JP6492564B2 - Liquid Crystal Alignment Agent, Liquid Crystal Alignment Film, Liquid Crystal Display Element, Retardation Film, Method of Producing Retardation Film, Polymer, and Compound - Google Patents

Description

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

  Heretofore, various liquid crystal display devices have been developed which have various driving methods different in electrode structure, physical properties of liquid crystal molecules used, manufacturing process, etc. For example, TN type, STN type, VA type, in-plane switching type ( Various liquid crystal display elements such as IPS type) and FFS type are known. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. As a material of a liquid crystal aligning film, a polyamic acid and a polyimide are generally used from the point which various characteristics, such as heat resistance, mechanical strength, and affinity with a liquid crystal, are favorable.

  Further, in recent years, with the increase in resolution of liquid crystal display elements, demands for reduction of the afterimage phenomenon and suppression of contrast decrease are increasing, and various liquid crystal alignment agents have been proposed to meet such demands (for example, Patent Document 1) ~ 6). In the devices described in these Patent Documents 1 to 6, reduction of accumulated charge in the liquid crystal display element and suppression of contrast reduction are achieved by introducing a diphenylamine unit into the liquid crystal aligning agent.

  Specifically, Patent Document 1 discloses that a liquid crystal aligning agent contains a polyamic acid or a polyimide obtained by reacting a diamine containing 4,4'-diaminodiphenylamine with a tetracarboxylic acid dianhydride. ing. Patent Document 2 discloses a liquid crystal polyimide obtained by reacting a diamine containing an oligoaniline such as (4-aminophenyl) (4-((4-aminophenyl) amino) phenylamine with tetracarboxylic acid dianhydride. Patent Document 3 discloses that a compound having two or more diphenylamine units is added separately from a polymer such as a polyamic acid or a polyimide, or two or more compounds are contained in an alignment agent. It is disclosed that a liquid crystal aligning agent contains a polyamic acid obtained by reacting a diamine having a diphenylamine unit with a tetracarboxylic acid dianhydride.

  Patent document 4 discloses diamine and tetracarboxylic acid dianhydride containing 1,3-bis-4- (N, N- (4-aminophenyl) aminophenyl) propane as a compound having two diphenylamine structures in the molecule. It is disclosed that a liquid crystal aligning agent contains a polyamic acid obtained by reacting with a substance. Patent documents 5 and 6 disclose polyamics obtained by reacting a diamine containing N, N'-bis (4-aminophenyl) -N, N'-dimethylethylenediamine with tetracarboxylic acid dianhydride. It is disclosed that the acid is contained in the liquid crystal aligning agent.

  In addition, various optical materials are used for the liquid crystal display element, and among them, the retardation film eliminates the viewing angle dependency that the display color and the contrast ratio change depending on the purpose of eliminating the coloring of the display and the visual direction. Used for the purpose of 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. ing. Also, in recent years, in the preparation of a liquid crystal alignment film in a retardation film, a photoalignment method of imparting liquid crystal alignment ability by irradiating a radiation-sensitive organic thin film formed on the substrate surface with polarized or non-polarized radiation is used. Various liquid crystal aligning agents for retardation films for producing a liquid crystal alignment film by such a method have been proposed (see, for example, Patent Document 7).

Patent No. 4052307 JP 2000-44683 A Patent No. 4924832 JP, 2011-207786, A JP, 2012-155311, A Patent No. 5130907 JP 2012-37868 A

  However, when the liquid crystal aligning agent of Patent Document 1 is used, the DC residual relaxation in the liquid crystal display element is insufficient, and the time until the afterimage disappears tends to be long. Moreover, in the conventional liquid crystal aligning agent containing the polymer which used the diamine which has two or more diphenylamine units for a monomer, although the performance of DC residual relaxation is improved, since the aromatic concentration goes up, the transmittance of a liquid crystal aligning film is There was a disadvantage such as low. In addition, the AC afterimage performance, which is one of the characteristics affecting the contrast of the liquid crystal display element, is not sufficient, and various characteristics are not well balanced. Further, with the diversification of liquid crystal display elements in recent years, it is assumed that liquid crystal display elements are used in more severe conditions, and liquid crystal display elements are required to have excellent heat resistance.

  A liquid crystal display is manufactured by opposingly arranging a pair of substrates on which a liquid crystal alignment film is formed, and arranging liquid crystal between the pair of opposed substrates. At this time, the pair of substrates is bonded using a sealing agent such as epoxy resin. Here, in a touch panel type display panel represented by a smartphone or a tablet PC, in order to make the movable area of the touch panel wider and to miniaturize the liquid crystal panel (element), it is attempted to narrow the frame There is. With such narrowing of the liquid crystal panel, display unevenness may be visually recognized around the sealing agent, and the display quality is not sufficiently satisfactory. In order to achieve high definition and long life of a liquid crystal display, a liquid crystal display element in which display unevenness in the vicinity of such a sealing agent is hard to be recognized (a bezel unevenness resistance is high) is required.

  The present invention has been made in view of the above problems, and the transparency of the liquid crystal alignment film is good, the display unevenness around the sealing agent is small, and various characteristics such as afterimage characteristics, high contrast and heat resistance are well balanced. It aims at providing a liquid crystal aligning agent for obtaining a liquid crystal display element.

  The inventor of the present invention diligently studied to achieve the problems of the prior art as described above, and by containing a polymer having a specific structure as a polymer component in a liquid crystal aligning agent, the problems can be solved. The present invention has been completed. Specifically, the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, retardation film, method for producing retardation film, polymer and compound are provided by the present invention.

The present invention relates, in one aspect, to a compound (C) having the following structure (a) and the following structure (b), and a structure (a) and the following structure (b1) and having the structure (a) Polymer (P) obtained by using, in the reaction, at least one compound (C ′) selected from the group consisting of compounds (C1) in which no reactive group involved in polymerization is bonded to the aromatic ring group in the Providing a liquid crystal aligning agent containing
(A) An aromatic amine structure formed by bonding two or three aromatic ring groups to the same nitrogen atom.
(B) a bivalent chain hydrocarbon group having 6 or more carbon atoms, and at least one methylene group in the chain hydrocarbon group are selected as -O-, -S-, -CO-, -NR-, -NRCO A chain structure selected from the group consisting of divalent groups substituted by-, -COO-, -COS- or -Si (CH ₃ ) _2- (wherein R is a hydrogen atom or a monovalent organic group).
(B1) a divalent linear hydrocarbon group having 1 to 5 carbon atoms, at least one methylene group in the linear hydrocarbon group is selected as -O-, -S-, -CO-, -NR ³ -,- ^{NR 3 CO -, - COO -} , - COS- or -Si _{(CH 3) 2} - a divalent group obtained by replacing, -O -, - S -, - CO -, - NR 3 CO- (R 3 is is a hydrogen atom or a monovalent organic group), -. COO -, - COS-, and -Si _{(CH 3) 2} - is selected from the group consisting of structures.

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

  The present invention relates, in another aspect, a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3) I will provide a. Further, at least one compound selected from the group consisting of tetracarboxylic acid dianhydrides, tetracarboxylic acid diester compounds and tetracarboxylic acid diester dihalides, a compound represented by the following formula (1-1), a compound represented by the following formula (1) Polyamic acid, polyamic acid ester and polyimide obtained by using, in the reaction, a diamine containing at least one selected from the group consisting of a compound represented by -2) and a compound represented by the following formula (1-3) Provided is a polymer selected from the group consisting of:

（式（１−１）中、Ａ^１及びＡ^３は、それぞれ独立に水素原子又は１価の有機基であり、Ａ^２及びＡ^４は、それぞれ独立に単結合又は２価の有機基である。Ｂ^１及びＢ^２は、それぞれ独立に単結合又は２価の有機基である。ただし、Ｂ^１が単結合である場合、Ａ^１及びＡ^２の少なくとも１個は芳香環で窒素原子に結合しており、Ｂ^１が２価の有機基である場合、Ａ^１、Ａ^２及びＢ^１のうち少なくとも２個は芳香環で窒素原子に結合している。Ｂ^２が単結合である場合、Ａ^３及びＡ^４の少なくとも１個は芳香環で窒素原子に結合しており、Ｂ^２が２価の有機基である場合、Ａ^３、Ａ^４及びＢ^２のうち少なくとも２個は芳香環で窒素原子に結合している。Ｌ^１１は、炭素数６以上の２価の鎖状炭化水素基における少なくとも１個のメチレン基を−Ｏ−、−Ｓ−、−ＣＯ−、−ＮＲ−、−ＮＲＣＯ−、−ＣＯＯ−、−ＣＯＳ−又は−Ｓｉ（ＣＨ_３）_２−（Ｒは水素原子又は１価の有機基である。）で置き換えてなる基を含む２価の基である。ただし、Ｌ^１１が炭素数１〜５のアルカンジイル基を有する場合、Ａ^１及びＡ^３の少なくともいずれかが水素原子であるか、又はＢ^１及びＢ^２の少なくともいずれかが２価の有機基である。）

(In formula (1-1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, and A ² and A ⁴ are each independently a single bond or a divalent organic group B ¹ and B ² are each independently a single bond or a divalent organic group, provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom When B ¹ is a divalent organic group, at least two of A ¹ , A ² and B ¹ are aromatic rings and are bonded to a nitrogen atom, and when B ² is a single bond, At least one of A ³ and A ⁴ is an aromatic ring and is bonded to a nitrogen atom, and when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are an aromatic ring .L ¹¹ attached to the nitrogen atom, at least one of the divalent chain hydrocarbon group having 6 or more carbon atoms Methylene -O -, - S -, - CO -, - NR -, - NRCO -, - COO -, - COS- or _{-Si (CH 3) 2 - (} R is a hydrogen atom or a monovalent organic group And, when L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, at least one of A ¹ and A ³ is a hydrogen atom. Or at least one of B ¹ and B ² is a divalent organic group.)

（式（１−２）中、Ｌ^１２は、炭素数６以上の２価の鎖状炭化水素基を含む２価の基である。Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ｂ^１及びＢ^２は上記式（１−１）と同義である。ただし、Ｌ^１２が炭素数６〜１０のアルカンジイル基である場合、Ａ^１及びＡ^３の少なくともいずれかが１価の有機基であるか、又はＢ^１及びＢ^２の少なくともいずれかが２価の有機基である。）

(In Formula (1-2), L ¹² is a divalent group containing a divalent chain hydrocarbon group having 6 or more carbon atoms. A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ² is as defined in the above formula (1-1), provided that when L ¹² is an alkanediyl group having 6 to 10 carbon atoms, at least one of A ¹ and A ³ is a monovalent organic group Or at least one of B ¹ and B ² is a divalent organic group.)

（式（１−３）中、Ａ^７は水素原子又は１価の有機基であり、Ａ^８及びＡ^９は、それぞれ独立に単結合又は２価の有機基である。ただし、Ａ^７、Ａ^８及びＡ^９のうち少なくとも２個は芳香環で窒素原子に結合している。Ｌ^４は上記構造（ｂ１）であり、Ｌ^５は単結合又は２価の有機基である。）

(In formula (1-3), A ⁷ is a hydrogen atom or a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond or a divalent organic group, provided that A ⁷ and A are ^At least two of ⁸ and A ⁹ are bonded to the nitrogen atom via an aromatic ring, L ⁴ is the above structure (b 1), and L ⁵ is a single bond or a divalent organic group.

  According to a liquid crystal aligning agent containing the above-mentioned polymer (P) as a polymer component, a liquid crystal display element having less display unevenness around the sealing agent and having various characteristics such as low afterimage, high contrast and heat resistance in a well-balanced manner You can get it. Moreover, a liquid crystal aligning film with favorable permeability can be obtained. Furthermore, the solubility of the polymer (P) in the solvent is good, and the storage stability of the liquid crystal aligning agent is also good.

The schematic block diagram of a FFS type liquid crystal cell. The top view schematic diagram of the top electrode used for manufacture of the liquid crystal display element by the optical orientation method. (A) is a top view of a top electrode, (b) is the elements on larger scale of a top electrode. The figure which shows four drive electrodes. The top view schematic diagram of the top electrode used for manufacture of the liquid crystal display element by rubbing process. (A) is a top view of a top electrode, (b) is the elements on larger scale of a top electrode.

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

<Polymer (P)>
The liquid crystal aligning agent of the present invention has, as a polymer component, a compound (C) having the above structure (a) and the above structure (b), and the above structure (a) and the above structure (b1) Compound (C1) in which a reactive group involved in polymerization is not bonded to the aromatic ring group in the structure (a), and at least one compound (C ′) selected from the group consisting of: It contains a polymer (P). In addition, below, the said structure (a) is also called "aromatic amine structure (a)", and the said structure (b) is also called "chain-like structure (b)."

・ Compound (C)
(Aromatic amine structure (a))
The aromatic amine structure (a) possessed by the compound (C) is a structure in which two or three aromatic ring groups are bonded to the same nitrogen atom. The aromatic ring group may be a group obtained by removing a hydrogen atom from the ring portion of an aromatic ring, and specifically, for example, an aromatic hydrocarbon ring such as a benzene ring, a toluene ring, a naphthalene ring, or an anthracene ring; And aromatic heterocyclic rings such as a pyrimidine ring, a pyrazine ring, a pyridazine ring, and a triazine ring; and groups in which a hydrogen atom is removed from a ring portion of an aromatic ring such as, for example. Among these, a benzene ring is preferable from the viewpoint of good affinity with liquid crystals.
The number of aromatic amine structures (a) in the molecule of the compound (C) is one or two or more, and preferably two or more from the viewpoint of enhancing the performance of the residual DC relaxation. Moreover, in the viewpoint of the transmittance | permeability of a liquid crystal aligning film, and the solubility of a polymer, More preferably, it is 2-4, More preferably, it is two or three pieces.

(Chain-like structure (b))
The chain structure (b) possessed by the above compound (C) is a divalent chain hydrocarbon group having 6 or more carbon atoms, or at least one of the divalent chain hydrocarbon groups having 6 or more carbon atoms The methylene group of -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS- or -Si (CH ₃ ) _2- (R is a hydrogen atom or monovalent) Group which is an organic group).

The bivalent chain hydrocarbon group in the chain structure (b) means a hydrocarbon group composed only of a linear or branched chain structure without containing a cyclic structure in the main chain. The divalent chain hydrocarbon group in the chain structure (b) may have 6 or more carbon atoms, and specific examples thereof include, for example, hexendyl group, heptane diyl group, octane diyl group, nonane diyl group, decane diyl group, dodecandyl Group, a saturated hydrocarbon group having 6 to 30 carbon atoms such as tetradecandyl group and icosandiyl group; and at least one carbon-carbon bond of the saturated hydrocarbon group having 6 to 30 carbon atoms is a double bond or a triple bond The C6-C30 unsaturated hydrocarbon group etc. can be mentioned. Although these may be linear or branched, they are preferably linear.
When the chain structure (b) is a divalent chain hydrocarbon group having 6 or more carbon atoms, the carbon chain number of the chain hydrocarbon group is preferably 6 to 30, and is 6 to 20. Is more preferred.

