JP6260150B2 - 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.

  In order to obtain a liquid crystal display element with a high display quality, the liquid crystal cell exhibits a high voltage holding ratio, the image sticking phenomenon is difficult to occur (an afterimage is difficult to occur), the heat resistance is good, and the rubbing resistance is good. As described above, various properties are required to be favorable, and various liquid crystal aligning agents for obtaining a high-quality liquid crystal display element have been proposed (see, for example, Patent Documents 1 and 2). In Patent Document 1, polyamic acid obtained by reacting a diamine having an aromatic ester structure with a tetracarboxylic acid derivative, such as di (4-aminophenyl) hexane-1,6-dioate, is used as a compound of a liquid crystal aligning agent. The use as a coalescence component is disclosed. In Patent Document 2, a diamine having two aromatic rings linked by an alkylene spacer structure, such as 1,3-bis (4-amino-2-methylphenyl) propane, is reacted with a tetracarboxylic acid derivative. It is disclosed that the obtained polyamic acid or the like is used as a polymer component of a liquid crystal aligning agent.

  In addition, various optical materials are used for liquid crystal display elements. Above all, retardation films eliminate the object of viewing color dependency and the viewing angle dependency that the display color and contrast ratio change depending on the visual direction. It is used for the purpose. As such a retardation film, one having a liquid crystal alignment film formed on the surface of a substrate such as a TAC film and a liquid crystal layer formed by curing a polymerizable liquid crystal on the surface of the liquid crystal alignment film is known. It has been. 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.

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

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

  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 can form a liquid crystal alignment film capable of exhibiting good liquid crystal alignment properties and various characteristics required for liquid crystal display elements such as high voltage holding ratio, heat resistance, and afterimage characteristics. One object is to provide a liquid crystal aligning agent capable of expressing the above in a balanced manner. 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 conducted polycondensation of a diamine having a specific structure and a tetracarboxylic dianhydride as a polymer component of a liquid crystal aligning agent. It has been found that the above-mentioned problems can be solved by including at least one of the polymer of polyamic acid, polyamic acid ester and polyimide obtained by the above, and the present invention has been completed. Specifically, the present invention provides the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, retardation film, method for producing the same, polymer and compound.

  In one aspect, the present invention includes at least one compound selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, and tetracarboxylic acid diester compound, and a compound represented by the following formula (d). Provided is a liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide obtained by reacting with diamine.

（式（ｄ）中、Ｒ^１〜Ｒ^８は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルケニル基、又は炭素数１〜２０のアルキル基若しくはアルケニル基に置換基が導入された１価の基である。Ｒ^９及びＲ^１０は、それぞれ独立に、ハロゲン原子又は炭素数１〜６のアルキル基若しくはアルコキシ基である。Ｚ^１及びＺ^２は、それぞれ独立に、単結合、−Ｏ−、＊−ＣＯＯ−、＊−ＯＣＯ−、−ＣＯ−、＊−ＮＨＣＯ−、＊−ＣＯＮＨ−又は＊−Ｏ−ＣＨ_２−（但し、「＊」はＸ^１との結合手を示す。）である。但し、Ｚ^１及びＺ^２が同時に単結合になることはない。Ｘ^１は、２価の有機基である。ｍ^１及びｍ^２は、それぞれ独立に０〜４の整数であり、ｎは０又は１である。但し、Ｒ^９，Ｒ^１０が複数存在する場合、複数のＲ^９，Ｒ^１０は、それぞれ同じでも異なっていてもよい。）

(In formula (d), R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. .R ⁹ and R ¹⁰ substituents or alkenyl group is a monovalent group introduced are each independently a halogen atom or an alkyl or alkoxy group having 1 to 6 carbon atoms .Z ¹ and Z ² is independently a single bond, —O—, * —COO—, * —OCO—, —CO—, * —NHCO—, * —CONH— or * —O—CH ₂ — (where “* "is a.) showing a bond to ^{X 1.} However, .X ^{1 Z 1} and ^{Z 2} do not become single bond at the same time, it is a divalent organic group .m ¹ and ^{m 2} , Each independently represents an integer of 0 to 4, and n is 0 or 1, provided that R ⁹ When ^a plurality ^{of R 10} s exist, a plurality of ^{R 9, R 10} may be the same or different.)

  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. Still further, at least one compound selected from the group consisting of the compound represented by the above formula (d), a diamine containing the compound, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, and tetracarboxylic acid diester compound. A polymer obtained by reacting with is provided.

  By using a liquid crystal aligning agent containing a polymer such as polyamic acid synthesized using the diamine represented by the above formula (d), a liquid crystal alignment film having good liquid crystal alignment can be obtained. In addition, since the liquid crystal alignment film obtained using the liquid crystal aligning agent of the present invention has a high voltage holding ratio of the liquid crystal cell and also has good heat resistance and afterimage characteristics, a high-quality liquid crystal display element is manufactured. Can do. 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.

  The liquid crystal aligning agent of this invention contains at least 1 type of polymer (henceforth a polymer (A)) chosen from the group which consists of a polyamic acid, a polyamic acid ester, and a polyimide. 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 (A); polyamic acid>
The polyamic acid (hereinafter also referred to as polyamic acid (A)) as the polymer (A) of the present invention can be obtained, for example, by reacting tetracarboxylic dianhydride with diamine.
[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid in the present invention include an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, and the like. Can be mentioned. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4, 5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane -2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- No 1,2-dicarboxylic acid Product, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-dianhydride, 4,9-di Oxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2 Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and the like;
Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like; respectively, and tetracarboxylic dianhydrides described in JP 2010-97188 A can be used. In addition, as tetracarboxylic dianhydride used for the synthesis | combination of a polyamic acid, these 1 type can be used individually or in combination of 2 or more types.

