JP2014211515A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display, phase difference film, method of producing phase difference film, polymer and compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal alignment agent which makes it possible to obtain a liquid crystal display with various excellent characteristics, such as a voltage retention rate.SOLUTION: A liquid crystal alignment agent comprises, as a polymer component, a polymer (P) having a structure represented by the formula (1), in which Ris a hydrogen atom or a 1-30C univalent hydrocarbon group, Xand Xindependently represent a divalent organic group, where two * symbols each represent a bond bonding to mutually different groups.

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, a retardation film, a method for producing a retardation film, a polymer, and a compound.

  Conventionally, as a liquid crystal display element, various drive systems having different electrode structures, physical properties of liquid crystal molecules to be used, manufacturing processes, and the like have been developed. For example, TN type, STN type, VA type, in-plane switching type (IPS type) ), Various liquid crystal display elements such as FFS type are known. These liquid crystal display 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.

  Liquid crystal display elements are required to have various characteristics such as voltage holding ratio, image sticking (afterimage characteristics), heat resistance and the like, and various liquid crystal aligning agents for obtaining high-quality liquid crystal display elements have been proposed. (For example, see Patent Documents 1 and 2). Among these, in Patent Document 1, polyamic acid obtained by reacting a diamine having an aromatic ester structure with a tetracarboxylic acid derivative, such as di (4-aminophenyl) hexane-1,6-dioate, is aligned with liquid crystal. It is disclosed that it is used as a polymer component of an agent. In Patent Document 2, a diamine having two aromatic rings linked by an alkylene spacer structure, such as 1,3-bis (4-amino-2-methylphenyl) propane, is reacted with a tetracarboxylic acid derivative. It is disclosed that the obtained polyamic acid or the like is used as a polymer component of a liquid crystal aligning agent.

  In addition, various optical materials are used for liquid crystal display elements. Above all, retardation films eliminate the object of viewing color dependency and the viewing angle dependency that the display color and contrast ratio change depending on the visual direction. It is used for the purpose. As such a retardation film, one having a liquid crystal alignment film formed on the surface of a substrate such as a TAC film and a liquid crystal layer formed by curing a polymerizable liquid crystal on the surface of the liquid crystal alignment film is known. It has been. Also, in recent years, in the preparation of liquid crystal alignment films in retardation films, a photo-alignment method has been used in which a radiation-sensitive organic thin film formed on a substrate surface is irradiated with polarized or non-polarized radiation to impart liquid crystal alignment capability. Has been. Various liquid crystal aligning agents for retardation films for producing a liquid crystal alignment film by a photo-alignment method have been proposed (see, for example, Patent Document 3).

  As a method for producing a retardation film on an industrial scale, a roll-to-roll method has been proposed (for example, see Patent Document 4). In this method, a film is unwound from a wound body of a long base film, a liquid crystal alignment film is formed on the unwound film, and a polymerizable liquid crystal is applied and cured on the liquid crystal alignment film. It is a method of performing the process and the process of laminating a protective film as necessary in a continuous process, and collecting the film after passing through these processes as a wound body.

Japanese Patent No. 4171543 Japanese Patent No. 4779339 JP 2012-37868 A JP 2000-86786 A

  In recent years, liquid crystal display elements are used not only for display terminals such as personal computers as in the past, but also for various applications such as liquid crystal televisions, car navigation systems, mobile phones, smartphones, and information displays. In addition, demands for higher performance of liquid crystal display elements are further increased, and liquid crystal alignment films are required that can improve various characteristics of liquid crystal display elements.

  In addition, for the retardation film, by adopting the above roll-to-roll method, it can be easily produced on an industrial scale, but when the adhesion between the liquid crystal alignment film and the substrate film is insufficient, the process ends. When the film is later used as a wound body, the liquid crystal alignment film may peel off from the substrate film. In this case, the product yield is reduced.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal display device having various characteristics such as voltage holding ratio. Another object of the present invention is to provide a liquid crystal aligning agent that can form a liquid crystal alignment film for a retardation film that has good liquid crystal alignment and good adhesion to a substrate.

  As a result of intensive studies to achieve the above-described problems of the prior art, the present inventor can solve the above-mentioned problems by incorporating a polymer having a specific structure into the liquid crystal aligning agent as a polymer component. As a result, the present invention has been completed. Specifically, the present invention provides the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, retardation film production method, polymer and compound.

  In one aspect, the present invention provides a liquid crystal aligning agent containing a polymer (P) having a structure represented by the following formula (1).

（式（１）中、Ｒ^１は、水素原子又は炭素数１〜３０の１価の炭化水素基であり、Ｘ^１及びＸ^２は、それぞれ独立に２価の有機基である。２つの「＊」は、互いに異なる基に結合する結合手を示す。）

(In Formula (1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and X ¹ and X ² are each independently a divalent organic group. “*” Represents a bond bonded to different groups.)

  In another aspect, the present invention provides a liquid crystal alignment film formed using the liquid crystal alignment agent. Moreover, a liquid crystal display element provided with the said liquid crystal aligning film and a phase difference film provided with the said liquid crystal aligning film are provided. Furthermore, in another aspect, the step of coating the liquid crystal aligning agent on a substrate to form a coating film, the step of irradiating the coating film with light, and the polymerization on the coating film after the light irradiation And a step of applying and curing a liquid crystal.

  In another aspect, the present invention provides a compound represented by the following formula (b-1). In addition, a weight obtained by reacting at least one compound selected from the group consisting of tetracarboxylic dianhydride and carboxylic acid halide with an amine compound containing a compound represented by the following formula (b-1). Provide coalescence.

（式（ｂ−１）中、Ｒ^１は、水素原子又は炭素数１〜３０の１価の炭化水素基であり、Ｘ^３及びＸ^４は、それぞれ独立に２価の有機基である。ｎは０又は１である。）

(In Formula (b-1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and X ³ and X ⁴ are each independently a divalent organic group. Is 0 or 1.)

  According to the liquid crystal aligning agent containing the polymer having the structure represented by the above formula (1) as the polymer component, a liquid crystal alignment film having good liquid crystal alignment properties as well as good applicability to the substrate is formed. be able to. Moreover, according to the liquid crystal aligning film produced with the liquid crystal aligning agent of this invention, a liquid crystal display element with a high voltage retention rate and favorable heat resistance and a residual image characteristic can be manufactured. Furthermore, the liquid crystal alignment film obtained using the liquid crystal aligning agent of this invention has favorable adhesiveness with respect to a board | substrate. Therefore, even when this is stored as a wound body, the liquid crystal alignment film and the substrate are difficult to peel off, and thus, for example, in the production of a retardation film, it is possible to suppress a decrease in product yield.

The schematic block diagram of a FFS type liquid crystal cell. The plane schematic diagram of a top electrode. (A) is a top view of a top electrode, (b) is the elements on larger scale of a top electrode.

  Below, each component contained in the liquid crystal aligning agent of this invention and the other component arbitrarily mix | blended as needed are demonstrated.

（式（１）中、Ｒ^１は、水素原子又は炭素数１〜３０の１価の炭化水素基であり、Ｘ^１及びＸ^２は、それぞれ独立に２価の有機基である。２つの「＊」は、互いに異なる基に結合する結合手を示す。） <Polymer component>
The liquid crystal aligning agent of this invention contains the polymer (P) which has a structure represented by following formula (1) as the said polymer component while containing a polymer component.

(In Formula (1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and X ¹ and X ² are each independently a divalent organic group. “*” Represents a bond bonded to different groups.)

In the above formula (1), examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms in R ¹ include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Here, in the present specification, the “chain hydrocarbon group” means a hydrocarbon group composed of only a chain structure without including a cyclic structure in the main chain. However, the chain structure may be linear or branched. The “alicyclic hydrocarbon group” means a hydrocarbon group that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. However, it is not necessary to be comprised only by the structure of an alicyclic hydrocarbon, The thing which has a chain structure in the part is also included. The “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.

Specific examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms in R ¹ include a chain hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, C1-C30 alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, icosanyl group; alkenyl groups having 1-30 carbon atoms such as ethenyl group, propenyl group, butenyl group; C1-C30 alkynyl groups, such as a propynyl group, etc. can be mentioned, These may be linear or branched. Examples of the alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group; examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a benzyl group, and a phenethyl group.
Among these, R ¹ is preferably a hydrogen atom or a chain hydrocarbon group having 1 to 30 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom or carbon number. More preferably, it is a 1-5 alkyl group.

Examples of the main skeleton of the polymer (P) include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyorganosiloxane, cellulose derivative, polyacetal derivative, polystyrene derivative, poly (styrene-phenylalemid) derivative, poly A skeleton composed of (meth) acrylate derivatives and the like can be given. As the polymer (A), one or more polymers having a skeleton selected from these polymers can be appropriately selected and used depending on the driving method and application of the liquid crystal display element. In addition, (meth) acrylate means containing an acrylate and a methacrylate. The main skeleton of the polymer (P) is preferably a skeleton composed of at least one selected from the group consisting of polyamic acid, polyimide and polyamic acid ester.
The polymer (P) preferably has a structure represented by the above formula (1) (hereinafter also referred to as “specific structure”) in the main chain. In this case, X ¹ and X ² in the specific structure have a structure derived from the skeleton of the monomer used for the synthesis of the polymer.

  The method for synthesizing the polymer (P) is not particularly limited. For example, at least one compound (a) selected from the group consisting of a tetracarboxylic dianhydride and a carboxylic acid halide, an amine compound (b), and Can be obtained by reacting. Here, examples of the carboxylic acid halide as the compound (a) include dicarboxylic acid dihalides, tetracarboxylic acid dihalides, and tetracarboxylic acid diester dihalides. As a halogen atom which carboxylic acid halide has, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom etc. are mentioned, for example, Among these, a chlorine atom is preferable.