The chain structure (b) is selected from the group consisting of at least one methylene group in a bivalent chain hydrocarbon group having 6 or more carbon atoms as -O-, -S-, -CO-, -NR-, -NRCO- When it is a group substituted by -COO-, -COS- or -Si (CH ₃ ) _2- (R is a hydrogen atom or a monovalent organic group), the number of the substitution is one or more than one. It may be set appropriately according to the number of carbons. It is preferable that it is 6-30, and, as for carbon number before substituting a methylene group by the said functional group, it is more preferable that it is 7-20.
The monovalent organic group for R is, for example, a chain hydrocarbon group having 1 to 5 carbon atoms such as an alkyl group or an alkenyl group, and a carbon-carbon bond of a chain hydrocarbon group having 1 to 5 carbon atoms. A group having -O-, -CO- or the like, a protective group of an amino group, and the like can be mentioned. Specific examples of the protecting group for amino group include, for example, t-butoxycarbonyl group, benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, 1,1-dimethyl-2-cyanoethyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, 2- (trimethylsilyl) ethoxycarbonyl group etc. are mentioned, Preferably it is t-butoxycarbonyl group.

The number of chain structures (b) in the molecule of compound (C) may be one or two or more. Preferably it is 1-5, More preferably, it is 1-3. In addition, the compound (C) has an aromatic amine structure (a) and a chain structure (b) as the main chain of the compound (C), specifically, the longest carbon chain of the compound (when having a functional group) Preferably have the longest carbon chain) containing it.
It is preferable that the molecular weight of the said compound (C) is 1,200 or less from the point which reduces the surface asperity of a liquid crystal aligning film. Therefore, it is preferable to set the number of the aromatic amine structures (a) and the chain length of the chain structures (b) so that the molecular weight of the compound (C) falls within the above range. The molecular weight is more preferably 1,000 or less, still more preferably 800 or less.

・ Compound (C1)
The compound (C1) has the aromatic amine structure (a) and the structure (b1). However, in the compound (C1), a reactive group involved in polymerization is not bonded to the aromatic ring group in the aromatic amine structure (a). The reactive group differs depending on the main skeleton of the polymer (P). For example, when the main skeleton of the polymer (P) is polyamic acid or polyimide, the reactive group is an acid anhydride group or a primary amino group In the case of a polyester, the reactive group is a hydroxyl group or a carboxyl group, and in the case of a polyamide, the reactive group is a carboxyl group or a primary amino group.
The description of the compound (C) can be applied to the description of the aromatic ring of the aromatic amine structure (a) possessed by the compound (C1). The number of aromatic amine structures (a) in one molecule of the compound (C1) is preferably one.

The structure (b1) possessed by the compound (C1) is a divalent chain hydrocarbon group having 1 to 5 carbon atoms, and at least one methylene group in the chain hydrocarbon group is —O—, —S—, — ^{CO -, - NR 3 -,} - NR 3 CO -, - COO -, - COS- or -Si _{(CH 3) 2} - a divalent group obtained by replacing, -O -, - S -, - CO-, It is a structure selected from the group consisting of -NR ³ CO-, -COO-, -COS-, and -Si (CH ₃ ) _2- (wherein R ³ is a hydrogen atom or a monovalent organic group). The compound (C1) may have only one of them in the molecule, or two or more of them in the molecule.
As a specific example of a C1-C5 bivalent chain hydrocarbon group in said structure (b1), a methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, vinylene group, propene diyl group, butene diyl group is mentioned, for example And pentendiyl groups. Although these may be linear or branched, they are preferably linear.

The structure (b1) is at least one methylene group in the divalent chain-like hydrocarbon group having 1 to 5 carbon atoms -O -, - S -, - CO -, - NR 3 -, - NR 3 CO When it is a divalent group substituted by-, -COO-, -COS- or -Si (CH ₃ ) _2- , the number of substitutions may be one or more, and is appropriately set according to the number of carbons be able to. The explanation of R in the compound (C) can be applied to the explanation of the monovalent organic group of R ³ .
The number of the structures (b1) in the molecule of the compound (C1) may be one or two or more. Preferably it is 2 or more, and it is especially preferable that it is two. The description of the compound (C) can be applied to the molecular weight of the compound (C1).

The main skeleton of the polymer (P) includes, for example, polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polysiloxane, polyorganosiloxane, cellulose derivative, polyacetal derivative, polystyrene derivative, poly (styrene-phenylmaleimide) derivative And skeletons composed of poly (meth) acrylate derivatives and the like. The polymer (P) can be used by appropriately selecting one or two or more of the polymers selected therefrom in accordance with the application and the like of the liquid crystal aligning agent. In addition, (meth) acrylate is meant to include acrylate and methacrylate. The polymer (P) may have the above-mentioned aromatic amine structure (a) and the above-mentioned chain structure (b) or structure (b1) in any of the main chain and side chain of the polymer, It is preferable to have in the main chain of a union.
The main skeleton of the polymer (P) is preferably at least one selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and the aromatic amine structure (a) and the chain structure (b) above are preferred. It is more preferable that it is at least one selected from the group consisting of a polyamic acid having a structure (b1) in the main chain, a polyimide and a polyamic acid ester. It is preferable that the said polymer (P) is a polymer obtained by using the said compound (C ') for a monomer.

  Here, the “main chain” of the polymer in the present invention refers to a “stem” portion consisting of a chain of the longest atoms in the polymer. In addition, it is acceptable that this "stem" part includes a ring structure. Therefore, “having the above-mentioned aromatic amine structure (a) and the above-mentioned chain structure (b) or structure (b1) in the main chain of the polymer” means that these structures constitute a part of the main chain Say However, in the polymer (P), the aromatic amine structure (a), the chain structure (b) and the structure (b1) are branched from a portion other than the main chain, for example, a side chain It does not exclude what is also present.

[Polyamic acid (P)]
When the polymer (P) is a polyamic acid (hereinafter, also referred to as "polyamic acid (P)"), it can be obtained, for example, by reacting tetracarboxylic acid dianhydride with diamine.

(Tetracarboxylic acid dianhydride)
Examples of the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid (P) include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride, etc. Can be mentioned. Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as butane tetracarboxylic acid dianhydride;
Examples of alicyclic tetracarboxylic acid dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic acid 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- Without 1,2-dicarboxylic acid 3,5,6-Tricarboxy-2-carboxymethyl norbornane-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 anhydride Oxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, bicyclo [2.2.2 Oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, ethylene glycol bis (anhydrotrimellitate), 1 , 3-Propylene glycol bis (an Hydrotrimellitate) etc;
Examples of the aromatic tetracarboxylic acid dianhydride include, for example, pyromellitic acid dianhydride and the like, and besides, tetracarboxylic acid dianhydride described in JP-A-2010-97188 can be used. In addition, as tetracarboxylic acid 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 the tetracarboxylic acid dianhydride used for the synthesis of the above polyamic acid (P), 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, in that the liquid crystal orientation and the solubility in a solvent can be made good. 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -C] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -C] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3'- (tetrahydrofuran-2 ', 5'-dione), 5 -(2, 5-dioxote Rahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxy norbornane-2: 3,5: 6-dianhydride, 4,9-Dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8- It is selected from the group consisting of tetracarboxylic acid dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, 1,3-propylene glycol bis (anhydrotrimellitate) and pyromellitic acid dianhydride It is preferable to include at least one compound (hereinafter, also referred to as “specific tetracarboxylic acid dianhydride”). The amount of the specific tetracarboxylic acid dianhydride used is preferably 5 mol% or more, and more preferably 10 mol% or more, based on the total amount of tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid. It is more preferable that the content be 20 mol% or more.

(Diamine)
The diamine used for the synthesis of the polyamic acid (P) is a diamine having the aromatic amine structure (a) and the chain structure (b) (hereinafter also referred to as "diamine (C)"), and It is preferable to include at least one compound (C ′) selected from the group consisting of a compound (C1) having the above structure (a1) and the above structure (b1).

（式（１）中、Ａ^１及びＡ^３は、それぞれ独立に水素原子又は１価の有機基であり、Ａ^２及びＡ^４は、それぞれ独立に単結合又は２価の有機基である。Ｂ^１及びＢ^２は、それぞれ独立に単結合又は２価の有機基である。ただし、Ｂ^１が単結合である場合、Ａ^１及びＡ^２の少なくとも１個は芳香環で窒素原子に結合しており、Ｂ^１が２価の有機基である場合、Ａ^１、Ａ^２及びＢ^１のうち少なくとも２個は芳香環で窒素原子に結合している。Ｂ^２が単結合である場合、Ａ^３及びＡ^４の少なくとも１個は芳香環で窒素原子に結合しており、Ｂ^２が２価の有機基である場合、Ａ^３、Ａ^４及びＢ^２のうち少なくとも２個は芳香環で窒素原子に結合している。Ｌ^１は、前記構造（ｂ）を含む２価の基である。） ・ Diamine (C)
The diamine (C) preferably has a structure capable of introducing the above-mentioned aromatic amine structure (a) and the above-mentioned chain structure (b) into the main chain of the polymer (P). It is preferable that it is a compound represented by following formula (1).

(In Formula (1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, and A ² and A ⁴ are each independently a single bond or a divalent organic group B. ¹ and B ² each independently represent a single bond or a divalent organic group, provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom When B ¹ is a divalent organic group, at least two of A ¹ , A ² and B ¹ are aromatic rings and are bonded to a nitrogen atom, and when B ² is a single bond, A ³ And at least one of A ⁴ is an aromatic ring bonded to a nitrogen atom, and when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are an aromatic ring and a nitrogen atom L ¹ is a divalent group including the structure (b).

In the above formula (1), as the monovalent organic group in A ¹ and A ³ , for example, a monovalent hydrocarbon group, —O—, —COO—, between carbon-carbon bonds in the monovalent hydrocarbon group, The monovalent group by which functional groups, such as -CO-, -NHCO-, -S-, -NH-, etc. are introduce | transduced, the protecting group of an amino group, etc. are mentioned. Incidentally, in the A ¹ and A ^3, hydrogen atoms bonded to carbon atoms of the hydrocarbon group, a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, iodine etc. iodine atom) may be substituted with or hydroxyl group . Specific examples of the protecting group for amino group include the groups exemplified in the explanation of R in the chain structure (b). Preferably it is t-butoxycarbonyl group.

  As said hydrocarbon group, a chain | strand-shaped hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group are mentioned. Here, in the present specification, the "chain hydrocarbon group" is as described above. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. However, it does not need to be comprised only with the structure of alicyclic hydrocarbon, and the thing which has chain structure in the part is also included. Also, "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed of only an aromatic ring structure, and a part thereof may contain a chain structure or an alicyclic hydrocarbon structure.

Specific examples of the monovalent hydrocarbon group in A ¹ and A ³ include, as a chain hydrocarbon group, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Alkyl groups having 1 to 30 carbon atoms such as nonyl, decyl, dodecyl, tetradecyl and icosanyl; alkenyls having 2 to 30 carbons such as ethenyl, propenyl and butenyl; ethynyl, propynyl and the like And an alkynyl group having 2 to 30 carbon atoms, and the like, which may be linear or branched. Moreover, as an alicyclic hydrocarbon group, for example, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group etc .; As an aromatic hydrocarbon group, for example, a phenyl group, a tolyl group, a benzyl group, a phenethyl group etc .; It can be mentioned.

Examples of the divalent organic group in A ² , A ⁴ , B ¹ and B ² include a divalent hydrocarbon group, and a carbon-carbon bond in a divalent hydrocarbon group, —O—, —COO—, And a divalent group having a functional group such as -CO-, -NHCO-, -S- or -NH- introduced, and the like, and a hydrogen atom bonded to a carbon atom of each of these groups is a halogen atom or a hydroxyl group Etc. may be substituted. As a specific example of a bivalent hydrocarbon group, the group etc. which removed one hydrogen atom from each group illustrated by the above-mentioned monovalent hydrocarbon group are mentioned. In the compound represented by the formula (1), the structure surrounding the nitrogen atom in the formula (1) corresponds to the aromatic amine structure (a).
B ¹ and B ² is preferably at least one of a single bond, and more preferably B ¹ and B ² are both single bonds.

（式（２）中、Ｌ^２及びＬ^３は、それぞれ独立に上記構造（ｂ）である。Ｑは、下記式（３）又は式（４）で表される２価の基である。ｎは０〜４の整数である。「＊」は結合手を示す。）

（式（３）中、Ａ^５は、水素原子又は１価の有機基である。Ｒ^１及びＲ^２は置換基であり、互いに同じでも異なっていてもよい。「＊」は結合手を示す。）

（式（４）中、Ａ^６は、水素原子又は１価の有機基である。「＊」は結合手を示す。） L ¹ is a divalent group containing the above-mentioned chain structure (b). Preferred examples of L ^1, for example, groups represented by the following formula (2).

(In Formula (2), L ² and L ³ are each independently the above structure (b), and Q is a divalent group represented by Formula (3) or Formula (4) below. Is an integer of 0 to 4. "*" indicates a bond.

(In formula (3), A ⁵ is a hydrogen atom or a monovalent organic group. R ¹ and R ² are substituents, which may be the same or different. “*” Represents a bond .)

(In formula (4), A ⁶ represents a hydrogen atom or a monovalent organic group. “*” Represents a bond.)

（式中、「＊」は結合手を示す。） In the above formulas (3) and (4), the explanation of the monovalent organic group of A ¹ and A ³ can be applied as the monovalent organic group of A ⁵ and A ⁶ . It is preferable that n in the said Formula (2) is 0 or 1.
As a specific example of group represented by the said Formula (2), group etc. which are represented by each of following formula (2-1)-formula (2-25) are mentioned, for example.

(In the formula, "*" indicates a bond.)

（式（１−１）中、Ｌ^１１は、炭素数６以上の２価の鎖状炭化水素基における少なくとも１個のメチレン基を−Ｏ−、−Ｓ−、−ＣＯ−、−ＮＲ−、−ＮＲＣＯ−、−ＣＯＯ−、−ＣＯＳ−又は−Ｓｉ（ＣＨ_３）_２−（Ｒは水素原子又は１価の有機基である。）で置き換えた基を含む２価の基である。Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ｂ^１及びＢ^２は、上記式（１）と同義である。ただし、Ｌ^１１が炭素数１〜５のアルカンジイル基を有する場合、Ａ^１及びＡ^３の少なくともいずれかが水素原子であるか、又はＢ^１及びＢ^２の少なくともいずれかが２価の有機基である。）

（式（１−２）中、Ｌ^１２は、炭素数６以上の２価の鎖状炭化水素基を含む２価の基である。Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ｂ^１及びＢ^２は、上記式（１）と同義である。） As a preferable specific example of a compound represented by the said Formula (1), the compound etc. which are represented, for example with a compound represented by a following formula (1-1), a following formula (1-2), etc. are mentioned.

In the formula (1-1), L ¹¹ represents at least one methylene group in a divalent chain hydrocarbon group having 6 or more carbon atoms as —O—, —S—, —CO—, —NR—, A divalent group containing a group substituted by -NRCO-, -COO-, -COS- or -Si (CH ₃ ) _2- (wherein R is a hydrogen atom or a monovalent organic group) A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ² are as defined in the above formula (1), provided that L ¹¹ has an alkanediyl group of 1 to 5 carbon atoms, A ¹ and A ³ Or at least one of B ¹ and B ² is a hydrogen atom, or at least one of B ¹ and B ² is a divalent organic group.

