JP6349726B2 - Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, retardation film, method for producing retardation film, polymer and compound - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, a retardation film, a method for producing a retardation film, a polymer that can be suitably used as a component of a liquid crystal aligning agent, and a compound used for producing the polymer. .

  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.

  Conventionally, various liquid crystal aligning agents have been proposed in order to improve the display quality of the liquid crystal display element (see, for example, Patent Documents 1 and 2). Patent Document 1 discloses a soluble polyimide obtained by a reaction between a diamine compound having two primary amino groups and a nitrogen-containing ring in a molecule and a tetracarboxylic dianhydride as a polymer component of a liquid crystal aligning agent. By using it, it is disclosed that the liquid crystal orientation is improved and the time until the afterimage is erased is shortened. Patent Document 2 discloses a liquid crystal alignment film by using a soluble polyimide obtained by a reaction between a diamine compound having two primary amino groups and a piperazine ring in the molecule and tetracarboxylic dianhydride. It is disclosed that heat resistance and charge leakage are improved.

  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. In recent years, a liquid crystal alignment film in a retardation film has been produced by using a photo-alignment method that imparts liquid crystal alignment ability by irradiating a radiation-sensitive organic thin film formed on the substrate surface with polarized or non-polarized radiation. Various liquid crystal aligning agents for retardation films for producing a liquid crystal aligning film by such a method have been proposed (for example, see 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 the method of performing the process and the process which laminates | stacks a protective film as needed in the continuous process, and collect | recovering the film after passing through these processes as a wound body.

JP-A-10-104633 JP 2010-2501 A 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. Further, the demand for higher performance of the liquid crystal display element is further increased, and the liquid crystal alignment film is required to be able to further improve various characteristics required for the liquid crystal display element.

  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, When the film is used as a wound body after completion of the process, the liquid crystal alignment film may be peeled off from the substrate film. In such a case, there may arise a problem that the product yield decreases.

  The present invention has been made in view of the above problems, and an object thereof is to provide a liquid crystal aligning agent for obtaining a liquid crystal aligning film capable of improving various characteristics required for a liquid crystal display element. . 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 solve the problems of the prior art as described above, the present inventors have used a polymer obtained by polycondensation of an amine compound having a specific structure and a polyvalent carboxylic acid or a derivative thereof. The formed coating film was found to be excellent in light transmittance and can be suitably used for applications such as a liquid crystal alignment film, and the present invention has been solved. Specifically, the present invention provides the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, retardation film, production method thereof, polymer and compound.

  In one aspect, the present invention is selected from the group consisting of a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid halide, a partially esterified product of a polyvalent carboxylic acid, and an acid halide of the partially esterified product. Provided is a liquid crystal aligning agent containing a polymer obtained by using at least one compound (A) and an amine compound (B) containing a compound represented by the following formula (1) as monomers.

（式（１）中、Ｒ^１は２価の有機基である。Ｚ^１は、脂肪族環の環骨格中の炭素−炭素結合間に「−ＮＨ−」を有する環員数５〜７の含窒素複素環基であり、当該含窒素複素環基の炭素原子に結合する水素原子が置換されていてもよい。Ｚ^２は、１級アミノ基、−ＮＨＲ^２（Ｒ^２は、炭素数１〜１５の１価の炭化水素基であり、Ｒ^２が芳香環を有する場合、当該芳香環は窒素原子に直接結合しない。）、又は脂肪族環の環骨格中の炭素−炭素結合間に「−ＮＨ−」を有する環員数５〜７の含窒素複素環基であり、当該含窒素複素環基の炭素原子に結合する水素原子が置換されていてもよい。但し、Ｚ^２が「−ＮＨＲ^２」の場合、Ｚ^２は、Ｒ^１が有する芳香環に直接結合しない。）

(In Formula (1), R ¹ is a divalent organic group. Z ¹ is a group having 5 to 7 ring members having “—NH—” between carbon-carbon bonds in the ring skeleton of the aliphatic ring. It is a nitrogen heterocyclic group, and a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group may be substituted. Z ² is a primary amino group, —NHR ² (R ² is a carbon number of 1 to 15 is a monovalent hydrocarbon group, and when R ² has an aromatic ring, the aromatic ring is not directly bonded to a nitrogen atom.), Or “— between carbon-carbon bonds in the ring skeleton of the aliphatic ring. It is a nitrogen-containing heterocyclic group having 5 to 7 ring members having “NH—”, and a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group may be substituted, provided that Z ² is “—NHR ² In this case, Z ² is not directly bonded to the aromatic ring of R ^1. )

  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. Furthermore, at least one compound selected from the group consisting of polyvalent carboxylic acids, polyvalent carboxylic anhydrides, polyvalent carboxylic acid halides, partially esterified products of polyvalent carboxylic acids, and acid halides of the partially esterified products; The polymer obtained by using as a monomer the amine compound containing the compound represented by the said Formula (1), and the compound represented by the said Formula (1) are provided.

  By using a polymer obtained by using the compound represented by the above formula (1) as the polymer component of the liquid crystal aligning agent, various properties such as coating properties to the substrate, light transmittance, and liquid crystal alignment properties are good. A liquid crystal alignment film can be formed. In addition, by forming a liquid crystal alignment film using the liquid crystal aligning agent of the present invention, heat resistance and voltage holding characteristics are good, and the accumulated charge with respect to the DC voltage is relaxed quickly, and the contrast is not lowered and image sticking hardly occurs. A liquid crystal display element can be obtained. 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.

