JP2015026052A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display, method of producing liquid crystal display, polymer and compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid crystal display with high reliability and little degradation with use.SOLUTION: A liquid crystal alignment agent contains a polymer (P) having a specific structure represented by the formula (1A), where Ris a divalent organic group, Xis a nitrogen containing aromatic heterocycle; Qis a nitrogen atom, a carbon atom or silicon atom, Yis a hydrogen atom or a 1-5C alkyl group; and, in the case of Qbeing a nitrogen atom, t=2 and s=0, in the case of Qbeing a silicon atom, t=3 and s=0, and in the case of Qbeing a carbon atom, t is 2 or 3 and s=3-t.

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, a method for manufacturing a liquid crystal display element, a polymer, and a compound, and more particularly to a technique suitable for manufacturing a PSA (Polymer Sustained Alignment) mode liquid crystal display element.

  In general, a liquid crystal display element includes a liquid crystal layer containing liquid crystal molecules between a pair of substrates arranged opposite to each other, and a liquid crystal alignment film arranged so as to sandwich the liquid crystal layer and controlling the liquid crystal molecules in a desired alignment state. ing. Conventionally, as a liquid crystal display element, various drive systems having different electrode structures and physical properties of liquid crystal molecules to be used have been developed. For example, an MVA (Multi-Domain Vertical Alignment) type panel conventionally known as a vertical alignment mode is intended to expand the viewing angle by regulating the tilting direction of liquid crystal molecules by projections formed in the liquid crystal panel. . However, according to this method, there is an inconvenience that the transmittance and contrast resulting from the protrusions are unavoidable and the response speed of the liquid crystal molecules is slow.

  In recent years, in order to solve the problems of the MVA panel, a PSA (Polymer Sustained Alignment) mode has been proposed as a new driving mode for controlling the alignment of liquid crystal molecules. In the PSA mode, a photopolymerizable monomer is mixed in a liquid crystal material, a liquid crystal cell is assembled, and then light is applied to the liquid crystal cell with a voltage applied between a pair of electrodes sandwiching the liquid crystal layer. This is a technique for controlling the molecular orientation of liquid crystal molecules by polymerizing polymerizable monomers. According to this technique, there is an advantage that the viewing angle can be increased and the response speed can be increased. In recent years, further rapid response of PSA type liquid crystal panels has been studied. As such a technique, a monofunctional liquid crystal compound having one of an alkenyl group and a fluoroalkenyl group (hereinafter referred to as “alkenyl”). Attempts have been made to introduce a liquid crystal layer into a liquid crystal layer (see, for example, Patent Documents 1 to 3).

JP 2010-285499 A JP-A-9-104644 JP-A-6-108053

  In recent years, liquid crystal display elements are used not only in display terminals such as personal computers as in the past, but also in various applications such as liquid crystal televisions, car navigation systems, mobile phones, smartphones, and information displays. . Due to such versatility, a highly reliable liquid crystal display element with little deterioration due to use is demanded, and a material for obtaining such a liquid crystal display element is desired.

  In addition, in a liquid crystal display element using alkenyl liquid crystals, the response speed can be increased, but by irradiating light during polymerization of the photopolymerizable monomer, the liquid crystal cell does not contain the alkenyl liquid crystals. It has become clear that the decrease in the voltage holding ratio is greater than that. From the viewpoint of improving the reliability of the liquid crystal display element, it is necessary to maintain a high voltage holding ratio even after light irradiation.

  The present invention has been made in view of the above problems, and a main object of the present invention is to provide a liquid crystal aligning agent for obtaining a highly reliable liquid crystal display element with little deterioration due to use.

  As a result of intensive studies to achieve the above-described problems of the prior art, the present inventors have found that the above-described problems can be solved by including a polymer having a specific structure in the liquid crystal aligning agent. The present invention has been completed. Specifically, the present invention provides the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, liquid crystal display element manufacturing method, polymer and compound.

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

(In the formula (1A), R ² is a divalent organic group, and X ¹ is a nitrogen-containing aromatic heterocycle. However, a plurality of R ² in the formula may be the same or different, and X ¹ may be the same or different, Q ¹ is a nitrogen atom, a carbon atom or a silicon atom, Y ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and when Q ¹ is a nitrogen atom Is t = 2 and s = 0, t = 3 and s = 0 when Q ¹ is a silicon atom, t is 2 or 3 when Q ¹ is a carbon atom and s = 3-t.)

  The structure represented by the formula (1A) is preferably a structure represented by the following formula (1).

(In formula (1), R ² and X ¹ are synonymous with the above formula (1A). “*” Represents a bond.)

  In another aspect, the present invention provides a liquid crystal alignment film formed using the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film. In addition, the liquid crystal aligning agent is applied on the conductive film of a pair of substrates each having a conductive film, and then heated to form a coating film, and the pair of substrates on which the coating film is formed, A step of constructing a liquid crystal cell by placing the coating film so as to face each other through a liquid crystal layer containing a liquid crystal compound, and a voltage applied to the liquid crystal cell between the conductive films of the pair of substrates And a step of irradiating with light.

  According to the liquid crystal aligning agent of the present invention, a highly reliable liquid crystal aligning film with little deterioration due to use can be obtained. Moreover, the liquid crystal display element manufactured by the liquid crystal display element of the present invention and the manufacturing method of the present invention has a liquid crystal alignment film formed using the liquid crystal aligning agent, so that there is little quality deterioration due to use and reliability. Are better.

The figure which shows the electrode pattern of the transparent electrode film used by the Example and the comparative example. The figure which shows the electrode pattern of the transparent electrode film used in the Example. The figure which shows the electrode pattern of the transparent electrode film used in the Example.

  The liquid crystal aligning agent of this invention contains the polymer (P) which has a specific structure as a polymer component, and contains the other component arbitrarily mix | blended as needed.

<Polymer (P)>
The polymer (P) of the present invention is a polymer having a structure represented by the following formula (1A).

(In the formula (1A), R ² is a divalent organic group, and X ¹ is a nitrogen-containing aromatic heterocycle. However, a plurality of R ² in the formula may be the same or different, and X ¹ may be the same or different, Q ¹ is a nitrogen atom, a carbon atom or a silicon atom, Y ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and when Q ¹ is a nitrogen atom Is t = 2 and s = 0, t = 3 and s = 0 when Q ¹ is a silicon atom, t is 2 or 3 when Q ¹ is a carbon atom and s = 3-t.)

The polymer (P) is preferably a polymer having a structure represented by the following formula (1).
(In formula (1), R ² and X ¹ are synonymous with the above formula (1A). “*” Represents a bond.)