As tetracarboxylic dianhydride used for synthesizing the polyamic acid (A) of the present invention, bicyclo [2.2.1] heptane-2, from the viewpoint that liquid crystal orientation and solubility in a solvent can be improved. 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 At least one selected from the group consisting of 6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and pyromellitic dianhydride It is preferable that the specific tetracarboxylic dianhydride which is these are included. Moreover, it is preferable that the usage-amount of the said specific tetracarboxylic dianhydride shall be 5 mol% or more with respect to the whole quantity of the tetracarboxylic dianhydride used for the synthesis | combination of polyamic acid, and shall be 10 mol% or more. It is more preferable that the amount be 20 mol% or more.
In addition, the said tetracarboxylic dianhydride is a liquid crystal aligning film with various characteristics, such as liquid crystal aligning property, voltage holding property, and heat resistance, by condensation polymerization with the diamine containing the compound represented by following formula (d). All of them have the same action in that a polyamic acid capable of forming an acid can be obtained. Accordingly, even those not described in the following examples can be used in the present invention.

[Diamine]
The diamine used for the synthesis of the polyamic acid (A) of the present invention includes a compound represented by the above formula (d).
In the above formula (d), examples of the halogen atom in R ^{1 to} R ⁸ (R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ ) include a fluorine atom, a chlorine atom, A bromine atom, an iodine atom, etc. are mentioned. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group. , Octadecyl group, icosyl group and the like, which may be linear or branched. Examples of the alkenyl group having 1 to 20 carbon atoms include a vinyl group, an allyl group, a propenyl group, and a hexenyl group, and these may be linear or branched. R ^{1 to} R ⁸ may be a monovalent group in which a substituent is introduced into the alkyl group having 1 to 20 carbon atoms or the alkenyl group having 1 to 20 carbon atoms. Examples of the substituent in this case include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; hydroxyl group and the like. R ^{1 to} R ⁸ may be the same as or different from each other.
R ^{1 to} R ⁸ preferably have a structure with small steric hindrance from the viewpoint of liquid crystal alignment and rubbing resistance. Specifically, it is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, and it is particularly preferable that all of R ^{1 to} R ⁸ are hydrogen atoms.

Regarding R ⁹ and R ^{10 in} the above formula (d), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group having 1 to 6 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Moreover, as a C1-C6 alkoxy group, a methoxy group, an ethoxy group, a propoxy group etc. are mentioned, for example. R ⁹ and R ¹⁰ may be the same as or different from each other. Also, if R ⁹ is more present in the formula (d), the plurality of R ⁹ may be the same as or different from each other, in the above formula (d) if a plurality ^of R ¹⁰ s exist, the plurality R ¹⁰ may be the same as or different from each other.
Of these, R ⁹ and R ¹⁰ are preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a fluorine atom. The number of introduced R ⁹ and R ¹⁰ (m ¹ , m ² ) is preferably an integer of 0 to 2, and more preferably 0 or 1.

Z ¹ and Z ² are a single bond, —O—, * —COO—, * —OCO—, —CO—, * —NHCO—, * —CONH— or * —O—CH ₂ —, and are the same as each other However, although they may be different, Z ¹ and Z ² do not become a single bond at the same time. It should be noted that the "*" indicates a bond to X ^1. Z ¹ and Z ² are each preferably —O—, * —COO—, * —OCO—, —CO—, * —NHCO—, * —CONH— or * —O—CH ₂ —, O-, * -COO-, * -OCO-, -CO-, * -NHCO- or * -CONH- is more preferable. In the case where at least one of Z ¹ and Z ² is —O—, * —COO—, * —OCO—, —CO—, * —NHCO— or * —CONH—, in the above formula (d) A phenethyl structure is introduced into the represented compound. More preferred is * -COO- or * -CONH-, and particularly preferred is * -COO-.

X ¹ is a divalent organic group, for example, a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and carbons of these hydrocarbon groups A divalent group having —O—, —COO—, —CO—, —NHCO—, —S— or the like between carbon bonds, and a substituent such as a halogen atom or an alkoxy group are introduced into the hydrocarbon group. And divalent groups. The chain hydrocarbon group means a saturated hydrocarbon group and an unsaturated hydrocarbon group that are composed only of a chain structure without including a cyclic structure in the main chain. However, both linear hydrocarbon groups and branched hydrocarbon groups are included. The alicyclic hydrocarbon group means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing 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. An aromatic hydrocarbon 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.
X ¹ is preferably an alkanediyl group having 1 to 18 carbon atoms or — [(CH ₂ ) ₂ O] _a — (CH ₂ ) ₂ — (where a is 1 from the viewpoint of maintaining good liquid crystal orientation. It is preferable that it is an integer of ~ 3). Here, specific examples of the alkanediyl group having 1 to 18 carbon atoms include, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decandiyl group. These may be linear or branched. X ¹ is preferably an alkanediyl group having 1 to 10 carbon atoms, more preferably an alkanediyl group having 2 to 8 carbon atoms, from the viewpoint of improving liquid crystal alignment and rubbing resistance. preferable.

  Regarding the two aminophenyl groups in formula (d), the bonding position of the primary amino group on the benzene ring is not particularly limited, but is preferably the 3rd or 4th position with respect to the other group (ethylene structure). The 4th position is more preferable. n is 0 or 1, and 1 is particularly preferable.

Specific examples of the compound represented by the formula (d) include compounds represented by the following formulas (d-1) to (d-11).

  In synthesizing the polyamic acid (A) of the present invention, one of the compounds represented by the above formula (d) can be used alone or in admixture of two or more. In addition, the compound represented by the said formula (d) has the same effect | action all at the point which can obtain the polymer which show | plays the effect of this invention. Therefore, even compounds that are not described in the following examples can be used in the present invention.

  In synthesizing the polyamic acid (A), only the compound represented by the formula (d) may be used as the diamine, but other diamines may be used in combination with the compound.

Examples of other diamines 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 aromatic diamines, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 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 ′-(p-phenylenediisopropylidene) Suaniline, 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, dodecanoxy-2,4-diaminobenzene, teto Decanoxy-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, cholestenyl 3,5-diaminobenzoate, 3,5-diaminobenzene Lanostanyl perfate, 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-heptylcyclohexyl) cyclohexa 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1- (2,4-diaminophenyl) piperazine-4-carboxylic acid, 4- (morpholine-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-diyl)] dianiline, and the following formula (D 1)

(In Formula (D-1), X ^I and X ^II are each a single bond, —O—, —COO— or —OCO—, and R ^I is an alkanediyl group having 1 to 3 carbon atoms. , A is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and n is 0 or 1. However, a and b are not 0 at the same time. .)
A compound represented by:
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; and the diamines described in JP-A 2010-97188 can be used.

