JP2017161602A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer and compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent which makes it possible to obtain a liquid crystal element having excellent display stability.SOLUTION: A liquid crystal aligning agent contains a polymer (PM) having a cyclic structure in which a structure represented by the formula (a1) forms part of a ring (Rand Rindependently represent a hydrogen atom, a halogen atom or a monovalent organic group, Rand Rmay bind to each other to form a ring. "*" and "*" each are a bond, where, "*" binds to a carbonyl group or >C=C(R)-*(Ris a hydrogen atom or a monovalent organic group, "*" is a bond binding to an oxygen atom in formula (a1)).SELECTED DRAWING: None

Description

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

  Conventionally, various types of liquid crystal elements having different liquid crystal operation principles have been developed. For example, a TN (Twisted Nematic) type, a STN (Super Twisted Nematic) type, a VA (Vertical Alignment) type, an IPS type ( Various liquid crystal elements such as an in-plane switching (FFS) type, an FFS (fringe field switching) type, and an OCB (Optically Compensated Bend) type are known. These liquid crystal elements have a liquid crystal alignment film for aligning liquid crystal molecules. As a material for the liquid crystal alignment film, polyamic acid or polyimide is generally used from the viewpoints of various properties such as heat resistance, mechanical strength, and affinity with liquid crystal. The liquid crystal alignment film is usually formed by applying a polymer composition in which a polymer component is dissolved or dispersed in a solvent to a substrate, and preferably heating (see, for example, Patent Document 1).

JP 2010-97188 A

  In recent years, demands for display performance of liquid crystal display panels have become more severe. For example, even when liquid crystal having a high response speed is used, a characteristic that can maintain stable display performance for a long period of time, that is, display stability is required. . There is also a need for new materials that can improve such display stability.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal element having good display stability.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by including a polymer or compound having a specific structure in the liquid crystal aligning agent. The present invention has been completed. Specifically, the present disclosure provides the following means.

（式（ａ１）中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、ハロゲン原子又は１価の有機基であり、Ｒ^１とＲ^２は互いに結合して環を形成していてもよい。「＊^１」及び「＊^２」は、それぞれ結合手であることを表す。ただし、「＊^１」は、カルボニル基又は＞Ｃ＝Ｃ（Ｒ^１２）−＊^３（Ｒ^１２は水素原子又は１価の有機基であり、「＊^３」は、式（ａ１）中の酸素原子に結合する結合手である。）に結合している。）
＜２＞ 下記式（ｃ１）で表される化合物を含有する液晶配向剤。

（式（ｃ１）中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、ハロゲン原子又は１価の有機基であり、Ｒ^１とＲ^２は互いに結合して環を形成していてもよい。Ｒ^１２は、水素原子又は１価の有機基である。Ｒ^１３は、単結合又は２価の連結基である。Ｒ^１４はｎ価の有機基であり、ｎは１〜１０の整数である。ｎが２以上の場合、複数のＲ^１、Ｒ^２、Ｒ^１２及びＲ^１３は、それぞれ独立して上記定義を有する。）
＜３＞ 上記＜１＞又は上記＜２＞の液晶配向剤を用いて形成された液晶配向膜。
＜４＞ 上記＜３＞の液晶配向膜を具備する液晶素子。
＜５＞ 下記式（ａ１−２）及び式（ａ１−３）で表される部分構造よりなる群から選ばれる少なくとも一種を有する重合体。

（式（ａ１−２）及び式（ａ１−３）中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、ハロゲン原子又は１価の有機基であり、Ｒ^１とＲ^２は互いに結合して環を形成していてもよい。Ｒ^１２は、水素原子又は１価の有機基である。Ｒ^１３は、単結合又は２価の連結基である。Ｒ^４１は、水素原子又は１価の有機基である。「＊」は、重合体の主鎖に結合する結合手であることを表す。）
＜６＞ 上記式（ｃ１）で表される化合物。 <1> A liquid crystal aligning agent containing a polymer (PM) having a cyclic structure in which a structure represented by the following formula (a1) forms part of a ring.

(In formula (a1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and R ¹ and R ² may be bonded to each other to form a ring. “* ¹ ” and “* ² ” each represent a bond, provided that “* ¹ ” represents a carbonyl group or> C═C (R ¹² ) − * ³ (R ¹² represents a hydrogen atom or 1 Is a valent organic group, and “* ³ ” is a bond bonded to an oxygen atom in the formula (a1).)
<2> A liquid crystal aligning agent containing a compound represented by the following formula (c1).

(In formula (c1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and R ¹ and R ² may be bonded to each other to form a ring. R ¹² is a hydrogen atom or a monovalent organic group, R ¹³ is a single bond or a divalent linking group, R ¹⁴ is an n-valent organic group, and n is an integer of 1 to 10. When n is 2 or more, a plurality of R ¹ , R ² , R ¹² and R ¹³ each independently have the above definition.)
<3> A liquid crystal alignment film formed using the liquid crystal aligning agent according to <1> or <2>.
<4> A liquid crystal element comprising the liquid crystal alignment film of <3> above.
<5> A polymer having at least one selected from the group consisting of partial structures represented by the following formula (a1-2) and formula (a1-3).

(In Formula (a1-2) and Formula (a1-3), R ¹ and R ² are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and R ¹ and R ² are bonded to each other. R ¹² may be a hydrogen atom or a monovalent organic group, R ¹³ may be a single bond or a divalent linking group, and R ⁴¹ may be a hydrogen atom or a monovalent organic group. “*” Represents a bond that is bonded to the main chain of the polymer.)
<6> A compound represented by the above formula (c1).

  According to the present disclosure, a liquid crystal element with good display stability can be obtained.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present disclosure includes a polymer (PM) having a cyclic structure (hereinafter also abbreviated as “specific cyclic structure”) in which the structure represented by the formula (a1) forms part of the ring, and the formula ( at least one of the compounds represented by c1) (hereinafter abbreviated as “compound (AM)”). Below, each component contained in the liquid crystal aligning agent of this indication and the other component arbitrarily mix | blended as needed are demonstrated.

In the present specification, “repeating unit” is a concept that means a monomer unit. Therefore, in the case of chain polymerization using one kind of monomer, the monomer and the repeating unit coincide with each other, and the chemical formula of the obtained polymer is represented by an integral multiple of the repeating unit. On the other hand, in the case of sequential polymerization, the monomer and the repeating unit do not match. For example, the repeating unit of the polymer obtained by sequential polymerization using the monomer A and the monomer B is “-AB”. -". “Organic group” means a group containing a hydrocarbon group, and the structure may contain a hetero atom.
The “hydrocarbon group” is a concept including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The “chain hydrocarbon group” means a linear or branched hydrocarbon group that does not include a cyclic structure and is composed only of a chain structure. The “alicyclic hydrocarbon group” means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure. However, it is not necessary to be constituted only by the structure of the alicyclic hydrocarbon, and a part thereof may have a chain structure. “Aromatic hydrocarbon group” means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure.