In the above formula (1A) and formula (1), when Q ¹ is a nitrogen atom or a carbon atom, examples of the divalent organic group for R ² include a divalent hydrocarbon group and a carbon-carbon bond in the hydrocarbon group. In between, —O—, —NH—, —CO—O—, —CO—NH—, —CO—, —S—, —SO ₂ —, —Si (CH ₃ ) ₂ —, —O—Si ( _{CH 3) 2 -, - O} -Si (CH 3) 2 divalent group having a functional group 2 -O-, etc., a hydrocarbon group, -O -, - NH -, - CO-O -, - CO _{-NH -, - CO -, -} S -, - SO 2 -, - Si (CH 3) 2 -, - O-Si (CH 3) 2 -, - O-Si (CH 3) 2 -O- , etc. At least one hydrogen atom in a divalent group or hydrocarbon group formed by linking with a functional group of a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom Such divalent group substituted by a child or a hydroxyl group. Examples of the divalent organic group for R ² when Q ¹ is a silicon atom include —O— and —CO—O— in addition to the specific examples of R ² when Q ¹ is a nitrogen atom or a carbon atom. Etc.

  Here, the “hydrocarbon group” in the present specification may be saturated or unsaturated, and includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Further, the “chain hydrocarbon group” means a linear hydrocarbon group and a branched hydrocarbon group that have only a chain structure without having a cyclic structure in the main chain. The alicyclic hydrocarbon group means a hydrocarbon group having only an alicyclic hydrocarbon structure as a ring structure and not having an aromatic ring structure. However, it is not necessary to be comprised only by the structure of an alicyclic hydrocarbon, The thing which has a chain structure in the part is also included. The “aromatic hydrocarbon group” means a hydrocarbon group having an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may have a chain structure or an alicyclic hydrocarbon structure.

The divalent hydrocarbon group for R ² preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms. Specific examples of the hydrocarbon group include chain hydrocarbon groups such as alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, vinylene group, propenylene group, etc. Examples of the alicyclic hydrocarbon group include a cyclohexylene group; and examples of the aromatic hydrocarbon group include a phenylene group. Among these, a chain hydrocarbon group or an alicyclic hydrocarbon group is preferable, and an alkanediyl group is more preferable.

Examples of the nitrogen-containing aromatic heterocyclic ring of X ^1, the nitrogen atom may be any aromatic ring containing 1 or more in the ring skeleton. Therefore, the ring skeleton may contain only nitrogen atoms as heteroatoms, or may contain nitrogen atoms and heteroatoms other than nitrogen atoms (oxygen atoms, sulfur atoms, etc.). Specific examples of the nitrogen-containing aromatic heterocycle in X ¹ include, for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, an indole ring, a benzimidazole ring, a purine ring, Quinoline ring, isoquinoline ring, naphthyridine ring, quinoxaline ring, phthalazine ring, triazine ring, azepine ring, diazepine ring, acridine ring, phenazine ring, phenanthroline ring, oxazole ring, thiazole ring, carbazole ring, thiadiazole ring, benzothiazole ring, phenothiazine Ring, oxadiazole ring and the like. X ¹ may be one in which a substituent is introduced into the carbon atom constituting the ring exemplified above. Examples of the substituent include a halogen atom, an alkyl group, and an alkoxy group.

Among these, as X ¹ , the ring skeleton is a pyrrole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, benzimidazole ring, naphthyridine ring, phthalazine ring, quinoxaline ring, triazine It is preferably a ring, an azepine ring, a diazepine ring or a phenazine ring, more preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring.
In the nitrogen-containing aromatic heterocycle, the bonding position with R ² is not particularly limited. For example, when the nitrogen-containing aromatic heterocycle as X ¹ is a 5-membered ring, the 1-position, 2-position or 3-position can be mentioned, and when it is a 6-membered ring, the 1-position, 2-position, 3 -Position or 4-position is mentioned.

Q ¹ in the above formula (1A) is preferably a nitrogen atom from the viewpoint of the reliability of the liquid crystal alignment film and the liquid crystal display element. Y ¹ is preferably a hydrogen atom, a methyl group or an ethyl group.
The structure represented by the above formula (1A) is preferably a structure represented by the following formula (1-1A).

(In Formula (1-1A), R ³ is an alkanediyl group having 1 to 5 carbon atoms when Q ¹ is a nitrogen atom or a carbon atom, and a single bond or carbon when Q ¹ is a silicon atom. An alkanediyl group having a number of 1 to 5. R ⁴ is a single bond or an alkanediyl group having a carbon number of 1 to 5, and A ¹ is a single bond, —O—, —CO—, * ¹ —COO—. , ^* 1 --OCO ^-, * 1 -CONH- or ^* 1 -NHCO -. (. ^{"* 1",} which indicates a bond to ^{R 3)} is provided that when ^{R 3} is a single bond, ^{a 1} Is —O— or * ¹ —OCO—, wherein a plurality of R ³ may be the same or different, a plurality of R ⁴ may be the same or different, and a plurality of A ¹ are the same or different; which may be ^{.X 1, Q 1, Y 1} , t and s are as defined in the above formula (1A). "*" indicates a bond )

The structure represented by the above formula (1) is preferably a structure represented by the following formula (1-1).
(In formula (1-1), R ³ , R ⁴ , and A ¹ are respectively synonymous with the above formula (1-1A). X ¹ is synonymous with the above formula (1). “*” Is a bond. Is shown.)

In the formula (1-1A) and the formula (1-1), examples of the alkanediyl group having 1 to 5 carbon atoms of R ³ and R ⁴ include a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a pentanediyl group. Groups may be mentioned, which may be linear or branched. R ³ and R ⁴ may be the same as or different from each other.
The R ^3, if Q ¹ is a nitrogen atom or a carbon atom, preferably 1 to 3 carbon atoms, and more preferably 1 to 2 carbon atoms. When Q ¹ is a silicon atom, R ³ is preferably a single bond or 1 to 2 carbon atoms, and more preferably a single bond. R ⁴ is preferably a single bond or 1 to 3 carbon atoms, and more preferably a single bond or 1 to 2 carbon atoms.
A ¹ represents a single ^{bond, -O -, - CO -,} * 1 -COO -, * 1 -OCO -, * 1 -CONH- or ^* 1 -NHCO - ( ^{"* 1"} is a bond between ^{R 3} Is shown.) Among them, a single ^{bond, -O -, * 1 -CONH -} , is preferably * 1 -COO- or ^* 1 -OCO-.

  Examples of the main skeleton of the polymer (P) include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, poly (meth) acrylate, polyester, polyamide, cellulose derivative, polyacetal derivative, polystyrene derivative, and poly (styrene-phenyl). Mention may be made of a skeleton formed by a maleimide) derivative or the like. Which of these is applied may be appropriately selected according to the driving mode or application of the liquid crystal display element, and among them, it may be at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide. Preferably, at least one selected from the group consisting of polyamic acid and polyimide is more preferable.