(In Formula (1-2), L ¹² is a divalent group containing a divalent chain hydrocarbon group having 6 or more carbon atoms. A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ² is as defined in the above formula (1).)

L ¹¹ in the above formula (1-1) represents at least one methylene group in a divalent chain hydrocarbon group having 6 or more carbon atoms as —O—, —S—, —CO—, —NR— The group substituted by -NRCO-, -COO-, -COS- or -Si (CH ₃ ) _2- may have only one or a plurality of groups. As a preferable specific example of L ¹¹ , a group represented by the above formula (2) (wherein L ² and L ³ are at least one methylene group in a bivalent chain hydrocarbon group having 6 or more carbon atoms) And -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS-, or -Si (CH ₃ ) _2- .
If L ¹¹ contains an alkanediyl group having 1 to 5 carbon atoms, at least one of ^{A 1} and ^{A 3} is a hydrogen atom, it is preferred that ^{A 1} and ^{A 3} are both hydrogen atoms.

L ¹² in the formula (1-2), to a divalent chain hydrocarbon group having 6 or more carbon atoms which may have only one, or may have a plurality. Preferred examples of L ^12, the equation (2) a group represented by (wherein, L ² and L ³ is a divalent chain hydrocarbon group having at least 6 carbon atoms.) In the like.
In the compound represented by the above formula (1-2), when the alkanediyl group possessed by L ¹² has 6 to 10 carbon atoms, at least one of A ¹ and A ³ is a monovalent organic group, Alternatively, it is preferable that at least one of B ¹ and B ² is a divalent organic group. When A ¹ and A ³ in the above formula (1-1) are hydrogen atoms, L ¹² is a divalent group having 7 or more carbon atoms in which L ² and L ^{3 of the} group represented by the above formula (2) are A chain hydrocarbon group is preferable, and a chain hydrocarbon group having a carbon number of 11 or more is more preferable.

（式中、Ｐｈはフェニル基を示す。） As a preferable specific example of the said diamine (C), the compound etc. which are represented, for example by following formula (DA-1)-formula (DA-10) and each formula (DA-41) can be mentioned. In addition, the said diamine (C) can be used individually by 1 type or in combination of 2 or more types.

(In the formula, Ph represents a phenyl group.)

（式（１−３）中、Ａ^７は水素原子又は１価の有機基であり、Ａ^８及びＡ^９は、それぞれ独立に単結合又は２価の有機基である。ただし、Ａ^７、Ａ^８及びＡ^９のうち少なくとも２個は芳香環で窒素原子に結合している。Ｌ^４は上記構造（ｂ１）であり、Ｌ^５は単結合又は２価の有機基である。） ・ Diamine (C1)
The diamine (C1) preferably has a structure capable of introducing the above-mentioned aromatic amine structure (a) and the above-mentioned structure (b1) into the main chain of the polymer (P). It is preferable that it is a compound represented by Formula (1-3).

(In formula (1-3), A ⁷ is a hydrogen atom or a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond or a divalent organic group, provided that A ⁷ and A are ^At least two of ⁸ and A ⁹ are bonded to the nitrogen atom via an aromatic ring, L ⁴ is the above structure (b 1), and L ⁵ is a single bond or a divalent organic group.

The description of the monovalent organic group of A ¹ and A ³ of the above-mentioned formula (1) can be applied to the above-mentioned formula (1-3) as the monovalent organic group of A ⁷ . As the divalent organic group of A ⁸ and A ⁹ , the description of A ² and A ⁴ of the above formula (1) can be applied. As the divalent organic group of L ⁵ , for example, a divalent linear hydrocarbon group having 1 to 20 carbon atoms, at least one methylene group in the linear hydrocarbon group can be —O—, —S—, — CO—, —NR ⁴ —, —NR ⁴ CO—, —COO—, —COS— or a divalent group replaced by —Si (CH ₃ ) ₂ —, —O—, —S—, —CO—, ^{-NR 4 CO -, - COO -} , - COS-, and _{-Si (CH 3) 2 - (} . R 4 is a hydrogen atom or a monovalent organic group) and the like. Among these, L ⁵ is preferably a structure (b1).
As a preferable specific example of the said diamine (C1), the compound etc. which are represented by each of following formula (DA-22)-a formula (DA-40) etc. can be mentioned, for example. In addition, the said diamine (C1) can be used individually by 1 type or in combination of 2 or more types.

  The diamine used in the synthesis of the polyamic acid (P) may be only the above diamine (C '), but other diamines other than the above may be used in combination with the diamine (C').

Examples of other amines that can be used here include aliphatic diamines, alicyclic diamines, aromatic diamines, diamino organosiloxanes and the like. As specific examples of these, as aliphatic diamines, for example, m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;
As alicyclic diamines, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylamine, 1,7- Bis (4-aminophenoxy) heptane, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4) -Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane Bread, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'- Bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, 1,4-bis -(4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4 -Diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5- Aminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, Cholestyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate Lanthanyl 3,5-diaminobenzoate 3,6-bis (4-aminobenzoyloxy) cholestane 3,6-bis (4-aminophenoxy) cholestane 4- (4'-trifluoromethoxybenzoyloxy) Cyclohexyl-3,5-di Minobenzoate, 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) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1- (1 2,4-diaminophenyl) piperazine-4-carboxylic acid, 1,3-bis (N- (4-aminophen) Piperidinyl) propane, α-amino-ω-aminophenyl alkylene, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-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, 4- (4-aminophenoxycarbonyl) -1- (4-aminophenyl) piperidine, the following formula (DA-18)

（式（Ｄ−１）中、Ｘ^I及びＸ^IIは、それぞれ独立に、単結合、−Ｏ−、＊−ＣＯＯ−又は＊−ＯＣＯ−（＊は式中のベンゼン環に結合する結合手であることを示す。）であり、Ｒ^Ｉは炭素数１〜３のアルカンジイル基であり、Ｒ^ＩＩは単結合又は炭素数１〜３のアルカンジイル基であり、ａは０又は１であり、ｂは０〜２の整数であり、ｃは１〜２０の整数であり、ｄは０又は１である。ただし、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。 And a compound represented by the following formula (D-1)

(In the formula (D-1), X ^I and X ^II each independently represent a single bond, -O-, * -COO- or * -OCO- (where * represents a bond to a benzene ring in the formula a.) indicating that, R ^I is an alkanediyl group having 1 to 3 carbon atoms, R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1. However, a and b can not be 0 simultaneously.)
Compounds and the like;
Examples of diaminoorganosiloxanes include, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and besides, diamines described in JP-A-2010-97188 can be used.

In the above formula (D-1) ^{"-X I - (R I -X II} ) d - " Examples of the divalent group represented by the alkanediyl group having 1 to 3 carbon atoms, * - O -, * -COO- or _{* -O-C 2 H 4 -O-} ( where bond marked with "*" is bonded to the diamino phenyl group.) is preferably. Specific examples of the group _"-C c _{H 2c + 1",} for example, a methyl group, an ethyl group, n- propyl group, n- butyl group, n- pentyl group, n- hexyl, n- heptyl, n- octyl 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 And n-eicosyl group. The two amino groups in the diaminophenyl group are preferably in the 2,4- or 3,5-position relative to the other group.

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、これらの化合物の１種を単独で又は２種以上を適宜選択して使用することができる。 As a specific example of a compound represented by the said Formula (D-1), the compound etc. which are represented by following formula (D-1-1)-(D-1-3), for example can be mentioned.

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

  As for the diamine used for the synthesis | combination of polyamic acid (P) of this invention, it is preferable that the use ratio of the said diamine (C ') shall be 0.5 mol% or more with respect to the total amount of the diamine used for a synthesis | combination. If it is less than 0.5 mol%, the effects of the present invention tend not to be sufficiently obtained. More preferably, it is 2 mol% or more, still more preferably 5 mol% or more, and particularly preferably 10 mol% or more. Moreover, the upper limit of the use ratio of the said diamine (C ') can be arbitrarily set in 100 mol% or less with respect to the total amount of the diamine used for a synthesis | combination. In order to improve the effect of the addition of other diamine (for example, printability, voltage holding ratio, liquid crystal alignment property, etc.), it is preferable to set the use ratio of the above diamine (C ') to 95 mol% or less.

When the liquid crystal aligning agent of the present invention is used to manufacture a TN type, STN type or vertical alignment type liquid crystal display element, at least a part of the polymer (P) to be contained in the liquid crystal aligning agent is pretilted with respect to the coating It may be a polymer having a group capable of imparting horn development ability (hereinafter also referred to as “pretilt angle development group”). As the pretilt angle developing group, for example, an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, And groups having a ring structure.
In order to obtain polyamic acid (P) having a pretilt angle developing group, it is preferable to carry out polymerization including a diamine having a pretilt angle developing group in the monomer composition in terms of the ease of introduction of the pretilt angle developing group . Specifically, it can be synthesized by using a diamine having a pretilt angle developing group as another diamine.
In the case of using a diamine having a pretilt angle developing group in the synthesis of polyamic acid (P), the amount thereof used is 5 moles relative to the total diamine used in the synthesis, from the viewpoint of exhibiting sufficiently high pretilt angle characteristics. % Or more is preferable, and 10 mol% or more is more preferable.

  When giving the liquid crystal aligning ability by the photoalignment method to the coating film produced using the liquid crystal aligning agent of this invention, at least one part of the polymer (P) to be contained in the said liquid crystal aligning agent is a photoalignment structure It is good also as a polymer which has. Here, the photoalignable structure is a concept including both a photoalignable group and a decomposable photoalignment unit. Specifically, as the photoalignable structure, a group which exhibits photoalignability by photoisomerization, photodimerization, photolysis or the like can be adopted. For example, an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton A group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, coumarin The coumarin-containing group which contains a derivative as a basic skeleton, the polyimide containing structure which contains polyimide or its derivative as a basic skeleton, etc. are mentioned.

  For example, when the polyamic acid, the polyimide, and the polyamic acid ester as the polymer (P) have a photoalignable structure, it is preferable to have a decomposable photoalignment portion as the photoalignable structure, specifically, bicyclo 2.2.2] A polymer having an octene skeleton or a cyclobutane skeleton is preferable. By having such a specific skeleton, the liquid crystal alignment of the coating can be further improved. For example, a polyamic acid (P) having a bicyclo [2.2.2] octene skeleton or a cyclobutane skeleton can be selected from bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid It can be obtained by the reaction of a tetracarboxylic acid dianhydride containing at least one of an anhydride and cyclobutanetetracarboxylic acid dianhydride with a diamine containing the above diamine (C ′).

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

As a molecular weight modifier, an acid monoanhydride, a monoamine compound, a monoisocyanate compound etc. can be mentioned, for example. As specific examples of these, as acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic acid Acid anhydrides, n-hexadecylsuccinic acid anhydrides, etc .; as monoamine compounds such as aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine etc. As the monoisocyanate compound, for example, phenyl isocyanate, naphthyl isocyanate and the like can be mentioned, respectively.
The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total of tetracarboxylic acid dianhydride and diamine used.

  The said diamine (C) and diamine (C1) can be synthesize | combined by combining the normal method of organic chemistry suitably. For example, for the compound represented by the above formula (1), for example, a dinitro intermediate having a nitro group in place of the primary amino group in the formula is synthesized, and then the nitro group of the obtained dinitro intermediate is The method of amination is carried out using a suitable reducing system.

The method for synthesizing the above dinitro intermediate can be appropriately selected according to the target compound. As an example thereof, when mention is made of the compound represented by the above formula (1), for example, a method of reacting a secondary amine compound having corresponding A ¹ , A ² and L ¹ with a halogenated nitrobenzene; corresponding A ^1. A method of reacting a halide having A ² and L ¹ with a secondary amine compound containing a nitrophenyl group; a carboxylic acid having a corresponding aminophenyl group and a nitro group, and a diol having a corresponding L ¹ Method of reacting: Method of reacting diamine compound having corresponding A ¹ , A ² and L ¹ with halogenated nitrobenzene having corresponding B ¹ ; hydroxyl group containing compound having corresponding aminophenyl group and nitro group, A method of reacting with the corresponding halide having L ¹ ; and the like.

The reaction to obtain the above nitro intermediate is preferably carried out in an organic solvent. Here, the organic solvent may be any solvent which does not affect the reaction, and examples thereof include methanol, ethanol, tetrahydrofuran, toluene, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and the like. . In addition, the reaction may be carried out in the presence of a catalyst, if necessary.
The reduction reaction of the above dinitro intermediate can be carried out preferably in an organic solvent, for example, using a catalyst such as palladium on carbon, platinum oxide, zinc, iron, tin, nickel and the like. As an organic solvent used here, ethyl acetate, toluene, tetrahydrofuran, alcohol type etc. are mentioned, for example. However, the synthesis procedure of diamine (C) and diamine (C1) is not limited to the said method.

[Synthesis of polyamic acid (P)]
The ratio of tetracarboxylic acid dianhydride and diamine used in the synthesis reaction of the polyamic acid (P) of the present invention is the acid anhydride group of tetracarboxylic acid dianhydride relative to one equivalent of the amino group of diamine. Is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents.
The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and more preferably 0 to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Here, examples of the organic solvent include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like. Specific examples of these organic solvents include, as aprotic polar solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, Hexamethylphosphortriamide etc. as phenolic solvents eg phenol, m-cresol, xylenol, halogenated phenol etc .;
As alcohol, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether etc .; As ketone, for example, acetone, methyl ethyl ketone, methyl isobutyl Ketone, cyclohexanone etc .; as the above ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, isoamyl Propionate, isoamyl isobutyrate etc. as ether; eg 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; as halogenated hydrocarbons, for example, 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 aprotic polar solvents and phenolic solvents (first group of organic solvents), or one or more selected from the first group of organic solvents, It is preferred to use a mixture with one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (the second group of organic solvents). In the latter case, the use ratio of the second group organic solvent is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the first group organic solvent and the second group organic solvent. Or less, more preferably 30% by weight or less. The amount (α) of the organic solvent used is such that the total amount (β) of the tetracarboxylic acid dianhydride and diamine is 0.1 to 50% by weight with respect to the total amount (α + β) of the reaction solution. Is preferred.

  As described above, a reaction solution in which the polyamic acid (P) is dissolved is obtained. The reaction solution may be used as it is for the preparation of a liquid crystal aligning agent, or may be used for the preparation of a liquid crystal aligning agent after isolating the polyamic acid (P) contained in the reaction solution, or the isolated polyamic acid After purifying (P), it may be used for preparation of a liquid crystal aligning agent. When polyamic acid (P) is subjected to dehydration ring closure to form a polyimide, the above reaction solution may be subjected to dehydration ring closure reaction as it is, and after the polyamic acid (P) contained in the reaction solution is isolated, dehydration ring closure is carried out. The reaction may be carried out, or the isolated polyamic acid (P) may be purified and then subjected to a dehydration ring closure reaction. The isolation and purification of the polyamic acid can be carried out according to known methods.