[Polymer (PM)]
In the above formula (1), examples of the monovalent organic group of R ¹ and R ² include a substituted or unsubstituted monovalent hydrocarbon group. R ¹ and R ² may be bonded to each other to form a ring. The ring formed in this case is preferably an aliphatic ring such as a cyclopentane ring or a cyclohexane ring. Specific examples in the case where R ¹ and R ² are halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable. R ¹ and R ² are preferably an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group.
The monovalent organic group for R ¹² is preferably an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group, and more preferably a methyl group or an ethyl group.

（式（ａ１−１）〜式（ａ１−３）中、Ｒ^１１は、水素原子又は１価の有機基であり、Ｒ^１３は、単結合又は２価の連結基である。Ｒ^１、Ｒ^２及びＲ^１２は、上記式（ａ１）と同義である。Ｒ^４１は、水素原子又は１価の有機基である。「＊」は、重合体の主鎖に結合する結合手であることを表す。） The polymer (PM) is a polymer having at least one selected from the group consisting of partial structures represented by the following formulas (a1-1) to (a1-3) as a partial structure including a specific cyclic structure. It is preferable that The polymer (PM) preferably has these partial structures in the side chain.

(In Formula (a1-1) to Formula (a1-3), R ¹¹ is a hydrogen atom or a monovalent organic group, and R ¹³ is a single bond or a divalent linking group. R ¹ , R ² and R ¹² have the same meaning as in the above formula (a1), R ⁴¹ represents a hydrogen atom or a monovalent organic group, and “*” represents a bond bonded to the main chain of the polymer. Represents.)

In the above formulas (a1-1) to (a1-3), the monovalent organic group of R ¹¹ and R ⁴¹ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group. preferable. R ¹¹ and R ⁴¹ are preferably a hydrogen atom or a methyl group.
Examples of the divalent linking group for R ¹³ include —O—, —CO—, —COO—, —NR ^a —, —CONR ^a — (wherein R ^a is a hydrogen atom, an alkyl having 1 to 5 carbon atoms). A substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms, and at least one methylene group of the hydrocarbon group is represented by —NR ^a —, —O—, —CO. And groups substituted with-, -COO- and the like. Examples of the substituent of the hydrocarbon group include a halogen atom.
R ¹³ is preferably a single bond, —O—, —CO—, —COO—, —NR ^a —, —CONR ^a —, or ^a divalent organic group having 1 to 6 carbon atoms. Preferable specific examples in the case where R ¹³ is a divalent organic group having 1 to 6 carbon atoms include an alkanediyl group having 1 to 6 carbon atoms, and at least one methylene group of the alkanediyl group is represented by —NR ^a —. And the group replaced by.

（式（ｄ１）中、Ｒ^３４は３価の有機基であり、Ｒ^３６は２価の有機基である。）

（式（ｂ１）中、Ｒ^３２は特定環状構造を有する基であり、Ｒ^３７は２価の有機基である。） The polymer (PM) is not particularly limited as long as it has a specific cyclic structure, but preferred specific examples include the following polymers <I> to <III>.
<I> A polymer (PM-D) having a repeating unit represented by the following formula (d1).
<II> A polymer (PM-A) having a repeating unit represented by the following formula (b1).
<III> A polymer (PM-B) having a structural unit derived from diamine having at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide and having a specific cyclic structure.

(In the formula (d1), R ³⁴ is a trivalent organic group, and R ³⁶ is a divalent organic group.)

(In the formula (b1), R ³² is a group having a specific cyclic structure, and R ³⁷ is a divalent organic group.)

（式（２）中、Ｒ^３２は特定環状構造を有する基であり、Ｒ^３３は３価の有機基である。）

（式（６）中、Ｒ^３０は１価の有機基である。） <I> Polymer (PM-D) In the above formula (d1), R ³² is not particularly limited as long as it has a specific cyclic structure, but the above formula (a1-1) to formula (a1-3) It is preferable that it is either of the partial structures represented by each. R ³⁴ is preferably a group in which three hydrogen atoms have been removed from the ring portion of the aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring is preferable.
The polymer (PM-D) is, among others, a kind selected from the group consisting of a dicarboxylic acid represented by the following formula (2), an epoxy group, a halogen atom, a group represented by the following formula (6), and a hydroxyl group. A polymer obtained by reacting a polyfunctional compound having two or more functional groups (hereinafter referred to as “polyfunctional compound (D)”) is preferable. In this case, R ³⁶ in the above formula (d1) is a divalent group derived from the polyfunctional compound (D).

(In formula (2), R ³² is a group having a specific cyclic structure, and R ³³ is a trivalent organic group.)

(In the formula (6), R ³⁰ is a monovalent organic group.)

（式（２１）及び式（２２）中、Ｒ^１及びＲ^２は、上記式（ａ１）と同義である。） In the above formula ^(2), for ^{R 33} is the description of ^{R 34} in the formula (d1) is ^applied, for ^{R 32} is the description of ^{R 32} in the formula (d1) is applied.
Specific examples of the compound represented by the formula (2) include compounds represented by the following formulas (21) and (22). Among these, a compound represented by the following formula (21) can be preferably used. In addition, the compound represented by the said Formula (2) can be used individually by 1 type or in combination of 2 or more types.

(In Formula (21) and Formula (22), R ¹ and R ² have the same meanings as in Formula (a1) above).

（スキーム２中、Ｒ^３２及びＲ^３３は上記式（２）と同義であり、Ｒ^５は、単結合又は２価の有機基である。） The polyfunctional compound (D) only needs to have two or more functional groups selected from the group consisting of an epoxy group, a halogen atom, a group represented by the above formula (6), and —COX ^2. The remaining structure is not particularly limited. When the polyfunctional compound (D) is an epoxy group-containing compound, for example, according to the following scheme 2, a polymer having a repeating unit represented by the following formula (1-1) is obtained as a polymer (PM-D). Can do.

(In Scheme 2, R ³² and R ³³ have the same meanings as the above formula (2), and R ⁵ is a single bond or a divalent organic group.)

（式（３−１）〜式（３−３）中、Ｒ^１８は２価の有機基であり、Ｚ^１は単結合又は２価の連結基であり、ｍは１〜６の整数であり、ｋは０〜１２の整数である。） As the epoxy group-containing compound represented by the above formula (3), a commercially available polyfunctional epoxy compound can be used. Preferable specific examples include, for example, compounds represented by the following formulas (3-1) to (3-3).

(In the formulas (3-1) to (3-3), R ¹⁸ is a divalent organic group, Z ¹ is a single bond or a divalent linking group, and m is an integer of 1 to 6. , K is an integer from 0 to 12.)

（式中、「＊」は結合手であることを表す。） R ^{18 in the} above formula (3-1) is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and at least one methylene group of the hydrocarbon group is replaced with —O—, —CO— or the like. Groups and the like. R ¹⁸ is preferably a group having an aromatic ring or a condensed ring from the viewpoint that the effect of improving the display stability is high, and specific examples thereof include groups represented by the following formulas.

(In the formula, “*” represents a bond.)