<Polymer component>
The liquid crystal aligning agent of the present invention comprises, as a polymer component, a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid halide, a partially esterified product of a polyvalent carboxylic acid, and an acid halide of the partially esterified product. A polymer obtained by reacting at least one compound (A) selected from the group consisting of and an amine compound (B) containing a compound represented by the above formula (1) (hereinafter referred to as “polymer (P)”). ").

[Compound (A)]
The polyvalent carboxylic acid as the compound (A) is a compound having two or more carboxyl groups, and the polyvalent carboxylic acid anhydride is an anhydride of a polyvalent carboxylic acid. The compound (A) may be a partially esterified product or acid halide of the polyvalent carboxylic acid, or a halide of the partially esterified product.
Specific examples of the compound (A) include, as polyvalent carboxylic acids, for example, aliphatic polyvalent carboxylic acids such as malonic acid, adipic acid, succinic acid, maleic acid, and butanetetracarboxylic acid; hexahydrophthalic acid, hexahydroterephthalate Cycloaliphatic polyacids such as acid, cyclobutanetetracarboxylic acid, cyclohexanetetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid Phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, aromatic polyvalent carboxylic acids such as 3,3 ′, 4,4′-biphenyltetracarboxylic acid, and the like.
Examples of the polyvalent carboxylic acid anhydrides include intramolecular acid anhydrides and intermolecular acid anhydrides of the above polyvalent carboxylic acids. Specifically, tetracarboxylic dianhydrides, dicarboxylic acid anhydrides, and the like. Is mentioned.
Examples of the polyvalent carboxylic acid halide include acid chlorides and acid bromides of the above polyvalent carboxylic acids. Specifically, dicarboxylic acid dichloride, dicarboxylic acid dibromide, tetracarboxylic acid dichloride, tetracarboxylic acid dibromide. Etc.
Examples of the partially esterified product of the polyvalent carboxylic acid include esters obtained by reacting the polyvalent carboxylic acid with alcohols or phenols, and examples thereof include tetracarboxylic acid diesters. Examples of the acid halide of the partially esterified product include acid chlorides and acid bromides of the above partially esterified products, and specific examples include tetracarboxylic acid diester dichloride and tetracarboxylic acid diester dibromide. It is done.

  When a polyvalent carboxylic acid is used as the compound (A), the reaction with the amine compound (B) must be carried out in the presence of a catalyst, and therefore a decatalytic step is required. Further, when an acid halide is used as the compound (A), a dehalogenation step is required for the use of the liquid crystal aligning agent. Therefore, from the viewpoint of obtaining a coating film with few impurities in a small number of steps, a polyvalent carboxylic acid anhydride can be preferably used as the compound (A) used for the synthesis of the polymer (P).

The main skeleton of the polymer (P) varies depending on the monomers (compound (A) and compound (B)) used in the synthesis. Specifically, for example, by using tetracarboxylic dianhydride as the compound (A) and using an amine compound containing diamine as the compound (B), at least selected from the group consisting of polyamic acid, polyimide and polyamic acid ester You can get a kind.
When tetracarboxylic dianhydride is used as compound (A) and only the compound represented by the above formula (1) is used as compound (B), a carbonyl group derived from tetracarboxylic dianhydride, A polymer having a group formed by bonding to the nitrogen atom of the nitrogen-containing heterocyclic ring in the above formula (1) in the main chain (hereinafter also referred to as “specific polymer”) can be obtained.
When tetracarboxylic acid diester or tetracarboxylic acid diester dihalide is used as the compound (A) and an amine compound containing a diamine is used as the compound (B), a polyamic acid ester can be obtained.
When dicarboxylic acid or dicarboxylic acid dihalide is used as the compound (A) and an amine compound containing a diamine is used as the compound (B), a polyamide can be obtained.
In addition, according to the polymerization using the compound (A) and the amine compound (B) as monomers, the polymer (P) obtained by reacting the compound (A) and the amine compound (B) is obtained. Can be obtained. “A polymer obtained by reacting the compound (A) with the amine compound (B)” means a polymer obtained only from the step of reacting the compound (A) with the amine compound (B), And a polymer obtained by a method including a step of reacting the compound (A) with the amine compound (B).

  As a polymer (P) contained in the liquid crystal aligning agent of this invention, from a viewpoint which makes various characteristics of a liquid crystal aligning film and a liquid crystal display element favorable, it is from the group which consists of a polyamic acid, a polyimide, a specific polymer, and a polyamic acid ester. It is preferably at least one selected. That is, as the compound (A), it is preferable to use at least one selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic diester and tetracarboxylic diester dihalide, and tetracarboxylic dianhydride is used. It is more preferable.

(Tetracarboxylic dianhydride)
Examples of the tetracarboxylic dianhydride used for the synthesis of the polymer (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 polymer (P), these 1 type can be used individually or in combination of 2 or more types.

  The tetracarboxylic dianhydride used for the synthesis of the polymer (P) is bicyclo [2.2.1] heptane-2,3,5 in that the liquid crystal orientation and solubility in a solvent can be improved. , 6-tetracarboxylic acid 2: 3,5: 6-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, bicyclo [3.3. 0] Octane-2,4,6,8-tetracar At least one compound selected from the group consisting of acid 2: 4,6: 8-dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and pyromellitic dianhydride (hereinafter, It is also preferable to include “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 a polymer (P), and 10 mol%. More preferably, it is more preferably 20 mol% or more.