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

なお、上記ポリアミック酸の合成に使用するその他のジアミンとしては、これらの化合物を１種単独で又は２種以上組み合わせて使用することができる。 Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-3).

In addition, as another diamine used for the synthesis | combination of the said polyamic acid, these compounds can be used individually by 1 type or in combination of 2 or more types.

  As the diamine used for the synthesis of the polyamic acid (A) of the present invention, the use ratio of the compound represented by the above formula (d) from the viewpoint of obtaining a liquid crystal alignment film having good liquid crystal alignment properties, heat resistance and afterimage characteristics. Is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, and more preferably 20 mol% or more with respect to the total amount of diamine used in the synthesis. It is particularly preferable to do this. Further, the upper limit value of the use ratio of the compound represented by the above formula (d) may be appropriately set according to the drive mode of the liquid crystal display device to be applied, and 100 mol with respect to the total diamine used in the synthesis. % Can be set arbitrarily.

In the case where liquid crystal alignment is imparted by a photo-alignment method to a coating film prepared using the liquid crystal aligning agent of the present invention, a part or all of the polymer (A) of the present invention is a polymer having a photo-alignment structure. It is good. Here, the photo-alignment structure is a concept including both a photo-alignment group and a decomposition type photo-alignment part. Specifically, as the photo-alignment structure, groups derived from various compounds exhibiting photo-alignment by photoisomerization, photodimerization, photolysis, etc. can be employed. For example, azobenzene or a derivative thereof is used as a basic skeleton. Contains azobenzene-containing group, group having cinnamic acid structure containing cinnamic acid or derivative thereof as basic skeleton, chalcone-containing group containing chalcone or derivative thereof as basic skeleton, containing benzophenone or derivative thereof as basic skeleton And a coumarin-containing group containing a group, coumarin or a derivative thereof as a basic skeleton, and a polyimide-containing structure containing a polyimide or a derivative thereof as a basic skeleton.
When the polymer (A) includes a polymer having a photoalignment structure (hereinafter also referred to as photoalignment polymer (A)), the polymer (A) is a polymer including a decomposable photoalignment part. Specifically, a polymer having a bicyclo [2.2.2] 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. Examples of the polymer having the specific skeleton include cyclobutanetetracarboxylic dianhydride and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. It can be obtained by reacting a tetracarboxylic dianhydride containing at least one with a diamine containing a compound represented by the above formula (d).
When the liquid crystal alignment ability is imparted to the coating film by the photo-alignment method, the use ratio of the photo-alignment polymer (A) is preferably 10% by weight or more based on the total amount of the polymer (A). It is more preferable to set it as 30 to 100 weight%, and it is still more preferable to set it as 50 to 100 weight%.

[Molecular weight regulator]
In synthesizing the polyamic acid (A), a terminal-modified polymer may be synthesized using an appropriate molecular weight regulator together with the tetracarboxylic dianhydride and diamine as described above. By using such a terminal-modified polymer, the applicability (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 (d)>
The compound represented by the formula (d) can be synthesized by appropriately combining organic chemistry methods. As an example, for example, a dinitro compound having two nitrophenyl groups instead of the two aminophenyl groups in the above formula (d) is synthesized, and then the nitro group of the obtained dinitro compound is converted into an appropriate reduction system. A method of amination using them is mentioned.

Here, the method for synthesizing the dinitro compound is not particularly limited, and for example, it can be appropriately synthesized according to Z ^1, Z ² , n, and the like. Specifically, for example, for a compound where n = 1, when Z ¹ and Z ² are “* -CO—NH—”, a primary amine compound containing a nitrophenethyl group such as nitrophenylethylamine; it can be synthesized by reacting the corresponding acid chloride of a dicarboxylic acid having X ^1. Further, when Z ¹ and Z ² are “* -NH—CO—”, for example, they can be synthesized by reacting a nitrophenethyl group-containing acid chloride with a corresponding diamine having X ^1. .
When Z ¹ and Z ² are “* -CO—O—”, for example, a nitrophenethyl group-containing alcohol such as nitrophenylethanol is reacted with an acid chloride of a corresponding dicarboxylic acid having X ¹ . Can be synthesized. When Z ¹ and Z ² are “* —O—CO—”, for example, they can be synthesized by reacting a nitrophenethyl group-containing acid chloride with a corresponding diol having X ^1. .
When Z ¹ and Z ² are “—O—” or “* —O—CH ₂ —”, for example, a nitrophenethyl group-containing alcohol such as nitrophenyl ethanol, nitrophenyl propanol, etc., and the corresponding X ¹ It can synthesize | combine by making it react with the dihalide which has. When Z ¹ and Z ² are “—CO—”, for example, Grignard reagent obtained by the reaction of alkyl dihalide and magnesium metal is used for nitrophenethyl group-containing aldehyde such as nitrophenethyl aldehyde. A secondary alcohol compound can be synthesized by acting, and the resulting secondary alcohol compound can be synthesized by oxidizing with an appropriate oxidizing reagent.

The reaction for obtaining the dinitro compound as the intermediate is preferably performed in an organic solvent. Here, the organic solvent may be any solvent that does not affect the reaction, and examples thereof include methanol, ethanol, tetrahydrofuran, toluene, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and 1-methyl-2-pyrrolidone. . Moreover, you may perform the said reaction in catalyst presence as needed.
The reduction reaction of the dinitro compound can be preferably carried out in an organic solvent using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin, nickel. 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 (d) is not limited to the above method.

