TWI810273B - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, polymer and compound - Google Patents

Abstract

The liquid crystal alignment agent contains a polymer (P), and the polymer (P) has: a structural unit U1 derived from a compound represented by formula (1); and a structural unit U2 derived from a compound represented by formula (2), formula (3), a structural unit of a compound having a partial structure represented by formula (4) or formula (5), and is different from structural unit U1. ^G1 is a group having a cyclic structure showing crosslinkability, a group having an aromatic condensed polycyclic structure, or a group having a nitrogen-containing heterocyclic structure. ^E1 is a group having a polymerizable carbon-carbon unsaturated bond, and the carbon atom of the polymerizable carbon-carbon unsaturated bond and ^G1 have a cross-linkable ring structure, an aromatic condensed polycyclic structure, or a group containing The rings of the azacyclic structure are bonded via a single bond or -COO- or the like. (E ¹ ) _i -(G ¹ ) _j ... (1)

Description

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

The disclosure relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal element, a polymer and a compound.

[Cross-reference to related applications]

This application is based on Japanese Patent Application No. 2018-80881 filed on April 19, 2018, and the contents described therein are incorporated herein by reference.

Liquid crystal elements are used in various applications represented by display devices such as televisions, personal computers, and smartphones. These liquid crystal elements include a liquid crystal alignment film capable of aligning liquid crystal molecules in a certain direction. Usually, the liquid crystal alignment film is formed on the substrate by applying a liquid crystal alignment agent obtained by dissolving polymer components in an organic solvent on the substrate, preferably by heating. As the polymer component of the liquid crystal alignment agent, polyamic acid or soluble polyimide is widely used in terms of mechanical strength, liquid crystal alignment, and affinity with liquid crystals (for example, refer to Patent Document 1 or Patent Document 2).

[Prior art literature]

[Patent Document]

[Patent Document 1] International Publication No. 2012/176822

[Patent Document 2] Japanese Patent Laid-Open No. 2017-138575

If the alignment restriction force of the liquid crystal molecules brought by the liquid crystal alignment film is weak, when the liquid crystal element is operated for a long time, the direction of the initial alignment will deviate from the initial direction of the liquid crystal element manufacturing, and sometimes a phenomenon called alternating current (alternating) will occur. current, AC) burn-in of the afterimage. In particular, when a liquid crystal alignment film is obtained by photo-alignment treatment, compared with rubbing treatment, the alignment-regulating force of liquid crystal molecules is not sufficient, and AC afterimage tends to easily occur. As a liquid crystal element, in order to meet the demand for further performance improvement in recent years, in addition to sufficiently reducing AC afterimages, it is desired to have excellent electrical characteristics (high voltage holding ratio), which are basic characteristics of liquid crystal elements.

This indication is made in view of the said situation, and one of the objects is to provide the liquid crystal aligning agent which can obtain the liquid crystal element which showed high voltage retention and reduced AC afterimage.

According to the present disclosure, the following methods are provided.

[1] A liquid crystal alignment agent, which contains a polymer (P), and the polymer (P) has: a structural unit U1 derived from a compound represented by the following formula (1); and a structural unit U2 derived from A structural unit of a compound having a partial structure represented by the following formula (2), formula (3), formula (4) or formula (5), and is different from the structural unit U1: (E ¹ ) _i -(G ¹ ) _j …(1)

(In formula (1), G ¹ is a group having a cyclic structure showing crosslinkability, a group having an aromatic condensed polycyclic structure, or a group having a nitrogen-containing heterocyclic structure; E ¹ is a group having a polymerizable carbon - A carbon unsaturated bond group, at least one carbon atom forming a polymerizable carbon-carbon unsaturated bond and a cyclic structure showing crosslinkability, an aromatic condensed polycyclic structure, or a nitrogen-containing heterocyclic structure possessed by ^G1 The ring of is bonded by a single bond, or via **-COO-, **-CONR ⁵⁰ -, **-CH ₂ -CONR ⁵⁰ -, -O- or phenylene (wherein, "**" represents bonded to a carbon atom that forms a polymerizable carbon-carbon unsaturated bond); R ⁵⁰ is a hydrogen atom, or represents a ring structure formed by bonding R ⁵⁰ to other groups; in i and j, where one is 1 and the other is 2, or i=j=1)

(In formula (2), R ¹ is a monovalent organic group with more than 1 carbon number, R ² and R ³ are each independently a hydrogen atom or a methyl group; in formula (3), R ⁴ is a monovalent organic group with more than 1 carbon number A valent organic group, R ⁵ is a hydrogen atom or a monovalent organic group with more than 1 carbon number, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group; in formula (4), R ⁸ is a monovalent organic group with more than 1 carbon number A valent organic group, R ¹¹ is a hydrogen atom or a monovalent organic group with more than 1 carbon number, R ⁹ and R ¹⁰ are independently a hydrogen atom or a methyl group; one of X ¹⁰ and X ¹¹ is a single bond, and the other Those are methylene groups; in formula (5), R ¹² is a monovalent organic group with more than 1 carbon number, R ¹³ and R ¹⁴ are independently a hydrogen atom or a methyl group).

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

[3] A liquid crystal element including the liquid crystal alignment film of the above [2].

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

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

(In formula (6), B ¹ is a monovalent group represented by the following formula (7), formula (8), formula (9) or formula (10), D ¹ is represented by the following formula (11) Divalent group, X ¹ and X ² are independently single bond, -CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO -, -O-CH ₂ -, -CH ₂ -O- or alkanediyl with 1~3 carbons, A ¹ and A ² are independently substituted or unsubstituted phenylene, cyclohexylene or Naphthyl, R ¹⁸ is alkyl, alkoxy, fluoroalkyl, fluoroalkoxy or -R ¹⁹ -Y ¹ with 2 to 20 carbons (wherein, R ¹⁹ is alkanediyl with 2 to 20 carbons , Y ¹ is a trialkylsilyl group); m is an integer of 0 to 2, and n is an integer of 1 to 3; when m is 2, multiple A ¹ and X ¹ independently have the above definitions; In the case where n is 2 or 3, a plurality of R ¹⁸ each independently have the above definition)

(In formula (7), R ² and R ³ have the same meaning as the formula (2); in formula (8), R ⁵ , R ⁶ and R ⁷ have the same meaning as the formula (3); In formula (9), R ⁹ , R ¹⁰ , R ¹¹ , X ¹⁰ and X ¹¹ have the same meanings as those in formula (4); in formula (10), R ¹³ and R ¹⁴ have the same meanings as in formula (5) respectively. ) have the same meaning; "*" means a bond key)

(In formula (11), A ³ , A ⁴ and A ⁵ are each independently substituted or unsubstituted phenylene or cyclohexylene, L ¹ and L ² are each independently a single bond, carbon number 1~ 5's alkanediyl group, or at least one methylene group of said alkanediyl group substituted by "-O-" (wherein the oxygen atoms are not continuous), ^X3 and ^X4 are independently -CO-O -, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO- or -O-, R ¹⁶ and R ¹⁷ are independently hydrogen atom, methyl , a halogen atom or a cyano group; k and r are independently 0 or 1; "* ¹ " and "* ² "represent bonding bonds; among them, including the case where "* ¹ " is bonded to B ¹ , and "* ² ” in the case of bonding with B ¹ ).

According to the liquid crystal alignment agent containing a polymer [P], the liquid crystal element which shows high voltage retention and has reduced AC afterimage can be obtained.

"Liquid Crystal Alignment Agent"

The liquid crystal alignment agent disclosed in the present disclosure contains a polymer (P), and the polymer (P) has: a structural unit U1 derived from the compound represented by the formula (1); and a structural unit U2 derived from the compound represented by the formula (1); The structural unit of the compound of the partial structure represented by formula (2), formula (3), formula (4) or formula (5) is different from the structural unit U1. Hereinafter, the components contained in the liquid crystal alignment agent of this disclosure, and other components arbitrarily blended as needed are demonstrated.

In addition, in this specification, the term "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The term "chain hydrocarbon group" refers to a straight chain hydrocarbon group and a branched hydrocarbon group that does not contain a cyclic structure in the main chain but only consists of a chain structure. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group including only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. Among them, it is not necessary to consist only of the structure of alicyclic hydrocarbon, and it is also included that it has a chain structure in a part of it. By. The "aromatic hydrocarbon group" refers to a hydrocarbon group including an aromatic ring structure as a ring structure. However, it is not necessary to consist only of an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in a part thereof.

<Polymer (P)>

． About structural unit U1

In the above formula (1), when ^G is a group having a cyclic structure showing crosslinkability, the cyclic structure is preferably formed between the same or different molecules by heat or light. The base of the covalent bond. Specific examples of ^G1 being a group having a cyclic structure showing crosslinkability include a group having a cyclic ether structure, a cyclic (thio)carbonate structure, a lactone structure, a lactamide structure, or an oxazole group. The base of the phylloline structure, etc. The cyclic ether structure is preferably oxirane (1,2-oxirane structure) or oxetanyl (1,3-propylene oxide structure), because of high reactivity by heat or light In terms of aspects, it is more preferably oxirane.

As a preferable specific example when ^G1 is a group having a cyclic structure showing crosslinkability, structures represented by the following formula (2-A-1) to formula (2-A-6) respectively can be mentioned .

(In formula (2-A-1) ~ formula (2-A-6), R ⁵¹ ~ R ⁵⁶ are each independently a monovalent substituent; r1, r3, r5, r7, r9 and r11 are each independently 0 An integer of ~2, r2, r4, r6, r8, and r10 are each independently an integer of 1 to 5; "*" represents a bond bonded to a carbon atom that forms a polymerizable carbon-carbon unsaturated bond in ^E1 key)

In the formulas (2-A-1) to (2-A-6), specific examples of R ⁵¹ to R ⁵⁶ include: methyl, ethyl, halogen atoms (for example, fluorine atoms, chlorine atoms , bromine atom, iodine atom, etc.) etc. r1, r3, r5, r7, r9 and r11 are preferably 0 or 1, more preferably 0.

Examples of aromatic condensed polycyclic structures include: aromatic hydrocarbon rings such as naphthalene rings, anthracene rings, and fluorene rings; naphthoquinone rings, anthraquinone rings, quinoline rings, quinazoline rings, benzimidazole rings, and indole rings; Aromatic heterocyclic rings such as rings, or structures in which substituents are introduced into the ring portions of these rings, and the like. As a substituent, a methyl group, an ethyl group, a halogen atom, a carboxyl group, a protected carboxyl group, an amino group, a protected amino group etc. are mentioned, for example. Among these, the aromatic condensed polycyclic structure is preferably a structure having a naphthalene ring, a fluorene ring, an anthracycline, 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 single ring or a condensed ring, for example, 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, benzomaleimide Nitrogen-containing heterocycles such as imides, and in A structure or the like in which a substituent is introduced into the nitrogen-containing heterocyclic ring. As this substituent, a C1-C5 alkyl group, an alkoxy group, etc. are mentioned, for example.

In the case where ^G is a monovalent group having a nitrogen-containing heterocyclic structure, preferred specific examples of ^G include: combining with pyrrole, imidazole, carbazole, purine, indole, morpholine, benzo The group obtained by removing the hydrogen atom bonded to the nitrogen atom of imidazole, dihydromaleimide or benzmaleimide; it will be combined with pyridine, pyrimidine, pyrazine, acridine, phenazine, quinoline, iso A group obtained by removing at least one hydrogen atom bonded to a carbon atom of quinoline, naphthyridine, isoxazole, 4,5-dihydrooxazole or benzoxazole, and the like.

In the above-mentioned formula (1), regarding the polymerizable carbon-carbon unsaturated bond possessed by ^E1 , at least one carbon atom forming the polymerizable carbon-carbon unsaturated bond and a ring structure showing crosslinkability, an aromatic The rings in the group condensed polycyclic structure or nitrogen-containing heterocyclic structure are bonded via single bonds, **-COO-, **-CONR ⁵⁰ -, **-CH ₂ -CONR ⁵⁰ -, -O- or phenylene groups Knot. Specifically, ^E1 is preferably any one of the groups respectively represented by the following formula (e-1) to formula (e-11).

[chemical 6]

(In formula (e-1) ~ formula (e-11), R ²⁰ ~ R ³⁴ , R ³⁶ ~ R ⁴⁰ , R ⁴² , R ⁴³ and R ⁴⁵ ~ R ⁴⁹ are independently a hydrogen atom or a methyl group; R ³⁵ , R ⁴¹ and R ⁴⁴ are each independently a hydrogen atom or a monovalent organic group with 1 or more carbons; "*3" represents the bond with the ring of G ¹ , and "*4" represents the bond with the ring of R ⁵⁰ bond key)

Specific examples of when R ³⁵ , R ⁴¹ , and R ⁴⁴ are monovalent organic groups include: a monovalent hydrocarbon group having 1 to 30 carbon atoms, at least one methylene group of which is via -O-, -CO-, - COO- or -NR ⁶⁰ - (wherein, R ⁶⁰ is a hydrogen atom or a monovalent hydrocarbon group. The same below) substituted group (hereinafter also referred to as "group α"), a monovalent hydrocarbon group or group α with 1 to 30 carbon atoms A group in which at least one hydrogen atom is replaced by a halogen atom, etc. R ³⁶ and R ⁴² are preferably a hydrogen atom or an alkyl group with 1-10 carbons, more preferably a hydrogen atom or an alkyl group with 1-3 carbons.