(Tetracarboxylic acid diester and tetracarboxylic acid diester dihalide)
Examples of the tetracarboxylic acid diester as the compound (A) include compounds obtained by ring-opening the tetracarboxylic dianhydride using alcohols such as methanol, ethanol, and propanol. Examples of the tetracarboxylic acid diester dihalide as the compound (A) include compounds obtained by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. . About the preferable example and usage-amount of the tetracarboxylic dianhydride used in order to obtain tetracarboxylic-acid diester and tetracarboxylic-acid diester dihalide, the description of the said tetracarboxylic dianhydride is applicable.

（式（１）中、Ｒ^１は２価の有機基である。Ｚ^１は、脂肪族環の環骨格中の炭素−炭素結合間に「−ＮＨ−」を有する環員数５〜７の含窒素複素環基であり、当該含窒素複素環基の炭素原子に結合する水素原子が置換されていてもよい。Ｚ^２は、１級アミノ基、−ＮＨＲ^２（Ｒ^２は、炭素数１〜１５の１価の炭化水素基であり、Ｒ^２が芳香環を有する場合、当該芳香環は窒素原子に直接結合しない。）、又は脂肪族環の環骨格中の炭素−炭素結合間に「−ＮＨ−」を有する環員数５〜７の含窒素複素環基であり、当該含窒素複素環基の炭素原子に結合する水素原子が置換されていてもよい。但し、Ｚ^２が「−ＮＨＲ^２」の場合、Ｚ^２は、Ｒ^１が有する芳香環に直接結合しない。） [Amine compound (B)]
The amine compound (B) used for the synthesis of the polymer (P) is a compound having a total of two or more primary amino groups and secondary amino groups in the molecule. In particular, the liquid crystal aligning agent of the present invention includes a compound represented by the following (1) as the amine compound (B).

(In Formula (1), R ¹ is a divalent organic group. Z ¹ is a group having 5 to 7 ring members having “—NH—” between carbon-carbon bonds in the ring skeleton of the aliphatic ring. It is a nitrogen heterocyclic group, and a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group may be substituted. Z ² is a primary amino group, —NHR ² (R ² is a carbon number of 1 to 15 is a monovalent hydrocarbon group, and when R ² has an aromatic ring, the aromatic ring is not directly bonded to a nitrogen atom.), Or “— between carbon-carbon bonds in the ring skeleton of the aliphatic ring. It is a nitrogen-containing heterocyclic group having 5 to 7 ring members having “NH—”, and a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group may be substituted, provided that Z ² is “—NHR ² In this case, Z ² is not directly bonded to the aromatic ring of R ^1. )

Examples of the divalent organic group represented by R ¹ in the formula (1) include divalent chain hydrocarbon groups, divalent alicyclic hydrocarbon groups, and divalent aromatic hydrocarbon groups. At least one of a hydrocarbon group, a carbon-carbon bond in the divalent hydrocarbon group, a position adjacent to Z ¹ in formula (1) and a position adjacent to Z ² in formula (1) Divalent groups into which functional groups such as O-, -COO-, -CO-, -NHCO-, -S-, -NH- are introduced (except for divalent groups having a heterocyclic ring). And a divalent group having a heterocyclic ring. In addition, each of these groups may have a substituent such as a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom).

  Here, in the present specification, the “hydrocarbon group” means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. In addition, the “chain hydrocarbon group” means a hydrocarbon group composed only of 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. “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 divalent hydrocarbon group in R ¹ include a divalent chain hydrocarbon group such as methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl group, Alkanediyl groups having 1 to 30 carbon atoms such as octanediyl group, nonanediyl group, decandiyl group, dodecadiyl group, tetradecandiyl group, and icosanediyl group; To 30 divalent chain unsaturated hydrocarbon groups; these may be linear or branched. Examples of the divalent alicyclic hydrocarbon group include a cyclohexylene group, and examples of the divalent aromatic hydrocarbon group include a phenylene group, a benzylene group, and a phenethylene group. Examples of the divalent group having a heterocyclic ring include a bivalent group obtained by removing two hydrogen atoms from a heterocyclic ring such as a piperidine ring and a pyridine ring, a chain hydrocarbon group, and a heterocyclic structure. And a divalent group comprising an alicyclic hydrocarbon structure and a heterocyclic structure.

Z ¹ is a nitrogen-containing heterocyclic group having 5 to 7 ring members having “—NH—” between carbon-carbon bonds in the ring skeleton of the aliphatic ring, such as a piperidine ring, pyrrolidine ring, morpholine ring, hexa Bonded to a ring structure in which one hydrogen atom bonded to a carbon atom constituting a ring such as a methyleneimine ring is removed, or a compound formed by substituting “—CH ₂ —” of norbornane with “—NH—” And a ring structure in which one hydrogen atom is removed. The ring may be substituted with, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group, an alkoxy group, or the like. Z ¹ is preferably a piperidyl group, more preferably a 3-piperidyl group or a 4-piperidyl group.

^{R 2} groups "-NHR ^2" in Z ² is a monovalent hydrocarbon group having 1 to 15 carbon atoms. Specific examples of R ² include straight chain such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, dodecanyl group, and tetradecanyl group. Branched monovalent chain hydrocarbon group; monovalent alicyclic hydrocarbon group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclohexylmethyl group, methylcyclohexyl group, norbornyl group Monovalent aromatic hydrocarbon groups such as phenylmethyl group and phenylcyclohexyl group; and the like. However, when the nitrogen atom of the group “—NHR ² ” is directly bonded to the aromatic ring, the reaction between the group “—NHR ² ” and the functional group of the compound (A) is difficult to proceed. Therefore, as the compound represented by the formula (1), it is preferable to use a compound in which the nitrogen atom of the group “—NHR ² ” is not directly bonded to the aromatic ring.
For the nitrogen-containing heterocyclic group having 5 to 7 ring members in Z ^2, the description of the nitrogen-containing heterocyclic ring having 5 to 7 ring members in Z ¹ can be applied. However, as in the case of R ² above, when Z ² is a group “—NHR ² ”, the group may not be directly bonded to the aromatic ring from the viewpoint of reactivity with the compound (A). preferable.
Among these, Z ² is preferably a primary amino group or the nitrogen-containing heterocyclic group.