<Synthesis of polyamic acid (A)>
The ratio of the tetracarboxylic dianhydride and diamine used in the synthesis reaction of the polyamic acid (A) of the present invention is such that the acid anhydride group of the tetracarboxylic dianhydride is equivalent to 1 equivalent of the amino group of the diamine. Is preferably a ratio of 0.2 to 2 equivalents, more preferably a ratio of 0.3 to 1.2 equivalents.
The polyamic acid synthesis reaction is preferably carried out in an organic solvent. The reaction temperature at this time is preferably −20 ° C. to 150 ° C., more preferably 0 to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

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

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

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

<Polymer (A); polyamic acid ester>
The polyamic acid ester (hereinafter also referred to as polyamic acid ester (A)) as the polymer (A) of the present invention is, for example, [I] a polyamic acid (P) obtained by the above synthesis reaction and a hydroxyl group-containing compound. , A method of synthesizing by reacting a halide, an epoxy group-containing compound, etc., [II] a method of reacting a tetracarboxylic acid diester compound and a diamine, and [III] a method of reacting a tetracarboxylic acid diester dichloride and a diamine. Can be obtained by:
Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol and propanol; phenols such as phenol and cresol. Examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like, and as an epoxy group-containing compound, Examples thereof include propylene oxide. The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid (A) using the above alcohols. The tetracarboxylic acid diester dichloride used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. The diamine used in the methods [II] and [III] includes the compound represented by the above formula (d), 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.

<Polymer (A); Polyimide>
The polyimide (hereinafter also referred to as polyimide (A)) as the polymer (A) of the present invention is obtained, for example, by dehydrating and ring-closing imidized polyamic acid (A) synthesized as described above. Can do.

  The polyimide may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure of the polyamic acid (A) which is the precursor, or by dehydrating and cyclizing only a part of the amic acid structure, It may be a partially imidized product in which an acid structure and an imide ring structure coexist. The polyimide in the present invention preferably has an imidation ratio of 30% or more, more preferably 40 to 99%, and still more preferably 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 the polyimide (A) 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, the polyimide (A) can be obtained by dehydrating and ring-closing the polyamic acid ester (A) to imidize.

<Solution viscosity / molecular weight of polymer>
The polyamic acid, the polyamic acid ester, and the polyimide as the polymer (A) obtained as described above have a solution viscosity of 10 to 800 mPa · s when this is a 10% by weight solution. It is preferable to have a solution viscosity of 15 to 500 mPa · s. In addition, the solution viscosity (mPa · s) of the above polymer is based on a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The value measured at 25 ° C. using an E-type rotational viscometer.
The polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, more preferably 2,000. ~ 300,000. Moreover, the molecular weight distribution (Mw / Mn) represented by the ratio between Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. By being in such a molecular weight range, it is possible to ensure good orientation and stability of the liquid crystal display element.

<Other ingredients>
Although the liquid crystal aligning agent of this invention contains the above polymers (A), it can contain another component as needed. For example, when using the liquid crystal aligning agent of this invention for manufacture of the liquid crystal aligning film in a liquid crystal display element, as other components which may be added to the said liquid crystal aligning agent, other polymers other than the said polymer (A) And 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 a polyamic acid obtained by reacting the above-exemplified tetracarboxylic dianhydride and the above other diamine (hereinafter, also referred to as “other polyamic acid”), and the other. Polyimide obtained by dehydrating and ring-closing polyamic acid (hereinafter also referred to as “other polyimide”), polyamic acid ester synthesized using the above-mentioned other diamine (hereinafter also referred to as “other polyamic acid ester”), polyester , Polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like.

Moreover, when using the liquid crystal aligning agent of this invention for retardation films, the polymer which has a photo-alignment structure can be used preferably as said other polymer. Specifically, it is preferable to include a polymer having a photoalignable group, and it is more preferable to include a polymer into which a group having a cinnamic acid structure is introduced as the photoalignable group. Among these, a polyorganosiloxane having a cinnamic acid structure is preferable in that it is easy to introduce a photoalignable group into the polymer.
In addition, the polymer which has a photoalignment group is compoundable by a conventionally well-known method. For example, the polyorganosiloxane having a photo-alignment group as another polymer is a polyorganosiloxane having an epoxy group and a carboxylic acid having a photo-alignment group, preferably an organic solvent such as ether, ester or ketone. It can synthesize | combine by making it react in presence of catalysts, such as a quaternary ammonium salt.

  When other polymers are added to the liquid crystal aligning agent, the blending ratio is preferably 50 parts by weight or less with respect to 100 parts by weight of the total polymer in the composition, and 0.1 to 40 parts by weight More preferably, it is more preferably 0.1 to 30 parts by weight.

[Epoxy group-containing compound]
The epoxy group-containing compound can be used to improve the adhesion of the liquid crystal alignment film to the substrate surface. Here, examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodi Preferred examples include phenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, and epoxy group-containing polyorganosiloxane described in WO2009 / 096598. Can be mentioned.
When these epoxy group-containing compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 40 parts by weight or less, and 0.1 to 30 parts by weight with respect to 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 (A) 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 range of the solid concentration varies depending on the use of the liquid crystal alignment film and the method used when applying the liquid crystal aligning agent to the substrate. For example, for a liquid crystal aligning agent for a liquid crystal cell, when 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 A range of 1.5 to 4.5% by weight is particularly preferable. 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 (for liquid crystal cells), 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 (1-1) to (1-3). In the step (1-1), a substrate to be used is different depending on a desired operation mode. Steps (1-2) and (1-3) are common to each operation mode.

[Step (1-1): 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.
(1-1A) When manufacturing a TN-type, STN-type, or VA-type liquid crystal display element, for example, first, a pair of two substrates on which patterned transparent conductive films are provided, 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.

  (1-1B) 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 (1-1A). As the metal film, for example, a film made of a metal such as chromium can be used.

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

[Step (1-2): 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 (1-1), 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 manufacturing a VA type liquid crystal display element, the coating film formed in the above step (1-1) can be used as a liquid crystal alignment film as it is, but even if the coating film is rubbed. Good. For the liquid crystal alignment film after the rubbing treatment, a process 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, 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 (1-3): Construction of liquid crystal cell]
Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates disposed to face each other. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, two substrates are arranged opposite to each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole. The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped at predetermined locations on the liquid crystal alignment film surface. After that, the other substrate is bonded so that the liquid crystal alignment film faces, and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell. can do. Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase and then gradually cooled to room temperature. It is desirable to remove.

  As the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenyl cyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals. Biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal, and the like can be used. Further, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck & Co., Inc.). A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.