M in the above formula (3-1) is preferably 1 to 3, and more preferably 1. K in the formula (3-2) is preferably 0 to 8, and more preferably 0 to 4. In the above formula (3-3), specific examples of the divalent linking group for Z ¹ include the groups exemplified for R ¹³ in the above formulas (a1-1) to (a1-3). Z ¹ is preferably —COO—.

  The reaction between the compound represented by the above formula (2) and the epoxy group-containing compound is preferably carried out in an organic solvent. The proportion of the monomer used is preferably 0.5 to 1.5 moles, preferably 0.8 to 1.2 moles of the epoxy group-containing compound with respect to 1 mole of the compound represented by the above formula (2). It is more preferable. As the solvent used in the above reaction, for example, an amide, ether, ester or hydrocarbon solvent can be used. Among these, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, γ-butyrolactone, anisole, diphenyl ether and the like are preferable. The proportion of the solvent used is preferably such that the monomer concentration is 1 to 50% by mass, more preferably 10 to 40% by mass. The reaction temperature is preferably 20 to 200 ° C, more preferably 50 to 180 ° C.

  In the above reaction, a catalyst may be used as necessary. The catalyst used is preferably an epoxy compound effect accelerator, and specifically includes tertiary amine salts such as imidazoles and tetrabutylammonium bromide. The ratio of the catalyst used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the compound represented by the above formula (2) and the epoxy group-containing compound, More preferably.

（式（１１）及び式（１２）中、Ｒ^３１及びＲ^３７は、それぞれ独立に２価の有機基である。） <II> Polymer (PM-A) In the above formula (b1), R ³² is any one of the partial structures represented by each of the above formulas (a1-1) to (a1-3). Is preferred. The method for synthesizing the polymer (PM-A) is not particularly limited, and can be appropriately selected according to R ³⁷ in the polymer (PM). A preferred synthesis method includes a method in which a polymer having a repeating unit represented by the following formula (11) or a repeating unit represented by the following formula (12) is reacted with a compound having a specific cyclic structure. .

(In Formula (11) and Formula (12), R ³¹ and R ³⁷ are each independently a divalent organic group.)

（スキーム５中、Ｒ^１及びＲ^２は上記式（ａ１）と同義であり、Ｒ^３７は上記式（ｂ１）と同義である。） R ³⁷ in the above formula (b1), formula (11) and formula (12) is preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an ethylene group.
Reaction of the polymer which has a repeating unit represented by the said Formula (11) or the repeating unit represented by the said Formula (12), and the compound which has a specific cyclic structure can be performed in accordance with the usual method of organic chemistry. As an example, for example, as shown in Scheme 5 below, a polymer (PM-A) having a repeating unit represented by the following formula (1-4) is allowed to undergo an addition reaction in the presence of an excess amount of triethyl formate. Coalescence can be obtained.

(In Scheme 5, R ¹ and R ² have the same meaning as in the above formula (a1), and R ³⁷ has the same meaning as in the above formula (b1).)

<III> About polymer (PM-B)-Polyamic acid When the polymer (PM-B) is a polyamic acid, the polyamic acid is, for example, a tetracarboxylic dianhydride and a diamine having a specific cyclic structure (hereinafter referred to as "polyamic acid"). , Abbreviated as “specific diamine”.) And a diamine compound.
Examples of the tetracarboxylic dianhydride used in the above reaction include an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, and an aromatic tetracarboxylic dianhydride. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride;

As the alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro 3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0] Octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride, bicyclo [2.2.1] heptane-2,3,5,6- Tetracarboxylic acid 2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2 , 4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclo Pentanetetracarboxylic dianhydride, ethylene glycol Bis (anhydro trimellitate), 1,3-propylene glycol bis (anhydro trimellitate), p-phenylene bis (trimellitic acid monoester anhydride), etc .;
Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like; respectively, and tetracarboxylic dianhydrides described in JP 2010-97188 A can be used. Tetracarboxylic dianhydride can be used alone or in combination of two or more thereof.

（式（７）中、Ｒ^３５は特定環状構造を有する１価の有機基である。） Although it will not restrict | limit especially if specific diamine has a specific cyclic structure, For example, the compound etc. which are represented by following formula (7) are mentioned.

(In formula (7), R ³⁵ is a monovalent organic group having a specific cyclic structure.)

（式（７−１）〜式（７−４）中、Ｒ^１及びＲ^２は、上記式（ａ１）と同義である。） R ^{35 in the} above formula (7) is preferably any one of the partial structures represented by each of the above formulas (a1-1) to (a1-3). Two primary amino ^groups, it is preferred for ^{R 35} is a 2,4-position or 3,5-position. Specific examples of the compound represented by the formula (7) include compounds represented by the following formulas (7-1) to (7-4). In addition, a specific diamine may be used individually by 1 type, and may be used in combination of 2 or more type.

(In the formulas (7-1) to (7-4), R ¹ and R ² have the same meanings as the above formula (a1).)

（式（Ｅ−１）中、Ｘ^I及びＸ^IIは、それぞれ独立に、単結合、−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−であり、Ｒ^Ｉは炭素数１〜３のアルカンジイル基であり、Ｒ^ＩＩは単結合又は炭素数１〜３のアルカンジイル基であり、ａは０又は１であり、ｂは０〜２の整数であり、ｃは１〜２０の整数であり、ｄは０又は１である。但し、ａ及びｂが同時に０になることはない。）
で表される化合物などを挙げることができるほか、特開２０１０−９７１８８号公報に記載のジアミン化合物を用いることができる。 In synthesizing the polyamic acid, the specific diamine may be used alone, or a diamine other than the specific diamine (hereinafter abbreviated as “other diamine”) may be used in combination. Specific examples of other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples thereof include, for example, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 4-aminophenyl-4′-aminobenzoate, 4,4 ′. -Diaminoazobenzene, 1,5-bis (4-aminophenoxy) pentane, 1,7-bis (4-aminophenoxy) heptane, bis [2- (4-aminophenyl) ethyl] hexanedioic acid, N, N- Bis (4-aminophenyl) methylamine, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diamino Biphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) Enyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro Propane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′- Bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3, 6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarb Vazole, N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -Piperazine, 3,5-diaminobenzoic acid, o-tolidine, 1,3-bis (4-aminophenyl) -2-propenoic acid, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino -2,3,5,6-tetramethylbenzene, 4,4'-diamino-3,3'-dimethoxybiphenyl, dodecanoxydiaminobenzene, octadecanoxydiaminobenzene, 1,3-bis (3-amino Propyl) -tetramethyldisiloxane, the following formula (E-1)

(In formula (E-1), X ^I and X ^II are each independently a single bond, —O—, —COO— or —OCO—, and R ^I is an alkanediyl group having 1 to 3 carbon atoms. R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1, provided that a and b are not 0 at the same time.)
In addition, diamine compounds described in JP 2010-97188 A can be used.

その他のジアミンは、１種を単独で又は２種以上を組み合わせて使用することができる。 Specific examples of the compound represented by the formula (E-1) include compounds represented by the following formula (E-1-1) and formula (E-1-2), for example. .

Other diamines can be used singly or in combination of two or more.