[Polymer (P): Polyamic acid]
When the polymer (P) is a polyamic acid, the polyamic acid having the specific structure (hereinafter also referred to as “polyamic acid (P)”) is, for example, a tetracarboxylic dianhydride as the compound (a) and It can be obtained by reacting with an amine compound (b).

(Tetracarboxylic dianhydride)
Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid (P) include an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, and an aromatic tetracarboxylic dianhydride. Can be mentioned. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 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- No 1,2-dicarboxylic acid Product, 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-di Oxatricyclo [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 and the like;
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. In addition, as tetracarboxylic dianhydride used for the synthesis | combination of a polyamic acid, these 1 type can be used individually or in combination of 2 or more types.

The tetracarboxylic dianhydride used for the synthesis of the polyamic acid (P) is 1,2,3,4-cyclobutanetetracarboxylic dianhydride in that the liquid crystal orientation and the solubility in a solvent can be improved. 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-dioxote Lahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8- It is preferable to include at least one compound selected from the group consisting of tetracarboxylic dianhydride and pyromellitic dianhydride (hereinafter also referred to as “specific tetracarboxylic dianhydride”). Moreover, it is preferable that the usage-amount of the said specific tetracarboxylic dianhydride shall be 5 mol% or more with respect to the whole quantity of the tetracarboxylic dianhydride used for the synthesis | combination of polyamic acid, and shall be 10 mol% or more. It is more preferable that the amount be 20 mol% or more.

（式（ｂ−１）中、Ｘ^３及びＸ^４は、それぞれ独立に２価の有機基である。ｎは０又は１である。Ｒ^１は上記式（１）のＲ^１と同義である。） (Amine compound)
The amine compound (b) used for the synthesis of the polyamic acid (P) preferably includes a compound having a group capable of introducing the specific structure into the main chain of the polymer. It is preferable that the compound represented by b-1) is included.

(In the formula (b-1), ^{X 3} and ^{X 4,} a is .n each independently a divalent organic group which is 0 or 1 .R ¹ has the same meaning as ^{R 1} in the formula (1) .)

Examples of the divalent organic group represented by X ³ and X ⁴ in the formula (b-1) include a hydrocarbon group such as a divalent chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, -O-, -COO-, -CO-, -NHCO-, -S-, -NH- at a position between carbon-carbon bonds in the hydrocarbon group or adjacent to the carbonyl group in formula (b-1). And a divalent group obtained by introducing a functional group such as. X ³ and X ⁴ may have a substituent such as a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom).
Specific examples of X ³ and X ⁴ include divalent chain hydrocarbon groups such as methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, C1-C30 alkanediyl groups such as nonanediyl, decandiyl, dodecadiyl, tetradecandiyl, icosanediyl; 2 to 1-30 carbons such as ethenylene, propenylene, butenylene, ethynylene, and propynylene Valent chain unsaturated hydrocarbon group; etc., and these may be linear or branched. Further, as the divalent alicyclic hydrocarbon group, for example, cyclohexylene group, etc .; as the divalent aromatic hydrocarbon group, for example, phenylene group, benzylene group, phenethylene group, etc .; carbon-carbon of the above hydrocarbon group Examples of the divalent group in which a functional group is introduced between the bonds include groups having a heterocyclic ring such as piperidine, pyrrolidine, hexamethyleneimine, pyridine, and pyrazine; X ³ and X ⁴ may be the same as or different from each other.

（式（ｂ−１−１）中、Ｘ^５及びＸ^６は、それぞれ独立に、単結合又は２価の有機基である。ｎは０又は１である。Ｒ^１は上記式（１）のＲ^１と同義である。） As X ³ and X ⁴ , it is preferable that at least one of X ³ and X ⁴ is a group having an aromatic ring, from the viewpoint of the strength and voltage holding ratio of the coating film to be formed. From the viewpoint, the aromatic ring is more preferably a benzene ring. Specifically, as the compound (b-1), a compound represented by the following formula (b-1-1) can be preferably used.

(In Formula (b-1-1), X ⁵ and X ⁶ are each independently a single bond or a divalent organic group. N is 0 or 1. R ¹ is represented by Formula (1) above. R ¹ as synonymous.)

Specific examples of the divalent organic group represented by X ⁵ and X ⁶ in the above formula (b-1-1) include those exemplified for X ³ and X ⁴ in the above formula (b-1). The divalent organic group of X ⁵ and X ⁶ preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.
n can be appropriately selected from 0 and 1 depending on the purpose of use. Specifically, n = 1 is preferable from the viewpoint of increasing the voltage holding ratio, and n is left from the viewpoint of increasing the relaxation rate of residual DC by allowing the carboxyl group to remain in the polymer after the coating film is formed. = 0 is preferred. When n = 0, R ¹ is preferably an alkyl group having 1 to 5 carbon atoms. The description of R ¹ in the above formula (1) can be applied to R ^{1 in} the formula (b-1) and the formula (b-1-1).

Specific examples of the compound represented by the above formula (b-1-1) include the following compounds. In synthesizing the polyamic acid (P) of the present invention, one kind of the compound represented by the above formula (b-1) can be used alone or in combination of two or more kinds.

  In synthesizing the polyamic acid (P), as the amine compound (b), only the compound represented by the formula (b-1) may be used, but other amines other than the above may be used in combination with the compound. May be.

Examples of other amines that can be used here include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. Specific examples thereof include aliphatic diamines such as m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

（式（Ｄ−１）中、Ｘ^I及びＸ^IIは、それぞれ、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、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、ｎ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；
ジアミノオルガノシロキサンとして、例えば、１，３−ビス（３−アミノプロピル）−テトラメチルジシロキサンなどを；それぞれ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を用いることができる。 As the aromatic diamine, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenylamine, 1,5- Diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,7-diaminofluorene, 4,4′- Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′-( -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-diaminocarbazole, N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N ′ -Dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecano Cis-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5 -Diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene Cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, 3,5-diaminobenzoic acid Cholestenyl, lanostannyl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4′-trifluoromethoxybenzoyloxy) ) Cyclohexyl-3,5-diaminobenzoate, 4- (4′-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl)- 4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-he (Ptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1- (2,4-diaminophenyl) piperazine-4-carboxylic acid, 4- ( Morpholin-4-yl) benzene-1,3-diamine, 1,3-bis (N- (4-aminophenyl) piperidinyl) propane, α-amino-ω-aminophenylalkylene, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene- 6-amine, 4-aminophenyl-4′-aminobenzoate, 4,4 ′-[4,4′-propane-1,3-diylbis (piperidine-1,4-di) Yl)] dianiline, 4- (tetradecaoxy) benzene-1,3-diamine and the following formula (D-1)

(In Formula (D-1), X ^I and X ^II are each a single bond, —O—, —COO— or —OCO—, and R ^I is 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 n is 0 or 1. However, a and b are not 0 at the same time. .)
A compound represented by:
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; and the diamines described in JP-A 2010-97188 can be used.

Examples of the divalent group represented by “—X ^I — (R ^I —X ^II ) _n —” in the formula (D-1) include an alkanediyl group having 1 to 3 carbon atoms, * —O—, * —COO— or * —O—C ₂ H ₄ —O— (however, a bond marked with “*” is bonded to a diaminophenyl group) is preferred. Specific examples of the group “—C _c H _{2c + 1} ” include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group. Group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group Group, n-eicosyl group and the like. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to other groups.

なお、上記ポリアミック酸の合成に使用するその他のアミンとしては、これらの化合物の１種を単独で又は２種以上を、液晶表示素子の駆動モード等に応じて適宜選択して使用することができる。 Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-3).

In addition, as another amine used for the synthesis | combination of the said polyamic acid, 1 type of these compounds can be used individually, or 2 or more types can be selected suitably according to the drive mode etc. of a liquid crystal display element. .

  The amine compound (b) used for the synthesis of the polyamic acid (P) of the present invention is capable of forming a coating film having good coatability and rubbing resistance to a substrate, heat resistance, and a liquid crystal display element having a good relaxation rate of residual DC. In that the proportion of the compound represented by the formula (b-1) is 0.5 mol% or more with respect to the total amount of the amine compound (b) used in the synthesis. Is preferably 2 mol% or more, more preferably 5 mol% or more, and particularly preferably 10 mol% or more. Further, the upper limit of the use ratio of the compound represented by the formula (b-1) may be appropriately set according to the drive mode of the liquid crystal display device to be applied, and the amine compound (b) used for the synthesis. It can be arbitrarily set within a range of 100 mol% or less with respect to the total amount of the above, and in the case where an improvement effect (for example, improvement in voltage holding ratio, improvement in liquid crystal orientation, etc.) due to addition of other amines is intended, % Or less is preferable.

  When providing the liquid crystal aligning ability with the photo-alignment method with respect to the coating film produced using the liquid crystal aligning agent of this invention, it is good also considering a polymer (P) as a polymer which has a photo-alignment structure. Here, the photo-alignment structure is a concept including both a photo-alignment group and a decomposition type photo-alignment part. Specifically, as the photoalignment structure, a group that exhibits photoalignment by photoisomerization, photodimerization, photolysis, or the like can be employed. For example, an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton. A group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, coumarin or a derivative thereof Examples include a coumarin-containing group containing a derivative as a basic skeleton, a polyimide-containing structure containing polyimide or a derivative thereof as a basic skeleton, and the like.

When the polymer (P) includes a polymer having a photo-alignment structure, the polymer (P) is preferably a polymer including a decomposable photo-alignment part, specifically, bicyclo [2.2 .2] A polymer having an octene skeleton or a cyclobutane skeleton is preferable. By having such a specific skeleton, the liquid crystal orientation of the coating film can be further improved. Such a polymer is, for example, at least one of cyclobutanetetracarboxylic dianhydride and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. It can be obtained by reacting any one of the tetracarboxylic dianhydrides and an amine compound containing the compound represented by the above formula (b-1).
When the liquid crystal alignment ability is imparted to the coating film by the photo-alignment method, the use ratio of the polymer having the photo-alignment structure and the specific structure is determined by the polymer (P ) Is preferably 10% by weight or more, more preferably 30 to 100% by weight, and still more preferably 50 to 100% by weight.