[Polyamic acid ester (P)]
The polyamic acid ester (hereinafter also referred to as polyamic acid ester (P)) as the polymer (P) is, for example, [I] a polyamic acid (P) obtained by the above synthesis reaction, a hydroxyl group-containing compound, Obtained by reacting compound with epoxy compound, compound containing epoxy group, etc., method of reacting [II] tetracarboxylic acid diester with diamine, method of reacting [III] tetracarboxylic acid diester dihalide with diamine, be able to.
In the present specification, the term "tetracarboxylic acid diester" means a compound in which two of four carboxyl groups possessed by a tetracarboxylic acid are esterified and the remaining two are carboxyl groups. The "tetracarboxylic acid diester dihalide" means a compound in which two of four carboxyl groups possessed by the tetracarboxylic acid are esterified and the remaining two are halogenated.

  Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol and propanol; and phenols such as phenol and cresol. Further, as the halide, for example, methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like can be mentioned, and as the epoxy group-containing compound, For example, propylene oxide and the like can be mentioned. The tetracarboxylic acid diester used in the method [II] can be obtained by ring-opening tetracarboxylic acid dianhydride using the above-mentioned alcohols. Also, the tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride. It is preferable that the diamine used by method [II] and [III] contains the said diamine (C '), and may use the said other diamine as needed. In addition, polyamic acid ester (P) may have only an amic acid ester structure, and may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.

[Polyimide (P)]
The polyimide as the polymer (P) (hereinafter, also referred to as polyimide (P)) can be obtained, for example, by dehydration ring closure and imidization of the polyamic acid (P) synthesized as described above .

  The polyimide (P) may be a completely imidized product in which all of the amic acid structure possessed by its precursor, polyamic acid (P), has been dehydrated and closed in a ring, and may be a completely imidized compound. Or a partial imidate in which an amic acid structure and an imide ring structure coexist. The imidation ratio of the polyimide contained in the liquid crystal aligning agent of the present invention is preferably 30% or more, more preferably 40 to 99%, and still more preferably 50 to 99%. The imidation ratio is a percentage representing the ratio of the number of imide ring structures to the total number of amic acid structures of polyimide and the number of imide ring structures. Here, part of the imide ring may be an isoimide ring.

  The dehydration ring closure of polyamic acid is preferably performed by a method of heating polyamic acid or a method of dissolving polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to this solution, and heating as necessary. . Among these, the latter method is preferred.

  In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to a solution of the above polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride and the like can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 moles relative to 1 mole of the polyamic acid's amic acid structure. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydrating ring closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. As an organic solvent used for a dehydration ring-closing reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. 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.

  Thus, a reaction solution containing polyimide (P) is obtained. The reaction solution may be used as it is for the preparation of a liquid crystal aligning agent, or may be used for the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring closure catalyst from the reaction solution. It may be subjected to the preparation of the alignment agent, or it may be subjected to the preparation of the liquid crystal alignment agent after purifying the isolated polyimide. These purification procedures can be performed according to known methods. In addition, polyimide (P) can also be obtained by imidation of polyamic acid ester (P).

The polyamic acid, polyamic acid ester and polyimide as the polymer (P) obtained as described above have a solution viscosity of 20 to 1,800 mPa · s when this is made into a solution with a concentration of 15% by weight Is more preferable, and it is more preferable to have a solution viscosity of 50 to 1,500 mPa · s. In addition, the solution viscosity (mPa · s) of the above polymer is a polymer solution having a concentration of 15% by weight prepared using a good solvent of the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) It is the value measured at 25 ° C. using an E-type viscometer.
The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the above polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, more preferably 2,000. 300,000. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. By being in such a molecular weight range, good alignment and stability of the liquid crystal display element can be secured.

<Other ingredients>
The liquid crystal aligning agent of the present invention contains the polymer (P) as described above, but may contain other components as required. As such other components, for example, polymers other than the above-mentioned polymer (P), compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compounds"), functional silane compounds And metal chelate compounds, curing accelerators, surfactants and the like.

[Other polymers]
The above other polymers can be used to improve solution properties and electrical properties. Examples of such other polymers include polymers obtained without using the above compound (C ′), and the main skeleton thereof is not particularly limited. Specifically, for example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate and the like as a main skeleton The polymer etc. which it has can be mentioned.
When the other polymer is added to the liquid crystal aligning agent, the blending ratio is preferably 50 parts by weight or less with respect to 100 parts by weight in total of the polymers contained in the liquid crystal aligning agent, The amount is more preferably 40 parts by weight, and further preferably 0.1 to 30 parts by weight or less.

  In addition, when the liquid crystal aligning ability is imparted to the coating film formed using the liquid crystal aligning agent of the present invention by a photoalignment method, a polymer having a photoalignment structure may be used as the other polymer. For example, in the case of a liquid crystal aligning agent for retardation film, a polymer having a photoalignable group can be preferably used as a photoalignable structure, and specifically, it has a cinnamic acid structure (cinnamic acid or its derivative) The polymer etc. which group was introduce | transduced are mentioned. Among them, polyorganosiloxanes having a cinnamic acid structure can be preferably used in that it is easy to introduce a photoalignable group into a polymer.

The polymer having a photoalignable group can be synthesized by a conventionally known method. For example, a polyorganosiloxane having a photoalignable group as another polymer comprises a polyorganosiloxane having an epoxy group and a carboxylic acid having a photoalignable group, preferably an organic solvent such as an ether, an ester, or a ketone It can be synthesized by reacting in the presence of a catalyst such as a quaternary ammonium salt.
When the liquid crystal alignment ability is imparted to the coating film by the photo alignment method, the use ratio of the polymer having the photo alignment structure (when the polymer (P) and the other polymers have the photo alignment structure, The total amount) is preferably 3% by weight or more, more preferably 5 to 100% by weight, and more preferably 10 to 100% with respect to the total amount of the polymer used for the preparation of the liquid crystal aligning agent of the present invention. It is more preferable to set it as weight%.

[Epoxy group-containing compound]
An epoxy group containing compound can be used in order to improve the adhesiveness with the substrate surface in a liquid crystal aligning film, and an electrical property. Examples of such an 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, glycerine diglycidyl ether, trimethylolpropane triglycidyl ether, 2, 2-dibromo neopentyl glycol diglycidyl ether, N, N, N ', N'- tetraglycidyl-m-xylylene di Amine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diamide Diphenylmethane, N, N-diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane, N, N-diglycidyl - may be mentioned as being preferred and cyclohexylamine. In addition, as an example of an epoxy-group containing compound, the epoxy-group-containing polyorganosiloxane of WO2009 / 096598 can be used.
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 based on 100 parts by weight in total of the polymers contained in the liquid crystal aligning agent. It is more preferable that the amount be 30 to 30 parts by weight.

[Functional Silane Compound]
The functional silane compound can be used for the purpose of improving the printability of the liquid crystal aligning agent. Such functional silane compounds include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) ) 3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl -3, 6- Methyl azanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycide And xylpropyltrimethoxysilane and the like.
When these functional silane compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 2 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent, and 0.02 It is more preferable that the amount be about 0.2 parts by weight.

[Metal chelate compound]
When the polymer component of the liquid crystal aligning agent has an epoxy structure, the above-mentioned metal chelate compound is a liquid crystal aligning agent for the purpose of securing the mechanical strength of a film formed by low temperature treatment (in particular, liquid crystal for retardation film) Contained in the alignment agent). As the metal chelate compound, it is preferable to use an acetylacetone complex or an acetoacetic acid complex of a metal selected from aluminum, titanium and zirconium. Specifically, for example, diisopropoxyethylacetoacetate aluminum, tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetonate) Titanium, tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium and the like can be mentioned. When the metal chelate compound is added, the use ratio thereof is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, based on 100 parts in total of the components including the epoxy structure. More preferably, it is 1 to 30 parts by weight.

[Hardening accelerator]
The curing accelerator is a liquid crystal for securing temporal stability of mechanical strength and liquid crystal alignment of a liquid crystal alignment film to be formed when the polymer component in the liquid crystal alignment agent has an epoxy structure. It is contained in an alignment agent (in particular, a liquid crystal alignment agent for retardation film). As the said hardening accelerator, the compound which has a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic anhydride group etc. can be used, for example, Especially a phenol group or a silanol group The compound which has is preferable. Specific examples thereof include, as compounds having a phenol group, for example, cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol and the like; and as compounds having a silanol group, for example, trimethylsilanol, triethylsilanol, 1 And 1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis (hydroxydimethylsilyl) benzene, triphenylsilanol, tri (p-tolyl) silanol, diphenylsilanediol, etc. be able to. When a curing accelerator is added, its use ratio is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, based on 100 parts in total of the components including the epoxy structure. Preferably, it is 1 to 30 parts by weight.

[Surfactant]
The surfactant can be contained in a liquid crystal aligning agent (in particular, a liquid crystal aligning agent for a retardation film) for the purpose of improving the coatability of the liquid crystal aligning agent on a substrate. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, fluorine-containing surfactants and the like. 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, based on 100 parts by weight of the total amount of the liquid crystal aligning agent.
In addition to the above, as other components, a compound having at least one oxetanyl group in the molecule, an antioxidant and the like can be mentioned.

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

  As an organic solvent to be used, for example, 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 methoxy propionate, ethyl ethoxy propionate, 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 combination 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. , Preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described later, and preferably heated to form a coating film which is a liquid crystal alignment film or a coating film which becomes a liquid crystal alignment film. 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, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coatability decreases. There is a tendency.

  The particularly preferable solid concentration range varies depending on the application of the liquid crystal aligning agent and the method used when applying the liquid crystal aligning agent to the substrate. For example, when a liquid crystal aligning agent for a liquid crystal alignment film is applied to a substrate by a spinner method, solid content concentration (the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) Is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable to set the solid content concentration in the range of 3 to 9% by weight and thereby to set the solution viscosity in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable to set the solid content concentration in the range of 1 to 5% by weight and thereby to set the solution viscosity in the range of 3 to 15 mPa · s. The temperature at the time of preparing the liquid crystal aligning agent of the present invention is preferably 10 to 50 ° C., more preferably 20 to 30 ° C. Moreover, about the liquid crystal aligning agent for retardation films, solid content concentration of a liquid crystal aligning agent is 0.2 to 10 weight% from a viewpoint of making coating property of a liquid crystal aligning agent, and the film thickness of the coating film formed appropriate. Is preferably in the range of 3 to 10% by weight.

  In addition, according to the liquid crystal aligning agent containing the said polymer (P), it is clear as a result of examination of this inventor that the surface can form a flat (the surface asperity is favorable) coating film. Although the reason is not necessarily clear, it estimates as follows. When the aromatic amine structure (a) is introduced to improve the performance of DC residual relaxation, in addition to the increase in crystallinity, it is considered that aggregation (crystallization) is facilitated by the polymer becoming rigid. In this case, it is assumed that polymer chains are intertwined at the time of coating film formation to cause a decrease in the surface asperity of the coating film. On the other hand, in the polymer (P) obtained by using the compound (C) for the reaction, a chain structure (b) having a sufficiently long chain length is introduced as a spacer unit together with the aromatic amine structure (a) Thus, it is considered that the entanglement of polymer chains is released by heating (post-baking) at the time of coating film formation, and the surface asperity of the coating film after heating is improved. Moreover, it is estimated that the said effect was acquired also about the polymer (P) obtained by using a compound (C1) for reaction for the same reason.

<Liquid crystal display element and retardation film>
A liquid crystal aligning film can be manufactured by using the liquid crystal aligning agent of this invention demonstrated above. Moreover, the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention can be preferably applied to the liquid crystal aligning film for liquid crystal display elements, and the liquid crystal aligning film for retardation films. Hereinafter, the liquid crystal display element and the retardation film of the present invention will be described.

[Liquid crystal display element]
The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed using the liquid crystal alignment 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. Can be applied to the driving method of The liquid crystal display element of the present invention can be produced, for example, by the following steps (I-1) to (I-3). Process (I-1) differs in the use board | substrate by the desired operation mode. Steps (I-2) and (I-3) are common to each operation mode.

[Step (I-1): Formation of Coating Film]
First, the liquid crystal aligning agent of the present invention is coated on a substrate, and then the coated surface is heated to form a coating film on the substrate.
(I-1A) For example, when manufacturing a TN type, STN type or VA type liquid crystal display element, first, each transparent conductive film is formed by using two substrates provided with the patterned transparent conductive film as a pair. On the surface, the liquid crystal aligning agent of the present invention is preferably applied by offset printing, spin coating, roll coating or inkjet printing. As the substrate, for example, glass such as float glass and soda glass; transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and poly (alicyclic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, a 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. It can be used. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo etching after forming a non-patterned transparent conductive film; a method of using a mask having a desired pattern when forming a transparent conductive film; And so on. At the time of application of 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 and a functional titanium compound are formed on the surface of the substrate surface on which the coating film is formed. It is possible to pre-treat application etc. beforehand.

  After the application of the liquid crystal alignment agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal alignment agent. The prebake 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, more preferably 0.5 to 5 minutes. Thereafter, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and optionally thermally imidizing the amic acid structure present in the polymer. The baking temperature (post-baking temperature) at this time is preferably 80 to 300 ° C., more preferably 120 to 250 ° C. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

  When manufacturing a liquid crystal display element of (I-1B) IPS type or FFS type, the electrode formation surface of the substrate in which the electrode which consists of a transparent conductive film or a metal film patterned in the shape of a comb is provided, and an electrode are provided. The liquid crystal aligning agent of the present invention is applied to one side of the opposite substrate which has not been treated, and then the coated surface is heated to form a coating film. The material of the substrate and the transparent conductive film used at this time, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or metal film, the pretreatment of the substrate, and the preferred thickness of the coating film formed It is the same as (I-1A). For example, a film made of a metal such as chromium can be used as the metal film.

  In any case of the above (I-1A) and (I-1B), after the liquid crystal aligning agent is applied on the substrate, the organic solvent is removed to form a coating film to be an alignment film. 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 imidation polymer having an imide ring structure and an amic acid structure, The dehydrating ring closure reaction may be advanced by further heating after the formation of the coating film to make a more imidized coating film.

[Step (I-2): Orientation ability-imparting treatment]
In the case of producing a TN type, STN type, IPS type or FFS type liquid crystal display device, the coating film formed in the step (I-1) is subjected to a treatment for imparting liquid crystal alignment ability. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. As the treatment, for example, rubbing treatment is performed such that the coating film is rubbed in a fixed direction with a roll wound with a cloth made of fibers such as nylon, rayon, cotton, etc. Can be mentioned. On the other hand, in the case of producing a VA-mode liquid crystal display element, the coating film formed in the above step (I-1) can be used as it is as a liquid crystal alignment film, May be

In the light alignment treatment, for example, ultraviolet light and visible light including light having a wavelength of 150 to 800 nm can be used as radiation for irradiating the coating film. If the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed from the direction perpendicular to the substrate surface, may be performed from an oblique direction, or may be performed in combination. In the case of irradiating non-polarized radiation, the direction of the irradiation is oblique.
As a light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser and the like can be used. Ultraviolet light in a preferred wavelength range can be obtained by means of using a light source in combination with, for example, a filter, a diffraction grating or the like. The dose of radiation is preferably 100 to 50,000 J / m ² , more preferably 300 to 20,000 J / m ² . In addition, light irradiation of the coating may be performed while heating the coating to enhance the reactivity. The temperature upon heating is usually 30 to 250 ° C, preferably 40 to 200 ° C, and more preferably 50 to 150 ° C.