Preferable specific examples of the compound represented by the formula (1) include, for example, compounds represented by the following formulas (DA-1) to (DA-8). In the following, for the sake of convenience, a compound represented by each of the following formulas (DA-1) to (DA-8) is also referred to as “compound (DA-x) (x is a number corresponding to the formula number)”. In the synthesis of the polymer (P), one type of the compound represented by the formula (1) can be used alone or in combination of two or more types.

In the synthesis of the polymer (P), only the compound represented by the above formula (1) may be used as the amine compound (B), but other amines other than the above may be used in combination with the compound. Good.
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、上記重合体（Ｐ）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 polymer (P), 1 type of these compounds is individual, or 2 or more types is suitably selected and used according to the drive mode etc. of a liquid crystal display element. be able to.

  The amine compound (B) used for the synthesis of the polymer (P) is a liquid crystal display device that makes the coating film light-transmitting good and that the stored charge with respect to the DC voltage is relaxed quickly, so that the contrast is not lowered and image sticking hardly occurs. From the viewpoint of obtaining the above, the proportion of the compound represented by the formula (1) is preferably 10 mol% or more with respect to the total amount of the amine compound (B) used in the synthesis, and is preferably 15 mol%. More preferably, it is more preferably 20 mol% or more, and particularly preferably 30 mol% or more. Further, the upper limit of the use ratio of the compound represented by the above formula (1) may be appropriately set according to the drive mode of the liquid crystal display device to be applied, and the entire amine compound (B) used for the synthesis. It can be arbitrarily set within a range of 100 mol% or less with respect to the amount.

  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. The polymer (P) having the above specific skeleton includes, for example, cyclobutanetetracarboxylic dianhydride and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dihydrate. It can be obtained by reacting a tetracarboxylic dianhydride containing at least one of anhydrides with an amine compound containing a compound represented by the above formula (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 is the total amount of the polymer (P) used for the preparation of the liquid crystal aligning agent of the present invention. On the other hand, it 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 polymer (P), a terminal-modified polymer may be synthesized using an appropriate molecular weight regulator together with the compound (A) 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 (1) above]
The compound represented by the above formula (1) can be synthesized by appropriately combining organic chemistry methods. As an example, when Z ² in the formula (1) is a primary amino group, a nitro intermediate having a nitro group is synthesized instead of the primary amino group, and then the obtained nitro intermediate is obtained. And a method of aminating the nitro group using an appropriate reduction system.

The method for synthesizing the nitro intermediate can be appropriately selected depending on the target compound. As an example thereof, a compound having a nitrogen-containing heterocycle corresponding to Z ¹ is used, and “—NH—” of the nitrogen-containing heterocycle is protected with a suitable protecting group such as t-butoxycarbonyl group, Examples thereof include a method of reacting with a nitro compound having a group corresponding to R ¹ .
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 above formula (1) is not limited to the above method.

[Synthesis of Polymer (P)]
(Synthesis of polyamic acid and specific polymer)
When synthesizing the polyamic acid or the specific polymer as the polymer (P), the proportion of the tetracarboxylic dianhydride and amine compound (B) used in the synthesis reaction is such that the amine compound (B) is used. The ratio of the acid group of the tetracarboxylic dianhydride to 0.2 to 2 equivalents with respect to 1 equivalent of the amino group that reacts with the acid anhydride group of the tetracarboxylic dianhydride in the amino group having The ratio is preferably 0.3 to 1.2 equivalents.
The synthesis reaction of the polyamic acid or the like is preferably performed 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-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, tetrahydrofuran and the like; Examples of the hydrocarbon include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like. Examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, Xylene and the like; 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 tetracarboxylic dianhydride and amine compound (B) is 0.1 to 50% by weight based on the total amount (α + β) of the reaction solution. It is preferable to make it an amount.

  As described above, a reaction solution in which polyamic acid or the like is dissolved is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, and after the polyamic acid contained in the reaction solution is isolated, it may be used for the preparation of the liquid crystal aligning agent, or the isolated polyamic acid or the like may be used. You may use for preparation of a liquid crystal aligning agent, after refine | purifying.

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

  When polyamic acid is dehydrated and cyclized to form polyimide, the reaction solution obtained by dissolving polyamic acid may be subjected to dehydration and cyclization reaction as it is, and the polyamic acid 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. Isolation and purification of the polyamic acid can be performed according to known methods.

  The polyimide may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure possessed by the polyamic acid that is the precursor, and only a part of the amic acid structure is dehydrated and cyclized, It may be a partially imidized product in which an imide ring structure coexists. 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 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 can also be obtained by imidation of polyamic acid ester.

[Polyamic acid ester as polymer (P)]
The polyamic acid ester (hereinafter also referred to as polyamic acid ester (P)) as the polymer (P) is, for example, [I] a polyamic acid as a polymer (P) obtained by the above synthesis reaction, and a hydroxyl group. Containing compound, halide, epoxy group-containing compound, and the like, [II] tetracarboxylic acid diester and amine compound (B), [III] tetracarboxylic acid diester dihalide and It can be obtained by a method of reacting with 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. As the tetracarboxylic acid diester used in the method [II] and the tetracarboxylic acid diester dihalide used in the method [III], the compounds described in the above compound (A) can be used. The amine compound (B) used in the methods [II] and [III] includes the compound represented by the above formula (1), and other amines may be used as necessary. The polyamic acid ester may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.

