis of the compound (M-2-1) of Synthesis example 2.

Synthesis example 40: synthesis of Compound (MI-42) ]

Compound (MI-42) was obtained in the same manner as compound (MI-37) except that 4-hydroxy-3-fluorophenylmaleimide was used in place of 4-hydroxyphenylmaleimide in the synthesis of compound (M-37). Furthermore, 4-hydroxy-3-fluorophenylmaleimide was synthesized by using 3-fluoro-4-hydroxyaniline in place of 4-hydroxycyclohexylamine in the synthesis of compound (M-2-1) of Synthesis example 2.

[ Synthesis example 41: synthesis of Compound (MI-43)

Compound (MI-43) was obtained in the same manner as Compound (MI-36) except that 2-fluoroacrylic acid was used in place of methacrylic acid in the synthesis of Compound (M-36).

< Synthesis of Polymer >

Examples 1 to 1: synthesis of Polymer (P-1)

5.00g (7.5mmol) of the compound (MI-27) obtained in Synthesis example 27, 1.05g (7.5mmol) of the compound (A-3), 4.80g (33.8mmol) of the compound (D-1), and 2.26g (26.3mmol) of the compound (D-4), 0.39g (1.6mmol) of 2,2' -azobis (2, 4-dimethylpentanenitrile) as a radical polymerization initiator, 0.39g (1.7mmol) of 2, 4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 52.5mL of N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP) as a solvent were added as polymerization monomers under nitrogen in a 100mL two-necked flask, and polymerized at 70 ℃ for 6 hours. After reprecipitation in methanol, the precipitate was filtered and vacuum-dried at room temperature for 8 hours, thereby obtaining the objective polymer (P-1). The weight average molecular weight Mw measured by polystyrene conversion using GPC was 30000 and the molecular weight distribution Mw/Mn was 2.

Examples 1-2 to examples 1-45 and comparative polymerization examples 1-1 to 1-8

Polymerization was carried out in the same manner as in example 1-1 except that the kinds and molar ratios of the polymerizable monomers shown in tables 7 and 8 below were changed to obtain polymers (P-2) to (P-45) and polymers (R-1) to (R-8) each having a weight average molecular weight and a molecular weight distribution equivalent to those of polymer (P-1). The total molar number of the polymerized monomers was 75.1mmol in the same manner as in example 1-1. The values in tables 7 and 8 represent the amounts of the monomers charged [ mol% ] relative to all the monomers used in the synthesis of the polymer.

[ Table 7]

[ Table 8]

Synthesis example 42: synthesis of Polyamic acid

11.0g (49.0mmol) of 2,3, 5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 10.0g (50.0mmol) of 4,4' -methylenedianiline as diamine were dissolved in 84g of NMP and reacted at 60 ℃ for 24 hours, thereby obtaining a solution containing 20 mass% of polyamic acid. Then, the polyamic acid solution was poured into a large excess of methanol and the reaction product was precipitated. The precipitate was washed with methanol and dried at 40 ℃ for 15 hours under reduced pressure, thereby obtaining polyamic acid (PAA).

< production and evaluation of optical vertical liquid Crystal display element >

[ example 2-1]

1. Preparation of liquid Crystal Aligning agent (AL-1)

NMP and Butyl Cellosolve (BC) were added as solvents to a container containing 10 parts by mass of the polymer (P-1) obtained in example 1-1 and 100 parts by mass of polyamic acid (PAA), to prepare a solution having a solvent composition of NMP/BC 50/50 (mass ratio) and a solid content concentration of 3.5 mass%. The solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal aligning agent (AL-1).

2. Manufacture of optical vertical liquid crystal display element

The prepared liquid crystal aligning agent (AL-1) was coated on the transparent electrode surface of the glass substrate with the transparent electrode including the ITO film using a spinner, and pre-baked at a hot plate of 80 ℃ for 1 minute. Thereafter, the resultant was heated at 230 ℃ for 1 hour in an oven in which the inside of the chamber was replaced with nitrogen gas, thereby forming a coating film having a thickness of 0.1 μm. Then, the surface of the coating film was irradiated with 1,000J/m of a bright line including 313nm from a direction inclined at 40 ℃ from the normal line of the substrate by using an Hg-Xe lamp and a Glan-Taylor prism (glan-taylor prism)²The polarizing ultraviolet ray of (2) imparts alignment ability to the liquid crystal. The same operation was repeated to produce a pair (two) of substrates having liquid crystal alignment films.

An epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was applied to the outer periphery of the surface having the liquid crystal alignment film of one of the substrates by screen printing, and then the liquid crystal alignment films of the pair of substrates were opposed to each other, and pressure-bonded so that the optical axes of the ultraviolet rays of the respective substrates were antiparallel to the projection direction of the substrate surfaces, and the adhesive was heat-cured at 150 ℃ for 1 hour. Then, a negative type liquid crystal (MLC-6608, manufactured by Merck) was filled in the gap between the substrates from the 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 mixture was heated at 130 ℃ and then gradually cooled to room temperature. Next, polarizing plates were bonded to both outer surfaces of the substrate so that the polarization directions of the polarizing plates were orthogonal to each other and that an angle of 45 ° was formed between the optical axis of the ultraviolet ray of the liquid crystal alignment film and the projection direction of the substrate surface, thereby producing a liquid crystal display element.

3. Evaluation of Voltage Holding Ratio (VHR)

In the liquid crystal display element manufactured in the 2, after a voltage of 5V was applied for an application time of 60 microseconds and a span (span) of 167 milliseconds, a voltage holding ratio after 167 milliseconds from the release of the application was measured. The measurement apparatus was VHR-1 manufactured by TOYO Technical (TOYO). In this case, the voltage holding ratio is "good (a)" when it is 90% or more, is "good (B)" when it is 70% or more and less than 90%, and is "poor (C)" when it is less than 70%. As a result, the voltage holding ratio in the example was evaluated as "excellent (a)".

4. Evaluation of pretilt Angle

In the liquid crystal display element manufactured in the above 2, a value of an inclination angle of liquid crystal molecules with respect to a substrate surface is measured by a crystal rotation method using a He — Ne laser according to a method described in non-patent document (Journal of Applied Physics, j.appl.phys.) "2013 (1980) of Journal of Applied Physics, j.appl.phys., et al, and the value is set as a pretilt angle. In this case, "good (a)" is obtained when the pretilt angle is 85.0 ° or more and less than 88.0 °, "good (B)" is obtained when the pretilt angle is 88.0 ° or more and less than 89.0 °, and "poor (C)" is obtained when the pretilt angle is 89.0 ° or more or less than 85.0 °. As a result, in the examples, the pretilt angle was evaluated as "good (B)".

Evaluation of AC afterimage characteristics

The liquid crystal display element manufactured in the above 2 was driven at an ac voltage of 15V for 20 hours, and then the pretilt angle was measured, and the difference in tilt Δ θ was obtained by the following equation (1).

Δθ＝θ1-θ2…(1)

(in equation (1), θ 1 is the pretilt angle before driving, and θ 2 is the pretilt angle after driving)

"good (a)" is set when Δ θ is 0.05 ° or less, "good (B)" is set when Δ θ is greater than 0.05 ° and less than 0.10 °, and "poor (C)" is set when Δ θ is 0.10 ° or more. As a result, the evaluation of "good (A)" in the examples was conducted.

Example 2-2 to example 2-49 and comparative example 2-1 to comparative example 2-8

Liquid crystal aligning agents were obtained in the same solid content concentrations as in example 1, except that the formulation compositions were changed as shown in tables 9 to 11 below. Further, an optical homeotropic liquid crystal display element was produced using each liquid crystal aligning agent in the same manner as in example 2-1, and various evaluations were performed. These results are shown in tables 9 to 11 below. In examples 2 to 8 and 2 to 24, the compound (ad-1) and the compound (ad-2) were respectively blended as additives into liquid crystal aligning agents.

[ Table 9]

[ Table 10]

[ Table 11]

As shown in tables 9 to 11, in examples 2-1 to 2-49 using the liquid crystal aligning agent containing the polymer (P), the voltage holding ratio was "A" or "B". In addition, the pretilt angle characteristics and the AC afterimage characteristics are also "a" or "B", and at least one is evaluated as "a", the electrical characteristics, the pretilt angle characteristics, and the AC afterimage characteristics are well-balanced and improved. On the other hand, the results of comparative examples 2-1 to 2-8 using the liquid crystal aligning agent containing no polymer (P) were inferior to those of examples 2-1 to 2-49. In comparative examples 2-2 and 2-4, the pretilt angle was evaluated as "C", but the pretilt angles thereof were high at 89 ℃ or higher.