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

[Phase difference film]
The liquid crystal aligning film formed using the liquid crystal aligning agent of this invention can be applied to the liquid crystal aligning film for retardation films. Below, the method to manufacture retardation film using the liquid crystal aligning agent of this invention is demonstrated. In the production of the retardation film of the present invention, it is possible to form a uniform liquid crystal alignment film while suppressing the generation of dust and static electricity during the process, and an appropriate photomask is used during radiation irradiation. It is preferable to use the photo-alignment method in that a plurality of regions having different liquid crystal alignment directions can be arbitrarily formed on the substrate. Specifically, it can be produced through the following steps (2-1) to (2-3).

[Step (2-1): 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. May be implemented.

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

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

[Step (2-2): Light irradiation step]
Next, the coating film formed on the substrate as described above is irradiated with light, thereby imparting liquid crystal alignment ability to the liquid crystal alignment 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 set to 0.1 mJ / cm ² or more 1,000 mJ / cm less than ^2, more preferably, to 1 to 500 mJ / cm ^2, further be 2~200mJ / cm ² preferable. In addition, when the liquid crystal aligning agent of this invention is used, even if light irradiation amount is 500 mJ / cm < ² > or less, Furthermore, 200 mJ / cm < ² > or less can provide favorable liquid crystal aligning ability by a photo-alignment method, and liquid crystal Contributes to reducing the manufacturing cost of the alignment film.

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

Next, the coating film of the polymerizable liquid crystal formed as described above is subjected to at least one treatment 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 in 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, mobile phones, smartphones, The present invention can be used for various display devices such as various monitors, liquid crystal televisions, and information displays.

  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 synthesis examples and comparative synthesis examples, the polymer weight average molecular weight Mw, imidation ratio 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 diamine>
[Example A-1; Synthesis of Compound (d-1)]
Compound (d-1) was synthesized according to the following scheme 1.

In a 2 L three-necked flask equipped with a dropping funnel, 332.36 g of 2- (4-nitrophenyl) ethylamine and 1,000 mL of pyridine were mixed, and a solution in which 154 g of succinyl chloride was dissolved in 500 mL of tetrahydrofuran was slowly dropped from the dropping funnel. . During the dropping, the system was cooled so as not to exceed 30 ° C. After completion of the dropping, the reaction was carried out by stirring at 45 ° C. for 2 hours. After the reaction, 2000 mL of ethyl acetate was added for extraction, and 200 mL of distilled water was added for separation and purification. After repeating the above extraction and purification 5 times, the solvent was removed from the organic layer by distillation under reduced pressure to obtain 320 g of a nitro intermediate (compound represented by the above formula (d-1-1)).
Next, under a nitrogen stream, 320 g of the above nitro intermediate, 16 g of 5% Pd / C, 500 mL of ethanol and 500 mL of tetrahydrofuran were added to a 2 L three-necked flask, and then replaced with hydrogen, and reacted at room temperature in the presence of hydrogen. It was. The reaction was traced by HPLC, followed by filtration after confirming the progress of the reaction. To the filtrate, 3000 mL of ethyl acetate was added, and 200 mL of distilled water was added for separation and purification. After the above extraction and purification was repeated 5 times, the solvent was removed from the organic layer by distillation under reduced pressure to precipitate a solid. The precipitated solid was recrystallized from ethanol to obtain 219 g of compound (d-1).

[Example A-2; Synthesis of Compound (d-5)]
Compound (d-5) was synthesized according to the following scheme 2.

In a 2 L three-necked flask equipped with a dropping funnel, 334.32 g of 2- (4-nitrophenyl) ethyl alcohol and 1,000 mL of pyridine were mixed, and a solution in which 183 g of adipic acid dichloride was dissolved in 500 mL of tetrahydrofuran was slowly added from the dropping funnel. It was dripped. During the dropping, the system was cooled so as not to exceed 30 ° C. After completion of dropping, the reaction was carried out by stirring at 45 ° C. for 2 hours. After the reaction, 2000 mL of ethyl acetate was added for extraction, and 200 mL of distilled water was added for separation and purification. After repeating the extraction and purification five times, the solvent was removed from the organic layer by distillation under reduced pressure to obtain 306 g of a nitro intermediate (compound represented by the above formula (d-1-2)).
Next, under a nitrogen stream, 306 g of the above nitro intermediate, 15.3 g of 5% Pd / C, 500 mL of ethanol and 500 mL of tetrahydrofuran were added to a 2 L three-necked flask, and then replaced with hydrogen, and in the presence of hydrogen at room temperature. Reacted. The reaction was traced by HPLC, followed by filtration after confirming the progress of the reaction. To the filtrate, 3000 mL of ethyl acetate was added, and 200 mL of distilled water was added for separation and purification. After the above extraction and purification was repeated 5 times, the solvent was removed from the organic layer by distillation under reduced pressure to precipitate a solid. The precipitated solid was recrystallized from ethanol to obtain 220 g of Compound (d-5).

[Example A-3; Synthesis of Compound (d-9)]
Compound (d-9) was synthesized according to the following scheme 3.

In a 2 L three-necked flask equipped with a dropping funnel, 362.38 g of 3- (4-nitrophenyl) propanol and 1600 ml of tetrahydrofuran were mixed and dissolved, and cooled in an ice bath. Next, a mixture of 400 ml of tetrahydrofuran and 84 g of sodium hydride was slowly added to the solution obtained above from the dropping funnel and stirred at room temperature for 1 hour. In addition, it cooled in the ice bath so that it might not exceed 30 degreeC during dripping. Next, 229.94 g of 1,5-dibromopentane and 6.45 g of tetrabutylammonium bromide (TBAB) were added and mixed, and reacted at 40 ° C. for 20 hours. After the reaction, 5000 mL of ethyl acetate was added for extraction, and 200 mL of distilled water was added for separation and purification. After the extraction and purification were repeated 5 times, the solvent was removed from the organic layer by distillation under reduced pressure to obtain a crude product. The obtained crude product was purified by silica column chromatography to obtain 327 g of a nitro intermediate (compound represented by the above formula (d-1-3)).
Then, under a nitrogen stream, 327 g of the above nitro intermediate, 16.35 g of 5% Pd / C, 500 mL of ethanol, and 500 mL of tetrahydrofuran were added to a 2 L three-necked flask, and then replaced with hydrogen again. Reacted. The reaction was traced by HPLC, followed by filtration after confirming the progress of the reaction. To the filtrate, 3000 mL of ethyl acetate was added, and 200 mL of distilled water was further added for separation and purification. After the above extraction and purification was repeated 5 times, the solvent was removed from the organic layer by distillation under reduced pressure to precipitate a solid. The precipitated solid was recrystallized from ethanol to obtain 190 g of Compound (d-9).