The polymer (P) obtained as described above preferably has a solution viscosity of 10 to 800 mPa · s when it is made into a solution having a concentration of 10% by weight. More preferably, it has a solution viscosity. 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 weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the polymer (P) is preferably 1,000 to 500,000, more preferably 2,000 to 300, 000. Moreover, the molecular weight distribution (Mw / Mn) represented by the ratio between Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. 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. Examples of other components that may be added to the liquid crystal aligning agent of the present invention include other polymers other than the polymer (P), compounds having at least one epoxy group in the molecule (hereinafter referred to as “epoxy group-containing”). Compound "), functional silane compounds, metal chelate compounds, curing accelerators, surfactants, 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 obtained by reaction of a diamine not containing the compound represented by the above formula (1) and tetracarboxylic dianhydride, polyimide obtained by dehydration ring closure of the polyamic acid, Polyamic acid ester obtained by esterification of the polyamic acid, polyamide, polyester, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene obtained by reaction of diamine and dicarboxylic acid not containing the compound represented by the above formula (1) A polymer having a derivative, a poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, or the like as 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. The polyorganosiloxane 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.

When the liquid crystal aligning agent of the present invention is used for photo-alignment, a polymer having a photo-alignment structure can be preferably used as the other polymer. Specifically, a polymer having a photoalignable group is preferably included, and a polymer into which a group having a cinnamic acid structure is introduced as the photoalignable group is more preferable. 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 photoalignable group as another polymer is a polyorganosiloxane having an epoxy group and a carboxylic acid having a photoalignable group, preferably an organic solvent such as ether, ester, ketone, etc. It can synthesize | combine by making it react in presence of catalysts, such as a quaternary ammonium salt.

[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 a total of 100 parts by weight of the polymer 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.

[Metal chelate compounds]
When the polymer component of the liquid crystal aligning agent has an epoxy structure, the metal chelate compound is a liquid crystal aligning agent (particularly a liquid crystal for a retardation film) for the purpose of ensuring the mechanical strength of the film formed by low-temperature treatment. Contained in the alignment agent). 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. It is contained in an aligning agent (particularly a liquid crystal aligning agent for a retardation film). 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 a liquid crystal aligning agent (particularly, a liquid crystal aligning agent for a retardation film) 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.

  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.

<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 closure 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 a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning 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, cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck) 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 the 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. It may be given.

  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 (II-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 be a composition further containing a known polymerization initiator or a suitable solvent.
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)]
Compound (DA-1) was synthesized according to the following scheme 1.

A 4-ml piperidine 64.6 g (0.5 mol), di-tert-butyl dicarbonate 163.7 g (0.75 mol), and tetrahydrofuran (THF) 500 ml were mixed in a 1000 ml three-necked flask equipped with a thermometer and a three-way cock. And stirred at 25 ° C. for 10 minutes. After adding 18.3 g (0.15 mol) of N, N-dimethylaminopyridine (DMAP), the mixture was stirred and reacted at 25 ° C. for 4 hours. Subsequently, after mixing with 500 ml of ethyl acetate, it was separated and washed with an aqueous sodium hydrogen carbonate solution and distilled water. The organic layer was concentrated and dried to obtain 69.3 g of an intermediate (DA-1-1).
Next, 69.3 g of the intermediate (DA-1-1), 46.1 g of 4-nitrophenol, and 600 ml of methylene chloride were stirred and mixed in an ice bath in a 2 L three-necked flask. Next, 186.9 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and 1.2 g of N, N-dimethylaminopyridine (DMAP) were sequentially added, and the mixture was placed in an ice bath for 1 hour. Then, the reaction was allowed to proceed at room temperature for 4 hours. After the reaction, 100 ml of trifluoroacetic acid was added, and further mixed with 500 ml of ethyl acetate, and then separated and washed with distilled water. Next, the organic layer was concentrated to cause solid precipitation. The precipitated solid was collected by filtration, washed thoroughly with ethanol, and dried to obtain 65.2 g of a nitro intermediate (DA-1-2).
Next, under nitrogen flow, 65.2 g of the above nitro intermediate (DA-1-2), 7 g of 5% Pd / C, 250 mL of ethanol and 250 mL of tetrahydrofuran were added to a 2 L three-necked flask, 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 200 mL of distilled water. 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 52.3 g of Compound (DA-1).

<Synthesis of polymer>
[Example 2-1; Synthesis of polymer (PA-1)]
34,95 g (98 mol parts) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 40.05 g (100 mol parts) of compound (DA-1) as an amine compound Was dissolved in 425 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C. for 10 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 at 40 ° C. under reduced pressure for 15 hours to obtain a polymer (PA-1). The obtained polymer (PA-1) was prepared so that it might become 10 weight% with NMP, and when the viscosity of this solution was measured, it was 1250 mPa * s. 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 2-7 and Synthesis Examples 1 to 3; Synthesis of Polymer (PA-2) to Polymer (PA-10)]
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 as shown in Table 1 below. The viscosity of the polymer solution prepared to be 10% by weight with NMP is also shown in Table 1 below. In addition, the numerical value of Table 1 shows the use ratio (mol%) with respect to the total amount of the tetracarboxylic dianhydride used for reaction about tetracarboxylic dianhydride, and about the amine compound used for reaction The ratio of use (mol%) based on the total amount of the 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.