[Molecular weight regulator]
In synthesizing the polyamic acid (P), a terminal-modified polymer may be synthesized using an appropriate molecular weight regulator together with the tetracarboxylic dianhydride and the amine compound (b) as described above. By using such a terminal-modified polymer, the coating property (printability) of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention.

Examples of molecular weight regulators include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like. Specific examples thereof include acid monoanhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic. Acid anhydrides, n-hexadecyl succinic acid anhydrides; monoamine compounds such as aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and diamine used.

[Synthesis of Compound Represented by Formula (b-1) above]
The compound represented by the above formula (b-1) can be synthesized by appropriately combining conventional methods of organic chemistry. As an example thereof, for example, a nitro intermediate having a nitro group is synthesized in place of the primary amino group in the above formula (b-1), and then the nitro group of the obtained nitro intermediate is used using an appropriate reduction system. And amination method.

The method for synthesizing the nitro intermediate can be appropriately selected depending on the target compound. As an example, for example, an amide compound having the corresponding X ³ and nitro groups, a method of reacting an acid chloride with a corresponding X ⁴ and nitro group; and acid chloride with a corresponding X ³ and nitro groups, A method of reacting a corresponding amide compound having X ⁴ and a nitro group; a method of reacting an acid chloride having a corresponding X ³ and nitro group with ammonia; and the like.
The reaction for obtaining the nitro intermediate is preferably carried out in an organic solvent. Here, the organic solvent may be any solvent that does not affect the reaction, and examples thereof include methanol, ethanol, tetrahydrofuran, toluene, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone. . Moreover, you may perform the said reaction in catalyst presence as needed.
The reduction reaction of the nitro intermediate can be preferably carried out in an organic solvent using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin, nickel or the like. Examples of the organic solvent used here include ethyl acetate, toluene, tetrahydrofuran, and alcohols. However, the synthesis procedure of the compound represented by the formula (b-1) is not limited to the above method.

[Synthesis of polyamic acid (P)]
The proportion of tetracarboxylic dianhydride and amine compound (b) used in the synthesis reaction of the polyamic acid (P) of the present invention is the amino group (primary amino group and secondary amino group) of the amine compound (b). The amino anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents per 1 equivalent of the amino group that reacts with the acid anhydride group of the tetracarboxylic dianhydride. The ratio is preferable, and more preferably 0.3 to 1.2 equivalent.
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., more preferably 0 to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Examples of the organic solvent include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Specific examples of these organic solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, Hexamethylphosphortriamide and the like; phenolic solvents such as phenol, m-cresol, xylenol, halogenated phenol and the like;
Alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc .; ketones such as acetone, methyl ethyl ketone, methyl isobutyl Ketone, cyclohexanone, etc .; as the above ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, isoamyl Propionate, isoamyl isobutyrate and the like; ethers such as diethyl ether, diisopentyl ether, ethylene glycol methyl Ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran and the like; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o- The Rorubenzen the like; as the hydrocarbon, e.g., hexane, heptane, octane, benzene, toluene, xylene and the like; may be mentioned, respectively.

  Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (first group of organic solvents), or one or more selected from the first group of organic solvents, It is preferable to use a mixture with one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second group organic solvent). In the latter case, the proportion of the second group organic solvent used is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the first group organic solvent and the second group organic solvent. Or less, more preferably 30% by weight or less. The amount (α) of the organic solvent used is such that the total amount (β) of the tetracarboxylic dianhydride and the amine compound (b) is 0.1 to 50% by weight with respect to the total amount (α + β) of the reaction solution. It is preferable to make it an amount.

  As described above, a reaction solution obtained by dissolving the polyamic acid (P) 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 isolating the polyamic acid (P) contained in the reaction solution, or the isolated polyamic acid. You may use for refinement | purification of a liquid crystal aligning agent, after refine | purifying (P). When the polyamic acid (P) is dehydrated and cyclized into a polyimide, the reaction solution may be subjected to the dehydration and cyclization reaction as it is, and the polyamic acid (P) contained in the reaction solution is isolated and then dehydrated and cyclized. You may use for reaction or you may use for dehydration ring closure after refine | purifying the isolated polyamic acid (P). Isolation and purification of the polyamic acid can be performed according to known methods.

[Polymer (P): Polyamic acid ester]
The polyamic acid ester (hereinafter also referred to as polyamic acid ester (P)) as the polymer (P) is, for example, [I] a polyamic acid (P) obtained by the above synthesis reaction, a hydroxyl group-containing compound, a halogen [II] a method of reacting a tetracarboxylic acid diester with an amine compound (b), [III] a tetracarboxylic acid diester dihalide and an amine compound (b) ).
Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol and propanol; phenols such as phenol and cresol. Examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like, and as an epoxy group-containing compound, Examples thereof include propylene oxide. The tetracarboxylic acid diester used in Method [II] can be obtained by ring-opening tetracarboxylic dianhydride using the above alcohols. The tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. The amine compound (b) used in the methods [II] and [III] preferably includes the compound represented by the above formula (b-1), and the other amines may be used as necessary. Good. The polyamic acid ester (P) 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.

[Polymer (P): Polyimide]
The polyimide (hereinafter also referred to as polyimide (P)) as the polymer (P) can be obtained, for example, by dehydrating and ring-closing and imidizing the polyamic acid (P) synthesized as described above. .

  The polyimide (P) may be a completely imidized product obtained by dehydrating and ring-closing all of the amic acid structure of the polyamic acid (P) that is the precursor, and only a part of the amic acid structure is dehydrating and ring-closing. Alternatively, it may be a partially imidized product in which an amic acid structure and an imide ring structure coexist. As for the polyimide contained in the liquid crystal aligning agent of this invention, it is preferable that the imidation ratio is 30% or more, It is more preferable that it is 40 to 99%, It is still more preferable that it is 50 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 the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. 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. It is preferable that the usage-amount of a dehydration ring-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents to be 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, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

  In this way, a reaction solution containing polyimide (P) 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 aligning agent, or you may use for preparation of a liquid crystal aligning agent, after purifying the isolated polyimide. These purification operations can be performed according to known methods. In addition, polyimide (P) can also be obtained by imidation of polyamic acid ester (P).

The polyamic acid, polyamic acid ester and polyimide as the polymer (P) obtained as described above have a solution viscosity of 10 to 800 mPa · s when this is a 10% by weight solution. It is preferable to have a solution viscosity of 15 to 500 mPa · s. In addition, the solution viscosity (mPa · s) of the above polymer is based on a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The value measured at 25 ° C. using an E-type rotational viscometer.
The polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, more preferably 2,000. ~ 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. By being in such a molecular weight range, it is possible to ensure good orientation and stability of the liquid crystal display element.

<Other ingredients>
Although the liquid crystal aligning agent of this invention contains the above polymers (P), you may contain another component as needed. The other components can be appropriately selected according to the use of the liquid crystal aligning agent. For example, when producing the liquid crystal aligning film for liquid crystal display elements using the liquid crystal aligning agent of this invention, as another component which may be added to the said liquid crystal aligning agent, other than said polymer (P) Examples thereof include a polymer, a compound having at least one epoxy group in the molecule (hereinafter referred to as “epoxy group-containing compound”), a functional silane compound, and the like.

[Other polymers]
The above other polymers can be used for improving solution properties and electrical properties. Examples of such other polymers include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, and poly (meth) acrylate. A polymer having a main skeleton and not having the specific structure can be used. As the other polymer, at least one selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, and polysiloxane can be preferably used. In addition, the polyamic acid as said other polymer can be obtained, for example by reaction of the tetracarboxylic dianhydride illustrated by description of polyamic acid (P), and the said other diamine, and a polyimide is the said polyamic acid. The polyamic acid ester can be obtained, for example, by esterification of the polyamic acid. The polyorganosiloxane as the other polymer can be obtained, for example, by hydrolysis / condensation reaction of a hydrolyzable silane compound. These polymers can be synthesized according to known methods.
When other polymers are added to the liquid crystal aligning agent, the blending ratio is preferably 50 parts by weight or less with respect to 100 parts by weight of the total polymer in the composition, and 0.1 to 40 parts by weight More preferably, it is more preferably 0.1 to 30 parts by weight.

[Epoxy group-containing compound]
The epoxy group-containing compound can be used to improve the adhesion of the liquid crystal alignment film to the substrate surface. Here, examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodi Preferred examples include phenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, and epoxy group-containing polyorganosiloxane described in WO2009 / 096598. Can be mentioned.
When these epoxy group-containing compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 40 parts by weight or less, and 0.1 to 30 parts by weight with respect to 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent. Is more preferable.

[Functional silane compounds]
The said functional silane compound can be used in order to improve the printability of a liquid crystal aligning agent. Examples of such functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 , 7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, methyl 9-triethoxysilyl-3,6-diazananoate, N -Benzyl-3-aminopropy Trimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxy A silane etc. can be mentioned.
When adding a functional silane compound to a liquid crystal aligning agent, the compounding ratio is preferably 2 parts by weight or less, and more preferably 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the total polymer.

  In addition, antioxidants such as phenolic antioxidants and amine antioxidants; polyfunctional (meth) acrylates such as ethylene glycol diacrylate and 1,6-hexanediol diacrylate; etc. are added to the liquid crystal aligning agent. May be.