  The liquid crystal alignment film after rubbing treatment is further irradiated with ultraviolet light to a part of the liquid crystal alignment film to change the pretilt angle of a part of the liquid crystal alignment film, or The resist film may be formed on the portion, and the rubbing treatment may be performed in a direction different from the rubbing treatment described above, and then the resist film may be removed to make the liquid crystal alignment film have 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. The liquid crystal alignment film suitable for a VA type liquid crystal display element can be suitably used also for a liquid crystal display element of PSA (Polymer sustained alignment) type.

[Step (I-3): Construction of Liquid Crystal Cell]
Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal is disposed between two substrates disposed opposite to each other to manufacture a liquid crystal cell. For example, the following two methods may be mentioned to manufacture a liquid crystal cell. The first method is a conventionally known method. First, two substrates are disposed opposite to each other with a gap (cell gap) in such a manner that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded using a sealing agent. After the liquid crystal is injected and filled in the cell gap partitioned by the above, the liquid crystal cell can be manufactured by sealing the injection hole. The second method is a method called ODF (One Drop Fill) method. For example, a UV-curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and then liquid crystal is dropped on a predetermined number of places on the liquid crystal alignment film. After that, the other substrate is pasted together so that the liquid crystal alignment film faces each other, 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 sealing agent. be able to. Regardless of which method is used, the liquid crystal cell manufactured 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 to remove the flow alignment at the time of liquid crystal filling. It is desirable to do.

  As the sealing agent, for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals Biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals, and the like can be used. In addition, cholesteric liquid crystals such as colestil chloride, cholesteryl nonaate, cholesteryl carbonate, and the like; and chiral agents such as those sold under the trade names "C-15" and "CB-15" (manufactured by Merck). And ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate may be added and used.

  Then, a polarizing plate is attached to the outer surface of the liquid crystal cell, whereby the liquid crystal display element of the present invention can be obtained. As a polarizing plate to be bonded to the outer surface of a liquid crystal cell, the polarizing plate or H film itself is a polarizing film called “H film” which absorbs iodine while drawing and orienting polyvinyl alcohol, sandwiched by a cellulose acetate protective film The polarizing plate which consists of can be mentioned.

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

[Step (II-1): Formation of Coating Film by Liquid Crystal Alignment Agent]
First, the liquid crystal aligning agent of the present invention is coated on a substrate to form a coating film. As a substrate used here, a transparent substrate made of a synthetic resin such as triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyamide, polyimide, polymethyl methacrylate, polycarbonate etc. is preferably exemplified. Can. Among these, TAC is generally used as a protective layer of a polarizing film in a liquid crystal display element. In addition, polymethyl methacrylate can be preferably used as a substrate for a retardation film in that the solvent has low hygroscopicity, good optical properties, and low cost. In addition, to the board | substrate used for application | coating of a liquid crystal aligning agent, in order to make the adhesiveness of a substrate surface and a coating film further favorable, the conventionally well-known pretreatment is carried out to the surface which forms a coating film among substrate surfaces. It may be implemented.

  Retardation films are often used in combination with polarizing films. At this time, in order to exhibit desired optical characteristics, it is necessary to precisely control the angle with respect to the polarization axis of the polarizing film in a specific direction to bond the retardation film. Therefore, here, by forming a liquid crystal alignment film having liquid crystal alignment ability in the direction of a predetermined angle on a substrate such as a TAC film or polymethyl methacrylate, the retardation film is controlled on the polarizing film while controlling the angle. The step of bonding can be omitted. Further, this can contribute to the improvement of the productivity of the liquid crystal display element. In order to form a liquid crystal alignment film having liquid crystal alignment ability in the direction of a predetermined angle, it is preferable to carry out by a photo alignment method using the liquid crystal alignment agent of the present invention.

The application of the liquid crystal alignment agent onto the substrate can be carried out by an appropriate application method, for example, roll coater method, spinner method, printing method, ink jet method, bar coater method, extrusion die method, direct gravure coater method, chamber Doctor coater method, offset gravure coater method, single roll kiss coater method, reverse kiss coater method using small diameter gravure roll, three reverse roll coater method, four 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 or the like can be employed.
After coating, the coated surface is heated (baked) to form a coating. The heating temperature at this time is preferably 40 to 150 ° C., and more preferably 80 to 140 ° C. The heating time is preferably 0.1 to 15 minutes, and more preferably 1 to 10 minutes. The film thickness of the coating film formed on the substrate is preferably 1 to 1,000 nm, more preferably 5 nm to 500 nm.

[Step (II-2): Light Irradiation Step]
Next, the coating film formed on the substrate as described above is irradiated with light to impart liquid crystal alignment ability to the coating film. Here, the description of the photoalignment treatment in the step (I-2) can be applied to the wavelength of light to be irradiated, the type of light, and the description of the light source to be used. The dose of light is preferably in a 0.1~1,000mJ / cm ^2, more preferably to 1 to 500 mJ / cm ^2, and more preferably be 2~200mJ / cm ^2.

[Step (II-3): Formation of Liquid Crystal Layer]
Next, a polymerizable liquid crystal is applied and cured on the coating film after the light irradiation as described above. Thereby, a coating film (liquid crystal layer) containing a polymerizable liquid crystal is formed. The polymerizable liquid crystal used herein is a liquid crystal compound or a liquid crystal composition which is polymerized by at least one treatment of heating and light irradiation. As such a polymerizable liquid crystal, conventionally known ones can be used. Specifically, for example, non-patent document 1 (“UV-curable liquid crystal and its application”, liquid crystal, Volume 3, No. 1 (1999) And pp. 34-42). In addition, it may be a cholesteric liquid crystal, a discotic liquid crystal, a twisted nematic alignment liquid crystal to which a chiral agent is added, or the like. 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, a suitable solvent and the like.
In order to apply the above polymerizable liquid crystal on a coating film formed using a liquid crystal aligning agent, for example, an appropriate coating method such as a bar coater method, a roll coater method, a spinner method, a printing method It can be adopted.

Next, the coating film of the polymerizable liquid crystal formed as described above is cured by one or more treatments selected from heating and light irradiation to form a liquid crystal layer. It is preferable to perform these treatments in a superimposed manner since good orientation can be obtained.
The heating temperature of the coating film should be appropriately selected according to the type of polymerizable liquid crystal to be used. For example, when using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40-80 ° C. The heating time is preferably 0.5 to 5 minutes.
As the irradiation light, non-polarized ultraviolet light 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 according to the desired optical characteristics. For example, in the case of producing a half-wave plate in visible light with a wavelength of 540 nm, the 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 capable of obtaining the desired retardation is different depending on the optical properties of the polymerizable liquid crystal used. For example, when using RMS 03-013C manufactured by Merck, the thickness for producing 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 device. 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, and known examples such as TN type, STN type, IPS type, FFS type and VA type It can be applied to various methods. The retardation film is used by sticking the surface of the retardation film on the substrate side to the outer surface of the polarizing plate disposed on the viewing side of the liquid crystal display element. Accordingly, it is preferable to use a mode in which the substrate of the retardation film is made of TAC or an acrylic substrate, and the substrate of the retardation film also functions as a protective film of the polarizing film.

  Here, there is a roll-to-roll method as a method of producing a retardation film on an industrial scale. In this method, a film is unwound from a roll of a long base film, and a liquid crystal alignment film is formed on the unrolled film, and a polymerizable liquid crystal is applied and cured on the liquid crystal alignment film. The process and the process of laminating the protective film as needed are performed in successive steps, and the film after these steps is collected as a wound body. The retardation film formed using the liquid crystal aligning agent of the present invention has good adhesion to the substrate, and the liquid crystal alignment film and the substrate are less likely to be peeled off even when stored as a wound body. Therefore, the fall of the product yield in the case of manufacturing retardation film by a roll to roll system can be controlled.

  The liquid crystal display device of the present invention can be effectively applied to various devices. For example, clocks, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various types It can be used for various display devices such as monitors, liquid crystal televisions, and information displays.

  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples.

In the following examples and synthesis examples, the weight average molecular weight Mw, the imidation ratio and the epoxy equivalent of the polymer, 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 conversion value measured by GPC under the following conditions.
Column: Tosoh Corp. TSKgel GRC XLII
Solvent: tetrahydrofuran, or lithium bromide and phosphoric acid containing N, N-dimethylformamide solution Temperature: 40 ° C.
Pressure: 68 kgf / cm ²
[Imidation rate of polymer]
A solution containing a polyimide is introduced into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature and then dissolved in deuterated dimethyl sulfoxide to measure ¹ H-NMR 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 formula (EX-1).
Imidation ratio (%) = (1−E ¹ / E ² × α) × 100 (EX-1)
(In the formula (EX-1), E ¹ is a proton-derived peak area of an NH group appearing near a chemical shift of 10 ppm, E ² is a peak area derived from other protons, and α is a precursor of a polymer ( It is the number ratio of other protons to one proton of NH group in polyamic acid).
[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 Compound (C)>
Synthesis Example 1-1 Synthesis of Compound (DA-1)
The compound (DA-1) was synthesized according to the following scheme 1. In addition, in formula, Bn shows a benzyl group (following the same).

The first step reaction was synthesized by the Williamson reaction. First, in a 2 L three-necked flask equipped with a dropping funnel, 83.7 g (0.2 mol) of N-benzyl-4-hydroxyaniline, 46 g (0.42 mol) of 1,5-dibromopentane, cesium fluoride 121. 5 g (0.8 mol) and 800 mL of dimethylformamide were mixed and dissolved, and the reaction was carried out by stirring at 60 ° C. for 4 hours. After the reaction, 2000 mL of ethyl acetate was added for extraction, and 200 mL of distilled water was added for liquid separation and purification. The above extraction and purification process is repeated five times, and then the solvent is removed from the organic layer by distillation under reduced pressure to obtain 76.4 g (0.0 g) of a dibenzyl intermediate (a compound represented by the above formula (DA-1-1). 16 moles) were obtained.
The second step reaction was synthesized by Ullmann condensation reaction. In a 2 L three-necked flask under a nitrogen stream, 76.4 g (0.16 mol) of the above dibenzyl intermediate (DA-1-1), 81.5 g (0.33 mol) of 4-iodonitrobenzene, 59 g (0 N) of phenanthroline .33 mol), 139 g (0.65 mol) of tripotassium phosphate, 9.4 g (0.05 mol) of copper iodide and 600 mL of dimethylacetamide, mixed and dissolved, and the reaction is stirred for 24 hours under reflux. went. After completion of the reaction, the reaction solution was filtered to remove the catalyst, and then the filtrate was poured into 2000 mL of distilled water to precipitate crystals. The precipitated solid was collected by filtration, washed thoroughly with ethanol, and recrystallized from tetrahydrofuran to obtain 35 g (0.05 mol) of a nitro intermediate (compound represented by the above formula (DA-1-2)) .
The third reaction was synthesized by hydrogen reduction. Under a nitrogen stream, add 35 g of the above nitro intermediate (DA-1-2), 3 g of 5% Pd / C, 50 mL of ethanol, 50 mL of tetrahydrofuran and 35 mL of hydrazine monohydrate in a 500 mL three-necked flask with hydrogen It replaced and reacted at room temperature in the presence of hydrogen. The reaction was followed by HPLC, and after confirming the progress of the reaction, it was filtered. 1000 mL of ethyl acetate was added to the filtrate, and 100 mL of distilled water was added thereto to separate and purify. After repeating the above extraction and purification five times, a solid was precipitated by removing the solvent from the organic layer by distillation under reduced pressure. The precipitated solid was recrystallized from a mixed solvent of tetrahydrofuran and ethanol to obtain 18.5 g (0.04 mol) of a compound (DA-1).

Synthesis Example 1-2 Synthesis of Compound (DA-2)
According to the following scheme 2, compound (DA-2) was obtained using the same synthesis reaction formula as compound (DA-1).

Synthesis Example 1-3 Synthesis of Compound (DA-3)
According to the following scheme 3, compound (DA-3) was obtained using the same synthesis reaction procedure as compound (DA-1). The reaction of the second step was synthesized using the method described in Non-Patent Document 2 (The Journal of Organic Chemistry, 2002, 67, 6479).

Synthesis Example 1-4 Synthesis of Compound (DA-4)
According to the following scheme 4, compound (DA-4) was obtained using the same synthesis reaction procedure as compound (DA-1). The reaction of the second step was synthesized by hydrolysis, and the third step was synthesized by a condensation reaction with 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride.

Synthesis Example 1-5 Synthesis of Compound (DA-5)
According to the following scheme 5, compound (DA-5) was obtained using the same synthesis reaction procedure as compound (DA-1).

Synthesis Example 1-6 Synthesis of Compound (DA-6)
According to the above-mentioned scheme 6, compound (DA-6) was obtained using the synthetic reaction formula similar to compound (DA-1).

Synthesis Example 1-7 Synthesis of Compound (DA-7)
According to the following scheme 7, compound (DA-7) was obtained using the same synthesis reaction procedure as compound (DA-1).

Synthesis Example 1-8 Synthesis of DA-8
According to the following scheme 8, compound (DA-8) was obtained using the same synthesis reaction procedure as compound (DA-1). The first step in the synthesis of the mononitromonoiodo intermediate (the compound represented by the above formula (DA-8-1)) is synthesized by the Friedel-Crafts reaction, and the second step is the strong acid trifluoromethanesulfone. It was synthesized using the reduction reaction of the silane carbonyl group with triethylsilane in the presence of an acid.

Synthesis Example 1-9 Synthesis of Compound (DA-9)
According to the following scheme 9, compound (DA-9) was obtained using the same synthesis reaction procedure as compound (DA-1).

Synthesis Example 1-10 Synthesis of Compound (DA-10)
According to the following scheme 10, compound (DA-10) was obtained using the same synthesis reaction procedure as compound (DA-1). The first step in the synthesis of mononitromonohydroxy intermediate (the compound represented by the above formula (DA-10-1)) is synthesized by the Friedel-Crafts reaction, and the second step is the removal of the methoxy group by lithium bromide. The third step was synthesized using a reduction reaction of a silane carbonyl group with triethylsilane in the presence of trifluoromethanesulfonic acid which is a strong acid.

［合成例１−１２；化合物（ＤＡ−２３）の合成］
下記スキーム１２に従い、化合物（ＤＡ−２２−１）を亜鉛存在下、水を触媒として還元することにより化合物（ＤＡ−２３）を得た。

<Synthesis of Compound (C1)>
Synthesis Example 1-11 Synthesis of Compound (DA-22)
According to the following scheme 11, compound (DA-22) was obtained. In the first stage synthesis, Kneenner gel reaction was performed to obtain an intermediate (a compound represented by the following formula (DA-22-1)). In the second step, reduction was carried out in the same manner as for compound (DA-1).

Synthesis Example 1-12 Synthesis of Compound (DA-23)
According to the following scheme 12, compound (DA-23) was reduced using water as a catalyst in the presence of zinc to obtain compound (DA-23).