<Synthesis of polymer>
[Example B-1; Synthesis of polyamic acid]
10.18 g of pyromellitic dianhydride and 9.16 g of 1,2,3,4-cyclobutanoic acid dianhydride as tetracarboxylic dianhydride, 13.25 g of compound (d-1) as diamine, 1-1) Compound 6.39 g and the following formula (1-2) 11.00 g are dissolved in N-methyl-2-pyrrolidone (NMP) 200 g and reacted at room temperature for 6 hours. went. A small amount of the reaction solution was taken and the solution viscosity was measured and found to be 1,810 mPa · s. 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 47.5 g of polyamic acid (P-1).

[Example B-2; Synthesis of polyimide]
10.5 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 11.7 g of 8-dianhydride and 13.18 g of the compound (d-9) as a diamine, 9.32 g of 4,4′-diaminodiphenylmethane and 5.2 g of the compound represented by the following formula (1-3) were added to 200 g of NMP. And reacted at room temperature for 6 hours. A small amount of the reaction solution was taken and the solution viscosity was measured and found to be 1,670 mPa · s.
Next, 250 g of NMP was added to the obtained polyamic acid solution, 14.88 g of pyridine and 19.20 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 90 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol, and then dried at 40 ° C. under reduced pressure for 15 hours to obtain 46.9 g of polyimide (P-2) having an imidation ratio of 94%.

[Example B-3; Synthesis of polyamic acid]
As tetracarboxylic dianhydride, 9.11 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3 , 5: 6-dianhydride 9.60 g and 31.28 g of the compound (d-5) as a diamine were dissolved in 200 g of NMP and reacted at room temperature for 6 hours. A small amount of the reaction solution was taken, and the solution viscosity was measured and found to be 1,250 mPa · s. 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 48.1 g of polyamic acid (P-3).

[Example B-4; Synthesis of polyamic acid]
1,3,3a, 4,5,9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan as tetracarboxylic dianhydride 13.11 g of 1,3-dione and 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan -1,3-dione 12.52 g, and 3.10 g of a compound (d-9) as a diamine, 11.43 g of a compound represented by the following formula (1-1), and a formula (1-2) 9.83 g of the resulting compound was dissolved in 200 g of NMP and reacted at room temperature for 6 hours. A small amount of the reaction solution was taken and the solution viscosity was measured and found to be 1,450 mPa · s. 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 48.7 g of polyamic acid (P-4).

[Example B-5; Synthesis of polyamic acid]
As the tetracarboxylic dianhydride, 3.88 g of pyromellitic dianhydride and 13.98 g of 1,2,3,4-cyclobutanoic dianhydride, and as the diamine, 30.98 g of the compound (d-1) and the following formula ( 1.15 g of the compound represented by 1-4) was dissolved in 200 g of NMP and reacted at room temperature for 6 hours. A small amount of the reaction solution was taken and the solution viscosity was measured and found to be 1,680 mPa · s. 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 49.1 g of polyamic acid (P-5).

[Synthesis Example 1; Synthesis of polyamic acid]
10.18 g of pyromellitic dianhydride and 9.15 g of 1,2,3,4-cyclobutanoic dianhydride as tetracarboxylic dianhydride, and the following formula (1-5) as diamine 30.66 g of the compound was dissolved in 200 g of NMP and reacted at room temperature for 6 hours. A small amount of the reaction solution was taken and the solution viscosity was measured and found to be 1,220 mPa · s. 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 46.7 g of polyamic acid (P-6).

[Synthesis Example 2; Synthesis of polyamic acid]
12.58 g of pyromellitic dianhydride and 11.31 g of 1,2,3,4-cyclobutanoic dianhydride as tetracarboxylic dianhydride and represented by the following formula (1-6) as diamine 26.11 g of the compound was dissolved in 200 g of NMP and reacted at room temperature for 6 hours. A small amount of the reaction solution was taken and the solution viscosity was measured, and it was 980 mPa · s. 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 47.1 g of polyamic acid (P-7).

  Table 1 below shows the types and molar ratios of tetracarboxylic dianhydride and diamine used in Examples B-1 to B-5 and Synthesis Examples 1 and 2.

In addition, the numerical value of Table 1 shows the use ratio (mol%) with respect to the whole quantity of the tetracarboxylic dianhydride used for reaction about tetracarboxylic dianhydride, About diamine, it is the diamine used for reaction. The ratio of use (mol%) to the total amount is shown.
Abbreviations in Table 1 have the following meanings.
(Tetracarboxylic dianhydride)
t-1: 1,2,3,4-cyclobutanoic acid dianhydride t-2: pyromellitic dianhydride t-3: 1,2,4,5-cyclohexanetetracarboxylic dianhydride t-4: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride t-5: 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride t- 6: Bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-dianhydride t-7: 1,3,3a, 4,5,9b- Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione t-8: 1,3,3a, 4,5,9b-hexahydro -8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] furan-1,3-dione (diamine)
da-1: Compound represented by the above formula (1-1) da-2: Compound represented by the above formula (1-2) da-3: Compound represented by the above formula (1-3) da- 4: 4,4′-diaminodiphenylmethane da-5: compound represented by the above formula (1-4) da-6: compound represented by the above formula (1-5) da-7: above formula (1- Compound represented by 6)

[Synthesis Example S-1; Synthesis of Polyorganosiloxane]
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine, and room temperature. And 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 1: FFS type liquid crystal display element]
(1) Preparation of liquid crystal aligning agent 100 parts by weight of the polyamic acid (P-1) obtained in Example B-1 as a polymer is a mixed solvent composed of γ-butyrolactone (GBL), NMP and butyl cellosolve (BC) (GBL: NMP: 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. Evaluation is that the coating property is “good” when neither film thickness unevenness nor pinhole is observed, and the coating property is “good” when at least one of film thickness unevenness and pinhole is slightly observed. When at least one of unevenness and pinholes was clearly observed, the coating property was “bad”. In this example, neither film thickness unevenness nor pinhole was observed, and the coating property was “good”.
(3) Evaluation of rubbing resistance The coating film obtained above was rubbed at a roll rotation speed of 1000 rpm, a stage moving speed of 20 cm / sec, and a hair foot indentation length of 0.4 mm by a rubbing machine having a roll wrapped with a cotton cloth. The treatment was 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 9 or less, and the rubbing resistance “bad” when 10 or more. As a result, the rubbing resistance of this coating film was “good”.