  A polyamic acid can be obtained by reacting the tetracarboxylic dianhydride and the diamine compound as described above together with a molecular weight modifier as necessary. The ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 with respect to 1 equivalent of the amino group of the diamine compound. A ratio of ˜2 equivalents is preferred. In synthesizing the polyamic acid, the specific diamine is preferably used in an amount of 10 mol% or more based on the total of the diamine compound used in the synthesis, from the viewpoint of sufficiently obtaining the effect of improving the display stability. It is more preferable to set it as 80 mol%, and it is more preferable to set it as 25-70 mol%.

  Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. Can be mentioned. It is preferable that the usage-amount of a molecular weight modifier shall be 20 mass parts or less with respect to 100 mass parts of total of the tetracarboxylic dianhydride and diamine compound to be used.

The polyamic acid synthesis reaction is preferably carried out in an organic solvent. The reaction temperature at this time is preferably −20 ° C. to 150 ° C. The reaction time is preferably 0.1 to 24 hours. Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol. And at least one selected from the group consisting of halogenated phenols, or a mixture of one or more of these with another organic solvent (for example, butyl cellosolve, diethylene glycol diethyl ether, etc.) preferable. The amount (a) of the organic solvent used is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 50% by mass with respect to the total amount (a + b) of the reaction solution. It is preferable.
As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution.

-Polyamic acid ester The polyamic acid ester as a polymer (PM-B) can be obtained, for example, by a method of reacting a tetracarboxylic acid diester dihalide with a diamine compound. The tetracarboxylic acid diester dihalide to be used is obtained by reacting, for example, tetracarboxylic dianhydride exemplified in the synthesis of polyamic acid with alcohols such as methanol and ethanol to obtain a tetracarboxylic acid diester, and then thionyl chloride. It can obtain by making it react with suitable chlorinating agents, such as. As the diamine compound, a specific diamine may be used alone, or another diamine may be used in combination. Specific examples of the diamine compound to be used include specific diamines and other diamines exemplified in the description of the synthesis of polyamic acid.

  The ratio of the tetracarboxylic acid diester dihalide and the diamine compound used in the synthesis reaction of the polymer (PM-B) is such that the tetracarboxylic acid diester dihalide group “—COX” is equivalent to 1 equivalent of the amino group of the diamine. The ratio in which “X is a halogen atom” ”is 0.2 to 2 equivalents is preferable. The reaction between the tetracarboxylic acid diester dihalide and the diamine compound is preferably carried out in an organic solvent in the presence of a base. The reaction temperature at this time is preferably −30 ° C. to 150 ° C. The reaction time is preferably 0.1 to 48 hours. As the organic solvent used for the reaction, the description of the organic solvent that can be used for the polyamic acid synthesis reaction can be applied. Examples of the base used in the above reaction include tertiary amines such as pyridine, triethylamine, N-ethyl-N, N-diisopropylamine; sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium, potassium and the like. These alkali metals can be preferably used. It is preferable that the usage-amount of a base shall be 2-4 mol with respect to 1 mol of diamines.

  As described above, a reaction solution obtained by dissolving the polyamic acid ester is obtained. This reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid ester contained in the reaction solution. The polyamic acid ester may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. The method for synthesizing the polyamic acid ester is not limited to the above. For example, a method of reacting a polyamic acid as a polymer (PM-B) with an alcohol or an alkyl halide, and reacting a tetracarboxylic acid diester with a diamine compound. It can also be obtained by the method of making it.

-Polyimide The polyimide as a polymer (PM-B) can be obtained by dehydrating and ring-closing the polyamic acid synthesize | combined as mentioned above, for example. When polyamic acid is dehydrated and cyclized into polyimide, the polyamic acid reaction solution may be subjected to dehydration and cyclization reaction as it is, or the polyamic acid contained in the reaction solution is isolated and subjected to dehydration and cyclization reaction. Also good.

  The polyimide may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure possessed by the polyamic acid that is the precursor, and only a part of the amic acid structure may be dehydrated and cyclized. It may be a partially imidized product in which a ring structure coexists. The polyimide used for the reaction preferably has an imidation ratio of 20% or more, more preferably 30 to 99%. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.

The polyamic acid is preferably dehydrated and closed by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating the solution as necessary. . Of these, the latter method is preferred. In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to a polyamic acid solution, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C. The reaction time is preferably 1.0 to 120 hours.
In this way, a reaction solution containing polyimide is obtained. This reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, and the liquid crystal after isolating the polyimide. You may use for preparation of an orientation agent.

  The solution viscosity of the polymer (PM) is appropriately selected according to the main skeleton, but when this is a solution having a concentration of 10% by mass, the solution viscosity is preferably 10 to 800 mPa · s, More preferably, it has a solution viscosity of 15 to 500 mPa · s. The solution viscosity (mPa · s) of the polymer (PM) is 10% by mass with a concentration of 10% by mass prepared using a good solvent for the polymer (PM) (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using an E-type viscometer for the polymer solution.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) for the polymer (PM) is preferably 1,000 to 500,000, more preferably 2,000 to 300, 000. Moreover, the molecular weight distribution (Mw / Mn) represented by the ratio between Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.
The blending ratio of the polymer (PM) in the liquid crystal aligning agent is preferably 1 mass with respect to a total of 100 parts by mass of the polymer contained in the liquid crystal aligning agent from the viewpoint of obtaining a liquid crystal element having good display stability. Part or more, more preferably 5 parts by weight or more.

（式（８−１）及び式（８−２）中、ａは１〜１２の整数である。） [Compound (AM)]
In the above formula (c1), the description of the above formula (a1) can be applied to the monovalent organic groups of R ¹ and R ² , and the monovalent organic group of R ¹² can be applied to the above formula (a1-3). The description of can be applied. Examples of R ¹⁴ include a hydrocarbon group having 1 to 20 carbon atoms or a group in which at least one methylene group of the hydrocarbon group is replaced with —O—, —CO—, —COO— or the like. The description of R ^{13 in} the above formulas (a1-1) to (a1-3) is applied to the description of R ¹³ . R ¹⁴ preferably has 1 to 12 carbon atoms. n is preferably from 2 to 6, and more preferably from 2 to 4.
Preferable specific examples of the compound (AM) include compounds represented by the following formulas (8-1) to (8-3), for example.

(In Formula (8-1) and Formula (8-2), a is an integer of 1 to 12)

A compound (AM) is compoundable according to the usual method of organic chemistry. As an example, “X ⁴ -R ⁴⁰ -X ⁴ (R ⁴⁰ is a divalent hydrocarbon group, X ⁴ is a halogen atom)” and t-butyl acetoacetate are reacted in the presence of a base. And then condensed by dihalogen. However, the synthesis method of the compound (AM) is not limited to the above.
The compounding ratio of the compound (AM) in the liquid crystal aligning agent is preferably 1 part by mass or more and 5 to 50 parts by mass with respect to 100 parts by mass in total of the polymer components in the liquid crystal aligning agent. More preferred. In addition, a compound (AM) can be used individually by 1 type or in combination of 2 or more types.