Other components that may be added to the liquid crystal aligning agent for the liquid crystal aligning agent for the retardation film include, for example, other polymers other than the polymer (P), metal chelate compounds, curing accelerators, and surfactants. And the like.
[Other polymers]
As said other polymer which may be added to the liquid crystal aligning agent for retardation films, it can be used for the improvement of a solution characteristic etc., Specifically, it is used for the liquid crystal aligning agent for liquid crystal display elements. The polymer etc. which were illustrated as another polymer which may be added are mentioned.
As the other polymer, a polymer having a photoalignment structure can be preferably used. Specifically, a polymer having a photoalignment group is preferably included, and a cinnamic acid structure is used as the photoalignment group. It is more preferable to include a polymer into which a group having s is introduced. Among them, a polyorganosiloxane having a cinnamic acid structure can be preferably used because it is easy to introduce a photoalignable group into the polymer.
In addition, the polymer which has a photoalignment group is compoundable by a conventionally well-known method. For example, the polyorganosiloxane having a photo-alignment group as another polymer is a polyorganosiloxane having an epoxy group and a carboxylic acid having a photo-alignment group, preferably an organic solvent such as ether, ester or ketone. It can synthesize | combine by making it react in presence of catalysts, such as a quaternary ammonium salt.
When the other polymer is added to the liquid crystal aligning agent, the blending ratio is preferably 50 parts by weight or less with respect to 100 parts by weight of the total polymer in the composition, and 0.1 to 40 parts by weight. More preferably, it is more preferably 0.1 to 30 parts by weight.

[Metal chelate compounds]
When the polymer component of the liquid crystal aligning agent has an epoxy structure, the metal chelate compound is contained in the liquid crystal aligning agent for the purpose of ensuring the mechanical strength of the film formed by the low temperature treatment. As the metal chelate compound, it is preferable to use an acetylacetone complex or acetoacetic acid complex of a metal selected from aluminum, titanium and zirconium. Specifically, for example, diisopropoxyethyl acetoacetate aluminum, tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetonate) Examples thereof include titanium, tri-n-butoxyethyl acetoacetate zirconium, and di-n-butoxybis (ethyl acetoacetate) zirconium. The proportion of the metal chelate compound used is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and 1 to 30 parts by weight with respect to 100 parts by weight of the total components including the epoxy structure. More preferably.

[Curing accelerator]
When the polymer component in the liquid crystal aligning agent has an epoxy structure, the curing accelerator is a liquid crystal in order to ensure the mechanical strength of the liquid crystal alignment film to be formed and the stability over time of the liquid crystal alignment. Contained in the alignment agent. As the curing accelerator, for example, a compound having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic anhydride group, or the like can be used. A compound having is preferred. Specific examples thereof include compounds having a phenol group such as cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol; compounds having a silanol group such as trimethylsilanol, triethylsilanol, 1 , 1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis (hydroxydimethylsilyl) benzene, triphenylsilanol, tri (p-tolyl) silanol, diphenylsilanediol, etc. be able to. The use ratio of the curing accelerator is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and 1 to 30 parts by weight with respect to a total of 100 parts by weight of the components including the epoxy structure. More preferably.

[Surfactant]
The surfactant can be contained in the liquid crystal aligning agent for the purpose of improving the applicability of the liquid crystal aligning agent to the substrate. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. be able to. The proportion of the surfactant used is preferably 10 parts by weight or less, and more preferably 1 part by weight or less with respect to 100 parts by weight of the total amount of the liquid crystal aligning agent.

<Solvent>
The liquid crystal aligning agent of the present invention is prepared as a liquid composition in which the polymer (P) and other components used as necessary are preferably dispersed or dissolved in an appropriate solvent.

  Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, 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 acetate, diethylene glycol dimethyl ether, diethylene glycol Recall 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, propylene carbonate, etc. be able to. These can be used alone or in admixture of two or more.

  The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. The range is preferably 1 to 10% by weight. That is, the liquid crystal aligning agent of this invention is apply | coated to a substrate surface so that it may mention later, Preferably the coating film which becomes a liquid crystal aligning film or a coating film used as a liquid crystal aligning film is formed by heating. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, 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.

  The particularly preferable solid content concentration range varies depending on the use of the liquid crystal aligning agent and the method used when the liquid crystal aligning agent is applied to the substrate. For example, when a liquid crystal aligning agent for a liquid crystal aligning film is applied to a substrate by a spinner method, the solid content concentration (the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) Is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s. The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-30 degreeC. Moreover, about the liquid crystal aligning agent for retardation films, the solid content density | concentration of a liquid crystal aligning agent is 0.2 to 10 weight% from a viewpoint which makes the applicability | paintability of a liquid crystal aligning agent, and the film thickness of the coating film formed moderate. It is preferable that it is the range of 3-10 weight%.

<Liquid crystal display element and retardation film>
By using the liquid crystal aligning agent of the present invention described above, a liquid crystal aligning film can be produced. Moreover, the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention is preferably applicable to the liquid crystal aligning film for liquid crystal display elements, and the liquid crystal aligning film for retardation films. Below, the liquid crystal display element and retardation film of this invention are demonstrated.

[Liquid crystal display element]
The liquid crystal display element of this invention comprises the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited. For example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type, etc. It can be applied to the driving method. The liquid crystal display element of the present invention can be produced, for example, by the following steps (I-1) to (I-3). In step (I-1), the substrate to be used varies depending on the desired operation mode. Steps (I-2) and (I-3) are common to each operation mode.

[Step (I-1): Formation of coating film]
First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, Then, a coating film is formed on a board | substrate by heating an application surface.
(I-1A) When manufacturing a TN-type, STN-type, or VA-type liquid crystal display element, for example, first, a pair of two substrates provided with patterned transparent conductive films is formed, and each transparent conductive film is formed. On the surface, the liquid crystal aligning agent of the present invention is preferably applied by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method, respectively. 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 order to obtain a patterned transparent conductive film, for example, after forming a transparent conductive film without a pattern, a method of forming a pattern by photo-etching; a method of using a mask having a desired pattern when forming a transparent conductive film; And so on. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or a functional titanium compound is formed on the surface of the substrate surface on which the coating film is formed. It is also possible to perform a pretreatment to apply the above in advance.

  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 pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 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, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. Thus, the film thickness of the formed film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

  (I-1B) When manufacturing an IPS type or FFS type liquid crystal display element, an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and an electrode are provided. The liquid crystal aligning agent of this invention is each apply | coated to one surface of the counter substrate which is not formed, Then, a coating film is formed by heating each application surface. Regarding the material used for the substrate and the transparent conductive film, the coating method, the heating conditions after coating, the patterning method for the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the coating film to be formed The same as (I-1A). As the metal film, for example, a film made of a metal such as chromium can be used.

  In both cases (I-1A) and (I-1B), after applying a liquid crystal aligning agent on the substrate, a coating film to be an alignment film is formed by removing the organic solvent. At this time, when the polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid, a polyamic acid ester, or an imidized polymer having an imide ring structure and an amic acid structure, It is good also as a more imidized coating film by advancing the dehydration ring-closing reaction by further heating after the coating film formation.

[Step (I-2): Orientation ability imparting treatment]
When manufacturing a TN type, STN type, IPS type, or FFS type liquid crystal display element, as a treatment for imparting liquid crystal alignment ability to the coating film formed in the above step (I-1), the coating film is made of, for example, nylon or rayon. A rubbing process is carried out by rubbing in a certain direction with a roll wound with a cloth made of fibers such as cotton. Thereby, the orientation ability of liquid crystal molecules is imparted to the coating film to form a liquid crystal orientation film. On the other hand, when producing a VA type liquid crystal display element, the coating film formed in the above step (I-1) can be used as it is as a liquid crystal alignment film, but even if the coating film is rubbed. Good. In addition, the liquid crystal alignment film after the rubbing treatment is further subjected to a treatment for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet light, or a surface of the liquid crystal alignment film. A resist film is formed on the part, and a rubbing process is performed in a direction different from the previous rubbing process, followed by a process of removing the resist film, so that the liquid crystal alignment film has different liquid crystal alignment capabilities for each region. . In this case, it is possible to improve the visibility characteristics of the obtained liquid crystal display element. Note that a liquid crystal alignment film suitable for a VA liquid crystal display element can also be suitably used for a PSA (Polymer sustained alignment) liquid crystal display element. As a process for imparting liquid crystal alignment ability to the coating film, a process by a photo-alignment method may be employed instead of the rubbing process.

[Step (I-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. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, two substrates are arranged opposite to each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole. The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped at predetermined locations on the liquid crystal alignment film surface. After that, the other substrate is bonded so that the liquid crystal alignment film faces, and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell. can do. Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase and then gradually cooled to room temperature. It is desirable to remove.

  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, phenyl cyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals. Biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal, and the like can be used. Further, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck & Co., Inc.). A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.

  And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell. As a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film itself in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films The polarizing plate which consists of can be mentioned.

[Phase difference film]
When producing a retardation film using the liquid crystal aligning agent of the present invention, it is possible to form a uniform liquid crystal aligning film while suppressing the generation of dust and static electricity during the process, suitable for irradiation with radiation. It is preferable to use a photo-alignment method in that a plurality of regions having different liquid crystal alignment directions can be arbitrarily formed on the substrate by using a simple photomask. Specifically, it can be produced through the following steps (II-1) to (II-3).

[Step (II-1): Formation of coating film by liquid crystal aligning agent]
First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, and a coating film is formed. As a substrate used here, a transparent substrate made of a synthetic resin such as triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, polymethyl methacrylate, polycarbonate, etc. is preferably exemplified. Can do. Of these, TAC is generally used as a protective layer for a polarizing film in a liquid crystal display device. In addition, polymethyl methacrylate can be preferably used as a substrate for a retardation film in that the hygroscopicity of the solvent is low, the optical properties are good, and the cost is low. In addition, for the substrate used for the application of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the coating film, a conventionally known pretreatment is performed on the surface of the substrate surface on which the coating film is formed. May be implemented.