ＤＡ−５； ４，４’−［４，４’−プロパン−１，３−ジイルビス（ピペリジン−１,４−ジイル）］ジアニリン
ＤＡ−６； パラフェニレンジアミン
ＤＡ−７； ４，４’−ジアミノジフェニルメタン
ＤＡ−８； ４−アミノフェニル−４’−アミノベンゾエート
ＤＡ−９； ２，４−ジアミノ−Ｎ，Ｎ−ジアリルアニリン
ＤＡ−１０； ４，４’−ジアミノジフェニルアミン
ＤＡ−１１； ３，５−ジアミノ安息香酸
ＤＡ−１２； ３，５−ジアミノ安息香酸コレスタニル
ＤＡ−１３； ４−（テトラデカオキシ）ベンゼン−１，３−ジアミン (Compound (A))
AN-1; 1,2,3,4-cyclobutanetetracarboxylic dianhydride AN-2; pyromellitic dianhydride AN-3; 2,3,5-tricarboxycyclopentylacetic 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 (compound (B))
DA-4; a compound represented by the following formula (d-4)

DA-5; 4,4 ′-[4,4′-propane-1,3-diylbis (piperidine-1,4-diyl)] dianiline DA-6; paraphenylenediamine DA-7; 4,4′-diamino Diphenylmethane DA-8; 4-aminophenyl-4′-aminobenzoate DA-9; 2,4-diamino-N, N-diallylaniline DA-10; 4,4′-diaminodiphenylamine DA-11; Diaminobenzoic acid DA-12; 3,5-diaminobenzoic acid cholestanyl DA-13; 4- (tetradecaoxy) benzene-1,3-diamine

[Example 2-8; Synthesis of polymer (PI-1)]
2,3,5-tricarboxycyclopentylacetic acid dianhydride 22.55 g (98 mol parts) as tetracarboxylic dianhydride, and 2.22 g (20 mol parts) of paraphenylenediamine as an amine compound, 4-aminophenyl- 7.03 g (30 mol parts) of 4′-aminobenzoate and 18.20 g (50 mol parts) of the compound (DA-3) were dissolved in 283.3 g of N-methyl-2-pyrrolidone (NMP), and 60 ° C. The reaction was carried out for 6 hours. Next, 166.7 g of NMP was added, 15.92 g of pyridine and 20.54 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 100 ° C. for 8 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 a polyimide having an imidization ratio of about 50% (referred to as “polymer (PI-1)”). The obtained polymer (PI-1) was prepared to be 10% by weight with NMP. The viscosity of this solution was measured and found to be 980 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.

[Synthesis Example 4; Synthesis of polymer by piperazine]
As tetracarboxylic dianhydride, 6.948 g (100 mol parts) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 3.052 g (100 mol parts) of piperazine were dissolved in 90 g of NMP, and the mixture was dissolved at room temperature. Time reaction was performed. A small amount of the reaction solution was taken and the solution viscosity was measured and found to be 17 mPa · s. For this reason, the reaction was further carried out at 60 ° C. for 24 hours, but the solution viscosity was 18 mPa · s. Therefore, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. However, the reaction product only became cloudy and did not solidify, making it impossible to obtain a polymer.

[Synthesis Example 5: Synthesis of polyorganosiloxane (S-1)]
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. Here, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and then the reaction was performed 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. And 6.3 g of polyorganosiloxane (S-1) having a liquid crystal alignment group as white powder was obtained. 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 100 parts by weight of the polymer (PA-1) obtained in Example 2-1 was mixed solvent (GBL: NMP: BC) composed of γ-butyrolactone (GBL), NMP and butyl cellosolve (BC). = 40:40:20 (weight ratio)) to obtain a solution having a solid content concentration of 4.0% by weight. A liquid crystal aligning agent was prepared by filtering this solution through a filter having a pore size of 0.2 μm.

(2) Evaluation of applicability The liquid crystal aligning agent prepared above was applied on a glass substrate using a spinner, pre-baked on an 80 ° C. hot plate for 1 minute, and then the interior of the chamber was purged with nitrogen. A coating film having an average film thickness of 1,000 mm was formed by heating (post-baking) in an oven for 1 hour. This coating film was observed with a microscope with a magnification of 20 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 light transmittance The light transmittance (%) at a wavelength of 400 nm is evaluated using a spectrophotometer (150-20 type double beam manufactured by Hitachi, Ltd.) for the coating film obtained above. did. In the evaluation, the light transmittance was “good” when it was 97% or more, and the light transmittance “bad” when it was less than 97%. As a result, the coating film was 99.1% and the light transmittance was “good”.

(4) 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 carried out 5 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 “good” when the number of foreign matters was 5 or less, “good” when 6 or more and 9 or less, and the rubbing resistance “bad” when 10 or more. As a result, the rubbing resistance of this coating film was “good”.
(5) Evaluation of orientation The refractive index anisotropy (retardation (retardation)) of the glass substrate with an orientation film subjected to the rubbing treatment (orientation treatment) obtained above using a liquid crystal orientation film inspection apparatus (RayScan) manufactured by MORITEX. nm)). In the evaluation, when the measurement result of the refractive index anisotropy was 0.025 nm or more, the orientation was “good”, and when it was less than 0.025 nm, the orientation was “bad”. As a result, this substrate was 0.036 nm and the orientation was “good”.

(6) 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 a counter glass substrate 11b provided with no electrode, and the liquid crystal aligning agent prepared above is applied to the surface having the electrode of the glass substrate 11a and one surface of the counter glass substrate 11b using a spinner. Thus, a coating film was formed. 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 example, a substrate having a top electrode having a line width d1 of the transparent electrode of 4 μm and a distance d2 between the electrodes of 6 μm was used.
Next, rubbing treatment was performed on each surface of the coating film formed on the glass substrate with cotton in the direction of the arrow in FIG. 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 10 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.