In terms of the aspect that can further improve the voltage holding ratio of the obtained liquid crystal element, the aspect that can further reduce the AC afterimage, and the aspect that the degree of freedom of selection of the monomer is high, among the above, E ¹ is preferably the above-mentioned formula Any of the groups represented by (e-1) to formula (e-4), more preferably any of the groups represented by the formula (e-1) to formula (e-3).

Both i and j are preferably 1.

As a specific example of the compound represented by the above-mentioned formula (1), as G1 is a compound having a group having a crosslinkable cyclic structure (hereinafter also referred to as "compound (G-1)"), for example, Examples include compounds represented by the following formula (1-1-1) to formula (1-1-18), compounds represented by the following formula ( ^1-3-11 ), etc.; Compounds having a polycyclic structure (hereinafter also referred to as "compound (G-2)") include, for example, compounds represented by the following formula (1-2-1) to formula (1-2-19), respectively etc.; as G ¹ is a compound having a nitrogen-containing heterocyclic structure (hereinafter also referred to as "compound (G-3)"), for example, the following formula (1-3-1) ~ formula (1- 3-18), the compounds represented by the formula (1-1-10), the formula (1-1-11), the formula (1-2-8) and the formula (1-2-9), etc. In addition, the polymer (P) may have the structural unit derived from 1 type of compound among these, and may have the structural unit derived from 2 or more types of compounds.

[chemical 7]

[chemical 8]

[chemical 9]

(In the formula, R is a hydrogen atom or a methyl group)

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

From the viewpoint of sufficiently obtaining the effect of improving the voltage retention ratio and the effect of reducing AC afterimages, the structure in the polymer (P) relative to the total amount of monomer-derived structural units contained in the polymer (P) The content ratio of the unit U1 is preferably at least 1 mol %, more preferably 3 mol % to 60 mol %, and still more preferably 4 mol % to 50 mol %.

． About structural unit U2

In the formulas (2) to ( ⁵ ), specific examples of monovalent organic groups for R and ^R can be applied to R in the formula (e- ⁶ ) and R in the formula (e-8). Illustration of ⁴¹ monovalent organic radicals.

Examples of monovalent organic groups for R ¹ , R ⁴ , R ⁸ and R ¹² include: monovalent hydrocarbon groups having 1 to 30 carbon atoms, at least one methylene group of the hydrocarbon group via -O-, -CO-, - COO- or -NR ⁶⁰ -substituted group α, a monovalent hydrocarbon group with 1 to 30 carbons or a group in which at least one hydrogen atom of the group α is replaced by a halogen atom, a monovalent group with a photoalignment group, and cross-linking base base etc.

By irradiating an organic film formed using a polymer (P) with polarized or non-polarized radiation to impart anisotropy to the film, the alignment of liquid crystals can be controlled. In this respect, the polymer (P) has At least a part of the structural unit U2 preferably has a photoalignment group. In this case, the polymer (P) has, as the structural unit U2, a structural unit in which R ¹ , R ⁴ or R ⁸ is a monovalent group having a photoalignment group.

The photoalignment group is preferably a function capable of imparting anisotropy to the film by photoisomerization reaction, photodimerization reaction, photo Fries rearrangement reaction, or photodecomposition reaction by light irradiation base. Specific examples of photoalignment groups include azobenzene-containing groups containing azobenzene or derivatives thereof as a basic skeleton, cinnamic acid-containing groups containing cinnamic acid or derivatives thereof (cinnamic acid structure) as a basic skeleton, and A structural group, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing a benzophenone or a derivative thereof as a basic skeleton, a coumarin or its derivative Derivatives as the basic skeleton of coumarin-containing groups, including A cyclobutane-containing structure containing cyclobutane or a derivative thereof as a basic skeleton, and the like. Among them, the photo-alignment group is preferably a group containing a cinnamic acid structure in terms of high sensitivity to light or ease of introduction into a polymer side chain.

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

(In formula (6), B ¹ is a monovalent group represented by the following formula (7), formula (8), formula (9) or formula (10), D ¹ is represented by the following formula (11) Divalent group, X ¹ and X ² are independently single bond, -CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO -, -O-CH ₂ -, -CH ₂ -O- or alkanediyl with 1~3 carbons, A ¹ and A ² are independently substituted or unsubstituted phenylene, cyclohexylene or Naphthyl, R ¹⁸ is alkyl, alkoxy, fluoroalkyl, fluoroalkoxy or -R ¹⁹ -Y ¹ with 2 to 20 carbons (wherein, R ¹⁹ is alkanediyl with 2 to 20 carbons , Y ¹ is a trialkylsilyl group); m is an integer of 0 to 2, and n is an integer of 1 to 3; when m is 2, multiple A ¹ and X ¹ independently have the above definitions; In the case where n is 2 or 3, a plurality of R ¹⁸ each independently have the above definition)

[chemical 11]

(In formula (7), R ² and R ³ have the same meaning as the formula (2); in formula (8), R ⁵ , R ⁶ and R ⁷ have the same meaning as the formula (3); In formula (9), R ⁹ , R ¹⁰ , R ¹¹ , X ¹⁰ and X ¹¹ have the same meanings as those in formula (4); in formula (10), R ¹³ and R ¹⁴ have the same meanings as in formula (5) respectively. ) have the same meaning; "*" means a bond key)

(In formula (11), A ³ , A ⁴ and A ⁵ are each independently substituted or unsubstituted phenylene or cyclohexylene, L ¹ and L ² are each independently a single bond, carbon number 1~ 5's alkanediyl group, or a group in which at least one methylene group of the alkanediyl group is substituted by "-O-" (wherein the oxygen atoms are not continuous), X ³ and X ⁴ are independently -CO-O- , -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO- or -O-, R ¹⁶ and R ¹⁷ are independently hydrogen atom, methyl, Halogen atom or cyano group; k and r are independently 0 or 1; "* ¹ " and "* ² " represent bonding bonds; where "* ¹ " and B ¹ are bonded, and "* ² ” in the case of bonding with B ¹ ).

In the formula (6), ^B1 is preferably represented by the formula (7), formula (8) or formula (9) from the viewpoint of being easy to carry out the polymerization reaction and obtaining a polymer with a sufficiently large molecular weight. group, particularly preferably a group represented by the formula (7) or formula (8). The formula (9) includes the following formula (9-1) and formula (9-2).

(In formula (9-1) and formula (9-2), R ⁹ , R ¹⁰ , R ¹¹ , X ¹⁰ and X ¹¹ have the same meanings as those in formula (4); "*" means a bond)

In terms of improving the effect of improving the voltage holding ratio of the obtained liquid crystal element, ^X1 and ^X2 are preferably single bonds, -CO-O-, -O-CO-, -O- or carbon number 1 to 3 alkanediyl, more preferably a single bond, -CO-O- or -O-CO-. When ^A1 and ^A2 have a substituent, the substituent includes, for example, a methyl group, an ethyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.). Specific examples of when R ¹⁶ and R ¹⁷ are halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. R ¹⁶ and R ¹⁷ are preferably hydrogen atoms.

It is preferable that m is 1 or 2 at the point which can further reduce the AC afterimage of the liquid crystal element obtained. In this case, "-A ² -X ² -(A ¹ -X ¹ )m-" in the formula (6) can further enhance the electrical characteristics of the liquid crystal element and the effect of improving the AC afterimage characteristics. It is preferably any one of the groups respectively represented by the following formula (a-1) to formula (a-9). Among these, the groups represented by the following formula (a-1) ~ formula (a-3), and formula (a-6) ~ formula (a-8) are more preferred, and the following formula ( The groups respectively represented by a-1), formula (a-7) and formula (a-8) are particularly preferably groups represented by the following formula (a-1) and formula (a-8).

(In the formula, "* ⁵ " represents the bond bonded to ^R18 , and "* ⁶ " represents the bond bonded to ^B1 )

The alkyl group, alkoxy group, fluoroalkyl group, fluoroalkoxy group and -R ¹⁹ -Y ¹ of R ¹⁸ may be linear or branched, preferably linear. In terms of further improving the voltage retention of the liquid crystal element and the effect of reducing AC afterimages, R ¹⁸ is preferably fluoroalkyl, fluoroalkoxy or -R ¹⁹ -Y ¹ , more preferably fluorine An alkyl group or a fluoroalkoxy group, particularly preferably a group represented by "-R ⁶¹ -Y ² " (wherein, R ⁶¹ is an alkanediyl group, Y ² is a perfluoroalkyl group, and the total carbon number of R ⁶¹ and Y ^{2 is} is 2 or more). n is preferably 1 or 2. When R ¹⁸ is alkyl, alkoxy, fluoroalkyl or fluoroalkoxy, the carbon number of R ¹⁸ is preferably 3 or more, more preferably 4 or more.

The compound represented by the formula (6) preferably has a compound represented by the following formula (b-1) in terms of further improving the electrical characteristics of the obtained liquid crystal element and the effect of reducing AC afterimage reduction. base. Furthermore, "R ⁸⁰ -(CF ₂ ) _a1 -(CH ₂ ) _a2 -X ⁵ -" in formula (b-1) corresponds to R ¹⁸ in formula (6).

(In formula (b-1), A ⁶ , A ⁷ and A ⁸ are independently substituted or unsubstituted 1,4-cyclohexylene or 1,4-phenylene, X ⁵ is a single bond or oxygen atom, R ⁸⁰ is a fluoromethyl or methyl group, a1 is an integer of 0 to 2, a2 is an integer of 1 to 20, and a3 is 0 or 1; wherein, when R ⁸⁰ is a methyl group, a1=0; "*" indicates a bond key)

In the formula (b-1), ^A6 is preferably a substituted or unsubstituted 1,4-cyclohexylene group in terms of further improving the effect of reducing the AC afterimage and the voltage retention rate, especially Preferably it is 1,4-cyclohexylene.

When a3 is 0, ^A8 is preferably 1,4-cyclohexylene, and when a3 is 1, ^A8 is preferably 1,4-phenylene, more preferably ^A7 is 1, 4-cyclohexylene, A ⁸ is 1,4-phenylene.

Examples of substituents that A ⁶ to A ⁸ may have include a methyl group, an ethyl group, and a 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 acquisition, a3 is preferably 1; and a3 is preferably 2 in terms of a high effect of improving afterimage characteristics. R ⁸⁰ is preferably a trifluoromethyl group from the viewpoint of further improving the electrical characteristics of the liquid crystal element and the effect of reducing AC afterimages.

Regarding the formula (11), the substituents that A ³ , A ⁴ , and A ⁵ may have can be applied to the description of the substituents in A ¹ and A ² .

In terms of the effect of improving the voltage holding ratio of the obtained liquid crystal element, ^X3 and ^X4 are preferably -CO-O-, -O-CO-, -O-, or those having 1 to 3 carbon atoms. Alkanediyl, more preferably -CO-O- or -O-CO-.

In the case where "* ² " is bonded to B ¹ , L ¹ is preferably a single bond, particularly preferably L ¹ is a single bond and k=0, in order to further increase the effect of reducing AC afterimages. or L ¹ is a single bond and X ³ is -CO-O- or -O-CO-. For the same reason, when "* ¹ " is bonded to B ¹ , when r=1, preferably L ² is a single bond, particularly preferably L ² is a single bond and X ⁴ is -CO -O- or -O-CO-.

As a specific example of a specific monomer, the compound etc. which are respectively represented by following formula (6-1) - a formula (6-41) are mentioned, for example. Among these, compounds in which "* ² " in formula (11) is bonded to B ¹ can be preferably used as the specific monomer. Furthermore, the polymer (P) may have only one type of structural unit derived from a specific monomer as the structural unit U1, or may have two or more types of structural units derived from the specific monomer as the structural unit U1.