Claims

1. A liquid crystal aligning agent comprising a polymer (P) having: a structural unit U1 derived from a compound represented by the following formula (1); and a structural unit U2 which is a structural unit derived from a compound having a partial structure represented by the following formula (2), formula (3), formula (4) or formula (5), and which is different from the structural unit U1:

(E¹)_i-(G¹)_j…(1)

(in the formula (1), G¹A group having a cyclic structure exhibiting crosslinkability, a group having an aromatic condensed polycyclic structure, or a group having a nitrogen-containing heterocyclic structure; e¹At least one carbon atom forming a polymerizable carbon-carbon unsaturated bond and G as a group having a polymerizable carbon-carbon unsaturated bond¹The ring having a cyclic structure, an aromatic condensed polycyclic structure or a nitrogen-containing heterocyclic structure exhibiting crosslinkability is bonded by a single bond or via a group of-COO-, -CONR⁵⁰-、**-CH₂-CONR⁵⁰-, -O-, or phenylene (wherein "-" represents a bond to a carbon atom forming a polymerizable carbon-carbon unsaturated bond); r⁵⁰Is a hydrogen atom, or represents R⁵⁰A ring structure formed by bonding with other groups; one of i and j is 1 and the other is 2, or i ═ j ═ 1)

[ solution 1]

(in the formula (2), R¹Is a monovalent organic group having 1 or more carbon atoms, R²And R³Each independently is a hydrogen atom or a methyl group; in the formula (3), R⁴Is a monovalent organic group having 1 or more carbon atoms, R⁵Is hydrogen atom or C1 or more monovalent organic group, R⁶And R⁷Each independently is a hydrogen atom or a methyl group; in the formula (4), R⁸Is a monovalent organic group having 1 or more carbon atoms, R¹¹Is hydrogen atom or C1 or more monovalent organic group, R⁹And R¹⁰Each independently is a hydrogen atom or a methyl group; x¹⁰And X¹¹One of them is a single bond and the other is a methylene group; in the formula (5), R¹²Is a monovalent organic group having 1 or more carbon atoms, R¹³And R¹⁴Each independently being a hydrogen atom or AA base).

2. The liquid crystal aligning agent according to claim 1, wherein the polymer (P) has at least one of an oxetanyl group and an oxetanyl group (excluding the oxetanyl group and the oxetanyl group of the structural unit U1).

3. The liquid crystal aligning agent according to claim 2, wherein the polymer (P) has a functional group that reacts with at least one of an oxetanyl group and an oxetanyl group by heating.

4. The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the polymer (P) has at least one selected from the group consisting of a carboxyl group, a protected carboxyl group, an amino group and a protected amino group.

5. The liquid crystal aligning agent according to any one of claims 1 to 4, further comprising at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.

6. The liquid crystal aligning agent according to any one of claims 1 to 5, wherein the polymer (P) is a polymer having photo-aligning groups.

7. The liquid crystal aligning agent according to any one of claims 1 to 5, wherein the structural unit U2 is a structural unit derived from a compound represented by the following formula (6):

[ solution 2]

(in the formula (6), B¹Is a monovalent group represented by the following formula (7), formula (8), formula (9) or formula (10), D¹Is a divalent group represented by the following formula (11), X¹And X²Independently represents a single bond, -CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-、-S-CO-、-O-CH₂-、-CH₂-O-or alkanediyl having 1 to 3 carbon atoms, A¹And A²Each independently being substituted or unsubstituted phenylene, cyclohexylene or naphthylene, R¹⁸Is alkyl, alkoxy, fluoroalkyl, fluoroalkoxy or-R with 2-20 carbon atoms¹⁹-Y¹(wherein, R¹⁹Is an alkanediyl group having 2 to 20 carbon atoms, Y¹Is a trialkylsilyl group); m is an integer of 0 to 2, and n is an integer of 1 to 3; in the case where m is 2, a plurality of A¹、X¹Each independently has the definition; in case n is 2 or 3, a plurality of R¹⁸Each independently having the definition

[ solution 3]

[ solution 4]

(in formula (11), A³、A⁴And A⁵Each independently being a substituted or unsubstituted phenylene or cyclohexylene group, L¹And L²Independently represents a single bond, an alkanediyl group having 1 to 5 carbon atoms or a group wherein at least one methylene group of the alkanediyl group is substituted with "-O-" (wherein oxygen atoms are not continuous), X³And X⁴Independently of each other-CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO-or-O-, R¹⁶And R¹⁷Each independently is a hydrogen atom, a methyl group, a halogen atom or a cyano group(ii) a k and r are each independently 0 or 1; "*¹' and²"represents a bond; wherein, includes¹And B¹The condition of bonding, and²and B¹In the case of a bond).