<Polyamic acid (P)>
The polyamic acid (hereinafter also referred to as “polyamic acid (P)”) as the polymer (P) in the present invention can be obtained by reacting a tetracarboxylic dianhydride and a diamine. In the point that it is easy to introduce the structure represented by the above formula (1A) into the polymer side chain, it is preferable to use a diamine having the structure represented by the above formula (1A) when synthesizing the polyamic acid (P).

[Tetracarboxylic dianhydride]
Examples of tetracarboxylic dianhydrides used for the synthesis of polyamic acid in the present invention include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. Can do. Specific examples thereof include aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4, 5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane -2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- No 1,2-dicarboxylic acid 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2 : 4,6: 8-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5 -Cyclohexanetetracarboxylic dianhydride (1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride, 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride, etc.), 1,2,3,4 -Cyclopentanetetracarboxylic dianhydride (1R, 2R, 3R, 4R-cyclopentanetetracarboxylic dianhydride etc.) and the like;
Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like; respectively, and tetracarboxylic dianhydrides described in JP 2010-97188 A can be used. In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

  The tetracarboxylic dianhydride used for the synthesis preferably contains an alicyclic tetracarboxylic dianhydride from the viewpoint of transparency and solubility in a solvent. Examples of the alicyclic tetracarboxylic dianhydride include 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, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic Selected from the group consisting of acid dianhydrides In particular, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and 1,2,3,4-cyclopentanetetra It is more preferable that it contains at least one tetracarboxylic dianhydride selected from the group consisting of carboxylic dianhydrides (hereinafter also referred to as specific tetracarboxylic dianhydrides).

  In the synthesis of polyamic acid (P), when the above-mentioned specific tetracarboxylic dianhydride is used, the use ratio (total amount) is the total amount of tetracarboxylic dianhydride used for the synthesis of polyamic acid (P). On the other hand, it is preferably 10 mol% or more, more preferably 20 to 100 mol%, still more preferably 50 to 100 mol%.

[Diamine]
The diamine used for the synthesis of the polyamic acid (P) in the present invention preferably includes a diamine having a structure represented by the above formula (1A). Specific examples of the diamine having the structure represented by the above formula (1A) include, for example, a compound represented by the following formula (d-1A), preferably the following formula (d-1). A compound.

(In the formula (d-1A), R ¹ is a single bond or a divalent organic group. R ² , X ¹ , Q ¹ , Y ¹ , t and s are as defined in the above formula (1A). )

(In Formula (d-1), R ¹ is a single bond or a divalent organic group. R ² and X ¹ have the same meanings as in Formula (1) above.)

As the divalent organic group of R ^{1 in} the above formula (d-1A) and the above formula (d-1), —CO—, * ² —OCO— (“* ² ” is bonded to a diaminophenyl group. And a group exemplified as the divalent organic group for R ² . Specific examples of preferred R ¹ include a group represented by the following formula (r-1).
(In formula (r-1), A ² is a single bond, —O—, —CO—, * ³ —OCO— or * ³ —COO—, and A ³ is a single bond, —CO— or —OCO—. * ⁴ , R ⁵ is a divalent divalent having —O—, —CO—O—, —CO—NH— or —CO— between the carbon-carbon bond of a single bond, alkanediyl group or alkanediyl group. “* ³ ” and “* ⁴ ” represent a bond, but “* ³ ” is bonded to a diaminophenyl group.)

The alkanediyl group in R ⁵ of the above formula (r-1) may be linear or branched, preferably has 1 to 8 carbon atoms, and more preferably has 1 to 4 carbon atoms. R ⁵ is preferably a single bond or an alkanediyl group having 1 to 8 carbon atoms, more preferably a single bond or an alkanediyl group having 1 to 4 carbon atoms, and a single bond, a methylene group or an ethylene group. More preferably it is. A ² is preferably a single bond, —CO— or * ³ —OCO—. Incidentally, the description of preferred examples of the group ^"-N- (R ₂ ^-X ₁₎ 2" can be applied to the description of the above formula (1).

Preferable specific examples of the compound represented by the formula (d-1) include, for example, compounds represented by the following formulas (da-1) to (da-68).

Further, the formula Specific examples of the compounds ^{Q 1} is a carbon atom or silicon atom (d-1A), for example, the following formula (da-69) ~ represented by each compound of (da-80), etc. Can be mentioned.

As the diamine used for the synthesis of the polyamic acid (P), a diamine having a structure represented by the above formula (1) (hereinafter also referred to as “specific diamine”) may be used alone. A diamine other than the specific diamine (hereinafter also referred to as “other diamine”) may be used together with the specific diamine.
Examples of other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. Specific examples of these diamines include aliphatic diamines such as m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like; 4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

Examples of aromatic diamines include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylene Riden) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamino Pyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N , N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 1- (4-aminophen 2) -2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3, 5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, 3,5-diamino Lanostanyl benzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5- Diaminobenzoate, 4- (4′-trifluoromethylbenzoyloxy) cyclohexyl-3,5-di Aminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, , 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, 1,3-diamino-4-octadecyloxybenzene, 3- (3,5-diaminobenzoyloxy) cholestane, 3,6-bis (4-aminobenzoyloxy) cholestane and the following formula (Y-1)
(In Formula (Y-1), X ^I and X ^II are each independently a single bond, —O—, —COO— or —OCO—, and R ^I and R ^II are each independently a carbon number. 1 to 3 alkanediyl groups, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, m is 0 or 1, and n is 0 or (However, a and b are not 0 at the same time.)
A compound represented by:

  Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, and the like, and diamines described in JP 2010-97188 A can be used.

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

Specific examples of the compound represented by the formula (Y-1) include compounds represented by the following formulas (Y-1-1) to (Y-1-4).
In addition, these diamine can be used individually by 1 type or in combination of 2 or more types.

  In the synthesis of the polyamic acid (P), the amount of the specific diamine used is preferably 0.1 to 80 mol%, and preferably 1 to 60 mol%, based on the total amount of diamine used for the synthesis. Is more preferable, it is still more preferable that it is 3-50 mol%, and it is especially preferable that it is 5-30 mol%.

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

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

<Synthesis of specific diamine>
The compound represented by the above formula (d-1A) and the compound represented by the above formula (d-1) can be synthesized by appropriately combining organic chemistry methods. As an example, a dinitro intermediate having a nitro group instead of the primary amino group in the above formula (d-1A) or the above formula (d-1) was synthesized, and then the nitro of the obtained dinitro intermediate was synthesized. A method of aminating a group using an applicable reduction system can be mentioned.