<Synthesis of polymer>
・ Synthesis of polyamic acid [Synthesis example 2-1; Synthesis of polymer (PAm-1)]
Into a reaction vessel, tetracarboxylic acid dianhydride and diamine are charged at a mixing ratio (mol part) described in Table 1 below so that the total weight is 30 g, and N-methyl-2-pyrrolidone (NMP) 170 g was added and dissolved, and the reaction was carried out at 60 ° C. for 6 hours. The resulting reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The collected precipitate was washed with methanol and then dried at 40 ° C. under reduced pressure for 15 hours to obtain a polymer (PAm-1). The numerical values in Table 1 indicate, for tetracarboxylic acid dianhydrides, the use ratio (mol%) to the total amount of tetracarboxylic acid dianhydrides used in the reaction, and for diamines, the diamine used for the reaction The usage ratio (mol%) to the total amount of Next, the polymer (PAm-1) obtained above was dissolved in NMP so as to be 15% by weight, and the viscosity of each solution was measured. The measurement results are shown together in Table 1 below. Further, when the polymer solution obtained above was allowed to stand at 20 ° C. for 3 days, it did not gel, and the storage stability was good.

Synthesis Example 2-2 to Synthesis Example 2-18 Synthesis of Polymer (PAm-2) to Polymer (PAm-18)
The same operation as in Synthesis Example 2-1 is carried out except that the mixing ratio of tetracarboxylic acid dianhydride and diamine is changed to the numerical values described in Tables 1 and 2 below, and the polymer (PAm-2) to the polymer (PAm) -18) were obtained respectively. The solution viscosity of each polymer was measured in the same manner as in Synthesis Example 2-1. The results are shown in Tables 1 and 2 below. In addition, each of the polymer solutions obtained above was left to stand at 20 ° C. for 3 days, except that the polymer (PAm-14) was not gelled at all, and the storage stability was good. . The polymer (PAm-14) proceeded to gelation and was no longer flowable.

・ Synthesis of polyimide [Synthesis example 3-1; Synthesis of polymer (PIm-1)]
A tetracarboxylic acid dianhydride and a diamine are added at a mixing ratio (mol part) described in Table 2 below so that the total weight is 30 g, and further 170 g of NMP is added to carry out the same operation as in Synthesis Example 2-1. The acid was synthesized. Next, 200 g of NMP was added, and pyridine and acetic anhydride were added in the amounts shown in Table 2 below (the numerical values indicate the molar parts relative to a total of 100 molar parts of acid dianhydride), and the ring closure was dehydrated at 80 ° C for 6 hours. Did. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The collected precipitate was washed with methanol and then dried at 40 ° C. under reduced pressure for 15 hours to obtain a polymer (PIm-1).
Next, the polymer (PIm-1) obtained above was dissolved in NMP so as to be 15% by weight, and the viscosity of each solution was measured. The imidation ratio was also measured. The measurement results are shown in Table 2 below. Furthermore, when the polymer solution obtained above was left to stand at 20 ° C. for 3 days, it did not gel, and the storage stability was good.

Synthesis Example 3-2 Synthesis of Polymer (PIm-2)
A polymer (PIm-2) was obtained in the same manner as in Synthesis Example 3-1 except that the mixing ratio of the tetracarboxylic acid dianhydride and the diamine was changed to the numerical values described in Table 2 below. The solution viscosity of the polymer (PIm-2) was measured in the same manner as in Synthesis Example 3-1, and the measurement results of the imidation ratio are also shown in Table 2 below. Further, when the polymer solution obtained above was allowed to stand at 20 ° C. for 3 days, it did not gel, and the storage stability was good.

Abbreviations of the compounds in Tables 1 and 2 have the following meanings. Further, in Table 2, with regard to the numerical values of pyridine and acetic anhydride, the mole parts with respect to a total of 100 mole parts of tetracarboxylic acid dianhydride used in the reaction are shown.
(Tetracarboxylic acid dianhydride)
AN-1; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride AN-2; pyromellitic acid dianhydride AN-3; 2,3,5-tricarboxycyclopentylacetic acid dianhydride AN-4; Ethylenediaminetetraacetic acid dianhydride AN-5; 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1 , 3-dione AN-6; bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride AN-7; 1,3-propylene glycol Bis (anhydro trimellitate)
AN-8; 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride

(Diamine)
DA-11; 1,7-bis (4-aminophenoxy) heptane DA-12; 4,4'-diaminodiphenylamine DA-13; compound DA-14 represented by the following formula (DA-13); Compound DA-15 represented by DA-14); Compound DA-16 represented by the following formula (DA-15); 4,4'-diaminodiphenylmethane DA-17; 4-aminophenyl-4'-aminobenzoate DA-18; Compound DA-19 represented by the above formula (DA-18); 4- (4-aminophenoxycarbonyl) -1- (4-aminophenyl) piperidine DA-20; 4- (tetradecaoxy) Benzene-1,3-diamine DA-21; cholestanyl 3,5-diaminobenzoate

. Synthesis of photoalignable group-containing polyorganosiloxane [Synthesis example 4-1; Synthesis of polymer (PSi-1)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine are charged, and room temperature Mixed. After 100 g of deionized water was added dropwise from a dropping funnel over 30 minutes, the reaction was carried out at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer is taken out and washed with a 0.2 wt% aqueous ammonium nitrate solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to obtain an oxiranyl group. The polyorganosiloxane was obtained as a viscous clear liquid. The ¹ H-NMR analysis of the polyorganosiloxane having the oxiranyl group showed that a peak based on the oxiranyl group was obtained in the vicinity of the chemical shift (δ) = 3.2 ppm according to the theoretical strength. It was confirmed that no side reaction had occurred. It was 186 g / equivalent when the epoxy equivalent of the polyorganosiloxane which has this oxiranyl group was measured.
Next, in a 100 mL three-necked flask, 9.3 g of the polyorganosiloxane having an oxiranyl group obtained above, 26 g of methyl isobutyl ketone, 3 g of 4-phenoxycinnamic acid and 0.10 g of UCAT 18X (trade name, manufactured by San Apro Co., Ltd.) The reaction was carried out with stirring at 80.degree. C. for 12 hours. After completion of the reaction, the reaction mixture is poured into methanol, and the formed precipitate is recovered, dissolved in ethyl acetate to form a solution, the solution is washed with water three times, and the solvent is distilled off to obtain an oxiranyl group. Thus, 6.3 g of a polyorganosiloxane (PSi-1) having a cinnamic acid structure was obtained as a white powder. The polystyrene equivalent weight average molecular weight Mw measured by GPC for this polyorganosiloxane (PSi-1) was 3,500.

[Example 1-1: Photo-alignment FFS-type liquid crystal display device]
(1) Preparation of Liquid Crystal Alignment Agent 50 parts by weight of the polymer (PAm-4) obtained in Synthesis Example 2-4 as a polymer and 50 parts by weight of the polymer (PAm-11) obtained in Synthesis Example 2-11 Dissolved in mixed solvent (GBL: NMP: BC = 40: 40: 20 (weight ratio)) consisting of γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC), and the solid concentration Was a 3.5 wt% solution. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent.

(2) Evaluation of Surface Roughness of Coating Film The liquid crystal aligning agent prepared above was coated on a glass substrate using a spinner, prebaked on a hot plate at 80 ° C. for 1 minute, and then nitrogen was substituted in the inside of the refrigerator By heating (post-baking) in an oven at 200 ° C. for 1 hour, a coating having an average film thickness of 1,000 Å was formed. This coating film was observed with an atomic force microscope (AFM) to measure the center average roughness (Ra). The evaluation was performed with the surface roughness "good" when Ra is less than 2.0 nm, "good" when it is 2.0 nm or more and less than 5.0 nm as "defective". In this example, Ra was 0.8 nm, and the surface asperity was “good”.
(3) Evaluation of transmittance With respect to the coating film obtained above, the light transmittance (%) at a wavelength of 400 nm was evaluated using a spectrophotometer (150-20 type double beam manufactured by Hitachi, Ltd.) . The evaluation was made as “good” when the light transmittance was 97% or more, “good” when it was 95% or more and less than 97%, “bad” when it was less than 95%. As a result, this coating film was 99.0%, and the permeability was "good".
(4) Evaluation of orientation With the Hg-Xe lamp and the Glan-Taylor prism, the coated film obtained above is irradiated with 300 J / m ² of polarized ultraviolet light including a bright line of 313 nm from the substrate normal direction to perform alignment treatment Applied. The refractive index anisotropy (nm) of the glass substrate with alignment film was measured using a liquid crystal alignment film inspection apparatus (LayScan) manufactured by MORITEX Corporation. The evaluation was made as “good” when it was 0.020 nm or more, “OK” when it was less than 0.020 nm and 0.010 nm or more as “defect” when it was less than 0.010. As a result, the refractive index anisotropy of this substrate was 0.037 nm, and the orientation was “good”.

(5) Production of FFS-Type Liquid Crystal Display Element Using Photoalignment Method An FFS-type liquid crystal display element 10 shown in FIG. 1 was produced. First, a glass substrate 11a having an electrode pair on one side of which is formed a bottom electrode 15 not having a pattern, a silicon nitride film as an insulating layer 14, and a top electrode 13 patterned in a comb shape in this order Using the spinner, the liquid crystal aligning agent prepared in the above (1) on the surface of the glass substrate 11a having the transparent electrode and the one surface of the opposite glass substrate 11b. It apply | coated and formed the coating film. Next, this coated film is prebaked on a hot plate at 80 ° C. for 1 minute, and then heated (post bake) at 230 ° C. for 15 minutes in a nitrogen-replaced oven for about 1,000 Å A coating was formed. A schematic plan view of the top electrode 13 used here is shown in FIG. 2 (a) is a top view of the top electrode 13, and FIG. 2 (b) is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2 (a). In this example, a substrate having a top electrode in which the line width d1 of the electrodes is 4 μm and the distance d2 between the electrodes is 6 μm was used. In addition, as the top electrode 13, four drive electrodes of an electrode A, an electrode B, an electrode C, and an electrode D were used. The structure of the drive electrode of this liquid crystal display element is shown in FIG. In this case, the bottom electrode 15 functions as a common electrode acting on all of the four drive electrodes, and each of the four drive electrode regions is a pixel region.

Next, each surface of the coating film is irradiated with polarized ultraviolet light 300 J / m ² including a bright line of 313 nm from the substrate normal direction using an Hg-Xe lamp and a Glan-Taylor prism, respectively, and a pair having a liquid crystal alignment film I got the substrate. At this time, the direction of irradiation of polarized ultraviolet light is from the normal direction of the substrate, and the direction of polarization plane is set so that the direction of the line segment of the polarization plane of polarized ultraviolet light projected onto the substrate is the direction of double-headed arrow in FIG. The light irradiation process was performed.

Then, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied by screen printing to the outer periphery of the surface of one of the substrates having the liquid crystal alignment film, and then the liquid crystal alignment film surface of a pair of substrates Of the polarized ultraviolet rays were superimposed so that the direction of projection of the polarized ultraviolet light onto the substrate was parallel, and pressed, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, liquid crystal injection port was filled with liquid crystal “MLC-6221” manufactured by Merck from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Thereafter, this was heated to 150 ° C. and then gradually cooled to room temperature in order to remove the flow alignment at the time of liquid crystal injection.
Next, polarizing plates were attached to both outer sides of the substrate to produce an FFS liquid crystal display element. At this time, one of the polarizing plates is attached so that the polarization direction is parallel to the projection direction of the polarization plane of the polarized ultraviolet light of the liquid crystal alignment film on the substrate surface, and the other has its polarization direction first. It stuck so as to be orthogonal to the polarization direction of the polarizing plate.
The above method was repeated to manufacture a total of five FFS liquid crystal display elements, one for evaluation of liquid crystal orientation, evaluation of heat resistance, evaluation of bezel unevenness, afterimage characteristics and contrast characteristics described below. However, in all cases, ultraviolet irradiation was not performed under voltage application. Moreover, the polarizing plate was not bonded about the liquid crystal cell used for evaluation of contrast characteristics.

(6) Evaluation of Liquid Crystal Alignment With the FFS-type liquid crystal display device manufactured above, the presence or absence of abnormal domain in the change of light and dark when the voltage of 5 V is turned on and off did. In the evaluation, the case where no abnormal domain was observed was regarded as “good” in liquid crystal alignment, and the case where an abnormal domain was observed was regarded as “defective” in liquid crystal alignment. In this liquid crystal display element, the liquid crystal alignment was "good".
(7) Evaluation of voltage holding ratio After applying a voltage of 5 V at a temperature of 23 ° C. for 60 microseconds and a span of 167 milliseconds for the FFS-type liquid crystal display device manufactured above, 167 milliseconds after the application release. The voltage holding ratio (VHR) was measured to be 99.4%. In addition, as a measuring apparatus, Toyo Co., Ltd. make and VHR-1 were used.
(8) Evaluation of heat resistance The voltage holding ratio was measured in the same manner as the evaluation of the (7) voltage holding ratio described above, and the value was used as the initial VHR (VHR _BF ). Then, the liquid crystal display element after the initial VHR measurement was allowed to stand in an oven at 100 ° C. for 500 hours. Thereafter, the liquid crystal display element was allowed to stand at room temperature and allowed to cool to room temperature, and then the voltage retention was measured in the same manner as described above, and the value was taken as VHR _AF . Moreover, the change rate ((DELTA) VHR (%)) of the voltage retention before and behind provision of heat stress was calculated | required by the following numerical formula (EX-2).
V VHR (%) = ((VHR _BF- VHR _AF ) ÷ VHR _BF ) × 100 ... (EX-2)
The heat resistance is evaluated as heat resistance “good” when change rate ΔVHR is less than 4%, heat resistance “good” when it is 4% or more and less than 5%, heat resistance when it is 5% or more It went as sex "defective". As a result, ΔVHR was 2.9%, and the heat resistance of this liquid crystal display element was “good”.

(9) Unevenness around the sealant (Bezel uneven)
The FFS-type liquid crystal display device manufactured above was stored for 30 days under conditions of 25 ° C. and 50% RH, and then was driven at an alternating voltage of 5 V to observe the lighting state. The evaluation is "excellent" if no luminance difference (more black or more white) is visually recognized around the sealing agent, but it is recognized if the luminance difference disappears within 5 minutes after lighting, "good", 5 minutes If the difference in brightness disappears within 20 minutes, the case where the difference in brightness is visible even after 20 minutes is regarded as "defective". As a result, the luminance difference of this liquid crystal display element was not visually recognized, and it was judged as "excellent".
(10) Evaluation of afterimage characteristics (DC afterimage evaluation)
The photoalignment type liquid crystal display device manufactured above was placed under an environment of 25 ° C. and 1 atm. The potential of the bottom electrode was set to a 0 V potential (ground potential), with the bottom electrode as a common electrode for all the four drive electrodes. The electrode B and the electrode D were short-circuited with the common electrode to apply 0 V, and a combined voltage of 3.5 V AC and 1 V DC was applied to the electrodes A and C for 2 hours. After 2 hours, a voltage of AC 1.5 V was immediately applied to all of the electrodes A to D. Then, from the time when a voltage of 1.5 V AC is started to be applied to all the drive electrodes, the drive stress application area (pixel area of the electrodes A and C) and the drive stress non-application area (pixel areas of the electrodes B and D) The time until the difference in brightness between the two and can not be visually confirmed was measured, and this was taken as the residual image elimination time. Note that as this time is shorter, afterimage is less likely to occur. When the residual image erasing time is less than 30 seconds is evaluated as “good”, the case of 30 seconds or more and less than 120 seconds is evaluated as “OK”, and the case of 120 seconds or more is evaluated as “defective”. The residual image erasing time of the liquid crystal display element of 1 was 1 second, and the residual image characteristic was evaluated as "good".
(11) Evaluation of contrast characteristics after driving stress (AC residual image evaluation)
Using an apparatus in which a polarizer and an analyzer are disposed between a light source and a light quantity detector after driving the FFS type liquid crystal cell manufactured above (with no polarizing plate attached) with an alternating voltage of 10 V for 30 hours The minimum relative transmittance (%) represented by the following formula (EX-3) was measured.
Minimum relative transmittance (%) = (β-B ₀ ) / (B ₁₀₀ -B ₀ ) × 100 (EX-3)
In Formula (EX-3), B ₀ is a blank and transmission of light under crossed nicols, B ₁₀₀ is a blank and transmission of light under paranicole, and β is polarized under crossed nicols It is the amount of light transmission that minimizes the liquid crystal display element between the element and the analyzer
The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element, and the smaller the black level in the dark state, the better the contrast characteristics. Those with a minimum relative transmittance of less than 0.5% were considered as “good”, those with at least 0.5% and less than 1.0% as “good”, and those with 1.0% or more as “bad”. As a result, the minimum relative transmittance of this liquid crystal display element was 0.2%, and the contrast characteristic was judged to be "good".