  In many cases, the retardation film is used in combination with a polarizing film. At this time, it is necessary to attach the retardation film by precisely controlling the angle with respect to the polarization axis of the polarizing film in a specific direction so that the desired optical characteristics can be exhibited. Accordingly, by forming a liquid crystal alignment film having a liquid crystal alignment ability in a predetermined angle direction on a substrate such as a TAC film or polymethyl methacrylate, the angle of the retardation film is controlled on the polarizing film. The step of bonding can be omitted. Thereby, it can contribute to the improvement of productivity of a liquid crystal display element. In order to form a liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle, it is preferable to carry out by a photo-alignment method using the liquid crystal aligning agent of the present invention.

The liquid crystal aligning agent can be applied onto the substrate by an appropriate application method such as a roll coater method, a spinner method, a printing method, an ink jet method, a bar coater method, an extrusion die method, a direct gravure coater method, a chamber. Doctor coater method, offset gravure coater method, single roll kiss coater method, reverse kiss coater method using small diameter gravure roll, 3 reverse roll coater method, 4 reverse roll coater method, slot die method, air doctor coater method A positive rotation roll coater method, a blade coater method, a knife coater method, an impregnation coater method, an MB coater method, an MB reverse coater method, and the like can be employed.
After coating, the coated surface is heated (baked) to form a coating film. The heating temperature at this time is preferably 40 to 150 ° C, more preferably 80 to 140 ° C. The heating time is preferably 0.1 to 15 minutes, and more preferably 1 to 10 minutes. The film thickness of the coating film formed on the substrate is preferably 1 to 1,000 nm, more preferably 5 nm to 500 nm.

[Step (II-2): Light irradiation step]
Next, the coating film formed on the substrate as described above is irradiated with light to impart liquid crystal alignment ability to the coating film. Here, examples of the light to be irradiated include ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm. Among these, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. Irradiation light may be polarized or non-polarized. As the polarized light, it is preferable to use light including linearly polarized light.
When the light to be used is polarized light, the light irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof. When irradiating non-polarized light, it is necessary to carry out from a direction oblique to the substrate surface.
Examples of the light source used include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and a mercury-xenon lamp (Hg-Xe lamp). Polarized light can be obtained by means of using these light sources in combination with, for example, a filter or a diffraction grating.
The dose of light is preferably less than 0.1 mJ / cm ² or more 1,000 mJ / cm ^2, more preferably to 1 to 500 mJ / cm ^2, further be 2~200mJ / cm ² preferable.

[Step (2-3): Formation of Liquid Crystal Layer]
Next, a polymerizable liquid crystal is applied and cured on the coating film after the light irradiation as described above. Thereby, the coating film (liquid crystal layer) containing a polymerizable liquid crystal is formed. The polymerizable liquid crystal used here is a liquid crystal compound or a liquid crystal composition that is polymerized by at least one treatment of heating and light irradiation. As such polymerizable liquid crystal, conventionally known ones can be used. Specifically, for example, Non-Patent Document 1 (“UV curable liquid crystal and its application”, Liquid Crystal, Vol. 3, No. 1 (1999) ), Pp 34-42). Further, cholesteric liquid crystal; discotic liquid crystal; twisted nematic alignment type liquid crystal to which a chiral agent is added may be used. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may further be a composition containing a known polymerization initiator, an appropriate solvent, and the like.
In order to apply the polymerizable liquid crystal as described above onto a coating film formed using a liquid crystal aligning agent, for example, an appropriate application method such as a bar coater method, a roll coater method, a spinner method, a printing method, an ink jet method or the like is used. Can be adopted.

Next, the coating film of the polymerizable liquid crystal formed as described above is subjected to one or more treatments selected from heating and light irradiation to cure the coating film to form a liquid crystal layer. It is preferable to perform these treatments in a superimposed manner because good alignment can be obtained.
The heating temperature of the coating film should be appropriately selected depending on the type of polymerizable liquid crystal used. For example, when using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40 to 80 ° C. The heating time is preferably 0.5 to 5 minutes.
As irradiation light, non-polarized ultraviolet rays having a wavelength in the range of 200 to 500 nm can be preferably used. The irradiation dose of light, preferably in the 50~10,000mJ / cm ^2, and more preferably a 100~5,000mJ / cm ^2.
The thickness of the liquid crystal layer to be formed is appropriately set depending on desired optical characteristics. For example, when manufacturing a half-wave plate for visible light having a wavelength of 540 nm, a thickness is selected such that the retardation of the formed retardation film is 240 to 300 nm. The thickness is selected such that the phase difference is 120 to 150 nm. The thickness of the liquid crystal layer from which the desired retardation is obtained varies depending on the optical characteristics of the polymerizable liquid crystal used. For example, when RMS03-013C manufactured by Merck is used, the thickness for manufacturing a quarter-wave plate is in the range of 0.6 to 1.5 μm.

  The retardation film obtained as described above can be preferably applied as a retardation film of a liquid crystal display element. The liquid crystal display element to which the retardation film manufactured using the liquid crystal aligning agent of the present invention is applied is not limited in its driving method. For example, TN type, STN type, IPS type, FFS type, VA type and the like are known. It can be applied to various methods. The retardation film is used by attaching the substrate-side surface of the retardation film to the outer surface of the polarizing plate disposed on the viewing side of the liquid crystal display element. Therefore, it is preferable that the retardation film substrate is made of TAC or an acrylic base, and the retardation film substrate also functions as a protective film for the polarizing film.

  The liquid crystal display element of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, cellular phones, smartphones, various types. It can be used for various display devices such as a monitor, a liquid crystal television, and an information display.

  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 and Synthesis Examples, the polymer weight average molecular weight Mw, imidization rate and epoxy equivalent, and the solution viscosity of the polymer solution were measured by the following methods.
[Weight average molecular weight Mw of polymer]
Mw is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Imidation rate of polymer]
A solution containing polyimide is poured into pure water, and the resulting precipitate is sufficiently dried at room temperature under reduced pressure, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR is measured at room temperature using tetramethylsilane as a reference substance. did. From the obtained ¹ H-NMR spectrum, the imidation ratio was determined using the following mathematical formula (1).
Imidation ratio (%) = (1-A ¹ / A ² × α) × 100 (1)
(In Formula (1), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a precursor of a polymer (polyamic acid). The number ratio of other protons to one proton of NH group in)
[Epoxy equivalent]
The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.
[Solution viscosity of polymer solution]
The solution viscosity (mPa · s) of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer.

<Synthesis of amine compounds>
[Example 1-1; Synthesis of Compound (DA-1)]
According to the following scheme 1, a compound represented by the following formula (DA-1) (hereinafter referred to as compound (DA-1)) was synthesized.

To a 3 L three-necked flask equipped with a thermometer, a three-way cock and a dropping funnel, 147.2 g (0.69 mol) of 3- (4-nitrophenyl) propanoic acid chloride and 500 ml of tetrahydrofuran (THF) were added and mixed. Subsequently, 1000 ml of 25% aqueous ammonia solution was slowly added dropwise. After reacting at 30 ° C. for 2 hours, it was mixed with 1500 ml of ethyl acetate, and then separated and washed with an aqueous sodium hydrogen carbonate solution and distilled water. Next, the organic layer was concentrated to precipitate a solid. The obtained solid was recrystallized from ethyl acetate and hexane, collected by filtration, and dried to obtain 113.8 g (0.59 mol) of 3- (4-nitrophenyl) propanamide.
Next, in a 2 L three-necked flask equipped with a thermometer, a three-way cock and a dropping funnel, 99.0 g (0.51 mol) of 3- (4-nitrophenyl) propanamide obtained above and 3- (4-nitrophenyl) ) 106.8 g (0.50 mol) of propanoic acid chloride and 1000 ml of THF were added, and the mixture was cooled to 5 ° C. in an ice bath and mixed with stirring. Next, 80 ml of pyridine was slowly dropped from the dropping funnel. During the dropping, the mixture was cooled in an ice bath so as not to exceed 10 ° C., and reacted at 0 ° C. to 10 ° C. for 1 hour and then at room temperature for 4 hours. After the reaction, it was mixed with 1000 ml of ethyl acetate and then separated and washed with distilled water. The obtained organic layer was concentrated to precipitate a solid. The precipitated solid was recrystallized from ethanol, collected by filtration and dried to obtain 102.5 g (0.28 mol) of nitro intermediate (DA-1-1).
Next, 102.5 g of the above nitro intermediate (DA-1-1), 10 g of 5% Pd / C, 280 mL of ethanol and 280 mL of tetrahydrofuran were added to a 2 L autoclave under a nitrogen stream, and then replaced with hydrogen again. The reaction was carried out at room temperature in the presence of hydrogen. The reaction was traced by HPLC, followed by filtration after confirming the progress of the reaction. The filtrate and 3000 mL of ethyl acetate were mixed and then separated and purified with distilled water. A solid was precipitated by removing the solvent from the obtained organic layer by distillation under reduced pressure. The precipitated solid was recrystallized from ethanol to obtain 75.6 g (0.24 mol) of Compound (DA-1).

[Example 1-2; Synthesis of compound (DA-2)]
According to the following scheme 2, a compound represented by the following formula (DA-2) (hereinafter referred to as compound (DA-2)) was synthesized.

To a 2 L three-necked flask equipped with a thermometer, a three-way cock and a dropping funnel, 30 g (0.50 mol) of urea, 224.3 g (1.05 mol) of 3- (4-nitrophenyl) propanoic acid chloride, and 500 ml of THF were added. The mixture was cooled to 5 ° C. in an ice bath and mixed with stirring. Next, 160 ml of pyridine was slowly dropped from the dropping funnel. During the dropping, the mixture was cooled in an ice bath so as not to exceed 10 ° C., and reacted at 0 ° C. to 10 ° C. for 1 hour and then at room temperature for 4 hours. After the reaction, it was mixed with 3000 ml of ethyl acetate and then separated and washed with distilled water. Next, the organic layer was concentrated to precipitate a solid. The precipitated solid was recrystallized from ethanol, collected by filtration and dried to obtain 151.2 g (0.37 mol) of a nitro intermediate (DA-2-1).
Next, 151.2 g of the above nitro intermediate (DA-2-1), 10 g of 5% Pd / C, 400 mL of ethanol and 400 mL of tetrahydrofuran were added to a 2 L autoclave under a nitrogen stream, and then replaced with hydrogen again. The reaction was carried out at room temperature in the presence of hydrogen. The reaction was traced by HPLC, followed by filtration after confirming the progress of the reaction. After filtration, the filtrate and 2000 mL of ethyl acetate were mixed and then separated and purified with distilled water. A solid was precipitated by removing the solvent from the obtained organic layer by distillation under reduced pressure. The precipitated solid was recrystallized from ethanol to obtain 103.4 g (0.33 mol) of Compound (DA-2).