The method for synthesizing the dinitro intermediate can be appropriately selected depending on the target compound. For example, in the case of a compound represented by the above formula (d-1), for example, [1] a secondary amine compound having a structure represented by the above formula (1) and a secondary amine compound in the secondary amine compound. A method of reacting a compound capable of reacting with an amino group and having R ¹ and a dinitrophenyl group (for example, acid chloride, carboxylic acid, etc.); [2] “R ^N —R ¹ —N—” ( R ^N has groups represented by.) showing a dinitrophenyl group, and a difunctional compound having two functional groups, a possible reaction with the difunctional compound, and a compound having an X ¹ And the like.
The reduction reaction of the dinitro intermediate can be preferably carried out in an organic solvent using a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin, nickel or the like. Examples of the organic solvent used here include ethyl acetate, toluene, tetrahydrofuran, and alcohols. However, the synthesis procedure of the compound represented by the above formula (d-1A) and the compound represented by the above formula (d-1) is not limited to the above method.

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

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

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

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. When polyamic acid is dehydrated and cyclized into a polyimide, the above reaction solution may be directly subjected to dehydration and cyclization, or the polyamic acid contained in the reaction solution may be isolated and then subjected to dehydration and cyclization. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. Isolation and purification of the polyamic acid can be performed 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) in the present invention is, for example, [I] a polyamic acid obtained by the above synthesis reaction, a hydroxyl group-containing compound, It can be obtained by a method of reacting a halide, an epoxy group-containing compound or the like, a method of reacting a [II] tetracarboxylic acid diester and a diamine, or a method of reacting a [III] tetracarboxylic acid diester dihalide and a diamine. .

  Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol and propanol; phenols such as phenol and cresol. Examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like, and as an epoxy group-containing compound, Examples thereof include propylene oxide. The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid with the alcohol. The tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. As the diamine used in the methods [II] and [III], a diamine having a structure represented by the above formula (1A), the above-mentioned other diamines, and the like can be used. The polyamic acid ester may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.

<Polyimide (P)>
The polyimide (hereinafter also referred to as “polyimide (P)”) as the polymer (P) contained in the liquid crystal aligning agent of the present invention is a polyamic acid (P) synthesized as described above and dehydrating and ring-closing. Can be obtained by imidization.

  The polyimide (P) may be a completely imidized product obtained by dehydrating and ring-closing all of the amic acid structure of the polyamic acid (P) that is the precursor, and only a part of the amic acid structure is dehydrating and ring-closing. Alternatively, it may be a partially imidized product in which an amic acid structure and an imide ring structure coexist. The polyimide in the present invention has an imidation ratio of preferably 30% or more, more preferably 40 to 99%, and more preferably 50 to 99%, from the viewpoint of improving the electrical characteristics of the liquid crystal display element. More preferably. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.

  The polyamic acid is preferably dehydrated and closed by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating the solution as necessary. . Of these, the latter method is preferred.

  In the method of imidizing a polyamic acid solution by adding a dehydrating agent and a dehydrating ring-closing catalyst, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used. It is preferable that the usage-amount of a dehydration ring-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents to be used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

  In this way, a reaction solution containing polyimide (P) is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, and the polyimide (P) was isolated. You may use for preparation of a liquid crystal aligning agent on the top, or you may use for preparation of a liquid crystal aligning agent, after purifying the isolated polyimide (P). These purification operations can be performed according to known methods.

  The polyamic acid, polyamic acid ester and polyimide as the polymer (P) obtained as described above have a solution viscosity of 10 to 800 mPa · s when this is a 10% by weight solution. It is preferable to have a solution viscosity of 15 to 500 mPa · s. In addition, the solution viscosity (mPa · s) of the above polymer is based on a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The value measured at 25 ° C. using an E-type rotational viscometer. Moreover, about the polyamic acid, polyamic acid ester, and polyimide which are contained in the liquid crystal aligning agent of this invention, the weight average molecular weight (Mw) of polystyrene conversion measured by gel permeation chromatography (GPC) is 500-100,000. It is preferable that it is 1,000-50,000.

  The polymer (P) having a skeleton other than polyamic acid, polyamic acid ester and polyimide as the main skeleton can also be synthesized by appropriately combining organic chemistry methods. As an example, a polymer (P) having a polyorganosiloxane as a main skeleton is obtained, for example, by reacting a polyorganosiloxane having an epoxy group with a carboxylic acid having a structure represented by the above formula (1A). be able to.

The content ratio of the polymer (P) in the liquid crystal aligning agent is 5% by weight or more based on the total amount of the polymer components contained in the liquid crystal aligning agent, from the viewpoint of suitably obtaining the effects of the present invention. Is preferable, and it is more preferable to set it as 10 weight% or more. Moreover, there is no restriction | limiting in particular in an upper limit, It can set arbitrarily in the range of 100 weight% or less.
The said specific structure which a polymer (P) has is a 1 * 10 < ^-5 > -1 * 10 < ^- > with respect to the whole quantity of the polymer component contained in a liquid crystal aligning agent from a viewpoint which obtains the effect of this invention suitably. It is preferable to set it as ² mol / g, and it is preferable to set it as 5 * 10 < ^-5 > ^-5 * 10 < ^-3 > mol / g. Therefore, it is desirable to set the type and amount of the compound used for the synthesis of the polymer (P) so that the amount of the specific structure that the polymer (P) has falls within the above range.

  In the present invention, when a liquid crystal alignment film of a PSA mode liquid crystal display element is formed using a liquid crystal aligning agent containing the polymer (P), a photopolymerizable compound (photopolymerizable monomer) is irradiated upon light irradiation to the liquid crystal cell. ) Can be assisted from the liquid crystal alignment film side so that the photopolymerization reaction is not hindered, and as a result, the polymerization reaction of the photopolymerizable compound can sufficiently proceed to obtain an improvement in reliability. Guessed.

<Other ingredients>
The liquid crystal aligning agent of this invention may contain the other component as needed. Examples of such other components include other polymers other than the polymer (P), compounds having at least one epoxy group in the molecule (hereinafter referred to as “epoxy group-containing compound”), and functional silane compounds. Etc.

[Other polymers]
The above other polymers can be used for improving solution properties and electrical properties. Examples of such other polymers include polymers having no specific structure, and examples of the main skeleton include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide, cellulose derivative, Examples include polyacetal, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like.
When other polymers are added to the liquid crystal aligning agent, the blending ratio is preferably 95 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. More preferably, it is 90 weight part, and it is still more preferable that it is 0.1-85 weight part.

[Epoxy group-containing compound]
The epoxy group-containing compound can be used to improve the adhesion and electrical properties with the substrate surface in the liquid crystal alignment film. Examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylylene diene Amine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diamy 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 the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used.
When these epoxy compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 40 parts by weight or less, and 0.1 to 30 parts by weight with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. More preferred.