<Other ingredients>
The liquid crystal aligning agent of this indication may contain other ingredients other than a polymer (PM) and a compound (AM). Such other components include, for example, a polymer having no specific cyclic structure (hereinafter also referred to as “other polymer”), a low molecular weight compound having a Meldrum acid structure and a molecular weight of 500 or less (hereinafter referred to as “Meldrum acid structure-containing”). Compound ")) and the like.

The above other polymers can be used to improve various properties (for example, printability and electrical properties) required for the liquid crystal aligning agent and the liquid crystal element. Examples of the other polymer include polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, or poly (meth) acrylate. . Among these, at least one polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, and polyorganosiloxane can be preferably used. In addition, the other polymer may use what was synthesize | combined according to the well-known method, and may use a commercial item.
When other polymers are blended with the liquid crystal aligning agent of the present disclosure, the blending ratio of the polymer (PM) is the weight contained in the liquid crystal aligning agent in order to sufficiently improve the display stability of the liquid crystal element. It is preferable to set it as 5-90 mass parts with respect to 100 mass parts of total amounts of a coalescence (PM) and another polymer, and it is more preferable to set it as 10-80 mass parts.

When preparing a liquid crystal aligning agent using a compound (AM), a liquid crystal aligning agent may be made to contain at least 1 type of polymer chosen from the group which consists of a polyamic acid, a polyimide, and a polyamic acid ester with a compound (AM). preferable. In this case, the polyamic acid, the polyimide, and the polyamic acid ester may be a polymer (PM) or other polymer.
In preparing the liquid crystal aligning agent, the blending ratio of the polyamic acid, polyimide and polyamic acid ester used together with the compound (AM) is included in the liquid crystal aligning agent from the viewpoint of obtaining a liquid crystal element having good liquid crystal aligning properties and electrical characteristics. Preferably it is 50 mass parts or more with respect to a total of 100 mass parts of polyamic acid, a polyimide and polyamic acid ester, and a compound (AM), More preferably, it is 60-99 mass parts, More preferably, it is 70-95 mass parts.

（式（９−２）及び式（９−３）中、ｊ、kはそれぞれ独立に２〜１０の整数である。） Examples of the Meldrum's acid structure-containing compound to be blended in the liquid crystal aligning agent include compounds having one or more partial structures represented by the above formula (a1-1) or formula (a1-2). Examples include compounds represented by formulas (9-1) to (9-5).

(In Formula (9-2) and Formula (9-3), j and k are each independently an integer of 2 to 10).

J and k in the above formula (9-2) and formula (9-3) are preferably 2 to 6.
When the Meldrum's acid structure-containing compound is blended in the liquid crystal aligning agent, the blending ratio is preferably 30 parts by mass or less with respect to a total of 100 parts by mass of the polymer contained in the liquid crystal aligning agent. It is more preferable to set it as -20 mass parts.

  In addition to the above, other components include compounds having at least one epoxy group in the molecule, functional silane compounds, compounds having at least one oxetanyl group in the molecule, antioxidants, metal chelate compounds, curing Accelerators, surfactants, fillers, dispersants, photosensitizers and the like can be mentioned. These blending proportions can be appropriately selected according to each compound within a range not impairing the effects of the present invention.

(solvent)
The liquid crystal aligning agent of the present disclosure is preferably a liquid in which at least one of the polymer (PM) and the compound (AM) and other components used as necessary are preferably dispersed or dissolved in an appropriate solvent. Prepared as a composition.

  Examples of the organic solvent used include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, γ-butyrolactone, γ-butyrolactam, and N, N-dimethylformamide. N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether Ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, A propylene carbonate etc. can be mentioned. These can be used alone or in admixture of two or more.

  The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc. It is the range of 1-10 mass%. That is, the liquid crystal aligning agent is applied to the substrate surface as will be described later, and preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by mass, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive, and the viscosity of the liquid crystal aligning agent increases and the applicability decreases. There is a tendency.

<Liquid crystal element>
The liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal aligning agent described above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited. For example, various modes such as TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type, etc. Can be applied to. The liquid crystal element of this indication can be manufactured by the method of including the following processes 1-3, for example. In step 1, the substrate to be used varies depending on the desired operation mode. Step 2 and step 3 are common to each operation mode.

[Step 1: Formation of coating film]
First, a liquid crystal aligning agent is applied on the substrate, and then the coating surface is heated to form a coating film on the substrate. As the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used. In the case of manufacturing a TN type, STN type, or VA type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. In the case of manufacturing an IPS-type or FFS-type liquid crystal element, a substrate provided with an electrode made of a transparent conductive film or metal film patterned in a comb shape and a counter substrate provided with no electrode are used. . As the metal film, for example, a film made of a metal such as chromium can be used. Application to the substrate is preferably performed on the electrode forming surface by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method.

  After applying the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent. The prebake temperature is preferably 30 to 200 ° C. The pre-bake time is preferably 0.25 to 10 minutes. Then, a baking (post-baking) process is implemented for the purpose of removing a solvent completely and heat imidating the amic acid structure which exists in a polymer as needed. The firing temperature (post-bake temperature) at this time is preferably 80 to 300 ° C., and the post-bake time is preferably 5 to 200 minutes. The thickness of the film thus formed is preferably 0.001 to 1 μm. After applying the liquid crystal aligning agent on the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film that becomes the liquid crystal alignment film.

[Step 2: Orientation treatment]
When manufacturing a TN type, STN type, IPS type, FFS type, or OCB type liquid crystal element, a treatment (orientation treatment) for imparting liquid crystal alignment ability to the coating film formed in the above step 1 is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. As the alignment treatment, for example, a rubbing treatment that imparts liquid crystal alignment ability to the coating film by rubbing the coating film in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, cotton, etc., a coating film formed on the substrate And a photo-alignment treatment for imparting liquid crystal alignment ability to the coating film. On the other hand, when manufacturing a vertical alignment type liquid crystal element, the coating film formed in the above step 1 can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment treatment.

[Step 3: Construction of liquid crystal cell]
Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates disposed to face each other. As a method of manufacturing a liquid crystal cell, for example, (1) two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are sealed. A method of sealing the injection hole after injecting and filling the liquid crystal into the cell gap defined by the surface of the substrate and the sealing agent, and (2) on one of the two substrates For example, an ultraviolet light curable sealant is applied in a predetermined place, and after dropping liquid crystal in predetermined places on the liquid crystal alignment film surface, the other substrate is bonded so that the liquid crystal alignment film faces each other. Examples include a method of spreading the liquid crystal over the entire surface of the substrate and then curing the sealant.

  As the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyls. Cyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, for example, a cholesteric liquid crystal, a chiral agent, or a ferroelectric liquid crystal may be added to these liquid crystals.

  Subsequently, a liquid crystal element is obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell as necessary. Examples of the polarizing plate include a polarizing plate comprising a polarizing film called an “H film” in which iodine is absorbed while stretching and orientation of polyvinyl alcohol is sandwiched between cellulose acetate protective films, or a polarizing plate made of the H film itself.