[chemical 16]

[chemical 17]

[chemical 18]

[chemical 19]

(In formula (6-1)～formula (6-41), B ¹ has the same meaning as described formula (6); R ⁶⁴ is a carbon number 2～20 alkylene or oxyalkylene, b1 is 2 Integer of ~20, b2 is 1 or 2)

The method for synthesizing a specific monomer is not particularly limited, and can be synthesized by appropriately combining conventional methods of organic chemistry according to the molecular structure of the desired compound. For example, a compound in which B ^is a group represented by the formula (7) can be obtained by making a hydroxyl-containing maleimide (4-hydroxyphenylmaleimide, 4-hydroxycyclohexyl Maleimide, 3-hydroxyphenylmaleimide, 4-hydroxy-2-methylphenylmaleimide, 4-hydroxy-3-methylphenylmaleimide, etc.) , Reaction with a cinnamic acid derivative having a corresponding group "R ¹⁸ -A ² -X ² -(A ¹ -X ¹ )m-". In addition, the compound in which B ¹ is a group represented by the above-mentioned formula (8) can be obtained, for example, by making the compound represented by "R ¹⁸ -A ² -X ² -(A ¹ -X ¹ )mD ¹ -NH ₂ " The indicated amine compound reacts with maleic anhydride. A compound in which B ¹ is a group represented by the formula (9) can be obtained, for example, by making the compound represented by "R ¹⁸ -A ² -X ² -(A ¹ -X ¹ )mD ¹ -NH ₂ " Amine compound, reaction with itaconic anhydride, B ¹ is the compound of the group represented by the formula (10), for example, by making B ¹ the ketone moiety in the compound B ¹ of the group represented by the formula (9) obtained by restoration. However, the synthesis method of a specific monomer is not limited to the said method.

The polymer (P) may contain only a structural unit having a photoalignment group (hereinafter, also referred to as "structural unit U2A") as a structural unit U2, but may also contain a structural unit that does not have a photoalignment group while including a structural unit U2A. The structural unit (hereinafter, also referred to as "structural unit U2B"). The structural unit U2B is not particularly limited, for example, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(4-glycidyl Oxyphenyl)maleimide, N-glycidylmaleic Amide, 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-methyl itaconimide, N-(m-methoxyphenyl) itaconimide , and these ring-opened bodies, etc.

The content ratio of the structural unit U2 in the polymer (P) relative to the total amount of monomer-derived structural units contained in the polymer (P) (in the case of having the structural unit U2A and the structural unit U2B, it is the total amount) is preferably at least 1 mol %, more preferably 3 mol % to 60 mol %, and still more preferably 4 mol % to 40 mol %.

From the viewpoint that the effect of reducing AC afterimages can be sufficiently obtained, the content ratio of the structural unit U2A is preferably 1 mole relative to the total amount of monomer-derived structural units contained in the polymer (P) % or more, more preferably 3 mol % to 50 mol %, and more preferably 4 mol % to 30 mol %.

The liquid crystal alignment agent disclosed in this disclosure can improve electrical characteristics and AC afterimage characteristics by containing polymers having structural units U1 and U2. In order to further improve the effect of improving these characteristics, the polymer (P) can also have structural units Other structural units other than U1 and structural unit U2. Regarding the polymer (P), as other structural units, it is preferable to have at least one of the following (x1) and (x2) in the side chain, and it is particularly preferable to have both (x1) and (x2) in the side chain. By.

(x1) A functional group of at least one of oxetanyl and oxiranyl (except for the oxetanyl and oxiranyl contained in the structural unit U1) (hereinafter also referred to as "Functional group (x1)")

(x2) A functional group that reacts with at least one of an oxetanyl group and an oxiranyl group by heating (hereinafter also referred to as "functional group (x2)")

(Regarding Functional Group (x1))

The case where the polymer (P) has a functional group (x1) is preferable in terms of obtaining a liquid crystal alignment film exhibiting high liquid crystal alignment even when the firing temperature at the time of alignment film formation is lowered. As the functional group (x1), among the oxetanyl group and the oxiranyl group (hereinafter also simply referred to as "epoxy group"), the oxiranyl group is preferable in terms of high reactivity. .

(Regarding Functional Group (x2))

It is preferable that the polymer (P) has a functional group (x2) from the point which can fully exhibit the reduction of an AC afterimage and a high voltage retention rate. Examples of the functional group (x2) include a carboxyl group, a hydroxyl group, an isocyanate group, an amine group, and a group in which each of these groups is protected with a protecting group, an alkoxymethyl group, and the like. In terms of improving the storage stability of the obtained liquid crystal alignment agent and high reactivity with the oxetane ring and the oxirane ring by heating, the functional group (x2) Preferably, it is selected from the group consisting of a carboxyl group, a protected carboxyl group (hereinafter also referred to as a "protected carboxyl group"), an amine group, and a protected amine group (hereinafter also referred to as a "protected amine group"). at least one of . Furthermore, the amine groups include primary amine groups, secondary amine groups and tertiary amine groups.

The protective carboxyl group is not particularly limited as long as it is detached by heat to form a carboxyl group. As a preferable specific example of protecting a carboxyl group, the structure represented by following formula (12), the acetal ester structure of a carboxylic acid, the ketal ester structure of a carboxylic acid, etc. are mentioned.

[chemical 20]

(In formula (12), R ³¹ , R ³² and R ³³ are each independently an alkyl group with 1 to 10 carbons or a monovalent alicyclic hydrocarbon group with 3 to 20 carbons, or R ³¹ and R ³² are bonded to each other And together with the carbon atoms bonded by R ³¹ and R ³² , a divalent alicyclic hydrocarbon group or cyclic ether group with 4 to 20 carbons is formed, and R ³³ is an alkyl group with 1 to 10 carbons, and an alkyl group with 2 to 2 carbons Alkenyl with 10 or aryl with 6~20 carbons; "*" means bond)

The protected amine group is not particularly limited as long as it is detached by heat to form a primary amine group. As a protecting group, a urethane-type protecting group, an amide-type protecting group, an imide-type protecting group, a sulfonamide-type protecting group, etc. are mentioned, for example. Among these, the tertiary butoxycarbonyl (BOC) group is particularly preferred in terms of high detachability by heat and the ability to minimize the remaining amount of the compound derived from the detached protecting group in the film. base).

The functional group (x1) and the functional group (x2) are preferably selected from styrene-based At least one selected from the group consisting of compounds and (meth)acrylic compounds is introduced into the polymer (P). Furthermore, in this specification, "(meth)acrylic compound" refers to a compound having only one (meth)acrylic group in one molecule, so that it is different from maleimide-based compounds and itaconimide The compounds are distinguished.

As other structural units, in the case of having a structural unit derived from a compound having a functional group (x1) (hereinafter also referred to as "compound E1"), compound E1 is preferably represented by the following formula (13): Part of the structure as a group with epoxy groups. R ⁷⁰ in the following formula (13) preferably has 2 or more carbon atoms.

*-R ⁷⁰ -G ² …(13)

(In formula (13), R ⁷⁰ is an alkanediyl group with 1 to 20 carbons or a group having -O-, -COO- or -OCO- between the carbon-carbon bonds of the alkanediyl group, and G ² is oxygen Heterobutyl, oxirane or 3,4-epoxycyclohexyl; "*" indicates a bond)

Compound E1 and a 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 monomers forming the structural unit U1 and the monomers forming the structural unit U2. In terms of the ease of polymerization and the high degree of freedom in the selection of monomers, it is preferably selected from the formula (e-1), formula (e-3) ~ formula (e-7) and formula (e -10) at least one of the group formed, more preferably at least one selected from the group consisting of formula (e-3) and formula (e-5) ~ formula (e-7).

Specific examples of compound E1 include, for example, styrenic compounds: 3-(glycidyloxymethyl)styrene, 4-(glycidyloxymethyl)styrene, 4-glycidyl-α -Methylstyrene etc.,

Examples of (meth)acrylic compounds include glycidyl (meth)acrylate, α-glycidyl ethacrylate, α-n-propyl glycidyl acrylate, α- Glycidyl n-butyl acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxybutyl α-ethacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate Ester, 6,7-epoxyheptyl (meth)acrylate, 6,7-epoxyheptyl α-ethacrylate, 4-hydroxybutyl glycidyl acrylate, (3-ethyl Oxetan-3-yl) methyl ester, etc. In addition, compound E1 may use these 1 type individually, and may use 2 or more types together.

Specific examples of compound E2 include, for example, styrene-based compounds: 3-vinylbenzoic acid, 4-vinylbenzoic acid, compounds represented by the following formulas (m1-1) to formula (m1-4), etc. , Examples of (meth)acrylic acid compounds include (meth)acrylic acid, α-ethyl acrylate, maleic acid, fumaric acid, vinylbenzoic acid, crotonic acid, citraconic acid, mesaconic acid, and itaconic acid. Acid, 3-maleimide benzoic acid, 3-maleimide propionic acid and other carboxyl-containing compounds; the following formula (m2-1) ~ formula (m2-12) respectively Compounds; amino-containing compounds represented by the following formula (m1-5) ~ formula (m1-7) respectively; protected amino groups represented by the following formula (m1-8) and formula (m1-9) compounds, etc. In addition, when synthesizing a polymer (P), compound E2 can use these 1 type individually or in combination of 2 or more types.

[chem 21]

(wherein, R ¹⁵ is 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 with respect to the total amount of the monomer-derived structural units contained in the polymer (P), and more preferably It is better to set it as 5 mol%~70 mol%, and then it is better to set it as It is 10 mol%~60 mol%.

The content ratio of the structural unit derived from the compound E2 is preferably at least 2 mol %, more preferably 3 mol, based on the total amount of the monomer-derived structural unit contained in the polymer (P). % to 60 mol%, and more preferably set to 5 mol% to 50 mol%.

A polymer (P) may have the structural unit derived from the monomer which does not have any of a functional group (x1) and a functional group (x2) as another structural unit. Examples of such monomers include alkyl (meth)acrylates, cycloalkyl (meth)acrylates, benzyl (meth)acrylates, and 2-ethylhexyl (meth)acrylates. (Meth)acrylic compounds; aromatic vinyl compounds such as styrene, methylstyrene, and divinylbenzene; conjugated 1,3-butadiene, 2-methyl-1,3-butadiene, etc. Diene compounds; maleic anhydride, etc. The content ratio of the monomer-derived structural unit relative to the total amount of the monomer-derived structural unit contained in the polymer (P) is preferably 20 mol % or less, more preferably 10 mol % mol% or less, 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 radically polymerizing the monomer in an organic solvent in the presence of a polymerization initiator. As the polymerization initiator used, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2' -Azo compounds such as azobis(4-methoxy-2,4-dimethylvaleronitrile). It is preferable that the usage ratio of a polymerization initiator shall be 0.01 mass part - 30 mass parts with respect to 100 mass parts of all the monomers used for reaction. Examples of the organic solvent used include alcohols, ethers, ketones, amides, esters, and hydrocarbon compounds.

In the polymerization reaction, the reaction temperature is preferably set at 30°C to 120°C, and the reaction The time is preferably set to 1 hour to 36 hours. The usage-amount (a) of the organic solvent is preferably such that the total amount (b) of the monomers used in the reaction becomes 0.1% by mass to 60% by mass with respect to the total amount (a+b) of the reaction solution. The reaction solution obtained by dissolving the polymer can be used for the preparation of the liquid crystal alignment agent after the polymer (P) contained in the reaction solution is separated using the following known separation method. The separation method is to inject the reaction solution into a large amount of A method of drying a precipitate obtained in a poor solvent under reduced pressure, a method of distilling off a reaction solution under reduced pressure using an evaporator, and the like. The polymer (P) can be synthesized by, for example, living radical polymerization using a RAFT reagent or the like.

The polystyrene conversion weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of a polymer (P) becomes like this. Preferably it is 1,000-300,000, More preferably, it is 2,000-100,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 7 or less, more preferably 5 or less. Furthermore, the polymer (P) used in the preparation of the liquid crystal alignment agent may be only one kind, or two or more kinds may be combined.

In terms of fully obtaining the improvement effect of the electrical characteristics of the liquid crystal element and low afterimage characteristics, the content of the polymer (P) in the liquid crystal alignment agent relative to the total amount of the polymer components contained in the liquid crystal alignment agent The ratio is preferably at least 1% by mass, more preferably at least 2% by mass, and still more preferably at least 3% by mass. The upper limit of the content ratio of the polymer (P) is not particularly limited, in order to sufficiently obtain the improvement of various characteristics (for example, liquid crystal alignment, electrical characteristics, etc.) brought about by using a polymer different from the polymer (P) effect, and in order to achieve cost reduction, compared to liquid crystal For all the polymers contained in the alignment agent, the upper limit of the content ratio of the polymer (P) is preferably 90% by mass or less, more preferably 60% by mass or less, further preferably 40% by mass %the following.

<other ingredients>

The liquid crystal alignment agent disclosed herein may also contain other components than the polymer (P) as needed. The other components are not particularly limited as long as they do not impair the effect of the present disclosure, and examples include the following components

(polymer (Q))

The liquid crystal alignment agent disclosed herein preferably contains at least one polymer (hereinafter, Also known as "Polymer (Q)"). In this case, the polymer (P) is biased to exist in the upper layer, so that the improvement effect of the polymer (P) on electrical characteristics and AC afterimage characteristics can be realized by using as little as possible of the polymer (P) , which is appropriate in this respect. Phase separation can easily occur by setting the polymer (P) as a polymer having a halogen atom or a silicon atom and the polymer (Q) as a polymer not having a halogen atom or a silicon atom. Words are better.