[Functional silane compounds]
The functional silane compound can be used for the purpose of improving the printability of the liquid crystal aligning agent. Examples of such functional silane compounds include 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 azananoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycid And xylpropyltrimethoxysilane.
When these functional silane compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 2 parts by weight or less, based on the total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent, 2 parts by weight is more preferred.
As other components, in addition to the above, a compound having at least one oxetanyl group in the molecule, an antioxidant, or the like can be used.

<Solvent>
The liquid crystal aligning agent of the present invention is prepared as a liquid composition in which the polymer (P) and other components optionally blended as necessary are preferably dispersed or dissolved in an organic solvent.
Here, examples of the solvent used for preparing the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether , Ethylene carbonate, propylene carbonate and the like. These can be used individually by 1 type or in mixture of 2 or more types.

  The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. The range is preferably 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described later, and preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film due to excessive film thickness, and the viscosity of the liquid crystal alignment agent tends to increase, resulting in poor coating characteristics. It is in.

  The particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s. The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-100 degreeC, More preferably, it is 20-80 degreeC.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment film of the present invention is formed by the liquid crystal aligning agent prepared as described above. Moreover, the liquid crystal display element of this invention comprises the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention. The drive mode to which the liquid crystal display element of the present invention is applied is not particularly limited, and can be applied to various drive modes such as TN type, STN type, IPS type, FFS type, VA type, MVA type, PSA type, In particular, the present invention can be preferably applied to the PSA mode.

The PSA mode liquid crystal display element of the present invention includes, for example, the following steps (1) to (3).
(1) A step of applying the liquid crystal aligning agent of the present invention onto each of the conductive films of a pair of substrates having a conductive film, and then heating this to form a coating film,
(2) a step of arranging a pair of substrates on which the coating film is formed so that the coating films face each other through a liquid crystal layer containing a liquid crystal compound, and (3) a pair of substrates. And a step of irradiating the liquid crystal cell with light while applying a voltage between the conductive films.

[Step (1): Formation of coating film]
First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, Then, a coating film is formed on a board | substrate by heating an application surface. As the substrate of the liquid crystal display element, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, or poly (alicyclic olefin) can be used. . As the conductive film included in the substrate, a transparent conductive film is preferably used. For example, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), indium oxide-tin oxide (In ₂ O ₃ —SnO _2). An ITO film made of or the like can be used. This conductive film is preferably a patterned conductive film partitioned into a plurality of regions. With such a conductive film, when a voltage is applied between the conductive films, the direction of the pretilt angle of the liquid crystal molecules can be changed for each region by applying a different voltage in each region. The characteristics can be made wider. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern when forming a transparent conductive film, etc. be able to.

  As a method of applying the liquid crystal aligning agent on the substrate, it can be preferably performed by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or functional titanium is formed on the surface of the substrate surface on which the coating film is to be formed. You may give the pretreatment which apply | coats a compound etc. previously.

  After applying the liquid crystal aligning agent to the substrate, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. Then, a baking (post-baking) process is implemented for the purpose of removing a solvent completely and heat imidating the amic acid structure which exists in a polymer as needed. The post-bake temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. Thus, the film thickness of the formed film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

  By removing the organic solvent by heating after applying the liquid crystal aligning agent, a coating film to be an alignment film is formed. At this time, when the polymer contained in the liquid crystal aligning agent is a polyamic acid, a polyamic acid ester, or an imidized polymer having an imide ring structure and an amic acid structure, a coating film It is good also as a more imidized coating film by advancing the dehydration ring-closing reaction by further heating after formation. In the case of the PSA mode, the following steps may be carried out using the coating film after post-baking as it is, but for the purpose of controlling the collapse of liquid crystal molecules and performing alignment division by a simple method, Weak rubbing treatment may be performed. The rubbing treatment can be performed by rubbing the coating film surface in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton.

[Step (2): Construction of liquid crystal cell]
A liquid crystal cell is manufactured by preparing two substrates on which a coating film is formed as described above, and disposing a liquid crystal layer between the two substrates facing each other at a predetermined interval. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method (vacuum injection method). First, the two substrates are placed opposite each other with a gap (cell gap) of, for example, 1 to 5 μm between the substrates so that the coating films on each substrate face each other, and the peripheral portions of the two substrates are sealed. The liquid crystal composition is bonded using an agent, the liquid crystal composition is injected and filled in the cell gap defined by the substrate surface and the sealing agent, and then the injection hole is sealed to manufacture a liquid crystal cell. The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealant is applied to a predetermined position on one of the two substrates on which the coating film is formed, and the liquid crystal composition is dropped onto predetermined positions on the coating film surface. After that, the other substrate is bonded so that the coating faces each other, the liquid crystal composition 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, thereby producing a liquid crystal cell. To do. Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the used liquid crystal molecules take an isotropic phase, and then gradually cooled to room temperature, whereby fluid alignment during liquid crystal filling is performed. May be removed.

As the liquid crystal composition to be used, those containing a liquid crystal compound and a photopolymerizable compound can be preferably used. As the liquid crystalline compound, nematic liquid crystal having negative dielectric anisotropy can be preferably used. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, A terphenyl liquid crystal or the like can be used. Moreover, as a liquid crystalline compound, you may use together an alkenyl type liquid crystal from a viewpoint of making the response speed of a PSA mode liquid crystal display element faster. A conventionally well-known thing can be used as the said alkenyl type liquid crystal, For example, the compound etc. which are represented by each of following formula (L1-1)-a formula (L1-9) can be mentioned. In addition, as a liquid crystalline compound, 1 type can be used individually or in combination of 2 or more types.

  As the photopolymerizable compound, a compound having a functional group capable of radical polymerization such as an acryloyl group, a methacryloyl group, and a vinyl group can be used. From the viewpoint of reactivity, polyfunctionality is preferable, and it is more preferable to have at least two of acryloyl group and methacryloyl group. From the viewpoint of stably maintaining the orientation of the liquid crystal molecules, a compound having a total of two or more of at least one of a cyclohexane ring and a benzene ring as the liquid crystal skeleton is used as the photopolymerizable compound. preferable. In addition, a conventionally well-known thing can be used as such a photopolymerizable compound. The blending ratio of the photopolymerizable compound is preferably 0.1 to 0.5% by weight with respect to the total amount of the liquid crystal compound to be used.

  In addition, the liquid crystal composition may contain other components such as a polymerization initiator, an antioxidant, an ultraviolet absorber, and a stabilizer in addition to the above compound. These blending amounts can be appropriately adjusted according to the other components used. The thickness of the liquid crystal layer is preferably 1 to 5 μm. Moreover, as a sealing agent, the epoxy resin etc. which contain the aluminum oxide sphere as a hardening | curing agent and a spacer, for example can be used.