8. The liquid crystal aligning agent according to any one of claims 1 to 7, wherein the structural unit U2 has a partial structure represented by the following formula (b-1):

[ solution 5]

(in the formula (b-1), A⁶、A⁷And A⁸Each independently being substituted or unsubstituted 1, 4-cyclohexylene or 1, 4-phenylene, X⁵Is a single bond or an oxygen atom, R⁸⁰Is fluoromethyl or methyl, a1 is an integer of 0-2, a2 is an integer of 1-20, a3 is 0 or 1; wherein, in R⁸⁰In the case of methyl, a1 ═ 0; "" indicates a bond).

9. A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 8.

10. A liquid crystal cell comprising the liquid crystal alignment film according to claim 9.

11. A polymer body having: a structural unit U1 derived from a compound represented by the following formula (1); and a structural unit U2 which is a structural unit derived from a compound having a partial structure represented by the following formula (2), formula (3), formula (4) or formula (5), and which is different from the structural unit U1:

(E¹)_i-(G¹)_j…(1)

(in the formula (1), G¹A group having a cyclic structure exhibiting crosslinkability, a group having an aromatic condensed polycyclic structure, or a group having a nitrogen-containing heterocyclic structure; e¹To be provided withA group of polymerizable carbon-carbon unsaturated bond, at least one carbon atom forming the polymerizable carbon-carbon unsaturated bond and G¹The ring having a cyclic structure, an aromatic condensed polycyclic structure or a nitrogen-containing heterocyclic structure exhibiting crosslinkability is bonded by a single bond or via a group of-COO-, -CONR⁵⁰-、**-CH₂-CONR⁵⁰-, -O-, or phenylene (wherein "-" represents a bond to a carbon atom forming a polymerizable carbon-carbon unsaturated bond); r⁵⁰Is a hydrogen atom, or represents R⁵⁰A ring structure formed by bonding with other groups; one of i and j is 1 and the other is 2, or i ═ j ═ 1)

[ solution 6]

12. A compound represented by the following formula (6):

[ solution 7]

(in the formula (6), B¹Is a monovalent group represented by the following formula (7), formula (8), formula (9) or formula (10),D¹is a divalent group represented by the following formula (11), X¹And X²Independently represents a single bond, -CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO-, -O-CH₂-、-CH₂-O-or alkanediyl having 1 to 3 carbon atoms, A¹And A²Each independently being substituted or unsubstituted phenylene, cyclohexylene or naphthylene, R¹⁸Is alkyl, alkoxy, fluoroalkyl, fluoroalkoxy or-R with 2-20 carbon atoms¹⁹-Y¹(wherein, R¹⁹Is an alkanediyl group having 2 to 20 carbon atoms, Y¹Is a trialkylsilyl group); m is an integer of 0 to 2, and n is an integer of 1 to 3; in the case where m is 2, a plurality of A¹、X¹Each independently has the definition; in case n is 2 or 3, a plurality of R¹⁸Each independently having the definition

[ solution 8]

(in the formula (7), R²And R³Each independently is a hydrogen atom or a methyl group; in the formula (8), R⁵Is hydrogen atom or C1 or more monovalent organic group, R⁶And R⁷Each independently is a hydrogen atom or a methyl group; in the formula (9), R¹¹Is hydrogen atom or C1 or more monovalent organic group, R⁹And R¹⁰Each independently is a hydrogen atom or a methyl group; x¹⁰And X¹¹One of them is a single bond and the other is a methylene group; in the formula (10), R¹³And R¹⁴Each independently is a hydrogen atom or a methyl group; "+" indicates a bond)

[ solution 9]

(in formula (11), A³、A⁴And A⁵Each independently being a substituted or unsubstituted phenylene or cyclohexylene group, L¹And L²Independently represents a single bond, an alkanediyl group having 1 to 5 carbon atoms or the alkanediyl groupA group in which at least one methylene group of the group is substituted by "-O-" (wherein the oxygen atoms are not continuous), X³And X⁴Independently of each other-CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO-or-O-, R¹⁶And R¹⁷Each independently is a hydrogen atom, a methyl group, a halogen atom or a cyano group; k and r are each independently 0 or 1; "*¹' and²"represents a bond; wherein, includes¹And B¹The condition of bonding, and²and B¹In the case of a bond).