[Example 1-2, Example 1-3 and Comparative Example 1-1]
A liquid crystal aligning agent was prepared in the same manner as in Example 1-1 except that the type and amount of the polymer used for preparing the liquid crystal aligning agent were as described in Table 3 below, respectively, and a liquid crystal display element Manufactured and evaluated. The evaluation results are shown in Table 3 below.

Example 2-1 Rubbing FFS-Type Liquid Crystal Display Device
(1) Preparation of Liquid Crystal Alignment Agent The polymer (PAm-1) obtained in Synthesis Example 2-1 as a polymer was converted to γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) The mixture was dissolved in a mixed solvent (GBL: NMP: BC = 40: 40: 20 (weight ratio)) to obtain a solution having a solid content concentration of 3.5% by weight. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent.

(2) Evaluation of Surface Roughness of Coating Film The liquid crystal aligning agent prepared above was coated on a glass substrate using a spinner, prebaked on a hot plate at 80 ° C. for 1 minute, and then nitrogen was substituted in the inside of the refrigerator By heating (post-baking) in an oven at 200 ° C. for 1 hour, a coating having an average film thickness of 1,000 Å was formed. This coated film was evaluated in the same manner as (1) of Example 1-1 above for the surface irregularity of the coated film. As a result, Ra of this coating film was 0.9 nm, and the surface asperity was "good".
(3) Evaluation of transmittance | permeability With respect to the coating film obtained above, the transmittance | permeability was evaluated similarly to (3) of the said Example 1-1. As a result, the transmittance of this coating film was 98.5%, and the transmittance was "good".

(4) Evaluation of Rubbing Resistance The coated 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 using a rubbing machine having a roll wound with cotton The treatment was carried out seven times. The foreign matter (pieces of the coating film) caused by rubbing on the obtained substrate was observed with an optical microscope, and the number of foreign matter in a region of 500 μm × 500 μm was measured. The evaluation was performed with rubbing resistance as “good” when the number of foreign matter is 3 or less, “good” when 4 or more and 7 or less, and rubbing resistance “poor” when 8 or more. As a result, no foreign matter was observed, and the rubbing resistance of this coating film was "good".
(5) Evaluation of Orientation The orientation was provided for evaluation on the glass substrate with an alignment film subjected to the rubbing orientation treatment obtained above, in the same manner as (4) in Example 1-1 above. As a result, in this substrate, the refractive index anisotropy was 0.031 nm and was “good”.
(6) Production of FFS-Type Liquid Crystal Display Device Using Rubbing Method In the same manner as in (5) of Example 1-1 above, an FFS-type liquid crystal display device shown in FIG. 1 was produced. A schematic plan view of the top electrode 13 used here is shown in FIG. 4 (a) is a top view of the top electrode 13, and FIG. 4 (b) is an enlarged view of a portion C1 surrounded by a broken line in FIG. 4 (a). In this example, a substrate having a top electrode in which the line width d1 of the electrodes is 4 μm and the distance d2 between the electrodes is 6 μm was used.

  Subsequently, the rubbing process was performed with cotton on each surface of the coating film formed on the glass substrate, and it was set as the liquid crystal aligning film 12. The rubbing direction with respect to the coating film formed on the glass substrate 11a is shown by the arrow in FIG. 4 (b). These substrates are pasted together via a spacer with a diameter of 3.5 μm so that the rubbing directions of the substrates 11a and 11b are in antiparallel, the liquid crystal MLC-6221 (manufactured by Merck) is injected, and the liquid crystal layer 16 is formed. It formed. Furthermore, the liquid crystal display element 10 was produced by bonding a polarizing plate (not shown) to the outer surface of board | substrate 11a, 11b so that the polarization direction of two polarizing plates might mutually orthogonally cross.

(7) Evaluation of Liquid Crystal Alignment Property The liquid crystal alignment property of the rubbing FFS type liquid crystal display element manufactured above was evaluated in the same manner as (6) of Example 1-1. As a result, in this liquid crystal display element, the liquid crystal alignment was “good”.
(8) Evaluation of Voltage Holding Ratio and Heat Resistance With respect to the rubbing FFS type liquid crystal display element manufactured above, the voltage holding ratio (VHR _BF ) is measured in the same manner as (7) of Example 1-1 above, In the same manner as (8) of Example 1-1, the heat resistance of the liquid crystal display element was evaluated by the change rate of the voltage holding ratio before and after the thermal stressing. As a result, VHR _BF was 99.4%. Moreover, (DELTA) VHR was 1.6% and was judged to be heat resistance "good."
(9) Unevenness around the sealant (Bezel uneven)
The bezel unevenness resistance was evaluated in the same manner as (9) in Example 1-1. As a result, the luminance difference of this liquid crystal display element was not visually recognized, and it was determined that bezel unevenness resistance was "excellent".

(10) Evaluation of afterimage characteristics (DC afterimage evaluation)
The DC residual image evaluation was performed in the same manner as in Example 1-1 (10) above. As a result, the afterimage erasing time of this liquid crystal display element was 2 seconds and was evaluated as "good".
(11) Evaluation of contrast characteristics after driving stress (AC residual image evaluation)
AC residual image evaluation was performed in the same manner as in Example 1-1 (10) above. Also in this case, evaluation was performed using a liquid crystal cell to which no polarizing plate is attached. As a result, the minimum relative transmittance was 0.1%, and the contrast characteristic was judged to be "good".

[Example 2-2 to Example 2-15 and Comparative Example 2-1 to 2-5]
A liquid crystal aligning agent was prepared in the same manner as in Example 2-1 except that the type and amount of the polymer used for preparing the liquid crystal aligning agent were as described in Table 4 below, respectively, and a liquid crystal display element was prepared. Manufactured and evaluated. However, in Comparative Example 2-4, the liquid crystal alignment was poor, and the evaluation regarding the liquid crystal cell was not performed. The evaluation results are shown in Tables 4 and 5 below.

  As shown in Tables 3 to 5, in the liquid crystal aligning agent containing a polymer obtained using the compound (C ′), good results are obtained for the surface asperity, permeability, rubbing resistance, and orientation of the coating film. was gotten. Moreover, the liquid crystal display element produced using these liquid crystal aligning agents has favorable all about the orientation of a liquid crystal molecule, voltage holding ratio, heat resistance, bezel nonuniformity tolerance, an afterimage characteristic (DC afterimage), and contrast characteristic (AC afterimage) Results were obtained, and the various characteristics were well balanced.

On the other hand, in Comparative Example 2-1 using a diamine having only an aromatic chain structure and no aromatic amine structure, the afterimage characteristics are "defective", and the bezel unevenness resistance and heat resistance are inferior to those of the examples. And was insufficient to achieve the object of the present invention.
Moreover, in Comparative Examples 1-1, 2-2, and 2-3 in which a diamine having only an aromatic amine structure was used, the heat resistance, bezel unevenness resistance, and contrast characteristics of the liquid crystal display element were “defective”. Comparative Example 4 using PAm-14 was not suitable for use as a liquid crystal display element because the storage stability of the polymer, the surface unevenness of the coating film, and the transmittance were poor and the alignment of the liquid crystal was poor. The Furthermore, in Comparative Example 2-5, the heat resistance and the bezel unevenness resistance were “poor”. In addition, when the transmittance of the coating film, the rubbing resistance and the orientation, the alignment of the liquid crystal in the liquid crystal display element, the voltage holding ratio, the heat resistance, the bezel unevenness resistance, the residual image characteristics and the contrast characteristics are comprehensively examined, any comparative example The result is also inferior to the example.

Example 3-1 TN-Type Liquid Crystal Display Device
(1) Preparation of Liquid Crystal Alignment Agent 50 parts by weight of the polymer (PAm-3) obtained in Synthesis Example 2-3 as a polymer and 50 parts by weight of the polymer (PAm-16) obtained in Synthesis Example 2-16 It was dissolved in a mixed solvent of NMP and BC (NMP: BC = 50: 50 (weight ratio)) to obtain a solution having a solid content concentration of 6.5% by weight. The solution was sufficiently stirred and then filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent.
(2) Evaluation of printability The liquid crystal aligning agent prepared in the above (1) was applied to a transparent electrode surface of a glass substrate with a transparent electrode formed of an ITO film using a liquid crystal alignment film printing machine (manufactured by Nissha Printing Co., Ltd.). After application 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 form a coating film having an average film thickness of 600 Å did. The coated film was observed with a microscope with a magnification of 20 times to examine the presence or absence of printing unevenness and pinholes. In the evaluation, printability “good” when neither printing unevenness nor pinhole was observed, “printability” acceptable when printing unevenness and at least one of pinholes were slightly observed, printing unevenness, and pins When at least one of the holes was frequently observed, the printability was determined as "defective". In this example, neither printing unevenness nor pinholes were observed, and the printability was “good”.
(3) Evaluation of transmittance | permeability With respect to the coating film obtained above, the transmittance | permeability was evaluated similarly to (3) of the said Example 1-1. As a result, the transmittance of this coating film was 98.4%, which was "good".

(4) Production of TN Liquid Crystal Cell The liquid crystal aligning agent prepared in the above (1) was subjected to a liquid crystal alignment film printing machine (Nippon Photo Printing Co., Ltd.) to obtain a transparent electrode of a glass substrate with a transparent electrode comprising an ITO film. 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 coat an average film thickness of 600 Å Formed. The coating film was subjected to rubbing treatment at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a hair-foot push-in length of 0.4 mm by a rubbing machine having a roll wound with rayon cloth to impart liquid crystal alignment ability. . Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film. Further, the above operation was repeated to obtain a pair (two sheets) of substrates having a liquid crystal alignment film.
Next, an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film on one of the pair of substrates, and then the pair of substrates is subjected to the liquid crystal alignment film surface The two were put on top of one another and crimped to cure the adhesive. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck) is filled between a pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive to produce a TN type liquid crystal cell. did.

(5) Evaluation of Liquid Crystal Alignment With the liquid crystal cell produced in (4) above, the presence or absence of abnormal domains when a voltage of 5 V was turned on / off under crossed nicols was observed at a magnification of 50 with a microscope. The evaluation was performed in the same manner as (6) of Example 1-1. As a result, in this liquid crystal display element, the liquid crystal alignment was “good”.

(6) Evaluation of pretilt angle stability For the liquid crystal cell manufactured in (4) above, the angle of inclination of liquid crystal molecules from the substrate surface is measured by a crystal rotation method using He-Ne laser light, and this value is used as an initial pretilt. It is assumed that the angle θ _IN . The crystal rotation method is described in Non-patent Document 3 (TJ Scheffer et. Al., J. Appl. Phys. Vol. 48, p 1783 (1977)) and Non-patent Document 4 (F. Nakano et. Al., JPN. J. Appl. Phys.vol.19, p2013 (1980)).
Next, an alternating voltage of 5 V was applied to the liquid crystal cell after measuring the initial pretilt angle θ _IN for 100 hours. Thereafter, the pretilt angle was measured again by the same method as described above, and this value was used as the pretilt angle θ _AF after voltage application. These measured values were substituted into the following formula (EX-4) to determine the amount of change in pretilt angle (Δθ (°)) before and after voltage application.
Δθ = | θ _AF −θ _IN | ... (EX-4)
The pretilt angle stability "good" when Δθ is less than 3%, the pretilt angle stability "good" when it is 3% or more and less than 4%, the pretilt angle stability when it is 4% or more When the liquid crystal display element was evaluated as “defective”, the pretilt angle change rate of this liquid crystal display element was 1.6%, and it was judged that the pretilt angle stability was “good”.

(7) Evaluation of Voltage Holding Ratio and Heat Resistance The voltage holding ratio (VHR _BF ) was measured in the same manner as (7) in Example 1-1 above, and was performed in the same manner as (8) in Example 1-1 above. The heat resistance of the liquid crystal display element was evaluated by the change rate of the voltage holding ratio before and after the heat stressing. As a result, VHR _BF was 98.6%. Moreover, (DELTA) VHR is 2.1% and was judged to be heat resistance "good."
(8) Non-uniformity resistance around bezel (bezel unevenness resistance)
The bezel unevenness resistance was evaluated in the same manner as (9) in Example 1-1. As a result, the luminance difference of this liquid crystal display element was not visually recognized, and it was judged as "excellent".
(9) Evaluation of afterimage characteristics (DC afterimage evaluation)
The DC residual image evaluation was performed in the same manner as in Example 1-1 (10) above. As a result, the afterimage erasing time of this liquid crystal display element was 12 seconds and was evaluated as "good".

Example 4-1 VA-Type Liquid Crystal Display Element
(1) Preparation of Liquid Crystal Alignment Agent 20 parts by weight of the polymer (PIm-2) obtained in Synthesis Example 3-2 as a polymer and 80 parts by weight of the polymer (PAm-3) obtained in Synthesis Example 2-3 And BC were added to form a solution having a solid concentration of 6.5% by weight and a solvent mixing ratio of NMP: BC = 50: 50 (weight ratio). The solution was sufficiently stirred and then filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent.
(2) Evaluation of Printability When the printability was examined in the same manner as (2) of Example 3-1 above using the liquid crystal aligning agent prepared in (1) above, both the printing unevenness and the pinholes were examined. Not observed, the printability was "good".
(3) Evaluation of transmittance | permeability With respect to the coating film obtained above, the transmittance | permeability was evaluated similarly to (3) of the said Example 1-1. As a result, this coating film was 99.2%, and the permeability of the coating film was "good".

(4) Production of VA-Type Liquid Crystal Cell A liquid crystal alignment film printing machine (Nippon Photography Printing Co., Ltd.) on the transparent electrode surface of a glass substrate with a transparent electrode (thickness 1 mm) made of ITO film. Product). Then, it was heated (prebaked) 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. to form a coating (liquid crystal alignment film) with an average film thickness of 800 Å. . This operation was repeated to obtain a pair (two sheets) of glass substrates having a liquid crystal alignment film on a transparent conductive film. Next, for one of the pair of substrates, an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film, and the pair of substrates is then subjected to the liquid crystal alignment film surface The two were put on top of one another and crimped to cure the adhesive. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck) was filled between a pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to manufacture a VA type liquid crystal cell. .