[Step (3): Light irradiation step]
After the construction of the liquid crystal cell, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. Moreover, as light to irradiate, the ultraviolet-ray and visible light which contain light with a wavelength of 150-800 nm can be used, for example, However, The ultraviolet-ray containing light with a wavelength of 300-400 nm is preferable. As a light source of irradiation light, 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, or the like can be used. In addition, the ultraviolet rays in the above preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter diffraction grating. The amount of light irradiation is preferably 1,000 J / m ² or more and less than 200,000 J / m ² , more preferably 1,000 to 150,000 J / m ² .

  And a liquid crystal display element can be obtained by bonding a polarizing plate on the outer surface of the liquid crystal cell after light irradiation. As a polarizing plate used here, a polarizing plate composed of a polarizing film called an “H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine and sandwiched between cellulose acetate protective films or a polarizing film made of the H film itself. Can be mentioned.

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

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

In the following Examples and Comparative Examples, the imidization ratio of polyimide in the polymer solution, the solution viscosity of the polymer solution, the weight average molecular weight of the polymer, and the epoxy equivalent were measured by the following methods.
[Imidation rate of polyimide]
The polyimide solution was poured into pure water, and the resulting precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidation ratio [%] was determined by the following mathematical formula (1).
Imidation ratio [%] = (1-A ¹¹ / A ¹² × α) × 100 (1)
(In Formula (1), A ¹¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ¹² is a peak area derived from other protons, and α is a precursor of a polymer (polyamic acid) The number ratio of other protons to one proton of NH group in)
[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 for a solution prepared to a polymer concentration of 10% by weight using a predetermined solvent.
[Weight average molecular weight of polymer]
The weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Epoxy equivalent]
The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

<Synthesis of compounds>
[Example 1A: Synthesis of compound (da-5)]
According to the following scheme 1, a compound represented by the above formula (da-5) (hereinafter also referred to as compound (da-5)) was synthesized.

Bis (3-pyridylmethyl) amine (12.5 g, 62.8 mmol), dichloromethane (150 ml) and triethylamine (15.9 ml, 114 mmol) were mixed, and cooled in an ice bath, 13.5-g of 3,5-dinitrobenzoyl chloride (57. 1 mmol) dissolved in 50 ml of dichloromethane was added dropwise, followed by stirring at room temperature for 3 hours. After the reaction, 500 ml of ethyl acetate and 500 ml of tetrahydrofuran were added, and the mixture was washed with 400 ml of distilled water four times. The organic layer was dried over magnesium sulfate, the solvent was distilled off, and the precipitated solid was filtered and dried, and 17.7 g of a brown powder dinitro compound (compound represented by the above formula (dm-5)) ( 45.0 mmol, yield 78.7%).
Next, 17.7 g (45.0 mmol) of the dinitro compound, 1.77 g of 5% palladium carbon (containing 50% water), 90 ml of tetrahydrofuran and 90 ml of ethanol were mixed, and a balloon filled with hydrogen gas was attached. Under a hydrogen atmosphere, Stir at room temperature for 5 hours. After the reaction, palladium carbon was removed by celite filtration, and the filtrate was concentrated to obtain 12.8 g (38.3 mmol, yield 85.1%) of a brown powder compound (da-5).

[Example 2A: Synthesis of compound (da-6)]
According to the following scheme 2, a compound represented by the above formula (da-6) (hereinafter, also referred to as compound (da-6)) was synthesized.

While mixing 11.3 g (50.0 mmol) of 2,4-dinitrophenylacetic acid, 9.96 g (50.0 mmol) of bis (3-pyridylmethyl) amine and 200 ml of dichloromethane, the mixture was cooled in an ice bath, and 1-ethyl-3 -(3-Dimethylaminopropyl) carbodiimide hydrochloride 11.5 g (60.0 mmol) and N, N-dimethyl-4-aminopyridine 1.22 g (10.0 mmol) were added, and the mixture was stirred at room temperature for 2 hours. After the reaction, 800 ml of ethyl acetate was added and washed with 400 ml of distilled water four times. The organic layer was dried over magnesium sulfate, the solvent was distilled off, and the precipitated solid was filtered and dried, and 16.4 g of a brown powder dinitro compound (compound represented by the above formula (dm-6)) ( 40.3 mmol, yield 80.5%).
Next, 16.4 g (40.3 mmol) of the dinitro compound, 1.64 g of 5% palladium carbon (containing 50% water), 80 ml of tetrahydrofuran, and 80 ml of ethanol were mixed, and a balloon filled with hydrogen gas was attached. Stir at room temperature for 6 hours. After the reaction, palladium carbon was removed by celite filtration, and the filtrate was concentrated to obtain 11.5 g (33.0 mmol, yield 82.0%) of a brown powder compound (da-6).

[Example 3A: Synthesis of compound (da-37)]
According to Scheme 3 below, a compound represented by the above formula (da-37) (hereinafter also referred to as compound (da-37)) was synthesized.

  A mixture of 12.9 g (96.7 mmol) of iminodiacetic acid and 145 ml of 2M aqueous sodium hydroxide solution, and 22.3 g (96.7 mmol) of 3,5-dinitrobenzoyl chloride dissolved in 30 ml of tetrahydrofuran while cooling in an ice bath Was added dropwise, followed by stirring at room temperature for 4 hours. After the reaction, while cooling in an ice bath, 300 ml of 1M diluted hydrochloric acid was added, and the precipitated solid was filtered and dried. Then, recrystallization is performed with 200 ml of ethyl acetate, the precipitated solid is filtered and dried, and 15.3 g (46.7 mmol) of a white powder dicarboxylic acid compound (compound represented by the above formula (dm-37-1)) is obtained. Yield 48.3%).

Next, 15.3 g (46.7 mmol) of the above dicarboxylic acid compound, 10.6 g (98.1 mmol) of 3-aminomethylpyridine and 200 ml of dichloromethane were mixed, and while cooling in an ice bath, 1-ethyl-3- (3- 21.5 g (112 mmol) of dimethylaminopropyl) carbodiimide hydrochloride and 2.28 g (18.7 mmol) of N, N-dimethyl-4-aminopyridine were added, and the mixture was stirred at room temperature for 3 hours. After the reaction, 800 ml of ethyl acetate was added and washed with 400 ml of distilled water four times. The solid obtained by drying and concentrating the organic layer with magnesium sulfate was recrystallized with 100 ml of ethyl acetate and 150 ml of hexane, and the precipitated solid was filtered and dried to give a dinitro form of the brown powder (formula (dm-37- 17.5 g (34.6 mmol, yield 74.1%) of the compound represented by 2) was obtained.
Next, 17.5 g (34.6 mmol) of the above dinitro compound, 1.75 g of 5% palladium carbon (containing 50% water), 70 ml of tetrahydrofuran and 70 ml of ethanol were mixed, and a balloon filled with hydrogen gas was attached. Under a hydrogen atmosphere, Stir at room temperature for 4 hours. After the reaction, palladium on carbon was removed by Celite filtration, and the filtrate was concentrated to obtain 13.5 g (30.3 mmol, yield 87.6%) of a brown powder compound (da-37).