The polymer (Q) can be synthesized according to conventionally known methods. For example, polyamic acid can be obtained by reacting tetracarboxylic dianhydride and diamine. In addition, in this specification, a "tetracarboxylic acid derivative" is the meaning which includes a tetracarboxylic dianhydride, a tetracarboxylic diester, and tetracarboxylic-acid diester dihalide.

The tetracarboxylic dianhydride used for polymerization is not specifically limited, Various tetracarboxylic dianhydrides can be used. Specific examples of these include butane tetracarboxylic dianhydride, ethylene glycol Aliphatic tetracarboxylic dianhydride such as amine tetraacetic dianhydride; 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho [1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho [1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentane tetra Alicyclic tetracarboxylic dianhydride such as carboxylic dianhydride and cyclohexane tetracarboxylic dianhydride; pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, Aromatic tetracarboxylic dianhydrides such as p-phenylene bis(trimellitic anhydride), ethylene glycol bis(trimellitic anhydride), 1,3-propanediol bis(trimellitic anhydride), etc. In addition, the tetracarboxylic dianhydride described in Unexamined-Japanese-Patent No. 2010-97188 can also be used. In addition, tetracarboxylic dianhydride may be used individually by 1 type, and may use it in combination of 2 or more types.

Examples of diamines used in the polymerization include: aliphatic diamines such as ethylenediamine and tetramethylenediamine; p-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine) ) and other alicyclic diamines; hexadecyloxydiaminobenzene, cholestanyloxydiaminobenzene, cholestyl diaminobenzoate, cholestenyl diaminobenzoate , Lanostyl diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane , 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 2,5-diamino-N,N-diallylaniline, the following Side-chain aromatic diamines such as compounds represented by formula (2-1) ~ formula (2-3) respectively; [Chemical 23]

p-Phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4-aminophenyl-4'-aminobenzoate, 4, 4'-Diaminoazobenzene, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 4,4'-diaminobiphenyl Base-3-carboxylic acid, 1,5-bis(4-aminophenoxy)pentane, bis[2-(4-aminophenyl)ethyl]adipic acid, bis(4-aminophenyl) base) amine, N,N-bis(4-aminophenyl)methylamine, N,N'-bis(4-aminophenyl)-benzidine, 2,2'-dimethyl-4, 4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-(phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy) Benzene, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 4,4'-[4,4'-propane-1,3-diylbis(piper Non-side-chain aromatic diamines such as pyridine-1,4-diyl)]diphenylamine; diamine-based silicones such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane In addition to oxane etc., the diamine described in Unexamined-Japanese-Patent No. 2010-97188 can also be used. In addition, diamine may be used individually by 1 type, and may use it in combination of 2 or more types.

The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20° C. to 150° C., and the reaction time is preferably 0.1 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 hydrocarbons. use of organic solvents The amount used is preferably an amount in which the total amount of the tetracarboxylic dianhydride and the diamine compound becomes 0.1 mass % to 50 mass % with respect 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: making the obtained polyamic acid and an esterifying agent (for example, methanol or ethanol, N, N-dimethylformamide diethyl acetal, etc.), the method of reacting tetracarboxylic acid diester and diamine compound in the presence of a suitable dehydration catalyst, making tetracarboxylic acid A method of reacting a diester dihalide with a diamine in the presence of a suitable base.

When the polymer (Q) is a polyimide, the polyimide can be obtained, for example, by dehydrating and ring-closing the obtained polyamic acid and imidizing it. The imidization rate of polyimide is preferably 20%-95%, more preferably 30%-90%. The imidization rate is a percentage representing the ratio of the number of imide ring structures of polyimide to the total number of the number of amide acid structures and the number of imide ring structures.

The weight average molecular weight (Mw) of polystyrene conversion measured by GPC about a polymer (Q) becomes like this. Preferably it is 1,000-500,000, More preferably, it is 2,000-300,000. The molecular weight distribution (Mw/Mn) is preferably 7 or less, more preferably 5 or less. In addition, the polymer (Q) contained in a liquid crystal alignment agent may be only 1 type, or may combine 2 or more types.

In the case of using the polymer (P) and the polymer (Q) as the polymer component of the liquid crystal alignment agent, from the viewpoint of sufficiently obtaining the improvement effect of the AC afterimage characteristic and the electrical characteristic, relative to the preparation of the liquid crystal alignment agent The polymer (Q) used in It is preferable that the compounding ratio of a polymer (P) shall be 1 mass part or more per 100 mass parts. More preferably, it is 2-50 mass parts, More preferably, it is 5-30 mass parts. In addition, a polymer (P) and a polymer (Q) may be used individually by 1 type, and may use it in combination of 2 or more types.

(solvent)

The liquid crystal alignment agent disclosed in the present disclosure is prepared in the form of a solution-like composition, and the solution-like composition is formed by dissolving the polymer component and optional components prepared as needed in an organic solvent. Examples of the organic solvent include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. The solvent component may be one of these, or a mixed solvent of two or more.

As the solvent component of the liquid crystal alignment agent, a solvent with high polymer solubility and leveling properties (hereinafter also referred to as "first solvent"), a solvent with good wetting and spreading properties (hereinafter also referred to as "second solvent"), and solvent), and these mixed solvents.

As specific examples of the solvent, the first solvent includes, for example: N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactamide, N,N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, diisobutyl ketone, ethyl 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-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, etc.; the second solvent is, for example, ethyl Glycol monobutyl ether (butyl cellosolve), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diacetone alcohol, diethylene glycol di Methyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, cyclopentanone, butyl lactate, Butyl Acetate, Methyl Methoxy Propionate, Ethyl Ethoxy Propionate, Isopentyl Propionate, Isopentyl Isobutyrate, Propylene Glycol Diacetate, Dipropylene Glycol Monomethyl Ether, Propylene glycol monobutyl ether, diisoamyl ether, etc. In addition, these solvents may be used individually by 1 type, and may use it in mixture of 2 or more types.

When the solvent component of the liquid crystal alignment 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 relative to the total amount of the solvent component, more preferably To set it as 15% by mass to 85% by mass.

As other components contained in the liquid crystal alignment agent, in addition to the above, for example, a polymer different from the polymer (P) and the polymer (Q), a molecular weight of 1000 having at least one epoxy group in the molecule The following low molecular weight compounds (for example, ethylene glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, N,N,N',N'-tetraglycidyl -4,4'-diaminodiphenylmethane, etc.), functional silane compounds, multifunctional (meth)acrylates, antioxidants, metal chelating compounds, hardening accelerators, surfactants, fillers, Dispersants, photosensitizers, etc. The compounding ratio of other components can be suitably selected according to each compound in the range which does not impair the effect of this indication.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1% by mass range of ~10% by mass. When the solid content concentration is less than 1% by mass, the film thickness of the coating film is too small to obtain Good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film is too large, making it difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases, which tends to reduce applicability.

"Liquid Crystal Alignment Film and Liquid Crystal Components"

The liquid crystal alignment film disclosed herein is formed from the liquid crystal alignment agent prepared as described above. In addition, the liquid crystal element disclosed herein includes a liquid crystal alignment film formed by using the liquid crystal alignment agent described above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited, for example, it can be applied to twisted nematic (Twisted Nematic, TN) type, super twisted nematic (Super Twisted Nematic, STN) type, vertical alignment (Vertical Alignment, VA) type (including vertical alignment-multi-domain vertical alignment (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) type, vertical alignment-patterned vertical alignment (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type, etc.), coplanar switching (In-Plane Switching, IPS) type, Fringe Field Switching (Fringe Field Switching, FFS) type, Optically Compensated Bend (Optically Compensated Bend, OCB) type, Polymer Sustained Alignment (Polymer Sustained Alignment, PSA) type and other modes. A liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, the board used differs depending on the desired operation mode. Step 2 and Step 3 are common in all operation modes.

<Step 1: Formation of coating film>

First, the liquid crystal alignment agent is coated on the substrate, preferably by heating the coated surface, thereby forming a coating film on the substrate. As the substrate, for example, a transparent substrate including glass such as float glass and soda glass; polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly( Alicyclic olefin) and other plastics. The transparent conductive film provided on one side of the substrate can be used: Nesser (NESA) film (registered trademark of U.S. PPG Corporation) containing tin oxide (SnO ₂ ), containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) indium tin oxide (Indium Tin Oxide, ITO) film, etc. In the case of manufacturing a TN-type, STN-type or VA-type liquid crystal element, two substrates provided with patterned transparent conductive films are used. On the other hand, when manufacturing an IPS type or an FFS type liquid crystal element, a substrate provided with electrodes patterned into a comb-shaped shape and a counter substrate provided with no electrodes are used. The coating of the liquid crystal alignment agent on the substrate is preferably carried out on the electrode formation surface by lithographic printing, flexographic printing, spin coating, roll coater or inkjet printing.

After applying the liquid crystal alignment agent, for the purpose of preventing dripping of the applied liquid crystal alignment agent, etc., it is preferable to perform preheating (prebaking). The pre-baking temperature is preferably 30° C. to 200° C., and the pre-baking time is preferably 0.25 minutes to 10 minutes. Thereafter, a calcination (post-baking) step is implemented for the purpose of completely removing the solvent and optionally thermally imidizing the amide acid structure present in the polymer. The calcination temperature (post-baking temperature) at this time is preferably from 80°C to 250°C, more preferably from 80°C to 200°C. The post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the film thus formed is preferably 0.001 μm to 1 μm.

<Step 2: Alignment processing>

When manufacturing a TN type, STN type, IPS type or FFS type liquid crystal element, the process (alignment process) which provides liquid crystal alignment ability to the coating film formed in the said process 1 is implemented. In this way, the coating film is provided with the ability to align liquid crystal molecules to form a liquid crystal alignment membrane. As the alignment treatment, it is possible to give liquid crystal alignment ability to the coating film by wiping the coating film in a certain direction with a roller wound with cloth containing fibers such as nylon (nylon), rayon (rayon), and cotton (cotton). Rubbing treatment, photo-alignment treatment in which the coating film formed on the substrate is irradiated with light to impart liquid crystal alignment ability to the coating film, etc. Among these, photo-alignment treatment is preferable. In the case of manufacturing a vertical alignment liquid crystal element, the coating film formed in step 1 can be directly used as a liquid crystal alignment film, but in order to further improve the liquid crystal alignment ability, the coating film can also be subjected to an alignment treatment.

Light irradiation for photoalignment can be performed by methods such as a method of irradiating the coating film after the post-baking step, a method of irradiating the coating film after the pre-baking step and before the post-baking step, A method of irradiating the coating film during heating of the coating film in at least 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 150 nm to 800 nm can be used. Ultraviolet rays including light having a wavelength of 200 nm to 400 nm are preferable. When the radiation is polarized light, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or may be performed in combination of these directions. The irradiation direction in the case of non-polarized radiation was defined as an oblique direction.

Examples of the light source used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, and excimer lasers. The radiation dose is preferably 400J/m ² -50,000J/m ² , more preferably 1,000J/m ² -20,000J/m ² . After being irradiated with light for imparting alignment ability, use of water, organic solvents (for example, methanol, isopropanol, 1-methoxy-2-propanol acetate, butyl cellosolve, etc.) on the substrate surface may also be performed. Ethyl lactate, etc.) or a mixture of these is cleaned, or the substrate is heated.

<Step 3: Construction of liquid crystal cell>

A liquid crystal cell is manufactured by preparing two substrates on which the liquid crystal alignment film is formed in the above manner, and disposing liquid crystal between the two substrates facing each other. When manufacturing a liquid crystal cell, for example, a method such as arranging two substrates facing each other through a gap so that the liquid crystal alignment films face each other, bonding the peripheral parts of the two substrates together with a sealant, and then bonding the substrate surfaces with the sealant A method of injecting/filling liquid crystal into the enclosed cell gap and sealing the injection hole; a method of using a liquid crystal drop filling (One Drop Fill, ODF) method. As the sealing agent, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred. In the PSA mode, after the liquid crystal cell is constructed, a voltage is applied between the conductive films included in the pair of substrates, and light irradiation processing is performed on the liquid crystal cell in this state.

Next, if necessary, a polarizing plate is bonded to the outer surface of the liquid crystal cell to prepare a liquid crystal cell. Examples of the polarizing plate include: a polarizing plate obtained by sandwiching a polarizing film called “H film” between cellulose acetate protective films, or a polarizing plate including the H film itself. Alcohol is extended and aligned to one side to absorb iodine.

The disclosed liquid crystal element can be effectively applied to various purposes, for example, it can be applied to clocks, portable game machines, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (Personal Digital Assistant, PDA) ), digital cameras, mobile phones, smart phones, various monitors, LCD TVs Various display devices such as TV sets and information displays, or light-adjustable films, retardation films, etc.

[Example]

Hereinafter, examples are used for specific description, but the present disclosure is not limited to the following examples.

In the following examples, the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of polymers 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. In addition, the molecular weight distribution (Mw/Mn) was calculated from the obtained Mw and Mn.