  The liquid crystal element of the present disclosure can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors. It can be used for various display devices such as liquid crystal televisions, light control films and the like. Moreover, the liquid crystal element formed using the liquid crystal aligning agent of this indication can also be applied to retardation film.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

In the following examples, the imidization ratio of the polymer and the solution viscosity of the polymer solution were measured by the following methods. Hereinafter, the compound represented by Formula X may be simply referred to as “Compound X”.
[Weight Average Molecular Weight Mw of Polymer]: A polystyrene conversion value measured by GPC under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: N, N-dimethylformamide (containing 30 mM lithium bromide and 5.6 mL phosphoric acid)
Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Solution viscosity of polymer solution (mPa · s)]: Measured at 25 ° C. using an E-type rotational viscometer.
[Epoxy equivalent]: Measured according to “hydrochloric acid-methyl ethyl ketone method” of JIS C2105.

[Synthesis Example 1]
Compound (2-1) was synthesized according to the following scheme 10.

  Meldrum acid (14.4 g) and trimethyl orthoformate (300 g) were added to a 500 mL eggplant flask equipped with a reflux tube and a nitrogen introduction tube, and the mixture was refluxed for 1 hour. After completion of the reaction, the precipitate was filtered, washed with hexane, and dried under vacuum to obtain 26.8 g of compound (2-1).

[Synthesis Example 2]
Compound (8-1-1) was synthesized according to the following scheme 11.

-Synthesis | combination of a compound (8-1A) 15.8 g of t-butyl acetoacetates, 600 mL of tetrahydrofuran, and 5.28 g of 50% (mineral oil) sodium hydride were added to a 1 L three neck flask equipped with a thermometer and a nitrogen introduction tube. Stir for 10 minutes. Subsequently, 10.8 g of 1,4-dibromobutane was added, and the mixture was returned to room temperature for 3 hours at 0 ° C. and stirred for a whole day and night. After completion of the reaction, 400 mL of 1M aqueous hydrochloric acid and diethyl ether were added to remove the aqueous layer, and after separating and washing three times with water, the organic layer was dried over magnesium sulfate, concentrated and dried. Then, it was fractionated with a silica column (developing solvent: hexane: ethyl acetate = 9: 1), concentrated and dried to obtain 11.1 g of compound (8-1A).
Synthesis of compound (8-1-1) To a 100 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube was added 11.1 g of the compound (8-1A), 12 mL of acetone, 4.3 mL of acetic anhydride, and 1 mL of concentrated sulfuric acid. The reaction was carried out at 30 ° C. for 24 hours. After completion of the reaction, diethyl ether was added and the mixture was washed three times with water, and then the organic layer was dried over magnesium sulfate, concentrated and dried. Then, it fractionated by the silica column (developing solvent: hexane: ethyl acetate = 9: 1), concentrated, and dried to obtain 6.09 g of the compound (8-1-1).

[Polymerization Example 1A]
In a 100 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 3.35 g of the compound (2-1) as the dicarboxylic acid, 3.40 g of the compound represented by the following formula (EP1) as the polyfunctional compound (D), N -Charged 35.3 g of methyl-2-pyrrolidone (NMP) (in which the monomer concentration is 20% by mass) and 0.44 g of imidazole (corresponding to 5 parts by mass with respect to 100 parts by mass of monomer), and at 80 ° C. for 12 hours. Reacted. After completion of the reaction, the reaction solution was poured into 10 times the amount of methanol, and the deposited precipitate was collected by filtration, washed with methanol, and then vacuum dried to obtain 6.08 g of polymer (PM1). Mw was 11000.

[Polymerization Examples 2A to 5A]
Polymerization was performed in the same manner as in Polymerization Example 1A with the monomer composition shown in Table 1 below.

In Table 1 above, compounds (EP1) to (EP5) are compounds represented by the following formulae, respectively.

[Polymerization Example 6A]
After adding 14.4 g of Meldrum's acid and 200 g of trimethyl orthoformate to a 500 mL eggplant flask equipped with a reflux tube and a nitrogen introduction tube, the mixture was refluxed for 1 hour, and then 11.8 g of Epomin SP-200 (manufactured by Nippon Shokubai Co., Ltd.) was added. Reflux for hours. After completion of the reaction, the reaction solution was poured into cyclohexane, and the deposited precipitate was filtered, washed with methanol, and vacuum-dried to obtain 21.0 g of a polymer (PM6).

[Polymerization Example 1B]
200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 210 g (1, .2) of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine. 0 mol) was dissolved in a mixed solvent of 370 g of NMP and 3300 g of γ-butyrolactone and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a solid content concentration of 10 mass% and a solution viscosity of 160 mPa · s. The obtained polyamic acid was used as a polymer (PA1).
[Polymerization Example 2B]
6.41 g (100 mole parts) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride, 4.11 g of compound represented by the following formula (D-1) as diamine (40 Mol part) and 9.48 g (60 mol part) of a compound represented by the following formula (D-2) are dissolved in 80 g of NMP and reacted at 40 ° C. for 3 hours to obtain a solid content concentration of 20% by mass and a solution viscosity of 100 mPa · A polyamic acid solution of s (measured value at a solid content concentration of 10% by mass) was obtained. The obtained polyamic acid was used as a polymer (PA2).

[Polymerization Example 3B]
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine, and room temperature. And mixed. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with 0.2% by mass aqueous ammonium nitrate solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain polyorganosiloxane (EPS- 1) was obtained as a viscous transparent liquid.
When this polyorganosiloxane (EPS-1) was subjected to ¹ H-NMR analysis, a peak based on the oxiranyl group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction occurred. Mw of the polyorganosiloxane (EPS-1) was 2200, and the epoxy equivalent was 186 g / mol.

[Polymerization Example 4B]
In a 100 mL three-necked flask, 1.77 g of polyorganosiloxane (EPS-1) synthesized in the above Polymerization Example 3B, 22.3 g of cyclopentanone, and 0.84 g of carboxylic acid represented by the following formula (C-1) ( The polyorganosiloxane (EPS-1) is equivalent to 20 mol% with respect to silicon atoms) and the trade name “UCAT 18X” (manufactured by San Apro Co., Ltd., epoxy compound curing accelerator) is charged for 5 hours. Refluxed. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate. A solution obtained by dissolving the precipitate in ethyl acetate was washed with water three times, and then the solvent was distilled off to remove the polymer (S1). 2.1 g of white powder was obtained. The weight average molecular weight of the polymer (S1) was 9800.