[Example 1-3; Synthesis of Compound (DA-3)]
According to the following scheme 3, a compound represented by the following formula (DA-3) (hereinafter referred to as compound (DA-3)) was synthesized.

  Under a nitrogen stream, 100 g (0.51 mol) of 3- (4-nitrophenyl) propanamide synthesized in the same manner as in Example 1-1 in a 2 L autoclave, 10 g of 5% Pd / C, 500 mL of ethanol, After adding 500 mL of tetrahydrofuran, it was replaced with hydrogen again and reacted at room temperature in the presence of hydrogen. The reaction was traced by HPLC, followed by filtration after confirming the progress of the reaction. The filtrate and 2000 mL of ethyl acetate were mixed, and then separated and purified with distilled water. A solid was precipitated by removing the solvent from the obtained organic layer by distillation under reduced pressure. The precipitated solid was recrystallized from ethanol to obtain 71.9 g (0.44 mol) of Compound (DA-3).

[Example 1-4; Synthesis of Compound (DA-4)]
According to the following scheme 4, a compound represented by the following formula (DA-4) (hereinafter referred to as compound (DA-4)) was synthesized.

In a 2 L three-necked flask equipped with a thermometer, a three-way cock and a condenser, 4-nitrofluorobenzene 74.4 g (0.53 mol), isonipecotamide 64.1 g (0.5 mol), potassium carbonate 207.3 g (1. 5 mol) and 1000 ml of N, N-dimethylformamide (DMF) were added and mixed. After reacting at 80 ° C. for 5 hours, the mixture was mixed with 700 ml of ethyl acetate, and then separated and washed with distilled water. Next, the organic layer was concentrated to precipitate a solid. The obtained solid was recrystallized from ethanol, collected by filtration, and dried to obtain 97.8 g (0.39 mol) of an intermediate (DA-4-1).
Next, in a 2 L three-necked flask equipped with a thermometer, a three-way cock and a dropping funnel, 97.8 g of the intermediate (DA-4-1) obtained above, 87.4 g of 4-nitrobenzoic acid chloride (0.47 mol) ) And 500 ml of THF were added, cooled to 5 ° C. in an ice bath, and mixed with stirring. Next, 65 ml of pyridine was slowly dropped from the dropping funnel. During the dropping, the mixture was cooled in an ice bath so as not to exceed 10 ° C., and reacted at 0 ° C. to 10 ° C. for 1 hour and then at room temperature for 4 hours. After the reaction, the mixture was mixed with 1000 ml of ethyl acetate, and then separated and washed with an aqueous sodium hydrogen carbonate solution and distilled water. Next, the organic layer was concentrated to cause solid precipitation. The precipitated solid was recrystallized from ethanol, collected by filtration and dried to obtain 70.5 g (0.18 mol) of a nitro intermediate (DA-4-2).
Next, under a nitrogen stream, 70.5 g of the above nitro intermediate (DA-4-2), 7 g of 5% Pd / C, 180 mL of ethanol and 180 mL of tetrahydrofuran were added to a 2 L autoclave, and then replaced with hydrogen again. The reaction was carried out at room temperature in the presence of hydrogen. The reaction was traced by HPLC, followed by filtration after confirming the progress of the reaction. A solid was precipitated by removing the solvent from the organic layer by distillation under reduced pressure. The precipitated solid was recrystallized from ethanol to obtain 43.1 g (0.13 mol) of Compound (DA-4).

[Example 1-5; Synthesis of Compound (DA-5)]
In accordance with the following scheme 5, a compound represented by the following formula (DA-5) (hereinafter referred to as compound (DA-5)) was synthesized.

  The same operation as in Example 1-3 was performed except that N-methyl-3- (4-nitrophenyl) propanamide was used in place of 3- (4-nitrophenyl) propanamide in Example 1-3. Compound (DA-5) was obtained.

<Synthesis of polymer>
[Example 2-1; Synthesis of polymer (PA-1)]
As a tetracarboxylic dianhydride, 11.84 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (98 mol parts with respect to 100 mol parts of the total amount of amine compounds used in the synthesis), and as an amine compound 1.382 g (10 mol parts) of 4-aminophenyl-4′-aminobenzoate and 16.97 g (90 mol parts) of compound (DA-1) were dissolved in 170 g of N-methyl-2-pyrrolidone (NMP). The reaction was conducted at 60 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried under reduced pressure at 40 ° C. for 15 hours to obtain 28.1 g of polyamic acid (hereinafter referred to as polymer (PA-1)). The obtained polymer (PA-1) was prepared so as to be 10% by weight with NMP, and the viscosity of this solution was measured and found to be 1,051 mPa · s. Further, when this polymer solution was allowed to stand at 20 ° C. for 3 days, it did not gel and the storage stability was good.

[Example 2-2 to Example 2-8; synthesis of polymer (PA-2) to polymer (PA-8)]
In Example 2-1 above, a polymer was obtained in the same manner as in Example 2-1, except that the types and amounts of tetracarboxylic dianhydride and amine compound used in the reaction were changed as shown in Table 1 below. In addition, the numerical value of Table 1 shows the use ratio (mol%) with respect to the whole quantity of the tetracarboxylic dianhydride used for reaction about the tetracarboxylic dianhydride, It used for reaction about the amine compound. The use ratio (mol%) with respect to the total amount of the amine compound is shown. Each of the polymer solutions obtained in the examples was allowed to stand at 20 ° C. for 3 days. None of them was gelled, and the storage stability was good.

Abbreviations of tetracarboxylic dianhydrides and amine compounds in Table 1 are as follows.
(Tetracarboxylic dianhydride)
AN-1; 1,2,3,4-cyclobutanetetracarboxylic dianhydride AN-2; pyromellitic dianhydride AN-3; 2,3,5-tricarboxycyclopentylacetic acid dianhydride AN-4; Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride AN-5; 5- (2,5-dioxotetrahydrofuran-3-yl ) -8-Methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione (amine compound)
DA-6; paraphenylenediamine DA-7; 4,4'-diaminodiphenylmethane DA-8; 4-aminophenyl-4'-aminobenzoate DA-9; 2,4-diamino-N, N-diallylaniline DA- 10; 4,4′-diaminodiphenylamine DA-11; 3,5-diaminobenzoic acid DA-12; 3,5-diaminobenzoic acid cholestanyl DA-13; 4- (tetradecaoxy) benzene-1,3-diamine

[Synthesis Example 1; Synthesis of Polymer (PI-1)]
As a tetracarboxylic dianhydride, 1.6 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (9.8 mol parts with respect to 100 mol parts of the total amount of amine compounds used in the synthesis) and bicyclo [ 3.3.0] Octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride 18.36 g (88.2 mol parts), and paraphenylenediamine 1 as the amine compound 0.8 g (20 mole parts), 4,4′-diaminodiphenylmethane 9.9 g (60 mole parts), 2,4-diamino-N, N-diallylaniline 1.69 g (10 mole parts) and 4,4′-diaminodiphenylmethane 1.66 g (10 mol parts) of 4′-diaminodiphenylamine was dissolved in 198.3 g of NMP and reacted at room temperature for 6 hours. Next, 266.7 g of NMP was added, 16.12 g of pyridine and 20.81 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 100 ° C. for 5 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried under reduced pressure at 40 ° C. for 15 hours to obtain polyimide (PI-1) having an imidation ratio of about 85%. The obtained polyimide (PI-1) was prepared so as to be 10% by weight with NMP. It was 844 mPa * s when the viscosity of this solution was measured.

[Synthesis Example 2; Synthesis of polyorganosiloxane]
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. Mixed with. 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was carried out at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer is taken out, washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to have an oxiranyl group. Polyorganosiloxane was obtained as a viscous transparent liquid. When ¹ H-NMR analysis was performed on the polyorganosiloxane having an oxiranyl group, a peak based on the oxiranyl group was obtained in the vicinity of the chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction occurred. The epoxy equivalent of the polyorganosiloxane having an oxiranyl group was measured and found to be 186 g / equivalent.
Next, in a 100 mL three-necked flask, 9.3 g of the polyorganosiloxane having the oxiranyl group obtained above, 26 g of methyl isobutyl ketone, 3 g of 4-phenoxycinnamic acid and UCAT 18X (trade name, manufactured by San Apro Co., Ltd.) 0.10 g Was reacted at 80 ° C. for 12 hours with stirring. After completion of the reaction, the reaction mixture was poured into methanol to collect a precipitate, which was dissolved in ethyl acetate to form a solution. The solution was washed with water three times, and then the solvent was distilled off to remove the oxiranyl group. 6.3 g of a polyorganosiloxane (S-1) having a cinnamic acid structure was obtained as a white powder. The weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography for this polyorganosiloxane (S-1) was 3,500.

<Preparation and evaluation of liquid crystal aligning agent>
[Example 3-1: FFS type liquid crystal display element]
(1) Preparation of liquid crystal aligning agent As a polymer, 100 parts by weight of the polymer (PA-1) obtained in Example 2-1 was mixed solvent (GBL) composed of γ-butyrolactone (GBL), NMP and butyl cellosolve (BC). : NMP: BC = 40: 40: 20 (weight ratio)) to obtain a solution having a solid content concentration of 4.0% by weight. The liquid crystal aligning agent (R-1) was prepared by filtering this solution through a filter having a pore diameter of 0.2 μm.