[Example 4A: Synthesis of compound (da-67)]
According to Scheme 4 below, a compound represented by the above formula (da-67) (hereinafter also referred to as compound (da-67)) was synthesized.

2,4-dinitrobenzyl bromide 13.1 g (50.0 mmol), bis (3-pyridylmethyl) amine 9.96 g (50.0 mmol), potassium carbonate 8.29 g (60.0 mmol), potassium iodide 1.66 g (10.0 mmol) and 200 ml of N, N-dimethylacetamide were mixed and stirred at 100 ° C. for 5 hours. After the reaction, 600 ml of ethyl acetate was added and washed with 600 ml of distilled water four times. The solid obtained by drying and concentrating the organic layer with magnesium sulfate is recrystallized with 200 ml of ethanol, and the precipitated solid is filtered and dried, and is expressed as a brown powder dinitro compound (the above formula (dm-67)). Compound (15.7 g) (41.4 mmol, yield 82.8%) was obtained.
Next, 15.7 g (41.4 mmol) of the above dinitro compound, 1.57 g of 5% palladium carbon (containing 50% water), 80 ml of tetrahydrofuran, and 80 ml of ethanol were mixed, and a balloon containing hydrogen gas was attached. Stir at room temperature for 4 hours. After the reaction, palladium on carbon was removed by Celite filtration, and the filtrate was concentrated to obtain 12.2 g (38.2 mmol, yield 92.3%) of a brown powder compound (da-67).

[Example 5A: Synthesis of compound (da-70)]
According to the following scheme 5, a compound represented by the above formula (da-70) (hereinafter also referred to as compound (da-70)) was synthesized.

A mixture of 102 g (750 mmol) of pentaerythritol, 41.8 ml (300 mmol) of triethylamine and 750 ml of tetrahydrofuran, and 12.8 g (75.0 mmol) of 3,5-dinitrobenzoyl chloride dissolved in 50 ml of tetrahydrofuran while cooling in an ice bath. After the dropwise addition, the mixture was stirred at room temperature for 5 hours. After the reaction, 1500 ml of ethyl acetate was added, and the mixture was washed with 750 ml of distilled water four times. The solid obtained by drying and concentrating the organic layer with magnesium sulfate was recrystallized with 100 ml of ethyl acetate and 300 ml of hexane, and the precipitated solid was filtered and dried to give a brown powder triol (formula (dm-70- 18.9 g (57.2 mmol, yield 76.3%) of the compound represented by 1) was obtained.
Next, 18.9 g (57.2 mmol) of the triol compound, 21.1 g (172 mmol) of nicotinic acid, and 250 ml of dichloromethane were mixed, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was cooled in an ice bath. 39.5 g (206 mmol) of the salt and 4.19 g (34.3 mmol) of N, N-dimethyl-4-aminopyridine were added, and the mixture was stirred at room temperature for 4 hours. After the reaction, 800 ml of ethyl acetate was added and washed with 400 ml of distilled water four times. The solid obtained by drying and concentrating the organic layer with magnesium sulfate is recrystallized with 200 ml of ethanol, and the precipitated solid is filtered and dried, and is expressed as a brown powder dinitro compound (the above formula (dm-70-2)). 29.6 g (45.9 mmol, yield 80.4%).
Next, 29.6 g (45.9 mmol) of the above dinitro compound, 2.96 g of 5% palladium carbon (containing 50% water), 100 ml of tetrahydrofuran and 100 ml of ethanol were mixed, a balloon filled with hydrogen gas was attached, and under a hydrogen atmosphere, Stir at room temperature for 4 hours. After the reaction, palladium on carbon was removed by Celite filtration, and the filtrate was concentrated to obtain 23.8 g (40.7 mmol, yield 88.7%) of a brown powder compound (da-70).

<Synthesis of polymer>
[Example 1B: Synthesis of polyimide (PI-1)]
2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) 100 mole parts as tetracarboxylic dianhydride, p-phenylenediamine (PDA) 70 mole parts as diamine, cholestanyl 3,5-diaminobenzoate (HCDA) ) 20 mol parts and 10 mol parts of compound (da-5) are dissolved in N-methyl-2-pyrrolidone (NMP), reacted at 60 ° C. for 6 hours, and a solution containing 20% by weight of polyamic acid is obtained. Obtained. A small amount of the obtained polyamic acid solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 80 mPa · s.
Next, NMP was added to the obtained polyamic acid solution to obtain a solution having a polyamic acid concentration of 7% by weight, and pyridine and acetic anhydride were each 1.0 times the total amount of tetracarboxylic dianhydride used. Each was added in moles, and a dehydration ring closure reaction was carried out at 110 ° C. for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with new NMP (by this operation, pyridine and acetic anhydride used in the dehydration cyclization reaction were removed from the system. The same applies hereinafter), whereby the imidation rate was about 60. A solution containing 26% by weight of polyimide (PI-1) was obtained.

[Examples 2B to 9B, Synthesis Examples 1 and 2]
The type and amount of tetracarboxylic dianhydride and diamine used, and the amount of pyridine and acetic anhydride used for imidization were changed as shown in Table 1 below in the same manner as in Example 1B. ) To (PI-11) were synthesized. The measurement results of the imidization ratio of the obtained polymer are shown in Table 1 below. In Example 7B, monoamine was used together with tetracarboxylic dianhydride and diamine during the synthesis of the polymer.