[Example 1]
(1) Preparation of Liquid Crystal Alignment Agent 10 parts by mass of the polymer (S1) obtained in Polymerization Example 4B and 90 parts by mass of the polymer (PM1) obtained by Polymerization Example 1A were used as polymers. -Phenoxyethanol (PE) was added, and it was set as the solution whose solvent composition is NMP: PE = 50: 50 (mass ratio) and whose solid content concentration is 5.0 mass%. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore size of 1 μm.
(2) Manufacture of liquid crystal display element for evaluation of vertical alignment On the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film, the liquid crystal aligning agent prepared in the above (1) is applied using a spinner, and 80 ° C. After pre-baking on the hot plate for 1 minute, it was heated at 200 ° C. for 1 hour in an oven in which the inside of the chamber was replaced with nitrogen to form a coating film having a thickness of 0.1 μm. Next, the surface of the coating film was irradiated with polarized ultraviolet rays 200 J / m ² containing a 313 nm emission line from a direction inclined by 40 ° from the normal to the liquid crystal alignment film using a Hg—Xe lamp and a Grand Taylor prism. The same operation was repeated to prepare a pair (two) of substrates having a liquid crystal alignment film.
After applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer periphery of the surface having one liquid crystal alignment film of the above substrates by screen printing, the liquid crystal alignment film surfaces of the pair of substrates are opposed to each other, The adhesive was heat-cured at 150 ° C. for 1 hour so that the projection direction of the optical axis of each substrate onto the substrate surface was antiparallel. Next, after filling the gap between the substrates from the liquid crystal injection port with negative type liquid crystal (MLC-6608, manufactured by Merck), the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 150 ° C. and then gradually cooled to room temperature. Next, the polarizing plates are bonded to both outer surfaces of the substrate so that the polarization directions thereof are orthogonal to each other and form an angle of 45 ° with the projection direction of the optical axis of the liquid crystal alignment film onto the substrate surface. Thus, a vertical alignment type liquid crystal display device was manufactured.

(3) Evaluation of vertical alignment type liquid crystal display element The liquid crystal display element manufactured as described above was evaluated for pretilt angle, voltage holding ratio, and stability of pretilt angle.
(3-1) Evaluation of pretilt angle The liquid crystal display device manufactured in (2) above is described in Non-Patent Document 2 (TJ Scheffer et. Al. J. Appl. Phys. Vo. 19. p2013 (1980)). According to the method, the pretilt angle was measured by a crystal rotation method using He—Ne laser light. When the measured value was 87 ° or more and less than 89 °, it was evaluated as “good”, and when it was less than 87 ° or more than 89 °, it was evaluated as “good”.
(3-2) Evaluation of voltage holding ratio After applying a voltage of 1 V at 60 ° C. for 60 microseconds and a span of 167 microseconds to the liquid crystal display device manufactured in (2) above, voltage application The voltage holding ratio VHR [%] 167 milliseconds after the release was measured. The measurement was performed using “VHR-1” manufactured by Toyo Corporation. At this time, when the VHR was 99% or more, it was evaluated as “good”, the case where it was 98% or more and less than 99% as “good”, and the case where it was less than 98% was evaluated as “bad”. 1 was “good”.
(3-3) Evaluation of Display Stability The voltage holding ratio VHR was measured on the liquid crystal display device manufactured in (2) above under the same conditions as in the evaluation of the voltage holding ratio in (3-2) above, and this was initially measured. The value VHRA1. Thereafter, it was placed at a distance of 5 cm under a 100 watt type white fluorescent lamp, irradiated with light for 500 hours, and again measured for the voltage holding ratio (this was referred to as “VHRA2”) under the same conditions as in (3-2) above. did. With respect to the liquid crystal display element, the display stability with respect to light was evaluated by the voltage holding ratio reduction rate ΔVHRA obtained by the following formula (2). When ΔVHRA is 1% or less, the display stability is “good”, when 1% is 2% or less, “good”, and when 2% is “bad” In Example 1, the display stability was “good”.
ΔVHRA [%] = ((VHRA1−VHRA2) / VHRA1) × 100 (2)

[Examples 2 to 7]
While preparing the liquid crystal aligning agent by the composition shown in following Table 2 similarly to Example 1, the liquid crystal display element was manufactured and various evaluation was performed. In Example 7, compound (8-1-1) was added to the liquid crystal aligning agent as an additive. The compounding quantity of an additive shows the ratio (mass part) with respect to 100 mass parts of total amounts of a polymer (PM) and another polymer. The evaluation results are shown in Table 2 below.
[Comparative Example 1]
NMP and butyl cellosolve (BC) are added as an organic solvent to 10 parts by mass of the polymer (S1) obtained in Polymerization Example 4B and 90 parts by mass of the polymer (PA1) obtained in Polymerization Example 1B as a polymer. Was a solution having NMP: BC = 50: 50 (mass ratio) and a solid content concentration of 5.0 mass%. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore size of 1 μm. Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 2 below.

[Example 8]
(1) Preparation of liquid crystal aligning agent To 20 parts by mass of the polymer (PA2) obtained in the above Polymerization Example 2B, NMP and butyl cellosolve (BC) are added as solvents, and the polymer (PM1) obtained in the above Polymerization Example 1A is further added. 80 parts by mass was added to obtain a solution having a solvent composition of NMP: BC = 50: 50 (mass ratio) and a solid content concentration of 6.0% by mass. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore size of 1 μm.

(2) Manufacture of FFS type liquid crystal cell The liquid crystal aligning agent prepared above was applied by a spinner on a glass substrate having a thickness of 1 mm having a chrome electrode provided in a comb shape on one side. Subsequently, after pre-baking for 1 minute on an 80 degreeC hotplate, it post-baked for 10 minutes on a 230 degreeC hotplate, and formed the coating film with a film thickness of about 0.08 micrometer. Using a rubbing machine having a roll wound with a nylon cloth, the formed coating surface is rubbed at a roll rotation speed of 1000 rpm, a stage moving speed of 25 mm / sec, and a hair foot indentation length of 0.4 mm. The treatment was performed to give liquid crystal alignment ability. Further, this substrate was ultrasonically cleaned in ultrapure water for 1 minute and dried in a 100 ° C. clean oven for 10 minutes to produce a substrate having a liquid crystal alignment film on the surface having comb-like chrome electrodes. The substrate having this liquid crystal alignment film was referred to as “substrate A”.
Separately, a liquid crystal aligning agent coating film is formed on one surface of a 1 mm thick glass substrate having no electrodes in the same manner as described above, rubbed, washed and dried, and a liquid crystal on one side. A substrate having an alignment film was manufactured. The substrate having this liquid crystal alignment film was referred to as “substrate B”.
Subsequently, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer edge of the surface of the substrate A having the liquid crystal alignment film, and then the rubbing direction in each liquid crystal alignment film is antiparallel. The two substrates A and B were placed opposite to each other, and the outer edge portions were brought into contact with each other and pressed to cure the adhesive. Next, a nematic liquid crystal (MLC-2042, manufactured by Merck & Co., Inc.) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive to produce an FFS type liquid crystal cell. did.