Device: "GPC-101" by Showa Denko Co., Ltd.

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

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

Column temperature: 40°C

Flow rate: 1.0mL/min

Sample concentration: 1.0% by mass

Sample injection volume: 100μL

Detector: Differential refractometer

Standard material: monodisperse polystyrene

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

[chem 25]

<Synthesis of Monomer>

[Synthesis Example 1: Synthesis of Compound (MI-01)]

Compound (MI-01) was synthesized according to Scheme 1 below.

． Synthesis of compound (MI-01)

Add 14.0 g of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-linked ( Cyclohexane)]-4-carbonyl)oxy)phenyl)acrylic acid, 20g of thionyl chloride, and 0.01g of N,N-dimethylformamide, and Stir at 80°C for 1 hour. Thereafter, excess thionyl chloride was removed by a diaphragm pump, and 100 g of tetrahydrofuran was added to prepare a solution A.

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

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

Compound (MI-02) was synthesized according to Scheme 2 below.

． Synthesis of compound (M-2-1)

Take 11.5g of 4-amino-cyclohexanol in a 1000mL three-necked flask equipped with a stirrer, add 150g of tetrahydrofuran, and conduct an ice bath. A solution containing 9.81 g of maleic anhydride and 150 g of tetrahydrofuran was added dropwise thereto, followed by stirring at room temperature for 3 hours. Thereafter, the precipitated white solid was recovered by filtration. Vacuum the white solid It was dried, whereby 20.2 g of Compound (M-2-1) were obtained.

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

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

． Synthesis of compound (MI-02)

In Synthesis Example 1, 14.0 g of the compound ( MI-02).

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

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

[chem 28]

． Synthesis of compound (M-3-1)

Take 11.5g of N-Boc-4-hydroxyaniline (N-BOC-4-hydroxyaniline), 23.3g of (E)-3-(4-((4'-( 4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4-carbonyl)oxy)phenyl)acrylic acid, 1000 g of dichloromethane was added and ice-bathed. Add 1.21 g of N,N-dimethylaminopyridine, 11.5 g of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride successively therein, and After stirring at temperature for 8 hours, liquid separation washing was performed 4 times with 500 g of distilled water. Thereafter, the organic layer was slowly concentrated using a rotary evaporator until the inner volume became 100 g, and the white solid precipitated on the way was collected by filtration. This white solid was vacuum-dried to obtain 31.6 g of compound (M-3-1).

． Synthesis of compound (M-3-2)

30.3 g of compound (M-3-1) and 33.8 g of trifluoroacetic acid were taken in a 300 mL eggplant-shaped flask equipped with a stirrer, 50 g of dichloromethane was added, and the mixture was stirred at room temperature for 1 hour. Then, after neutralizing with saturated sodium bicarbonate aqueous solution, liquid-separation washing|cleaning was performed 4 times with 50 g of distilled water. Thereafter, the organic The layer was slowly concentrated until the inner volume became 50 g, and the white solid precipitated on the way was recovered by filtration. The white solid was vacuum-dried to obtain 24.8 g of compound (M-3-2).

． Synthesis of compound (MI-03)

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

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

Compound (MI-04) was synthesized according to Scheme 4 below.

． Synthesis of Compound (MI-04)

Add 6.53g of monomethyl maleate, 25g of thionyl chloride, and 0.01g of N,N-dimethylformamide to a 500mL eggplant-shaped flask equipped with a stirrer, and stir at 60°C 2 hours. Thereafter, excess thionyl chloride is removed by a diaphragm pump, Furthermore, 50 g of tetrahydrofuran was added to prepare solution A.

26.8 g of compound (M-3-2), 500 g of tetrahydrofuran, and 13.2 g of triethylamine were newly added to a 1000 mL three-necked flask equipped with a stirrer, and ice-bathed. Solution A was added dropwise thereto and stirred at room temperature for 8 hours. The reaction liquid was reprecipitated with 1200 mL of water, and the obtained white solid was vacuum-dried to obtain 25.4 g of compound (MI-04).

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

In synthesis example 3, except having used itaconic anhydride instead of maleic anhydride, the compound (MI-05) 19.1g was obtained by the method similar to synthesis example 3.

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

In Synthesis Example 1, it was obtained by the same method as Synthesis Example 1 except that 4-hydroxy-2-methylphenylmaleimide was used instead of 4-hydroxyphenylmaleimide 14.4 g of compound (MI-06). Furthermore, in the synthesis of M-2-1 in Synthesis Example 2, 4-hydroxy-2-methylphenylmaleic acid was synthesized using 2-methyl-4-hydroxyaniline instead of 4-hydroxycyclohexylamine imine.

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

In Synthesis Example 1, it was obtained by the same method as Synthesis Example 1 except that 4-hydroxy-3-methylphenylmaleimide was used instead of 4-hydroxyphenylmaleimide 14.5 g of compound (MI-07). Furthermore, in the synthesis of the compound (M-2-1) of Synthesis Example 2, 4-hydroxy-3-methylphenyl was synthesized using 3-methyl-4-hydroxyaniline instead of 4-hydroxycyclohexylamine. maleimide.

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

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

． Synthesis of 4-Hydroxy-α-Methylcinnamic Acid (Compound (M-8-1))

9.74 g of 4-hydroxybenzaldehyde, 25 g of propionic anhydride, and 15.2 g of sodium propionate were mixed in a 200 mL three-necked flask equipped with a stirrer, and stirred at 145° C. for 16 hours under a nitrogen atmosphere. After the reaction, it was cooled in an ice bath, 100 ml of water was added and stirred for 3 hours, and a solid was precipitated and filtered. The obtained solid was added to a 10% aqueous sodium hydroxide solution, and stirred at 0° C. for 30 minutes. After filtering the insoluble matter, hydrochloric acid was added to the filtrate to make it acidic, and the generated solid was filtered. The solid was dissolved in 200 ml of ethyl acetate, and washed three times with water. After drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 8.73 g of 4-hydroxy-α-methylcinnamic acid (this is referred to as compound (M-8-1)).

． Synthesis of compound (M-8-2)

4'-(4,4,4-trifluorobutyl)-[1,1'-linked (cyclohexane)]-4-carboxylic acid and 4-hydroxy-α - methyl cinnamic acid reaction, thereby obtaining 15.0 g of compound (M-8-2).

． Synthesis of Compound (MI-08)

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- 14.6 g of compounds (MI-08) were obtained by the method similar to synthesis example 1 except having used compound (M-8-2) for carbonyl)oxy) phenyl) acrylic acid.

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

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

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- 14.5 g of compounds (MI-09) were obtained by the method similar to synthesis example 1 except having used compound (M-9-1) for carbonyl)oxy) phenyl) acrylic acid. Furthermore, in Synthesis Example 8, the compound (M-9- 1).

[Synthesis Example 10: Synthesis of Compound (MI-10)]

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

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- 14.5 g of compound (MI-10) was obtained by the method similar to synthesis example 1 except having used compound (M-10-1) for carbonyl)oxy) phenyl) acrylic acid. Furthermore, in Synthesis Example 8, the compound (M-10- 1).

[Synthesis Example 11: Synthesis of Compound (MI-11)]

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

[chem 33]

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- Carbonyl)oxy)phenyl)acrylic acid while using (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane) ]-4-carbonyl)thio)phenyl)acrylate, the compound (MI-11) 14.4g was obtained by the method similar to synthesis example 1.

Furthermore, (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4-carbonyl)thio ) phenyl) acrylic acid is using 4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4-carboxylic acid and 4-mercaptocinnamic acid and by Synthesized in the same way as the process 8. 4-Mercaptocinnamic acid can be synthesized by the method described in Japanese Patent No. 2646314.

[Synthesis Example 12: Synthesis of Compound (MI-12)]

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- Carbonyl)oxy)phenyl)acrylic acid and (E)-3-(4-((4'-pentyl-[1,1'-bi(cyclohexane)]-4-carbonyl)oxy)benzene 13.4 g of compounds (MI-12) were obtained by the method similar to synthesis example 1 except having used acrylic acid.

[Synthesis Example 13: Synthesis of Compound (MI-13)]

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

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- carbonyl)oxy)phenyl)acrylic acid while using (E)-3-(4-((4-(4-(4,4,4-trifluorobutyl)cyclohexyl)benzoyl)oxy) The compound (MI-13) of 12.3 g was obtained by the method similar to the synthesis example 1 except for this. Furthermore, (E)-3-(4-((4-(4-(4,4,4-trifluorobutyl)cyclohexyl)benzoyl)oxy)phenyl)acrylate was obtained using 4 -(4-(4,4,4-trifluorobutyl)cyclohexyl)benzoic acid and coumaric acid were synthesized by the same method as Scheme 8.

[Synthesis Example 14: Synthesis of Compound (MI-14)]

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- Carbonyl)oxy)phenyl)acrylic acid and (E)-3-(4-((4-(4-(3-(trimethylsilyl)propoxy)cyclohexyl)benzoyl)oxy 15.7 g of compound (MI-14) was obtained by the method similar to the synthesis example 1 except having carried out base) phenyl) acrylic acid.

[Synthesis Example 15: Synthesis of Compound (MI-15)]

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

． Synthesis of compound (M-15-1)

Put 6.36 g of potassium tert-butoxide into a 300 mL three-necked flask, and replace with nitrogen. Then, 28.3 g of 4,4,4-trifluorobutyltriphenylphosphonium iodide dissolved in 180 ml of tetrahydrofuran was added dropwise, and it was made to react at room temperature for 1 hour. Then, 10.4 g of 4-(1,4-dioxaspiro[4.5]dec-8-yl)cyclohexanone was added, and it was made to react at room temperature for 72 hours. After distilling off the solvent with a rotary evaporator, extraction was performed with diethyl ether, and purification was performed with a silica gel column using hexane/ethyl acetate as a developing solvent. The solvent was removed with a rotary evaporator to obtain 8.1 g of compound (M-15-1).

． Synthesis of compound (M-15-2)

7.7 g of compound (M-15-1) was put into a 500 mL three-necked flask, and nitrogen substitution was performed. Then, add 225ml of methanol and 1.23g of palladium-activated carbon (Pd10%), replace the inside of the flask with hydrogen, and install a hydrogen-filled balloon (balloon). After stirring vigorously at room temperature for 12 hours, it was filtered through celite, and the residue was washed with dichloromethane. The filtrate was separated and washed with water three times, and the solvent was removed with a rotary evaporator to obtain 7.5 g of compound (M-15-2).

． Synthesis of compound (M-15-3)

7.5 g of the compound (M-15-2) was placed in a 200 mL three-necked flask, and replaced with nitrogen. Then, after adding 30 ml of acetone and 15 ml of water, 23.4 ml of trifluoroacetic acid was added dropwise and reacted 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 removing the solvent with a rotary evaporator, vacuum drying was performed to obtain 4.6 g of compound (M-15-3).

． Synthesis of compound (M-15-4)

0.44 g of magnesium was put into a 100 mL three-necked flask, and replaced with nitrogen. Next, 10 ml of dehydrated tetrahydrofuran was added, and cooled with an ice bath. 0.15 ml of benzene iodide dissolved in 4 ml of dehydrated tetrahydrofuran was slowly added dropwise, and the mixture was reacted at room temperature for 30 minutes and then at 70° C. for 30 minutes. After returning to room temperature and cooling with an ice bath, 4.6 g of compound (M-15-3) dissolved in 20 ml of dehydrated tetrahydrofuran was slowly added dropwise. After returning to room temperature, the solution reacted for 5 hours was poured into a saturated aqueous solution of ammonium chloride. The organic layer was recovered, washed twice with a saturated ammonium chloride aqueous solution, and purified with a silica gel column using hexane/ethyl acetate as a developing solvent. The solvent was removed with a rotary evaporator to obtain 4.1 g of compound (M-15-4).

． Synthesis of compound (M-15-5)

Put the compound (M-15-4) of 4.1g in the 100mL three-necked flask, and carry out Perform nitrogen replacement. Next, 2.5 ml of acetic acid, 0.25 g of palladium-activated carbon (Pd 10%), and 20 ml of tetrahydrofuran were added, and the mixture was replaced with a hydrogen atmosphere, followed by stirring 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, ethyl acetate was added, and the mixture was stirred at 0° C. for 1 hour. The precipitated solid was filtered and vacuum-dried to obtain 3.4 g of compound (M-15-5).

． Synthesis of compound (M-15-6)

3.4 g of compound (M-15-5) and 0.03 g of iron(III) chloride were placed in a 100 mL three-necked flask, and replaced with nitrogen. Then, after adding 5.5 g of 15% hydrobromic acid aqueous solution, 7.4 g of 10% sodium hypochlorite aqueous solution were added dropwise, and it stirred at room temperature for 2 hours. The organic layer was recovered, and sequentially separated and washed with 5% aqueous sodium bicarbonate and distilled water. After removing the solvent with a rotary evaporator, vacuum drying was performed to obtain 2.5 g of compound (M-15-6).