(7) Evaluation of liquid crystal orientation With respect to the FFS type liquid crystal display device manufactured as described above, the presence or absence of an abnormal domain in the change in light and dark when a voltage of 5 V is turned ON / OFF (applied / released) at a magnification of 50 times using a microscope. Observed. 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”.
(8) Evaluation of voltage holding ratio After applying the voltage of 5V to the FFS type liquid crystal display device manufactured as described above at a temperature of 23 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, 167 milliseconds from the release of application. When the subsequent voltage holding ratio (VHR) was measured, the voltage holding ratio was 99.4%. In addition, as a measuring apparatus, Toyo Technica Co., Ltd. make and VHR-1 were used.
(9) Evaluation of heat resistance The voltage holding ratio was measured in the same manner as in (8) above, and the value was defined as the initial VHR (VHR _BF ). Next, the liquid crystal display element after the initial VHR measurement was left in an oven at 100 ° C. for 500 hours. Thereafter, the liquid crystal display element was left to stand at room temperature and allowed to cool to room temperature, and then the voltage holding ratio was measured (VHR _AF ) in the same manner as described above. Moreover, the change rate (ΔVHR (%)) of the voltage holding ratio before and after the application of thermal stress was determined by the following mathematical formula (2).
ΔVHR (%) = ((VHR _BF −VHR _AF ) ÷ VHR _BF ) × 100 (2)
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 was 2.9%, and the heat resistance of the liquid crystal display element was “excellent”.

(10) Contrast evaluation after driving stress (AC afterimage characteristics evaluation)
The FFS type liquid crystal display device manufactured above is expressed by the following formula (3) using a device in which a polarizer and an analyzer are arranged between a light source and a light amount detector after being driven at an AC voltage of 10 V for 30 hours. The minimum relative transmittance (%) was measured.
Minimum relative transmittance (%) = (β−B ⁰ ) / (B ¹⁰⁰ −B ⁰ ) × 100 (3)
(In the formula (3), B ⁰ is a transmission amount of light under a crossed Nicol in a blank. B ¹⁰⁰ is a transmission amount of light in a blank and under a Paranicol. Β is a polarizer under a crossed Nicol. (This is the minimum light transmission amount with the liquid crystal display element sandwiched between the analyzers.)
The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element. In the FFS type display element, the smaller the black level in the dark state, the better the contrast. A sample having a minimum relative transmittance of less than 0.5% was evaluated as “good”, a sample having a minimum relative transmittance of less than 0.5% and less than 1.0% was evaluated as “good”, and a sample having a minimum relative transmittance of 1.0% or more was determined as “bad”. As a result, the minimum relative transmittance of this liquid crystal display element was 0.3%, which was judged as “good”.

(11) Evaluation of relaxation rate of residual DC (Evaluation of DC 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 relaxation rate of the residual DC was obtained by calculating the average residual DC relaxation rate from the maximum value of the 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 an afterimage is so hard to produce that this relaxation rate is quick. The residual DC relaxation rate of the liquid crystal display element of this example was 4.9 mV / sec, and the residual DC relaxation property was judged to be “excellent”.

[Examples 3-2 to 3-7 and Comparative Examples 1 to 3]
A liquid crystal aligning agent was prepared in the same manner as in Example 3-1, except that the polymers shown in Table 2 below were used as polymers, and an FFS type liquid crystal display device was produced and evaluated. The evaluation results are shown in Table 2 below.

  As shown in Table 2, in Examples 3-1 to 3-4, 3-6 and 3-7, the coating property of the liquid crystal aligning agent, the light transmittance of the coating film, the rubbing resistance and the orientation property, and the liquid crystal display element The liquid crystal orientation, voltage holding ratio, heat resistance, contrast after driving stress, and relaxation rate of residual DC were all “good” or “excellent”. Further, in Example 3-5, the contrast after the driving stress was “good” except that the contrast was “good”. On the other hand, in Comparative Example 1, the evaluation of the orientation of the coating film, the heat resistance of the liquid crystal display element and the contrast after driving stress was “bad”, and the residual DC relaxation rate was inferior to that of the example. Further, in Comparative Example 2, the light transmittance was “defective”, and in Comparative Example 3, the relaxation rate of the residual DC was “defective”.

[Example 3-8: 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 was prepared by filtering through a filter having a pore size of 0.2 μm.
(2) Evaluation of printability The liquid crystal aligning agent prepared in the above (1) is applied to the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.). Apply and heat for 1 minute on a hot plate at 80 ° C (pre-bake) to remove the solvent, then heat on a hot plate at 200 ° C for 10 minutes (post-bake) to form a coating film with an average film thickness of 600 mm did. This coating film was observed with a microscope with 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 Transparent electrode of glass substrate with transparent electrode made of ITO liquid crystal aligning agent prepared in (1) above using liquid crystal alignment film printer (Nissha Printing Co., Ltd.) After coating on the surface 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 a coating film with an average film thickness of 600 mm 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, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edge of the surface having one liquid crystal alignment film of the pair of substrates, the liquid crystal alignment film surfaces of the pair of substrates are relative to each other. The adhesive was cured by overlapping and pressing. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive. 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 (7). 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 (θ _IN ) was used. Non-Patent Document 1 (TJ. Scheffer 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)).
Next, an AC voltage of 5 V was applied to the liquid crystal cell after measuring the initial pretilt (θ _IN ) 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 (4), the amount of change in the pretilt angle (Δθ (°)) before and after voltage application was determined.
Δθ = | θ _AF −θ _IN | (4)
When Δθ is less than 3%, pretilt angle stability is “excellent”, 3% or more and less than 4% is evaluated as “good”, and 4% or more is evaluated as “bad”. The pretilt angle change rate of the liquid crystal display element was 2.6%, and the pretilt angle stability was determined to be “excellent”.