(2) Evaluation of applicability The liquid crystal aligning agent (R-1) prepared above was applied on a glass substrate using a spinner, prebaked on a hot plate at 80 ° C. for 1 minute, and then the interior was filled with nitrogen. By heating (post-baking) in a substituted 200 ° C. oven for 1 hour, a coating film having an average film thickness of 1,000 mm was formed. This coating film was observed with a microscope having a magnification of 100 times to examine the presence or absence of film thickness unevenness and pinholes. The evaluation was carried out when the coating property was “good” when neither the film thickness unevenness nor the pinhole was observed, and when the film thickness unevenness or the pinhole was clearly observed as the coating property “bad”. . In this example, neither film thickness unevenness nor pinhole was observed, and the coating property was “good”.

(3) Evaluation of rubbing resistance The coating film obtained above was rubbed at a roll rotation speed of 1000 rpm, a stage moving speed of 20 cm / sec, and a hair foot indentation length of 0.4 mm by a rubbing machine having a roll wrapped with a cotton cloth. The treatment was performed 7 times. Foreign matter (a piece of coating film) due to rubbing scraping on the obtained substrate was observed with an optical microscope, and the number of foreign matters in a 500 μm × 500 μm region was measured. In the evaluation, the rubbing resistance was “excellent” when the number of foreign substances was 3 or less, and “good” when 4 or more and 7 or less were present, and the rubbing resistance “bad” when 8 or more. As a result, the rubbing resistance of this coating film was “excellent”.

(4) Manufacture of FFS type liquid crystal display element The liquid crystal display element of the FFS type liquid crystal display element shown in FIG. 1 was produced. First, a glass substrate 11a having two electrode pairs on one side each having a bottom electrode 12 having no pattern, a silicon nitride film 13 as an insulating layer, and a top electrode 14 patterned in a comb shape in this order. And the counter glass substrate 11b provided with no electrodes, and the liquid crystal prepared in (1) above on the surface of the glass substrate 11a having the transparent electrodes (12, 14) and one surface of the counter glass substrate 11b. The alignment agent (R-1) was applied using a spinner to form a coating film. Next, this coating film was pre-baked for 1 minute on a hot plate at 80 ° C., and then heated (post-baked) at 230 ° C. for 15 minutes in an oven in which the inside of the chamber was replaced with nitrogen, so that the average film thickness was 1,000 mm. A coating film was formed. A schematic plan view of the top electrode 14 is shown in FIG. 2A is a top view of the top electrode 14, and FIG. 2B is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2A. In this embodiment, the line width d1 of the electrode 14 is 4 μm, and the distance d2 between the electrodes is 6 μm.

  Subsequently, the surface of the coating film formed on the glass substrate was rubbed with cotton. In FIG.2 (b), the rubbing direction with respect to the coating film formed on the glass substrate 11a is shown by the arrow. These substrates were bonded together through a spacer having a diameter of 3.5 μm so that the rubbing directions of the substrates were antiparallel, and liquid crystal MLC-6221 (manufactured by Merck) was injected. Furthermore, the liquid crystal display element was produced by bonding a polarizing plate on both outer surfaces of the substrate so that the polarization directions of the two polarizing plates were orthogonal to each other.

(5) Evaluation of liquid crystal orientation For the FFS type liquid crystal display device manufactured as described above, the presence or absence of abnormal domains in the change in brightness when a voltage of 5 V is turned ON / OFF (applied / released) is observed with a microscope at a magnification of 50 times. did. In the evaluation, when the abnormal domain was not observed, the liquid crystal alignment was “good”, and when the abnormal domain was observed, the liquid crystal alignment was “bad”. In this liquid crystal display element, the liquid crystal orientation was “good”.
(6) Evaluation of voltage holding ratio For the FFS type liquid crystal display device manufactured as described above, a voltage of 5 V was applied at 23 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, and 167 milliseconds after the release of application. When the voltage holding ratio (VHR) of was measured, it was 99.1%. In addition, as a measuring apparatus, Toyo Technica Co., Ltd. make and VHR-1 were used.

(7) per FFS type liquid crystal display device manufactured in heat-resistant evaluation above, to measure the voltage holding ratio similarly to the above (6), and its value as an initial VHR _{(VHR BF).} Next, the liquid crystal display element after the initial VHR measurement was left in an oven at 100 ° C. for 300 hours. Thereafter, the liquid crystal display element was left at room temperature and allowed to cool to room temperature, and then the voltage holding ratio (VHR _AF ) was measured in the same manner as described above. Further, the rate of change in voltage holding ratio (ΔVHR (%)) before and after application of thermal stress was determined by the following mathematical formula (EX-1).
ΔVHR = ((VHR _BF −VHR _AF ) ÷ VHR _BF ) × 100 (EX−1)
In the evaluation of heat resistance, when the rate of change ΔVHR is less than 4%, heat resistance is “excellent”, when 4% or more and less than 5% is “good”, and when it is 5% or more, heat resistance is “ Went as "bad". As a result, ΔVHR of the liquid crystal display element of this example was 2.1%, and the heat resistance was “excellent”.

(8) Evaluation of residual DC relaxation rate (evaluation of afterimage characteristics)
About the liquid crystal display element manufactured above, the relaxation rate of residual DC was measured by a dielectric absorption method using a 6254C type liquid crystal physical property evaluation apparatus manufactured by Toyo Technica. The measurement was performed in an environment of 60 ° C., after applying a DC voltage of 10 V for 30 minutes, the battery was discharged for 1 second, and then the residual DC for 30 minutes was measured. The residual DC relaxation rate was determined by calculating the average residual DC relaxation rate from the maximum value of residual DC and the residual DC value one minute after the time when the maximum value was exhibited. In the evaluation, the residual DC relaxation property is “excellent” when the residual DC relaxation rate is 4 mV / sec or more, and the residual DC relaxation property is “good” when it is 2 mV / sec or more and less than 4 mV / sec. Residual DC relaxation was performed as “bad”. In addition, it shows that an afterimage characteristic is so favorable that a residual image is so hard to produce that the relaxation rate of residual DC is quick. The residual DC relaxation rate of the liquid crystal display element of this example was 4.2 mV / sec, and the residual DC relaxation property was judged to be “excellent”.

[Example 3-2 to Example 3-6 and Comparative Example 1]
In Example 3-1 above, a liquid crystal aligning agent was prepared in the same manner as in Example 3-1, except that the polymer shown in Table 2 was used, and an FFS type liquid crystal display device was produced. Various evaluations were performed. The evaluation results are shown in Table 2 below.

  As shown in Table 2, in Examples 3-1 to 3-6, good results were obtained for the coating property of the liquid crystal aligning agent and the rubbing resistance of the coating film. Moreover, it was a result of "good" or "excellent" about liquid crystal orientation, a voltage holding ratio, heat resistance, and the relaxation rate of residual DC. On the other hand, in the comparative example 1, the applicability | paintability of the liquid crystal aligning agent was "poor", and it was a result inferior to the Example also about the rubbing tolerance of a coating film. Further, in the liquid crystal display element of Comparative Example 1, all of the liquid crystal orientation, voltage holding ratio, heat resistance, and residual DC relaxation rate were inferior to those of the examples.

[Example 3-7: TN liquid crystal display element]
(1) Preparation of liquid crystal aligning agent 100 parts by weight of the polymer (PA-7) obtained in Example 2-7 as a polymer was used as a mixed solvent of NMP and BC (NMP: BC = 50: 50 (weight ratio)). This was dissolved to obtain a solution having a solid content concentration of 6.5% by weight. After sufficiently stirring this solution, a liquid crystal aligning agent (R-7) was prepared by filtering through a filter having a pore size of 0.2 μm.
(2) Evaluation of printability The glass substrate with a transparent electrode which consists of an ITO film | membrane using the liquid crystal aligning agent (R-7) prepared by said (1) using a liquid crystal aligning film printer (Nissha Printing Co., Ltd. product). The film was coated on the transparent electrode surface, heated on a hot plate at 80 ° C. for 1 minute (pre-baked) to remove the solvent, and then heated on a hot plate at 200 ° C. for 10 minutes (post-baked) to obtain an average film thickness of 600 mm. The coating film was formed. This coating film was observed with a microscope having a magnification of 20 times to examine the presence or absence of printing unevenness and pinholes. In the evaluation, when neither printing unevenness nor pinhole was observed, the printability was “good”, and when at least one of printing unevenness and pinhole was slightly observed, printability was “good”, printing unevenness and pin The case where at least one of the holes was frequently observed was regarded as “printing failure”. In this example, neither printing unevenness nor pinholes were observed, and the printability was “good”.

(3) Manufacture of TN type liquid crystal cell With liquid crystal aligning agent (R-7) prepared by said (1), with a transparent electrode which consists of an ITO film | membrane using a liquid crystal aligning film printer (Nissha Printing Co., Ltd. product). After coating on the transparent electrode surface of the glass substrate and heating (pre-baking) on a hot plate at 80 ° C. for 1 minute to remove the solvent, heating (post-baking) on a hot plate at 200 ° C. for 10 minutes to obtain an average film A coating film having a thickness of 600 mm was formed. This coating film was rubbed with a rubbing machine having a roll wrapped with a rayon cloth at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.4 mm to give liquid crystal alignment ability. . Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then drying was performed in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. The above operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film.
Next, for one of the pair of substrates, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film, and then the pair of substrates is aligned with the liquid crystal alignment film surface. The adhesives were cured by overlapping and pressing them so that they face each other. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) is filled between a pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, whereby a TN liquid crystal cell is obtained. Manufactured.

(4) Evaluation of liquid crystal orientation About the liquid crystal cell manufactured by said (3), the presence or absence of the abnormal domain when the voltage of 5V was turned on / off under crossed Nicols was observed with the microscope at 50 time magnification. Evaluation was performed in the same manner as in Example 3-1 (5). As a result, this liquid crystal display element had “good” liquid crystal alignment.