． Synthesis of compound (M-15-7)

0.43 g of acrylic acid and 2.02 g of potassium tert-butoxide were put into a 100 mL three-necked flask, and replaced with nitrogen. Then, after adding 12 ml of water and stirring at room temperature for 10 minutes, 1.35 g of palladium acetate and 2.5 g of compound (M-15-6) were added thereto, and stirred at 100° C. for 24 hours. After returning to room temperature, hydrochloric acid aqueous solution was added dropwise until the pH value was 1. Thereafter, extraction was performed with dichloromethane, followed by liquid separation and washing with brine (brine), aqueous sodium sulfate solution, and water in this order. Purification was performed by flash column chromatography, and the solvent was removed by a rotary evaporator and vacuum-dried to obtain 2.1 g of compound (M-15-7).

． Synthesis of compound (MI-15)

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- 1.7 g of compound (MI-15) was obtained by the method similar to synthesis example 1 except having used compound (M-15-7) as carbonyl)oxy) phenyl) acrylic acid.

[Synthesis Example 16: Synthesis of Compound (MI-16)]

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

． Synthesis of compound (M-16-1)

22.4 g of 4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4-carboxylic acid was put into a 500 mL three-necked flask, and nitrogen substitution was performed. Next, 200 mL of THF was added, followed by stirring at 0°C. After adding 3.3 g of sodium borohydride thereto, 12.1 g of boron trifluoride diethyl ether was slowly added dropwise, and reacted for 18 hours. After completion of the reaction, the reaction solution was transferred to a 2 L beaker, neutralized with hydrochloric acid, and 1.5 L of water was added thereto. After filtering the precipitated solid, vacuum drying was carried out to obtain 20.6 g Compound (M-16-1).

． Synthesis of compound (M-16-2)

Add 20.6g of compound (M-16-1), 0.819g of N,N-dimethyl-4-aminopyridine, 200mL of dichloromethane, 13.6g of triethylamine in a 1L three-necked flask, and Cool to 0 °C. A solution obtained by dissolving 14.1 g of p-toluenesulfonyl chloride in 100 mL of dichloromethane was slowly added dropwise thereto, and then reacted for 20 hours. After completion of the reaction, 100 mL of dichloromethane was added, the reaction liquid was separated three times with 500 mL of water, the organic layer was dried with magnesium sulfate, and then the magnesium sulfate was removed by filtration. Then, the solvent of the filtrate was distilled off with a rotary evaporator, and the generated solid was vacuum-dried to obtain 29.3 g of compound (M-16-2).

． Synthesis of compound (M-16-3)

Add 29.3g of compound (M-16-2), 7.82g of 4-hydroxybenzaldehyde, 13.3g of potassium carbonate, 200mL of N,N-dimethylformamide to a 1L three-necked flask, and The reaction was carried out for 5 hours. After completion of the reaction, 500 mL of ethyl acetate was added, liquid separation was performed three times with 500 mL of water, and the organic layer was dried with magnesium sulfate. Next, magnesium sulfate was removed by filtration. Then, magnesium sulfate was filtered by filtration, the solvent of the filtrate was distilled off with the rotary evaporator, and the generated solid was vacuum-dried to obtain 23.4 g of compound (M-16-3).

． Synthesis of compound (M-16-4)

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

． Synthesis of compound (MI-16)

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- 17.8 g of compound (MI-16) was obtained by the method similar to synthesis example 1 except having used compound (M-16-4) for carbonyl)oxy) phenyl) acrylic acid.

[Synthesis Example 17: Synthesis of Compound (MI-17)]

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

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- Carbonyl)oxy)phenyl)acrylic acid and (E)-3-(4-((4-(4,4,4-trifluorobutoxy)benzoyl)oxy)phenyl)acrylate , except that, the compound (MI-17) 12.6g was obtained by the method similar to the synthesis example 1.

[Synthesis Example 18: Synthesis of Compound (MI-18)]

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

[chem 38]

． Synthesis of compound (M-18-1)

Put 82g of methyl 4-hydroxybenzoate, 166g of potassium carbonate, and 400mL of N,N-dimethylacetamide into a 1L eggplant-shaped flask, and stir at room temperature for 1 hour, then add 95g of 4,4,4-trifluoro-1-iodobutane, and reacted at room temperature under stirring for 5 hours. After completion of the reaction, reprecipitation was performed with water. Next, 32 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 4 hours to perform a hydrolysis reaction. After completion of the reaction, neutralization was performed with hydrochloric acid, and the generated precipitate was recrystallized with ethanol to obtain 80 g of compound (M-18-1).

． Synthesis of compound (M-18-2)

46.4 g of compound (M-18-1) was taken in a reaction vessel, 200 mL of thionyl chloride and 0.2 mL of N,N-dimethylformamide were added thereto, and stirred at 80° C. for 1 hour. Next, after distilling off thionyl chloride under reduced pressure, tetrahydrofuran was added to prepare a solution A. Secondly, drop 30g of 4-hydroxyl in a 2L three-necked flask different from the above benzoic acid, 55 g of potassium carbonate, 2.4 g of tetrabutylammonium, 200 mL of tetrahydrofuran, and 400 mL of water. The aqueous solution was ice-cooled, solution A was slowly added dropwise, and the reaction was further carried out under stirring for 2 hours. After the reaction was completed, hydrochloric acid was added to the reaction mixture for neutralization, and after extraction with ethyl acetate, the extract was dried with magnesium sulfate, concentrated, and then recrystallized with ethanol to obtain 39 g of the compound ( M-18-2) as white crystals.

． Synthesis of compound (M-18-3)

As a raw material, compound (M-18-2) was used instead of compound (M-18-1), and 4-hydroxycinnamic acid was used instead of 4-hydroxybenzoic acid. -2) 33 g of compound (M-18-3) was obtained by the same method.

． Synthesis of compound (MI-18)

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- 15.4 g of compound (MI-18) was obtained by the method similar to synthesis example 1 except having used compound (M-18-3) for carbonyl)oxy) phenyl) acrylic acid.

[Synthesis Example 19: Synthesis of Compound (MI-19)]

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

[chem 39]

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- 16.1 g of compound (MI-19) was obtained by the method similar to synthesis example 1 except having used compound (M-19-3) as carbonyl)oxy) phenyl) acrylic acid. Furthermore, in Synthesis Example 18, the compound (M- 19-1) ~ compound (M-19-3).

[Synthesis Example 20: Synthesis of Compound (MI-20)]

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- Carbonyl)oxy)phenyl)acrylic acid and (E)-4-((3-(4-((4-(4,4,4-trifluorobutoxy)benzoyl)oxy)benzene 16.1 g of compound (MI-20) was obtained by the method similar to synthesis example 1 except having carried out (group) acryl) oxy) benzoic acid.

[Synthesis Example 21: Synthesis of Compound (MI-21)]

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

[chemical 40]

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- 15.8 g of compound (MI-21) was obtained by the method similar to synthesis example 1 except having used compound (M-21-3) for carbonyl)oxy) phenyl) acrylic acid. Furthermore, in Synthesis Example 22, in addition to replacing the starting material from 4-hydroxy-2,3,5,6-tetrafluorophenylbenzoic acid with 3-fluoro-4-hydroxybenzoic acid, by The same method is used to synthesize compound (M-21-1) ~ compound (M-21-3).

[Synthesis Example 22: Synthesis of Compound (MI-22)]

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

[chem 41]

． Synthesis of compound (M-22-1)

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

． Synthesis of compound (M-22-2)

In Synthesis Example 18, compound (M-22-1) was used instead of compound (M-18-2), except that, it was synthesized by the same method to obtain 22.1 g of compound (M-22-2 ).

． Synthesis of compound (M-21-3)

In Synthesis Example 18, compound (M-22-2) was used instead of compound (M-18-1), except that, it was synthesized by the same method to obtain 17.1 g of compound (M-22-3 ).

． Synthesis of compound (MI-22)

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- 17.2 g of compound (MI-22) was obtained by the method similar to synthesis example 1 except having used compound (M-22-3) for carbonyl)oxy) phenyl) acrylic acid.

[Synthesis Example 23: Synthesis of Compound (MI-23)]

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

[chem 42]

． Synthesis of compound (M-23-1)

In a 500mL three-necked flask equipped with a stirrer, add 16.8g of 3,4-methyl dihydroxybenzoate, 53.0g of 4,4,4-trifluoro-1-iodobutane, 83.2g of potassium carbonate, and 500 mL of dimethylacetamide was heated at 90° C. for 10 hours under nitrogen atmosphere. After the reaction, it was poured into 500 mL 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, it was acidified with 1 N hydrochloric acid, and the generated precipitate was filtered and then dried with a vacuum dryer to obtain 28.0 g of compound (M-23-1).

． Synthesis of compound (M-23-2)

In Synthesis Example 18, compound (M-23-1) was used instead of compound (M-18-2), except that, it was synthesized by the same method to obtain 23.4 g of compound (M-23-2 ).

． Synthesis of compound (M-23-3)

In Synthesis Example 18, compound (M-23-2) was used instead of compound (M-18-1), except that, it was synthesized by the same method to obtain 17.3 g of compound (M-23-2 ).

． Synthesis of compound (MI-23)

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- 17.2 g of compound (MI-23) was obtained by the method similar to synthesis example 1 except having used compound (M-23-3) for carbonyl)oxy) phenyl) acrylic acid.

[Synthesis Example 24: Synthesis of Compound (MI-24)]

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

． Synthesis of compound (M-24-1)

Add 10.0 g of 4'-(4,4,4-trifluorobutyl)-[1,1'-linked (cyclohexane)]-4-carboxylic acid, 37 g of thionyl chloride and 0.02 g of N,N-dimethylformamide were stirred at 60° C. for 2 hours. Thereafter, excess thionyl chloride was removed by a diaphragm pump, and 250 g of tetrahydrofuran was added to prepare a solution A.

6.8 g of hydroquinone, 140 g of tetrahydrofuran, and 4.9 g of pyridine were newly added to a 1000 mL three-necked flask equipped with a stirrer, and ice-bathed. Solution A was added dropwise thereto and stirred at room temperature for 8 hours. The reaction solution was reprecipitated with 2500 mL of water, and the obtained white solid was vacuum-dried. Ethyl acetate was used for extraction, and hexane/ethyl acetate was used as a developing solvent, and silica gel column was used for purification. After removing the solvent with a rotary evaporator, vacuum drying was performed to obtain 3.8 g of compound (M-24-1).

． Synthesis of compound (MI-24)

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

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

[Synthesis Example 25]

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

[chem 44]

． Synthesis of compound (M-25-1)

In Synthesis Example 18, except for using 6-hydroxy-2-naphthoic acid methyl ester instead of 4-hydroxybenzoic acid methyl ester, it was synthesized by the same method to obtain 30.1 g of the compound (M-25- 1).

． Synthesis of compound (M-25-2)

In Synthesis Example 18, compound (M-25-1) was used instead of compound (M-18-2), except that, it was synthesized by the same method to obtain 15.0 g of compound (M-25-2 ).

． Synthesis of compound (MI-25)

In Synthesis Example 1, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4- 13.5 g of compound (MI-25) was obtained by the method similar to synthesis example 1 except having used compound (M-25-2) for carbonyl)oxy) phenyl) acrylic acid.

[Synthesis Example 26: Synthesis of Compound (MI-26)]

In Synthesis Example 1, except that 3-hydroxyphenylmaleimide was used instead of 4-hydroxyphenylmaleimide, 14.2 g Compound (MI-26).

[Synthesis Example 27: Synthesis of Compound (MI-27)]

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

． Synthesis of compound (M-27-1)

Take 6.90 g of (4-aminophenyl) ethanol in a 2000 mL three-necked flask equipped with a stirrer, add 200 g of tetrahydrofuran, and conduct an ice bath. A solution containing 5.11 g of maleic anhydride and 200 g of tetrahydrofuran was added dropwise thereto, and stirred at room temperature for 3 hours. Thereafter, the precipitated solid was recovered by filtration. This solid was vacuum-dried to obtain 11.5 g of Compound (M-27-1).

． Synthesis of compound (M-27-2)

10.9 g of compound (M-27-1), 9.38 g of zinc (II) chloride, and 250 g of toluene were added to a 500 mL three-necked flask equipped with a stirrer, and heated and stirred at 80°C. Add dropwise thereto the bis(trimethylsilyl)amine containing 14.8g and the formazan of 100g Benzene solution and stirred at 80°C for 5 hours. Thereafter, 300 g of ethyl acetate was added to the reaction liquid, and liquid separation washing with 1 mol/L hydrochloric acid was performed twice, liquid separation washing with an aqueous sodium bicarbonate solution was performed once, and liquid separation washing with saturated saline was performed once. . Thereafter, the organic layer was slowly concentrated using a rotary evaporator until the inner volume became 50 g, and the white solid precipitated on the way was collected by filtration. The white solid was vacuum-dried to obtain 5.86 g of compound (M-27-2).