(6) Evaluation of heat resistance The voltage holding ratio (VHR _BF ) is measured in the same manner as (8) in Example 3-1 above, and the thermal stress is measured in the same manner as in (9) in Example 3-1 above. The heat resistance was evaluated by the change rate ΔVHR of the voltage holding ratio before and after the application. As a result, the initial voltage holding ratio VHR _BF was 99.1%. Further, ΔVHR was 2.8%, and the heat resistance was judged as “excellent”.

[Example 3-9: 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-6) obtained in Example 2-6, 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 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 prepared in (1) above, the printability was examined in the same manner as in Example 3-8 (2). It was not observed and the printability was “good”.
(3) Manufacture of VA type liquid crystal cell The liquid crystal aligning agent prepared above is liquid crystal aligning film printer (Nissha Printing Co., Ltd.) on the transparent electrode surface of a glass substrate with a transparent electrode (thickness 1 mm) made of ITO film. )), And heated (pre-baked) for 1 minute on a hot plate at 80 ° C. and further heated (post-baked) for 60 minutes on a hot plate at 200 ° C. 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, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edge of the surface having one liquid crystal alignment film of the pair of substrates, the liquid crystal alignment film surfaces of the pair of substrates are relative to each other. The adhesive was cured by overlapping and pressing. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive. Manufactured.

(4) Evaluation of liquid crystal alignment 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 3-8. The property was “good”. Further, the voltage holding ratio (VHR _BF ) is measured in the same manner as (8-1) in Example 3-1, and the voltage holding ratio before and after applying thermal stress is measured in the same manner as in (9) in Example 3-1. The heat resistance was evaluated based on the change rate ΔVHR. As a result, the initial voltage holding ratio VHR _BF was 99.4%. Further, ΔVHR was 2.9%, and the heat resistance was judged as “excellent”.

[Example 3-10: 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 5 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 was prepared by filtering this solution through a filter having a pore size of 0.2 μm.
(2) Production of retardation film The liquid crystal aligning agent prepared above was applied to one surface of a TAC film as a substrate using a bar coater, and baked in an oven at 120 ° C for 2 minutes to have a film thickness of 100 nm. A coating film was formed. Next, the surface of the coating film was irradiated with polarized ultraviolet rays of 10 mJ / cm ² containing a 313 nm emission line perpendicularly from the substrate normal line using a Hg—Xe lamp and a Grand Taylor prism to form a liquid crystal alignment film. Next, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck & Co., Inc.) is filtered through a filter having a pore size of 0.2 μm, and this polymerizable liquid crystal is applied onto the liquid crystal alignment film by a bar coater to form a polymerizable liquid crystal coating film. did. 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 the above (2), the adhesiveness of the liquid crystal alignment film 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 display element, 11a, 11b ... Glass substrate, 12 ... Bottom electrode, 13 ... Silicon nitride film, 14 ... Top electrode, 15a, 15b ... Liquid crystal aligning film.

Claims (9)

At least one compound (A) selected from the group consisting of polycarboxylic acids, polycarboxylic anhydrides, polyhydric carboxylic acid halides, partially esterified products of polycarboxylic acids, and acid halides of the partially esterified products; The liquid crystal aligning agent containing the polymer obtained using the amine compound (B) containing the compound represented by following formula (1) as a monomer.

(In Formula (1), R ¹ is a divalent organic group. Z ¹ is a group having 5 to 7 ring members having “—NH—” between carbon-carbon bonds in the ring skeleton of the aliphatic ring. Except for a nitrogen heterocyclic group, wherein a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group is substituted. Z ² is a primary amino group, —NHR ² (R ² is carbon number 1 To 15 monovalent hydrocarbon groups, and when R ² has an aromatic ring, the aromatic ring is not directly bonded to a nitrogen atom.), Or between carbon-carbon bonds in the ring skeleton of the aliphatic ring. A nitrogen atom-containing heterocyclic group having 5 to 7 ring members having —NH— ”, and a hydrogen atom bonded to a carbon atom of the nitrogen-containing heterocyclic group may be substituted, provided that Z ² is“ —NHR ”. ^In the case of “ ² ”, Z ² is not directly bonded to the aromatic ring of R ^1. )   The liquid crystal aligning agent of Claim 1 whose ratio of the compound represented by the said Formula (1) among the said amine compounds (B) is 10 mol% or more.   The liquid crystal aligning agent of Claim 1 or 2 whose said compound (A) is at least 1 type chosen from the group which consists of tetracarboxylic dianhydride, tetracarboxylic-acid diester, and tetracarboxylic-acid diester dihalide. The compound (A) is tetracarboxylic dianhydride,
As the tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-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, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride 1,2,4,5-cyclohexanetetracarboxylic acid Things, and at least one selected from the group consisting of pyromellitic dianhydride, the liquid crystal aligning agent according to claim 1 or 2. R ¹ is a divalent hydrocarbon group, or at least one of a position adjacent to Z ¹ and a position adjacent to Z ² between carbon-carbon bonds in the divalent hydrocarbon group; O-, -COO-, -CO-, -NHCO-, -S- or -NH- is a divalent group formed by introduction or a divalent group having a heterocyclic ring, The liquid crystal aligning agent as described in any one of Claims 1-4 which you may have.   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.

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