(5) Evaluation of Liquid Crystal Alignment Property, Voltage Holding Ratio, and Heat Resistance With respect to the liquid crystal cell manufactured in the above (4), the liquid crystal alignment property was evaluated in the same manner as (6) in Example 1-1. The liquid crystal alignment of the cell was "good". Further, the voltage holding ratio (VHR _BF ) is measured in the same manner as (1) of Example 1-1, and the heat resistance (voltage before and after the application of thermal stress) is performed in the same manner as (8) in Example 1-1. The rate of change of the retention rate was evaluated. As a result, VHR _BF was 99.0%. Moreover, (DELTA) VHR was 2.3% and was judged to be heat resistance "good".
(6) Non-uniformity resistance around bezel (bezel unevenness resistance)
The bezel unevenness resistance was evaluated in the same manner as (9) in Example 1-1. As a result, the luminance difference of this liquid crystal cell was not visually recognized, and it was judged as "good".

Example 5-1 Retardation Film
(1) Preparation of Liquid Crystal Alignment Agent NMP and 100 parts by weight of the polymer (PAm-1) obtained in Synthesis Example 2-1 and 10 parts by weight of the polymer (PSi-1) obtained in Synthesis Example 4-1 It was dissolved in a mixed solvent (NMP: BC = 50: 50 (weight ratio)) composed of BC to obtain a solution having a solid content concentration of 3.5% by weight. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent.
(2) Production of Retardation Film The liquid crystal alignment agent prepared above is coated on one surface of a TAC film as a substrate using a bar coater, and baked at 120 ° C. for 2 minutes in an oven to coat a 100 nm thick film. A film was formed. Then, 10 mJ / cm ² of polarized ultraviolet light containing a 313 nm bright line was irradiated perpendicularly to the substrate normal using the Hg-Xe lamp and a Glan-Taylor prism. Next, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck) is filtered through a filter with a pore diameter of 0.2 μm, and the polymerizable liquid crystal is coated on the coating after light irradiation by a bar coater to coat the polymerizable liquid crystal. A film was formed. After baking for 1 minute in an oven adjusted to a temperature 50 ° C., using an Hg-Xe lamp with ultraviolet 1,000 mJ / cm ² of unpolarized light irradiated from a direction perpendicular to the coated surface containing the 365nm emission lines A retardation film was produced by curing the polymerizable liquid crystal to form a liquid crystal layer.

(3) Evaluation of Liquid Crystal Alignment Property The liquid crystal alignment property of the retardation film produced in (2) above was observed by visual observation under crossed nicols and the presence or absence of abnormal domain with a polarization microscope (2.5 times magnification) Photo-orientation) was evaluated. The evaluation was that when the alignment was good visually and no abnormal domain was observed with a polarizing microscope, the liquid crystal alignment "good", no abnormal domain was observed visually, but the abnormal domain was observed with a polarizing microscope The case where the liquid crystal alignment was "poor", the case where the abnormal domain was observed by visual observation and a polarization microscope was performed as the liquid crystal alignment "defect". As a result, this retardation film was evaluated as liquid crystal alignment "good".

(4) Adhesion Using the retardation film produced in (2) above, the adhesion of the coating film formed with the liquid crystal aligning agent to the substrate was evaluated. First, cuts were made from the surface on the liquid crystal layer side of the retardation film with a cutter knife using equally spaced spacers with guides to form 10 × 10 grid patterns in the range of 1 cm × 1 cm. The depth of each cut was made to reach from the surface of the liquid crystal layer to the middle of the substrate thickness. Next, cellophane tape was adhered to cover the entire surface of the lattice pattern, and then the cellophane tape was peeled off. The adhesion was evaluated by observing the cut portion of the lattice pattern after peeling by visual observation under cross nicol. In the evaluation, the adhesion is "good" when peeling is not confirmed in the portion along the cut line and in the crossing portion of the lattice pattern, the number of lattices in which peeling is observed in the above portion is the number of whole lattice patterns. On the other hand, when the ratio is less than 15%, the adhesiveness is "good", and when the number of lattices in which peeling is observed in the above part is 15% or more with respect to the total number of grating patterns, the adhesiveness is "bad". went. As a result, this retardation film had good adhesion "good".

  DESCRIPTION OF SYMBOLS 10 ... Liquid crystal display element, 11a, 11b ... Glass substrate, 12 ... Liquid crystal aligning film, 13 ... Top electrode, 14 ... Insulating layer, 15 ... Bottom electrode, 16 ... Liquid crystal layer

Claims (16)

Obtained following Formula (1) compound represented by (C) and a compound represented by the following formula (1-3) at least one compound selected from the group consisting of (C1) a (C ') used in the reaction Liquid crystal aligning agent containing a polymer (P).

(In Formula (1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, and A ² and A ⁴ are each independently a single bond or a divalent organic group B. ¹ and B ² each independently represent a single bond or a divalent organic group, provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom When B ¹ is a divalent organic group, at least two of A ¹ , A ² and B ¹ are aromatic rings and are bonded to a nitrogen atom, and when B ² is a single bond, A ³ And at least one of A ⁴ is an aromatic ring bonded to a nitrogen atom, and when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are an aromatic ring and a nitrogen atom bound to .L ¹ is a divalent chain hydrocarbon group having 7 or more straight, and the chain hydrocarbon At least one methylene group in the group -O -, - S -, - CO -, - NR -, - NRCO -, - COO -, - COS- or _{-Si (CH 3) 2 - (} R is a hydrogen atom Or a monovalent organic group) which is a bivalent group containing in the main chain a structure (b) which is a linear chain structure selected from the group consisting of divalent groups substituted by

(In formula (1-3), A ⁷ is a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond or a divalent organic group, provided that A ⁷ , A ⁸ and A are ^At least two of the aromatic ring ⁹ are bonded to a nitrogen atom via an aromatic ring L ⁴ is a divalent C 1-5 linear hydrocarbon group, at least one methylene group in the linear hydrocarbon group -O a ^{-, - S -, - CO} -, - NR 3 -, - NR 3 CO -, - COO -, - COS- or -Si _{(CH 3) 2} - in the divalent radical is replaced, -O -, - S -, - CO -, - NR 3 CO-, (R 3 is a hydrogen atom or a monovalent organic group.) - COO -, - COS- , and -Si _{(CH 3) 2} - from a structure selected from the group consisting of, L ⁵ represents a single bond or a divalent organic group. However, one molecule of the compound represented by formula (1-3) In an aromatic amine structure in which two or three aromatic ring group is attached to the same nitrogen atom is one.) The liquid crystal aligning agent according to claim 1, wherein the polymer (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide. At least one of the B ¹ and the B ² is a single bond, the liquid crystal alignment agent according to claim 1 or 2. The liquid crystal aligning agent according to any one of claims 1 to 3 , wherein L ¹ is represented by the following formula (2).

(In Formula (2), L ² and L ³ are each independently the structure (b), and Q is a divalent group represented by the following Formula (3) or Formula (4) n Is an integer of 0 to 4. "*" indicates a bond.

(In formula (3), A ⁵ is a hydrogen atom or a monovalent organic group. R ¹ and R ² are substituents, which may be the same or different. “*” Represents a bond .)

(In formula (4), A ⁶ represents a hydrogen atom or a monovalent organic group. “*” Represents a bond.) The liquid crystal aligning agent according to any one of claims 1 to 4, wherein the compound (C) is a compound represented by the following formula (1-1).

(In the formula ^{(1-1), L 11} is at least one methylene group in the divalent chain-like hydrocarbon group having 7 or more straight -O -, - S -, - CO-, 2 containing in the main chain a group substituted by -NR-, -NRCO-, -COO-, -COS- or -Si (CH ₃ ) _2- (wherein R is a hydrogen atom or a monovalent organic group) A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ² are as defined in the above formula (1), provided that L ¹¹ is an alkanediyl group having 1 to 5 carbon atoms. When it exists, at least one of A ¹ and A ³ is a hydrogen atom, or at least one of B ¹ and B ² is a divalent organic group. The liquid crystal aligning agent according to any one of claims 1 to 4, wherein the compound (C) is a compound represented by the following formula (1-2).

(In the formula ^{(1-2), L 12} is a divalent group containing a divalent chain hydrocarbon group having 7 or more straight in the main chain ^{.A 1, A} 2, A ³ , A ⁴ , B ¹ and B ² are as defined in the above formula (1).) The polymer (P) is at least one selected from the group consisting of a polyamic acid, a polyamic acid ester, and a polyimide obtained by reacting tetracarboxylic acid dianhydride and a diamine containing the compound (C ′). ,
The tetracarboxylic acid dianhydride is 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b -Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8 -Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2, 4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2 -Dicarboxylic acid anhydride, 3,5 6-tricarboxy-2-carboxy norbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.02,6] undecane-3,5,8,10 -Tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, 1,3-propylene glycol The liquid crystal aligning agent as described in any one of Claims 1-6 containing at least 1 type chosen from the group which consists of bis (anhydro trimellitate) and pyromellitic dianhydride. The molecular weight of the compound (C ') is 1,000 or less, the liquid crystal alignment agent according to any one of claims 1-7. The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-8 . The liquid crystal display element which comprises the liquid crystal aligning film of Claim 9 . The retardation film which comprises the liquid crystal aligning film of Claim 9 . The process of apply | coating the liquid crystal aligning agent as described in any one of Claims 1-8 on a board | substrate, and forming a coating film, the process of light-irradiating to the said coating film, and the coating film after the said light irradiation. And (ii) applying and curing a polymerizable liquid crystal on the film. A polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide,
At least one compound selected from the group consisting of a tetracarboxylic acid dianhydride, a tetracarboxylic acid diester compound and a tetracarboxylic acid diester dihalide; a compound represented by the following formula (1-1); The polymer obtained by using for reaction the diamine containing at least 1 type chosen from the group which consists of a compound represented by these, and a compound represented by following formula (1-3).

(In formula (1-1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, and A ² and A ⁴ are each independently a single bond or a divalent organic group B ¹ and B ² are each independently a single bond or a divalent organic group, provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom When B ¹ is a divalent organic group, at least two of A ¹ , A ² and B ¹ are aromatic rings and are bonded to a nitrogen atom, and when B ² is a single bond, At least one of A ³ and A ⁴ is an aromatic ring and is bonded to a nitrogen atom, and when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are an aromatic ring .L ¹¹ attached to the nitrogen atom is less in the divalent chain-like hydrocarbon group having 7 or more straight , - - S - -O one methylene group, - CO -, - NR - , - NRCO -, - COO -, - COS- or _{-Si (CH 3) 2 - (} R is a hydrogen atom or a A divalent organic group containing in the main chain a group substituted by a substituted organic group, provided that L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, at least ^one of A ¹ and A ³ Either is a hydrogen atom, or at least one of B ¹ and B ² is a divalent organic group.

(In the formula ^{(1-2), L 12} is a divalent group containing a divalent chain hydrocarbon group having 7 or more straight in the main chain ^{.A 1, A} 2, A ³ , A ⁴ , B ¹ and B ² are as defined in the above formula (1-1), provided that L ¹² is an alkanediyl group having 7 to 10 carbon atoms, at least one of A ¹ and A ³ Is a monovalent organic group, or at least one of B ¹ and B ² is a divalent organic group.

(In formula (1-3), A ⁷ is a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond or a divalent organic group, provided that A ⁷ , A ⁸ and A are ^At least two of the aromatic ring ⁹ are bonded to a nitrogen atom via an aromatic ring L ⁴ is a divalent C 1-5 linear hydrocarbon group, at least one methylene group in the linear hydrocarbon group -O a ^{-, - S -, - CO} -, - NR 3 -, - NR 3 CO -, - COO -, - COS- or -Si _{(CH 3) 2} - in the divalent radical is replaced, -O -, -S-, -CO-, -NR ³ CO- (wherein R ³ is a hydrogen atom or a monovalent organic group), -COO-, -COS-, or -Si (CH ₃ ) _2- there .L ⁵ is a single bond or a divalent organic group. However, in the one molecule of the compound represented by the formula (1-3), 2, or 3 The aromatic ring group aromatic amine structure formed by binding to the same nitrogen atom is one.) The compound represented by following formula (1-1).

(In formula (1-1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, and A ² and A ⁴ are each independently a single bond or a divalent organic group B ¹ and B ² are each independently a single bond or a divalent organic group, provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom When B ¹ is a divalent organic group, at least two of A ¹ , A ² and B ¹ are aromatic rings and are bonded to a nitrogen atom, and when B ² is a single bond, At least one of A ³ and A ⁴ is an aromatic ring and is bonded to a nitrogen atom, and when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are an aromatic ring .L ¹¹ attached to the nitrogen atom is less in the divalent chain-like hydrocarbon group having 7 or more straight , - - S - -O one methylene group, - CO -, - NR - , - NRCO -, - COO -, - COS- or _{-Si (CH 3) 2 - (} R is a hydrogen atom or a A divalent organic group containing in the main chain a group which is substituted by a divalent organic group, provided that L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, and it is preferable that A ¹ and A ³ At least one of them is a hydrogen atom, or at least one of B ¹ and B ² is a divalent organic group. The compound represented by following formula (1-2).

(In Formula (1-2), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, and A ² and A ⁴ are each independently a single bond or a divalent organic group B ¹ and B ² are each independently a single bond or a divalent organic group, provided that when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom When B ¹ is a divalent organic group, at least two of A ¹ , A ² and B ¹ are aromatic rings and are bonded to a nitrogen atom, and when B ² is a single bond, At least one of A ³ and A ⁴ is an aromatic ring and is bonded to a nitrogen atom, and when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are an aromatic ring .L bonded to the nitrogen atom ¹² include divalent chain-like hydrocarbon group having 7 or more straight in the main chain Is the valence of the group. ^However, when ^{L 12} is an alkanediyl group having 7-10 carbon atoms, at least one of ^{A 1} and ^{A 3} is a monovalent organic group, or ^{B 1} and ^{B 2} At least one of them is a divalent organic group.) The compound represented by following formula (1-3).

(In formula (1-3), A ⁷ is a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond or a divalent organic group, provided that A ⁷ , A ⁸ and A are ^At least two of the aromatic ring ⁹ are bonded to a nitrogen atom via an aromatic ring L ⁴ is a divalent C 1-5 linear hydrocarbon group, at least one methylene group in the linear hydrocarbon group -O a ^{-, - S -, - CO} -, - NR 3 -, - NR 3 CO -, - COO -, - COS- or -Si _{(CH 3) 2} - in the divalent radical is replaced, -O -, -S-, -CO-, -NR ³ CO- (wherein R ³ is a hydrogen atom or a monovalent organic group), -COO-, -COS-, or -Si (CH ₃ ) _2- there .L ⁵ is a single bond or a divalent organic group. However, in the one molecule of the compound represented by the formula (1-3), 2, or 3 The aromatic ring group aromatic amine structure formed by binding to the same nitrogen atom is one.)

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