． Synthesis of compound (MI-27)

Add 9.37g of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-linked( Cyclohexane)]-4-carbonyl)oxy)phenyl)acrylic acid, 25 g of thionyl chloride, 0.02 g of N,N-dimethylformamide, and stirred at 80° C. for 1 hour. Thereafter, excess thionyl chloride was removed using a diaphragm pump to obtain compound (M-27-3). 100 g of tetrahydrofuran was added thereto to prepare a solution A.

4.34 g of compound (M-27-2), 200 g of tetrahydrofuran, and 2.58 g of triethylamine were newly added to a 500 mL three-necked flask equipped with a stirrer, and ice-bathed. Solution A was added dropwise thereto and stirred at room temperature for 3 hours. The reaction liquid was reprecipitated with 800 mL of water, and the obtained white solid was vacuum-dried to obtain 8.78 g of compound (MI-27).

[Synthesis Example 28: Synthesis of Compound (MI-28)]

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

[chem 46]

In the synthesis of compound (MI-27) in Synthesis Example 27, 1-[4-(hydroxymethyl)phenyl was used as a raw material instead of compound (M-27-3) and compound (M-27-2) ] Pyrrole-2,5-dione and the compound (MI-28) of 24.1g were obtained by the method similar to the synthesis|combination of the compound (MI-27) of the synthesis example 27 except this.

[Synthesis Example 29: Synthesis of Compound (MI-29)]

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

[chem 47]

． Synthesis of compound (M-29-1)

15.1 g of 4-(4-aminophenyl)propan-1-ol and 1000 g of tetrahydrofuran were taken in a 2000 mL three-necked flask equipped with a stirrer, and 15.2 g of triethylamine was added thereto, followed by ice-bathing. A solution comprising 26.1 g of tert-butyl dicarbonate and 100 g of tetrahydrofuran was added dropwise thereto, and stirred at room temperature for 10 hours, after which 300 g of ethyl acetate was added to the reaction solution, and 4 times were performed using 200 g of distilled water. Liquid separation cleaning. Thereafter, the organic layer was slowly concentrated using a rotary evaporator until the inner volume became 100 g, and the white solid precipitated on the way was collected by filtration. The white solid was vacuum-dried to obtain 23.6 g of compound (M-29-1).

． Synthesis of compound (M-29-2)~compound (M-29-4)

In Synthesis Example 3, as a raw material, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutane base)-[1,1'-bi(cyclohexane)]-4-carbonyl)oxy)phenyl)acrylic acid and N-Boc-4-hydroxyaniline to use compound (M-29-1), except Except that, the compound (M-29-4) of 30.0g was obtained by the method similar to the synthesis example 3.

． Synthesis of compound (MI-29)

30.0 g of compound (M-29-4), 8.79 g of zinc (II) chloride, and 250 g of toluene were added to a 2000 mL three-necked flask equipped with a stirrer, and heated and stirred at 80°C. A solution containing 13.8 g of bis(trimethylsilyl)amine and 100 g of toluene was added dropwise thereto, and stirred at 80° C. for 5 hours. Thereafter, 300 g of ethyl acetate was added to the reaction liquid, and liquid separation washing with 1 mol/L hydrochloric acid was performed twice, liquid separation washing with an aqueous sodium bicarbonate solution was performed once, and liquid separation washing with saturated saline was performed once. . Thereafter, the organic layer was slowly concentrated using a rotary evaporator until the inner volume became 50 g, and the white solid precipitated on the way was collected by filtration. The white solid was vacuum-dried to obtain 9.18 g of compound (MI-29).

[Synthesis Example 30: Synthesis of Compound (MI-30)]

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

[chem 48]

． Synthesis of compound (M-30-1)

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

． Synthesis of compound (MI-30)

In the synthesis of compound (M-29-1) to compound (M-29-4) and compound (MI-29) in Synthesis Example 29, as a raw material, compound (M-29-1) was used instead of compound (M-29-1). -30-1), except that, the compound (MI-30) 32.0g was obtained by the method similar to the synthesis example 29.

[Synthesis Example 31: Synthesis of Compound (MI-31)]

In Synthesis Example 27, instead of (E)-3-(4-((4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)] -4-carbonyl)oxy)phenyl)acrylic acid (E)-3-(4-((4'-pentyl-[1,1'-bi(cyclohexane)]-4-carbonyl)oxy)phenyl)acrylic acid, in addition, by 14.4 g of compound (MI-31) was obtained in the same manner as in Synthesis Example 27.

[Comparative Example Synthesis Example 1 and Comparative Synthesis Example 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)]

In Synthesis Example 15, except that methacrylic acid was used instead of acrylic acid, compound (MI-34) was obtained by the same method as compound (MI-15) (see the following scheme 32).

[Synthesis Example 33: Synthesis of Compound (MI-35)]

In Synthesis Example 15, except that 4-hydroxy-3-methylphenylmaleimide was used instead of 4-hydroxyphenylmaleimide, by the same method as compound (MI-15), Compound (MI-35) was obtained by this method (see Scheme 33 below).

[Synthesis Example 34: Synthesis of Compound (MI-36)]

In Synthesis Example 15, in addition to using methacrylic acid instead of acrylic acid, and using 4-hydroxy-3-methylphenylmaleimide instead of 4-hydroxyphenylmaleimide, by Compound (MI-36) was obtained in the same manner as compound (MI-15).

[Synthesis Example 35: Synthesis of Compound (MI-37)]

In the synthesis of compound (MI-34), pentyltriphenylphosphonium iodide was used instead of 4,4,4-trifluorobutyltriphenylphosphonium iodide, and in addition, by combining with compound (MI- 34) Compound (MI-37) was obtained in the same manner (see Scheme 35 below).

[Chemical 51]

[Synthesis Example 36: Synthesis of Compound (MI-38)]

In the synthesis of compound (MI-35), pentyltriphenylphosphonium iodide was used instead of 4,4,4-trifluorobutyltriphenylphosphonium iodide, and in addition, by combining with compound (MI- 35) Compound (MI-38) was obtained by the same method.

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

In the synthesis of compound (MI-36), pentyltriphenylphosphonium iodide was used instead of 4,4,4-trifluorobutyltriphenylphosphonium iodide, and in addition, by combining with compound (MI- 36) Compound (MI-39) was obtained by the same method.

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

In the synthesis of compound (MI-37), except that 2-(trifluoromethyl)acrylic acid was used instead of methacrylic acid, compound (MI-40) was obtained by the same method as compound (MI-37). ).

[Synthesis Example 39: Synthesis of Compound (MI-41)]

In Synthesis Example 15, instead of 4-hydroxyphenylmaleimide, 4-hydroxy-3- Compound (MI-41) was obtained by the same method as compound (MI-15) except for methoxyphenylmaleimide. Furthermore, regarding 4-hydroxy-3-methoxyphenylmaleimide, 4-hydroxycyclohexylamine was used instead of 4-hydroxycyclohexylamine in the synthesis of compound (M-2-1) in Synthesis Example 2. -Hydroxy-3-methoxyaniline to synthesize.

[Synthesis Example 40: Synthesis of Compound (MI-42)]

In the synthesis of compound (M-37), instead of 4-hydroxyphenylmaleimide, 4-hydroxyl-3-fluorophenylmaleimide was used, and in addition, by combining with compound (MI- 37) Compound (MI-42) was obtained by the same method. Furthermore, regarding 4-hydroxyl-3-fluorophenylmaleimide, 3-fluorocyclohexylamine was used instead of 4-hydroxycyclohexylamine in the synthesis of compound (M-2-1) in Synthesis Example 2. -4-Hydroxyaniline to synthesize.

[Synthesis Example 41: Synthesis of Compound (MI-43)]

In the synthesis of compound (M-36), compound (MI-43) was obtained by the method similar to compound (MI-36) except having used 2-fluoroacrylic acid instead of methacrylic acid.

<Synthesis of Polymer>

[Example 1-1: Synthesis of polymer (P-1)]

Under nitrogen, 5.00 g (7.5 mmol) of the compound (MI-27) obtained in the synthesis example 27 and 1.05 g (7.5 mmol) of the compound (A- 3), 4.80g (33.8mmol) of compound (D-1), and 2.26g (26.3mmol) of compound (D-4), 0.39g (1.6mmol) of 2,2 as a radical polymerization initiator '-Azobis(2,4-dimethylvaleronitrile), 0.39 g (1.7 mmol) of 2,4-diphenyl-4-methyl-1-pentene as chain transfer agent, and 52.5 ml of N-methyl-2-pyrrolidone (NMP) was used as a vehicle, and polymerized at 70°C for 6 hours. After reprecipitation in methanol, the precipitate was filtered and vacuum-dried at room temperature for 8 hours, thereby obtaining the target polymer (P-1). The weight average molecular weight Mw measured by the polystyrene conversion by GPC was 30000, and the molecular weight distribution Mw/Mn was 2.

[Example 1-2~Example 1-45 and Comparative Polymerization Example 1-1~Comparative Polymerization Example 1-8]

Except that the monomers to be polymerized were the types and molar ratios shown in the following Tables 7 and 8, polymerization was carried out in the same manner as in Example 1-1 to obtain a weight equivalent to that of the polymer (P-1). Polymer (P-2)~polymer (P-45) and polymer (R-1)~polymer (R-8) of average molecular weight and molecular weight distribution. In addition, the total number of moles of polymerized monomers was set to 75.1 mmol in the same manner as in Example 1-1. The numerical values in Table 7 and Table 8 represent the input amount [mol %] of each monomer relative to all the monomers used in the synthesis of the polymer.

[Synthesis Example 42: Synthesis of Polyamic Acid]

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

<Manufacture and evaluation of optical vertical type liquid crystal display element>

[Example 2-1]

1. Preparation of liquid crystal alignment agent (AL-1)

NMP and butyl cellosolve (BC ), the solvent composition is made into a solution of NMP/BC=50/50 (mass ratio), and a solid content concentration of 3.5% by mass. The liquid crystal alignment agent (AL-1) was prepared by filtering the solution through a filter with a pore diameter of 1 μm.

2. Manufacture of optical vertical type liquid crystal display element

The prepared liquid crystal alignment 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 with a heating plate at 80° C. for 1 minute. Then, it heated at 230 degreeC for 1 hour in the oven which substituted the inside of a chamber with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. Next, using a Hg-Xe lamp and a Glan-Taylor prism, the surface of the coating film was irradiated with polarized ultraviolet rays of 1,000 J/m ² including a bright line of 313 nm from a direction inclined 40° from the normal line of the substrate. And endow the liquid crystal with alignment ability. Repeat the same operation to make a pair (two) of substrates with liquid crystal alignment films.

On the outer periphery of the surface with the liquid crystal alignment film of one of the substrates, use screen printing to coat the epoxy resin adhesive with alumina balls with a diameter of 3.5 μm, and then make the liquid crystal alignment film of the pair of substrates The surfaces faced each other, and pressure bonding was performed so that the optical axis of the ultraviolet rays of each substrate was antiparallel to the projection direction of the substrate surface, and the adhesive was thermally cured at 150° C. for 1 hour. Next, after filling the gap between the substrates from the liquid crystal injection port with a negative type liquid crystal (MLC-6608, manufactured by Merck), The epoxy-based adhesive seals the liquid crystal injection port. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, it heated at 130 degreeC, and cooled gradually to room temperature. Next, on the two outer surfaces of the substrate, the polarizing plates are attached in such a way that the polarization directions of the polarizing plates are perpendicular to each other and form an angle of 45° with the projection direction of the ultraviolet light of the liquid crystal alignment film on the substrate surface, thereby manufacturing a liquid crystal display element. .

3. Evaluation of voltage retention ratio (VHR)

For the liquid crystal display element produced in the above 2., after applying a voltage of 5 V for an application time of 60 microseconds and a span of 167 milliseconds, the voltage retention rate after 167 milliseconds after the release of the application was measured. As a measurement device, VHR-1 manufactured by TOYO Technica Co., Ltd. was used. At this time, when the voltage retention rate is 90% or more, it is rated as "excellent (A)", when it is 70% or more and less than 90%, it is rated as "good (B)", and when it is less than 70% Set to "Bad (C)". As a result, the voltage retention rate in this example was evaluated as "excellent (A)".

4. Evaluation of pretilt angle

Regarding the liquid crystal display element produced in the above 2., according to the non-patent literature (T.J. Scheffer et al. Journal of Applied Physics. Vol. vo.19, p.2013(1980))), the value of the inclination angle of the liquid crystal molecules relative to the substrate surface is measured by the crystal rotation method using He-Ne laser light, and the value is set as pretilt angle. At this time, when the pretilt angle is 85.0° or more and less than 88.0°, it is regarded as "excellent (A)", when it is 88.0° or more and less than 89.0°, it is regarded as "good (B)", and when it is 89.0° or more Or when it is less than 85.0°, it is set as "failure (C)". As a result, in this example, the pretilt angle was evaluated as "good (B)". price.