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

  Next, the surface of the coating film formed on the glass substrates 11a and 11b was rubbed with cotton in the direction of arrow f in FIG. These substrates 11a and 11b were bonded to each other through a spacer having a diameter of 3.5 μm so that the rubbing directions of the substrates were antiparallel to each other, and an empty cell without liquid crystal injection was produced. Liquid crystal MLC-6221 (manufactured by Merck & Co., Inc.) was injected into this cell to form a liquid crystal layer 16. Furthermore, the liquid crystal display element 10 of Example 1 was produced by bonding a polarizing plate (not shown) on both outer surfaces of the substrates 11a and 11b so that the polarization directions of the two polarizing plates were orthogonal to each other. This series of operations was repeated to produce a total of three FFS type liquid crystal display elements, which were each subjected to the following evaluation of liquid crystal orientation, evaluation of heat resistance, and evaluation of relaxation rate of residual DC.

(5) 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 brightness when a voltage of 5 V is turned ON / OFF (applied / released) is measured at a magnification of 100 times and a magnification. Observed at 50 times. In the evaluation, the liquid crystal alignment was “excellent” when no abnormal domain was observed even at a magnification of 100 ×, and the liquid crystal alignment was observed when an abnormal domain was observed at a magnification of 50 × The case where the property was “good” and the abnormal domain was observed even at a magnification of 50 times was determined as “poor” in the liquid crystal alignment. In this liquid crystal cell, the liquid crystal orientation was “excellent”.
(6) Evaluation of heat resistance For the FFS type liquid crystal display device manufactured as described above, after applying a voltage of 5 V with an application time of 60 microseconds and a span of 167 milliseconds, the voltage holding ratio after 167 milliseconds from the application release. (Initial voltage holding ratio (VHR _BF )) was measured using “VHR-1” manufactured by Toyo Corporation. Next, the liquid crystal display element after VHR _BF measurement was left in an oven at 100 ° C. for 1,000 hours. Thereafter, the liquid crystal display element was left at room temperature and allowed to cool to room temperature, and then the voltage holding ratio (VHR _AF ) was measured under the same conditions as the measurement of the initial voltage holding ratio VHR _BF . 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, when the change rate ΔVHR was less than 5%, the heat resistance was “good”, and when it was 5% or more, the heat resistance was “bad”. As a result, VHR _BF was 99.6% and the heat resistance of the liquid crystal display element was “good”.

(7) Evaluation of relaxation rate of residual DC (Evaluation of afterimage characteristics)
About the liquid crystal display element manufactured above, the relaxation rate of residual DC was measured by a dielectric absorption method using a 6254C type liquid crystal physical property evaluation apparatus manufactured by Toyo Technica. The measurement was performed in an environment of 60 ° C., a DC voltage of 10 V was applied to the cell for 30 minutes, the battery was discharged for 1 second, and then the residual DC for 30 minutes was measured. The residual DC relaxation rate was determined by calculating the average residual DC relaxation rate from the maximum value of residual DC and the residual DC value one minute after the time when the maximum value was exhibited. In the evaluation, the residual DC relaxation property is “excellent” when the residual DC relaxation rate is 4 mV / sec or more, and the residual DC relaxation property is “good” when it is 2 mV / sec or more and less than 4 mV / sec. Residual DC relaxation was performed as “bad”. In addition, it shows that an afterimage characteristic is so favorable that 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 5.2 mV / sec, and the residual DC relaxation property was judged to be “excellent”.

[Examples 2 and 3 and Comparative Examples 1 and 2]
In Example 1 above, a liquid crystal aligning agent was prepared in the same manner as in Example 1 except that polymers of the type shown in Table 2 below were used as polymers, and FFS type liquid crystal display elements were produced and evaluated. The evaluation results are shown in Table 2 below.

  As shown in Table 2, in the examples, all of the coating property of the liquid crystal aligning agent, the rubbing resistance of the coating film, the liquid crystal alignment property, the initial voltage holding ratio, the heat resistance, and the residual DC relaxation rate in the liquid crystal display element. Good results were obtained. On the other hand, in Comparative Examples 1 and 2, the initial voltage holding ratio of the liquid crystal display element was less than 99%, which was lower than that of the example. Further, in Comparative Example 1, the heat resistance of the liquid crystal display element was “defective”, and in Comparative Example 2, the relaxation property of residual DC was “defective”.

[Example 4: TN liquid crystal display element]
(1) Preparation of liquid crystal aligning agent 100 parts by weight of the polyimide (P-2) obtained in Example B-2 as a polymer was dissolved in a mixed solvent of NMP and BC (NMP: BC = 50: 50 (weight ratio)). Thus, a solution having a solid content concentration of 6.5% by weight was obtained. 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 having a magnification of 20 times to check for the presence 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.
By repeating the above series of operations, a total of three TN type liquid crystal cells were produced, and each liquid crystal cell was subjected to the evaluation of liquid crystal alignment, the evaluation of pretilt angle stability, and the evaluation of heat resistance shown below. .

(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 100 times magnification and 50 times magnification. . Evaluation was performed in the same manner as in Example 5 (5). As a result, in this liquid crystal cell, the liquid crystal orientation was “excellent”.

(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. The crystal rotation method is described in Non-Patent Document 1 (T. J. 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 (3), the amount of change in the pretilt angle (Δθ (°)) before and after voltage application was determined.
Δθ = | θ _AF −θ _IN | (3)
When this value Δθ is less than 0.05 °, the pretilt angle stability is “excellent”, when it is 0.05 ° or more and less than 0.2 °, the pretilt angle stability is “good”, when it is 0.2 ° or more. When the pretilt angle stability was evaluated as “bad”, the change amount Δθ of the pretilt angle in this liquid crystal cell was less than 0.2 °, and the pretilt angle stability was “excellent”.