(3) Evaluation of display stability Using the liquid crystal cell produced in (2) above, display stability against heat was evaluated. Evaluation was performed as follows. First, a voltage of 5 V was applied to the liquid crystal cell with an application time of 60 microseconds and a span of 167 milliseconds, and then a voltage holding ratio (VHRB1) after 167 milliseconds from the application release was measured. Next, the liquid crystal cell was allowed to stand in an 80 ° C. oven for 200 hours, and then allowed to stand at room temperature and naturally cooled to room temperature. After cooling, a voltage of 5 V was applied to the liquid crystal cell with an application time of 60 microseconds and a span of 167 milliseconds, and the voltage holding ratio (VHRB2) 167 milliseconds after the application release was measured. The measuring device used was “VHR-1” manufactured by Toyo Corporation. The change rate (ΔVHRB) of VHR at this time was calculated by the following mathematical formula (3), and the display stability of the liquid crystal cell was evaluated by ΔVHRB. In the evaluation, when ΔVHRB was less than 1%, the display stability was “good”, when it was 1% or more and less than 2%, “good”, and when it was 2% or more, it was judged as “bad”. As a result, in this example, the display stability was “OK”.
ΔVHRB [%] = (VHRB1−VHRB2) / VHRB1) × 100 (3)

(4) Evaluation of liquid crystal orientation With respect to the liquid crystal cell produced in (2) above, the presence or absence of abnormal domains when the voltage is turned on / off (applied / released) is observed with a polarizing microscope. When the orientation was “good” and there was even one abnormal domain, the liquid crystal orientation was judged as “poor”. As a result, the liquid crystal cell of this example had “good” liquid crystal alignment.
(5) Afterimage characteristics (burn-in characteristics)
Except for using as a pair a glass substrate having two metal electrodes (electrode a and electrode b) made of chromium patterned in a comb shape on one side and a counter glass substrate on which no electrode is provided as a substrate. An FFS type liquid crystal cell was produced in the same manner as (2) above. Next, polarizing plates were bonded to both outer surfaces of the substrate of the liquid crystal cell. This FFS type liquid crystal display element was placed in an environment of 25 ° C. and 1 atm. A voltage was applied to electrode b, and a combined voltage of AC voltage 3.5V and DC voltage 5V was applied to electrode a for 2 hours. Immediately thereafter, an AC voltage of 4 V was applied to both electrode a and electrode b. The time from when the voltage of 4 V AC was started to be applied to both electrodes until the difference in light transmittance between the electrodes a and b could not be visually confirmed was measured. When this time is less than 100 seconds, the afterimage characteristics are “good”, afterimage characteristics when the time is more than 100 seconds and less than 150 seconds are “good”, and afterimage characteristics when it exceeds 150 seconds are “bad”. It was evaluated. As a result, in the liquid crystal cell of this example, the afterimage characteristic was “good”.

[Examples 9 to 13, Comparative Example 2]
Liquid crystal aligning agents were prepared at the same solvent ratio and solid content concentration as in Example 8 except that the type and amount of the polymer used were changed as shown in Table 3 below. Moreover, using each liquid crystal aligning agent, the liquid crystal cell and the liquid crystal display element were manufactured similarly to Example 8, and various evaluation was performed. The results are shown in Table 3 below.

  From the above results, the liquid crystal aligning agents (Examples 1 to 13) containing at least one of the polymer (PM) and the compound (AM) have good initial liquid crystal alignment properties and good or good display stability. It was evaluation of. On the other hand, the liquid crystal aligning agent (Comparative Examples 1 and 2) which contains neither a polymer (PM) nor a compound (AM) was inferior to the Example in display stability. Further, the comparative example had inferior image characteristics as compared with the examples.

Claims (11)

A liquid crystal aligning agent containing a polymer (PM) having a cyclic structure in which a structure represented by the following formula (a1) constitutes a part of a ring.

(In formula (a1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and R ¹ and R ² may be bonded to each other to form a ring. “* ¹ ” and “* ² ” each represent a bond, provided that “* ¹ ” represents a carbonyl group or> C═C (R ¹² ) − * ³ (R ¹² represents a hydrogen atom or 1 Is a valent organic group, and “* ³ ” is a bond bonded to an oxygen atom in the formula (a1).) The polymer (PM) has at least one selected from the group consisting of partial structures represented by the following formulas (a1-1) to (a1-3) as a partial structure including the cyclic structure, Item 2. A liquid crystal aligning agent according to Item 1.

(In Formula (a1-1) to Formula (a1-3), R ¹¹ and R ¹² are each independently a hydrogen atom or a monovalent organic group. R ¹³ is a single bond or a divalent linking group. R ⁴¹ is a hydrogen atom or a monovalent organic group, R ¹ and R ² have the same meanings as in the above formula (a1), “*” is a bond bonded to the main chain of the polymer. It means that there is.) The liquid crystal aligning agent according to claim 1 or 2, wherein the polymer (PM) is a polymer having a repeating unit represented by the following formula (d1).

(In the formula (d1), R ³² is a group having the cyclic structure, R ³⁴ is a trivalent organic group, and R ³⁶ is a divalent organic group.) The polymer (PM) has 2 functional groups selected from the group consisting of a compound represented by the following formula (2), an epoxy group, a halogen atom, a group represented by the following formula (6), and a hydroxyl group. The liquid crystal aligning agent as described in any one of Claims 1-3 which is a polymer obtained by making the polyfunctional compound which has more than one react.

(In Formula (2), R ³² is a group having the cyclic structure, and R ³³ is a trivalent organic group.)

(In the formula (6), R ³⁰ is a monovalent organic group.) The liquid crystal aligning agent according to claim 1 or 2, wherein the polymer (PM) is a polymer having a repeating unit represented by the following formula (b1).

(In the formula (b1), R ³² is a group having the cyclic structure, and R ³⁷ is a divalent organic group.) The polymer (PM) is obtained by reacting a polymer having a repeating unit represented by the following formula (11) or a repeating unit represented by the following formula (12) with a compound having the cyclic structure. The liquid crystal aligning agent of Claim 5 which is a polymer.

(In Formula (11) and Formula (12), R ³¹ and R ³⁷ are each independently a divalent organic group.) The liquid crystal aligning agent containing the compound represented by a following formula (c1).

(In formula (c1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and R ¹ and R ² may be bonded to each other to form a ring. R ¹² is a hydrogen atom or a monovalent organic group, R ¹³ is a single bond or a divalent linking group, R ¹⁴ is an n-valent organic group, and n is an integer of 1 to 10. When n is 2 or more, a plurality of R ¹ , R ² , R ¹² and R ¹³ each independently have the above definition.)   The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-7.   A liquid crystal device comprising the liquid crystal alignment film according to claim 8. The polymer which has at least 1 type chosen from the group which consists of the partial structure represented by a following formula (a1-2) and a formula (a1-3).

(In Formula (a1-2) and Formula (a1-3), R ¹ and R ² are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and R ¹ and R ² are bonded to each other. R ¹² may be a hydrogen atom or a monovalent organic group, R ¹³ may be a single bond or a divalent linking group, and R ⁴¹ may be a hydrogen atom or a monovalent organic group. “*” Represents a bond that is bonded to the main chain of the polymer.) A compound represented by the following formula (c1).

(In formula (c1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom or a monovalent organic group, and R ¹ and R ² may be bonded to each other to form a ring. R ¹² is a hydrogen atom or a monovalent organic group, R ¹³ is a single bond or a divalent linking group, R ¹⁴ is an n-valent organic group, and n is an integer of 1 to 10. When n is 2 or more, a plurality of R ¹ , R ² , R ¹² and R ¹³ each independently have the above definition.)