5. Evaluation of AC afterimage characteristics

The liquid crystal display element produced in the above-mentioned 2. was driven for 20 hours with an AC voltage of 15 V, and then the pretilt angle was measured, and the inclination difference Δθ was obtained by the following formula (1).

△θ=θ1-θ2…(1)

(In formula (1), θ1 is the pre-tilt angle before driving, and θ2 is the pre-tilt angle after driving)

When Δθ is 0.05° or less, it is rated as "Excellent (A)", when it is greater than 0.05° and less than 0.10°, it is rated as "Good (B)", and when it is greater than 0.10°, it is rated as "Bad". (C)". As a result, it was evaluated as "excellent (A)" in this Example.

[Example 2-2~Example 2-49, and Comparative Example 2-1~Comparative Example 2-8]

Except having changed the preparation composition as shown in following Table 9-Table 11, it prepared with the same solid content concentration as Example 1, and obtained the liquid crystal alignment agent, respectively. Moreover, the optical vertical type liquid crystal display element was manufactured similarly to Example 2-1 using each liquid crystal aligning agent, and various evaluations were performed. These results are shown in Tables 9 to 11 below. Furthermore, in Examples 2-8 and Examples 2-24, compound (ad-1) and compound (ad-2) were prepared as additives in liquid crystal alignment agents, respectively.

As shown in Tables 9 to 11, in Examples 2-1 to 2-49 using the liquid crystal alignment agent containing the polymer (P), the voltage retention rate was "A" or "B". In addition, the pretilt angle characteristics and AC afterimage characteristics are also "A" or "B", and at least one of them is "A" in the evaluation, and the electrical characteristics, pretilt angle characteristics, and AC afterimage characteristics are improved in a well-balanced manner. On the other hand, in the comparative example 2-1 - the comparative example 2-8 which used the liquid crystal alignment agent which does not contain a polymer (P), it was a result inferior to Example 2-1 - Example 2-49. In addition, in Comparative Example 2-2 and Comparative Example 2-4, the evaluation of the pretilt angle was "C", but these pretilt angles were all high values of 89° or more.

Claims (11)

A liquid crystal alignment agent, which contains a polymer (P), the polymer (P) has: a structural unit U1 derived from a compound represented by the following formula (1); and a structural unit U2 derived from the following formula (6) A compound represented by a compound different from the structural unit U1: (E ¹ ) _i -(G ¹ ) _j ... (1) (In formula (1), G ¹ is a ring having crosslinkability A group with a structure like structure, a group with an aromatic condensed polycyclic structure, or a group with a nitrogen-containing heterocyclic structure; ^E1 is a group with a polymerizable carbon-carbon unsaturated bond, and a group that forms a polymerizable carbon-carbon unsaturated bond At least one carbon atom is bonded by a single bond to a cyclic structure showing crosslinkability, an aromatic condensed polycyclic structure, or a nitrogen-containing heterocyclic ring in ^G1 , or via **-COO-, **-CONR ⁵⁰ -, **-CH ₂ -CONR ⁵⁰ -, -O-, or phenylene (wherein, "**" represents a bond to a carbon atom that forms a polymerizable carbon-carbon unsaturated bond bond) and bonding; R ⁵⁰ is a hydrogen atom, or represents a ring structure formed by R ⁵⁰ bonding with other groups; among i and j, one of them is 1 and the other is 2, or i=j=1 )

(In formula (6), B ¹ is a monovalent group represented by the following formula (7), formula (8), formula (9) or formula (10), D ¹ is represented by the following formula (11) Divalent group, X ¹ and X ² are independently single bond, -CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO -, -O-CH ₂ -, -CH ₂ -O- or alkanediyl with 1~3 carbons, A ¹ and A ² are independently substituted or unsubstituted phenylene, cyclohexylene or Naphthyl, R ¹⁸ is alkyl, alkoxy, fluoroalkyl, fluoroalkoxy or -R ¹⁹ -Y ¹ with 2 to 20 carbons (wherein, R ¹⁹ is alkanediyl with 2 to 20 carbons , Y ¹ is a trialkylsilyl group); m is an integer of 0 to 2, and n is an integer of 1 to 3; when m is 2, multiple A ¹ and X ¹ independently have the above definitions; In the case where n is 2 or 3, a plurality of R ¹⁸ each independently have the above definition)

(In formula (7), R ² and R ³ are independently a hydrogen atom or a methyl group; in formula (8), R ⁵ is a hydrogen atom or a monovalent organic group with more than one carbon number, R ⁶ and R ⁷ are respectively are independently a hydrogen atom or a methyl group; in formula (9), R ¹¹ is a hydrogen atom or a monovalent organic group with more than 1 carbon number, R ⁹ and R ¹⁰ are independently a hydrogen atom or a methyl group; X ¹⁰ and X One of ¹¹ is a single bond, and the other is a methylene group; in formula (10), R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group; "*" represents a bond)

(In formula (11), A ³ , A ⁴ and A ⁵ are each independently substituted or unsubstituted phenylene or cyclohexylene, L ¹ and L ² are each independently a single bond, carbon number 1~ 5's alkanediyl group, or at least one methylene group of said alkanediyl group substituted by "-O-" (wherein the oxygen atoms are not continuous), ^X3 and ^X4 are independently -CO-O -, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO- or -O-, R ¹⁶ and R ¹⁷ are independently hydrogen atom, methyl , a halogen atom or a cyano group; k and r are independently 0 or 1; "* ¹ " and "* ² "represent bonding bonds; among them, including the case where "* ¹ " is bonded to B ¹ , and "* ² ” in the case of bonding with B ¹ ). The liquid crystal alignment agent as described in Item 1 of the patent scope of the application, wherein the polymer (P) has an oxetanyl group and an oxetanyl group (wherein, the oxetanyl group contained in the structural unit U1 group and oxirane group) at least one. The liquid crystal alignment agent as described in claim 2, wherein the polymer (P) has a functional group that reacts with at least one of oxetanyl and oxiranyl by heating. The liquid crystal alignment agent as described in any one of items 1 to 3 in the scope of the patent application, wherein the polymer (P) has a composition selected from carboxyl groups, protected carboxyl groups, amine groups, and protected amine groups. At least one of the groups of . The liquid crystal alignment agent described in any one of items 1 to 3 of the scope of the patent application further contains polyamide acid, polyamide ester, and polyimide. At least one polymer in the group formed. The liquid crystal alignment agent described in any one of items 1 to 3 of the patent application, wherein the polymer (P) is a polymer having a photoalignment group. The liquid crystal alignment agent described in any one of the first to third items of the scope of the patent application, wherein the structural unit U2 has a partial structure represented by the following formula (b-1):

(In formula (b-1), A ⁶ , A ⁷ and A ⁸ are independently substituted or unsubstituted 1,4-cyclohexylene or 1,4-phenylene, X ⁵ is a single bond or oxygen atom, R ⁸⁰ is a fluoromethyl or methyl group, a1 is an integer of 0 to 2, a2 is an integer of 1 to 20, and a3 is 0 or 1; wherein, when R ⁸⁰ is a methyl group, a1=0; "*" indicates a bond key). A liquid crystal alignment film, which is formed by using the liquid crystal alignment agent described in any one of items 1 to 7 of the patent application. A liquid crystal element, which includes the liquid crystal alignment film described in item 8 of the patent application. A polymer, which has: a structural unit U1 derived from a compound represented by the following formula (1); and a structural unit U2 derived from a compound represented by the following formula (6), and combined with the structural unit U1 Different: (E ¹ ) _i -(G ¹ ) _j ... (1) (In formula (1), G ¹ is a group having a cyclic structure showing crosslinkability, a group having an aromatic condensed polycyclic structure, Or a group with a nitrogen-containing heterocyclic structure; E ¹ is a group with a polymerizable carbon-carbon unsaturated bond, and at least one carbon atom forming a polymerizable carbon-carbon unsaturated bond exhibits crosslinkability with G ¹ The ring structure of the ring structure, aromatic condensed polycyclic structure or nitrogen-containing heterocyclic structure is bonded by a single bond, or via **-COO-, **-CONR ⁵⁰ -, **-CH ₂ -CONR ⁵⁰ -, -O- or a phenylene group (wherein, "**" represents a bond bonded to a carbon atom forming a polymerizable carbon-carbon unsaturated bond); R ⁵⁰ is a hydrogen atom, or represents R ⁵⁰ is a ring structure formed by bonding with other groups; among i and j, one of them is 1 and the other is 2, or i=j=1)

(In formula (6), B ¹ is a monovalent group represented by the following formula (7), formula (8), formula (9) or formula (10), D ¹ is represented by the following formula (11) Divalent group, X ¹ and X ² are independently single bond, -CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO -, -O-CH ₂ -, -CH ₂ -O- or alkanediyl with 1~3 carbons, A ¹ and A ² are independently substituted or unsubstituted phenylene, cyclohexylene or Naphthyl, R ¹⁸ is alkyl, alkoxy, fluoroalkyl, fluoroalkoxy or -R ¹⁹ -Y ¹ with 2 to 20 carbons (wherein, R ¹⁹ is alkanediyl with 2 to 20 carbons , Y ¹ is a trialkylsilyl group); m is an integer of 0 to 2, and n is an integer of 1 to 3; when m is 2, multiple A ¹ and X ¹ independently have the above definitions; In the case where n is 2 or 3, a plurality of R ¹⁸ each independently have the above definition)

(In formula (7), R ² and R ³ are independently a hydrogen atom or a methyl group; in formula (8), R ⁵ is a hydrogen atom or a monovalent organic group with more than one carbon number, R ⁶ and R ⁷ are respectively are independently a hydrogen atom or a methyl group; in formula (9), R ¹¹ is a hydrogen atom or a monovalent organic group with more than 1 carbon number, R ⁹ and R ¹⁰ are independently a hydrogen atom or a methyl group; X ¹⁰ and X One of ¹¹ is a single bond, and the other is a methylene group; in formula (10), R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group; "*" represents a bond)

(In formula (11), A ³ , A ⁴ and A ⁵ are each independently substituted or unsubstituted phenylene or cyclohexylene, L ¹ and L ² are each independently a single bond, carbon number 1~ 5's alkanediyl group, or at least one methylene group of said alkanediyl group substituted by "-O-" (wherein the oxygen atoms are not continuous), ^X3 and ^X4 are independently -CO-O -, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO- or -O-, R ¹⁶ and R ¹⁷ are independently hydrogen atom, methyl , a halogen atom or a cyano group; k and r are independently 0 or 1; "* ¹ " and "* ² "represent bonding bonds; among them, including the case where "* ¹ " is bonded to B ¹ , and "* ² ” in the case of bonding with B ¹ ). A compound represented by the following formula (6):

(In formula (6), B ¹ is a monovalent group represented by the following formula (7), formula (8), formula (9) or formula (10), D ¹ is represented by the following formula (11) Divalent group, X ¹ and X ² are independently single bond, -CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO -, -O-CH ₂ -, -CH ₂ -O- or alkanediyl with 1~3 carbons, A ¹ and A ² are independently substituted or unsubstituted phenylene, cyclohexylene or Naphthyl, R ¹⁸ is alkyl, alkoxy, fluoroalkyl, fluoroalkoxy or -R ¹⁹ -Y ¹ with 2 to 20 carbons (wherein, R ¹⁹ is alkanediyl with 2 to 20 carbons , Y ¹ is a trialkylsilyl group); m is an integer of 0 to 2, and n is an integer of 1 to 3; when m is 2, multiple A ¹ and X ¹ independently have the above definitions; In the case where n is 2 or 3, a plurality of R ¹⁸ each independently have the above definition)

(In formula (7), R ² and R ³ are independently a hydrogen atom or a methyl group; in formula (8), R ⁵ is a hydrogen atom or a monovalent organic group with more than one carbon number, R ⁶ and R ⁷ are respectively are independently a hydrogen atom or a methyl group; in formula (9), R ¹¹ is a hydrogen atom or a monovalent organic group with more than 1 carbon number, R ⁹ and R ¹⁰ are independently a hydrogen atom or a methyl group; X ¹⁰ and X One of ¹¹ is a single bond, and the other is a methylene group; in formula (10), R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group; "*" represents a bond)

(In formula (11), A ³ , A ⁴ and A ⁵ are each independently substituted or unsubstituted phenylene or cyclohexylene, L ¹ and L ² are each independently a single bond, carbon number 1~ 5's alkanediyl group, or at least one methylene group of said alkanediyl group substituted by "-O-" (wherein the oxygen atoms are not continuous), ^X3 and ^X4 are independently -CO-O -, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO- or -O-, R ¹⁶ and R ¹⁷ are independently hydrogen atom, methyl , a halogen atom or a cyano group; k and r are independently 0 or 1; "* ¹ " and "* ² "represent bonding bonds; among them, including the case where "* ¹ " is bonded to B ¹ , and "* ² ” in the case of bonding with B ¹ ).