(6) Evaluation of heat resistance In the same manner as in (6) of Example 1 above, the initial voltage holding ratio VHR _BF was measured, and the heat resistance was evaluated based on the rate of change in voltage holding ratio before and after thermal stress application. . As a result, the initial voltage holding ratio VHR _BF was 99.1%. Further, the heat resistance was “good”.

[Example 5: VA liquid crystal display element]
(1) Preparation of liquid crystal aligning agent NMP and BC were added to 100 parts by weight of the polyamic acid (P-5) obtained in Example B-5 as a polymer, the solid content concentration was 6.5% by weight, and the mixing ratio of the solvent 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, when the printability was examined in the same manner as in (2) of Example 4, both printing unevenness and pinholes were observed. 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 produced in the above (3) was evaluated in the same manner as in (4) of Example 4. As a result, the liquid crystal alignment of this liquid crystal cell was “good”. . Further, the initial voltage holding ratio VHR _BF was measured in the same manner as in (6) of Example 1, and the heat resistance (the rate of change of the voltage holding ratio before and after applying thermal stress) was evaluated. As a result, the initial voltage holding ratio VHR _BF was 99.4%, and the heat resistance was “good”.

[Example 6: Retardation film]
(1) Preparation of liquid crystal aligning agent 100 parts by weight of polyamic acid (P-1) obtained in Example B-1 and 5 parts by weight of polyorganosiloxane (S-1) obtained in Synthesis Example S-1 were mixed with NMP. And BC (NMP: BC = 50: 50 (weight ratio)) to obtain a solution having a solid content 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 the 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, 11 ... Glass substrate, 12 ... Liquid crystal aligning film, 13 ... Top electrode, 14 ... Insulating layer (silicon nitride film), 15 ... Bottom electrode, 16 ... Liquid crystal layer, f ... Rubbing direction.

Claims (10)

Obtained by reacting at least one compound selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride and tetracarboxylic acid diester compound with a diamine containing a compound represented by the following formula (d). A liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide.

(In formula (d), R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. .R ⁹ and R ¹⁰ substituents or alkenyl group is a monovalent group introduced are each independently a halogen atom or an alkyl or alkoxy group having 1 to 6 carbon atoms .Z ¹ and Z ² is independently a single bond, —O—, * —COO—, * —OCO—, —CO—, * —NHCO—, * —CONH— or * —O—CH ₂ — (where “* "is a.) showing a bond to ^{X 1.} However, .X ^{1 Z 1} and ^{Z 2} do not become single bond at the same time, it is a divalent organic group .m ¹ and ^{m 2} And each independently represents an integer of 0 to 4, and n is 0 or 1, provided that X ¹ Is —CH═CH—Ph—CH═CH—, and Z ¹ and Z ² are * —COO— (where “*” represents a bond to X ¹ ), and X ¹ Is —CH═CH—, Z ¹ is * —COO— (where “*” represents a bond to X ¹ ), Z ² is a single bond, and n is 0. If the ^{.R 9, R 10,} excluding the presence of a plurality, the plurality of ^{R 9, R 10} may be the same or different.)   The liquid crystal aligning agent according to claim 1, wherein n is 1. The X ¹ is an alkanediyl group having 1 to 18 carbon atoms or — [(CH ₂ ) ₂ O] a— (CH ₂ ) ₂ — (where a is an integer of 1 to 3). 2. A liquid crystal aligning agent according to 2. The polymer is a polymer obtained by reacting tetracarboxylic dianhydride and diamine,
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 , Cyclohexanetetracarboxylic dianhydride, and pyromelli Comprises at least one selected from the group consisting of preparative dianhydride, liquid crystal alignment agent according to any one of claims 1 to 3.   The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-4.   A liquid crystal display element provided with the liquid crystal aligning film of Claim 5.   A retardation film comprising the liquid crystal alignment film according to claim 5. Applying the liquid crystal aligning agent according to any one of claims 1 to 4 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. It is obtained by reacting at least one compound selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride and tetracarboxylic acid diester compound with a diamine containing a compound represented by the following formula (d). Polymer.

(In formula (d), R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. .R ⁹ and R ¹⁰ substituents or alkenyl group is a monovalent group introduced independently, .Z ¹ and a halogen atom, or an alkyl or alkoxy group having 1 to 6 carbon atoms Z ² each independently represents a single bond, —O—, * —COO—, * —OCO—, —CO—, * —NHCO—, * —CONH— or * —O—CH ₂ — (where “ * "is.) showing a bond to ^{X 1.} However, .X ^{1 Z 1} and ^{Z 2} do not become single bond at the same time, it is a divalent organic group .m ¹ and ^{m 2} is each independently an integer of 0 to 4, n is 1. However, ^{X 1} is CH = CH-Ph-CH = CH- and a by ^{Z 1} and ^{Z 2} is * -COO- (where "*" indicates a bond to ^{X 1.)} Unless it is. ^R 9, R When a plurality of ¹⁰ are present, the plurality of R ⁹ and R ¹⁰ may be the same or different.) A compound represented by the following formula (d).

(In formula (d), R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. .R ⁹ and R ¹⁰ substituents or alkenyl group is a monovalent group introduced independently, .Z ¹ and a halogen atom, or an alkyl or alkoxy group having 1 to 6 carbon atoms Z ² each independently represents a single bond, —O—, * —COO—, * —OCO—, —CO—, * —NHCO—, * —CONH— or * —O—CH ₂ — (where “ * "is.) showing a bond to ^{X 1.} However, .X ^{1 Z 1} and ^{Z 2} do not become single bond at the same time, it is a divalent organic group .m ¹ and ^{m 2} is each independently an integer of 0 to 4, n is 1. However, ^{X 1} is CH = CH-Ph-CH = CH- and a by ^{Z 1} and ^{Z 2} is * -COO- (where "*" indicates a bond to ^{X 1.)} Unless it is. ^R 9, R When a plurality of ¹⁰ are present, the plurality of R ⁹ and R ¹⁰ may be the same or different.)

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