(5) Evaluation of pretilt angle stability With respect to the liquid crystal cell produced in (3) above, the angle of inclination of the liquid crystal molecules from the substrate surface was measured by a crystal rotation method using He—Ne laser light, and this value was used as the initial pretilt. The angle was θ _IN . Non-Patent Document 1 (TJScheffer et.al., J. Appl. Phys. Vol. 48, p1783 (1977)) and Non-Patent Document 2 (F. Nakano et.al., JPN. J. Appl). Phys. Vol. 19, p2013 (1980)).
Then, the liquid crystal display device was measured for initial pretilt angle theta _IN, and the alternating voltage of 5V was applied for 100 hours. Thereafter, the pretilt angle was measured again by the same method as described above, and this value was defined as the pretilt angle θ _AF after voltage application. By substituting these measured values into the following formula (EX-2), the amount of change in the pretilt angle (Δθ (°)) before and after voltage application was determined.
Δθ = | θ _AF −θ _IN | (EX-2)
Pretilt angle stability “excellent” when Δθ is less than 3%, pretilt angle stability “good” when it is 3% or more and less than 4%, pretilt angle stability when it is 4% or more As a result of evaluation as “defective”, the pretilt angle change rate of this liquid crystal display element was 2.8%, and it was judged that the pretilt angle stability was “excellent”.

(6) Evaluation of voltage holding ratio and heat resistance The initial voltage holding ratio VHR _BF was measured in the same manner as in (6) of Example 3-1 and as in (7) of Example 3-1 above. The heat resistance of the liquid crystal display element was evaluated based on the change rate of the voltage holding ratio before and after application of thermal stress. As a result, the initial voltage holding ratio VHR _BF was 98.9%. Further, ΔVHR was 2.9%, and the heat resistance was judged as “excellent”.

[Example 3-8: VA liquid crystal display element]
(1) Preparation of liquid crystal aligning agent As a polymer, NMP and BC were added to 100 parts by weight of the polymer (PA-8) obtained in Example 2-8, the solid content concentration was 6.5% by weight, and the solvent mixing ratio. Was a solution of NMP: BC = 50: 50 (weight ratio). After sufficiently stirring this solution, a liquid crystal aligning agent (R-8) was prepared by filtering through a filter having a pore size of 0.2 μm.
(2) Evaluation of printability Using the liquid crystal aligning agent (R-8) prepared in (1) above, the printability was examined in the same manner as in (2) of Example 3-7. Neither pinhole was observed, and the printability was “good”.

(3) Manufacture of VA type liquid crystal cell The liquid crystal aligning agent (R-8) prepared above is liquid crystal aligning film printing machine (on the transparent electrode surface of the glass substrate with a transparent electrode (thickness 1 mm) made of ITO film ( Nissha Printing Co., Ltd.), heated on a hot plate at 80 ° C. for 1 minute (pre-baked), and further heated on a hot plate at 200 ° C. for 60 minutes (post-baked) to obtain an average film thickness An 800-mm coating film (liquid crystal alignment film) was formed. This operation was repeated to obtain a pair (two) of glass substrates having a liquid crystal alignment film on the transparent conductive film.
Next, for one of the pair of substrates, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film, and then the pair of substrates is aligned with the liquid crystal alignment film surface. The adhesives were cured by overlapping and pressing so that they face each other. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled between the pair of substrates through the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to produce a VA liquid crystal cell. .

(4) Evaluation of liquid crystal alignment, voltage holding ratio and heat resistance The liquid crystal cell manufactured in (3) above was evaluated for liquid crystal alignment in the same manner as in (4) of Example 3-7. The liquid crystal alignment of the display element was “good”. Further, the initial voltage holding ratio VHR _BF is measured in the same manner as in Example 3-1 (6), and the heat resistance (voltage holding before and after applying thermal stress) is measured in the same manner as in Example 3-1 (7). Rate of change) was evaluated. As a result, the initial voltage holding ratio VHR _BF was 99.2%. Further, ΔVHR was 2.4%, and it was judged that the heat resistance was “excellent”.

[Example 3-9: Retardation film]
(1) Preparation of liquid crystal aligning agent 100 parts by weight of the polymer (PA-2) obtained in Example 2-2 and 5 parts by weight of the polyorganosiloxane (S-1) obtained in Synthesis Example 2 were mixed with NMP and BC. In a mixed solvent (NMP: BC = 50: 50 (weight ratio)) to obtain a solution having a solid concentration of 3.5% by weight. A liquid crystal aligning agent (R-9) was prepared by filtering this solution through a filter having a pore diameter of 0.2 μm.
(2) Manufacture of retardation film The liquid crystal aligning agent (R-9) prepared above was applied to one side of a TAC film as a substrate using a bar coater, and baked at 120 ° C for 2 minutes in an oven. Thus, a coating film having a thickness of 100 nm was formed. Next, the surface of the coating film was irradiated perpendicularly from the substrate normal line with polarized ultraviolet rays of 10 mJ / cm ² containing an emission line of 313 nm using a Hg—Xe lamp and a Grand Taylor prism. Next, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck & Co., Inc.) was filtered through a filter having a pore size of 0.2 μm, and this polymerizable liquid crystal was applied onto the coated film after light irradiation by a bar coater. A coating film was formed. After baking for 1 minute in an oven adjusted to a temperature of 50 ° C., an unpolarized ultraviolet ray containing 365 nm emission line was irradiated at 1,000 mJ / cm ² from a direction perpendicular to the coating surface using an Hg-Xe lamp. A retardation film was produced by curing a polymerizable liquid crystal to form a liquid crystal layer.

(3) Evaluation of liquid crystal orientation About the retardation film manufactured by said (2), liquid crystal orientation is observed by observing the presence or absence of an abnormal domain by visual observation under crossed Nicols and a polarizing microscope (magnification 2.5 times). evaluated. The evaluation was that the alignment was good visually and the abnormal domain was not observed with a polarizing microscope. The liquid crystal alignment was “excellent”. The abnormal domain was not observed with the visual observation, but the abnormal domain was observed with a polarizing microscope. The case where the liquid crystal orientation was “good”, and the case where an abnormal domain was observed visually and with a polarizing microscope was regarded as “bad”. As a result, this retardation film was evaluated as “excellent” in liquid crystal orientation.

(4) Adhesiveness Using the retardation film produced in (2) above, the adhesiveness of the coating film formed with the liquid crystal aligning agent to the substrate was evaluated. First, using a regular spacer with a guide, a cutter knife was used to cut from the surface on the liquid crystal layer side of the retardation film to form 10 × 10 lattice patterns. The depth of each cut was made to reach the middle of the substrate thickness from the surface of the liquid crystal layer. Next, after attaching a cellophane tape so as to cover the entire surface of the lattice pattern, the cellophane tape was peeled off. The notches in the lattice pattern after peeling were observed visually under crossed Nicols to evaluate the adhesion. In the evaluation, the adhesion was “excellent” when no peeling was confirmed at the portion along the cut line and at the intersection of the lattice pattern, and the number of lattices where separation was observed in the above portion was the number of the entire lattice pattern. On the other hand, when the amount is less than 15%, the adhesion is “good”, and when the number of lattices where peeling is observed in the above portion is 15% or more with respect to the total number of lattice patterns, the adhesion is “bad” went. As a result, this retardation film had excellent adhesion.

  DESCRIPTION OF SYMBOLS 10 ... Liquid crystal cell, 11a, 11b ... Glass substrate, 12 ... Bottom electrode, 13 ... Silicon nitride film, 14 ... Top electrode, 15a, 15b ... Liquid crystal aligning film.

Claims (11)

The liquid crystal aligning agent containing the polymer (P) which has a structure represented by following formula (1).

(In Formula (1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and X ¹ and X ² are each independently a divalent organic group. “*” Represents a bond bonded to different groups.)   The liquid crystal aligning agent according to claim 1, wherein the polymer (P) is at least one selected from the group consisting of polyamic acid, polyimide, and polyamic acid ester. The polymer (P) is a polymer obtained by reacting at least one compound (a) selected from the group consisting of tetracarboxylic dianhydride and carboxylic acid halide with an amine compound (b). ,
The liquid crystal aligning agent of Claim 1 or 2 in which the said amine compound (b) contains the compound represented by a following formula (b-1).

(In Formula (b-1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and X ³ and X ⁴ are each independently a divalent organic group. Is 0 or 1.) The compound (a) is tetracarboxylic dianhydride,
As the tetracarboxylic dianhydride, 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-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane-3,5, It contains at least one selected from the group consisting of 8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic dianhydride. 3. A liquid crystal aligning agent according to 3. The liquid crystal aligning agent of Claim 3 or 4 whose compound represented by the said Formula (b-1) is a compound represented by a following formula (b-1-1).

(In Formula (b-1-1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and X ⁵ and X ⁶ are each independently a single bond or a divalent group. (It is an organic group. N is 0 or 1.)   The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-5.   A liquid crystal display device comprising the liquid crystal alignment film according to claim 6.   A retardation film comprising the liquid crystal alignment film according to claim 6. Applying the liquid crystal aligning agent according to any one of claims 1 to 5 on a substrate to form a coating film;
Irradiating the coating film with light;
A method of producing a retardation film, comprising: applying a polymerizable liquid crystal on the coating film after the light irradiation and curing the liquid crystal. A polymer obtained by reacting at least one compound selected from the group consisting of tetracarboxylic dianhydride and carboxylic acid halide and an amine compound containing a compound represented by the following formula (b-1).

(In Formula (b-1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and X ³ and X ⁴ are each independently a divalent organic group. Is 0 or 1.) A compound represented by the following formula (b-1).

(In Formula (b-1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and X ³ and X ⁴ are each independently a divalent organic group. Is 0 or 1.)

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