In Table 1, the numerical value in parentheses for tetracarboxylic dianhydride represents the usage ratio [molar part] with respect to a total of 100 molar parts of the tetracarboxylic dianhydride used for the synthesis of the polymer. The numerical value in () of diamine and monoamine represents the usage ratio [mole part] with respect to 100 mol parts in total of the tetracarboxylic dianhydride used for the synthesis of the polymer. Abbreviations in Table 1 have the following meanings, respectively. In Table 1, “-” means that the compound in the corresponding column was not used.
<Tetracarboxylic dianhydride>
TCA: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride BODA: 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride CB: 1,2,3,4-cyclobutanetetracarboxylic dianhydride MTDA: 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -Naphtho [1,2-c] furan-1,3-dione PMDA: pyromellitic dianhydride <diamine>
PDA: p-phenylenediamine HCDA: cholestanyl 3,5-diaminobenzoate 35DAB: 3,5-diaminobenzoic acid HCODA: cholestanyloxy-2,4-diaminobenzene LDA: represented by the above formula (Y-1-4) Compound D-1: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene (represented by the formula (Y-1-2) above) Compound)
D-2: 1,3-bis (3-aminopropyl) -tetramethyldisiloxane D-3: 3,6-bis (4-aminobenzoyloxy) cholestane D-5: 2,2′-bis (trifluoro) Methyl) -4,4'-diaminobiphenyl D-6: 4,4'-diaminodiphenylmethane D-7: 2,2'-dimethyl-4,4'-diaminobiphenyl D-8: 4,4'-diaminodiphenyl ether da-x: Compound represented by the following formula (da-x)
<Monoamine>
D-4: Aniline

[Synthesis Example 3: Synthesis of polyamic acid (PA-1)]
100 mol parts of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CB) as tetracarboxylic dianhydride, 100 mol parts of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine, It is dissolved in a mixed solvent of NMP and γ-butyrolactone (γBL) (NMP: γBL = 10: 90 (weight ratio)), reacted at 40 ° C. for 3 hours, and contains 10% by weight of polyamic acid (PA-1). A solution was obtained. The solution viscosity measured by collecting a small amount of the obtained polyamic acid solution was 180 mPa · s.

[Synthesis Example 4: Synthesis of polyamic acid (PA-2)]
Except having changed the kind and quantity of the tetracarboxylic dianhydride and diamine to be used as shown in Table 1 above, 10% by weight of polyamic acid (PA-2) is contained by performing the same operation as in Synthesis Example 3. A solution was obtained. The solution viscosity measured by taking a small amount of the obtained polyamic acid solution was 150 mPa · s.

[Synthesis Example 5: Synthesis of polyorganosiloxane (APS-1)]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were added. Charged and mixed at room temperature. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the reaction was performed at 80 ° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer is taken out, washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure, thereby reactive polyorganosiloxane. (EPS-1) was obtained as a viscous transparent liquid. When this reactive polyorganosiloxane was subjected to ¹ H-NMR analysis, a peak based on an epoxy group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity. Was confirmed not to happen. The obtained reactive polyorganosiloxane had a weight average molecular weight Mw of 3,500 and an epoxy equivalent of 180 g / mol.
Next, in a 200 mL three-necked flask, 10.0 g of reactive polyorganosiloxane (EPS-1), 30.28 g of methyl isobutyl ketone as a solvent, 3.98 g of 4-dodecyloxybenzoic acid as a reactive compound, and UCAT as a catalyst 0.10 g of 18X (trade name, manufactured by San Apro Co., Ltd.) was charged, and the reaction was performed at 100 ° C. with stirring for 48 hours. After completion of the reaction, a solution obtained by adding ethyl acetate to the reaction mixture was washed with water three times, the organic layer was dried using magnesium sulfate, and then the solvent was distilled off to obtain a liquid crystal alignment polyorganosiloxane (APS-). 9.0 g of 1) was obtained. The weight average molecular weight Mw of the obtained polymer was 9,900.

[Examples 10B and 11B]
The type and amount of tetracarboxylic dianhydride and diamine to be used, and the amount of pyridine and acetic anhydride to be used for imidization were changed in the same manner as in Example 1B except that polyimide (PI-12) was used. ) And (PI-13) were synthesized. The measurement results of the imidization ratio of the obtained polymer are shown in Table 2 below. The explanation of each numerical value, abbreviation and “-” in Table 2 is the same as in Table 1 above.

<Preparation of liquid crystal composition>
[Preparation of Liquid Crystal Composition LC1]
A liquid crystal composition LC1 was obtained by adding 0.3% by weight of a photopolymerizable compound represented by the following formula (pc-1) to 10 g of nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) and mixing them. .
[Preparation of Liquid Crystal Composition LC2]
5% by weight of a liquid crystalline compound represented by the above formula (L1-1) and a photopolymerizable compound represented by the following formula (pc-1) with respect to 10 g of nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) A liquid crystal composition LC2 was obtained by adding 0.3% by weight and mixing.

[Example 1C]
<Preparation of liquid crystal aligning agent>
NMP and butyl cellosolve (BC) are added as organic solvents to the solution containing the polyimide (PI-1) obtained in Example 1B as a polymer, and the solvent composition is NMP: BC = 50: 50 (weight ratio), solid. A solution having a partial concentration of 6.0% by weight was obtained. A liquid crystal aligning agent (S1) was prepared by filtering this solution using a filter having a pore diameter of 1 μm.

<Manufacture of liquid crystal cells>
The liquid crystal aligning agent (S1) of Example 1C prepared above was patterned on a slit shape as shown in FIG. 1 and on each electrode surface of two glass substrates each having an ITO electrode partitioned into a plurality of regions. Then, using a liquid crystal alignment film printing machine (Nissha Printing Co., Ltd.), and removing the solvent by heating (prebaking) on a hot plate at 80 ° C. for 1 minute, and then on a hot plate at 150 ° C. The film was heated (post-baked) for 10 minutes to form a coating film having an average film thickness of 600 mm. This coating film was subjected to ultrasonic cleaning in ultrapure water for 1 minute, and then dried in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a coating film to be a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a coating film. The used electrode pattern is the same type as the electrode pattern in the PSA mode.
Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to each outer edge having the coating film on the pair of substrates, and then superimposed and pressure-bonded so that the coating film faces each other. Cured. Next, after filling the liquid crystal composition LC1 prepared above between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an acrylic photo-curing adhesive. Then, in the state which applied the voltage between the electrically conductive films of the obtained liquid crystal cell, it irradiated with light with the irradiation amount of 100,000 J / m < ² >.

<Reliability evaluation>
Using the liquid crystal cell produced above (liquid crystal cell after light irradiation), the reliability of the liquid crystal alignment film (liquid crystal display element) was evaluated. Evaluation was performed as follows. First, a voltage of 5 V was applied to the liquid crystal cell with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio (VHR1) after 167 milliseconds from the release of application was measured. Next, the liquid crystal cell was allowed to stand in an 80 ° C. oven under LED lamp irradiation for 200 hours, and then allowed to stand at room temperature and naturally cooled to room temperature. After cooling, a voltage of 5 V was applied to the liquid crystal cell with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio (VHR2) 167 milliseconds after the application release was measured. The measuring device used was “VHR-1” manufactured by Toyo Corporation. The change rate (ΔVHR) of VHR at this time was calculated by the following mathematical formula (2), and the reliability of the liquid crystal alignment film was evaluated by ΔVHR. In the evaluation, when ΔVHR was less than 1.0%, reliability “very good (()”, and when ΔVHR was 1.0% or more and less than 1.5%, reliability “good (◯)”, When 1.5% or more and less than 2.0%, the reliability was “possible (Δ)”, and when 2.0% or more, the reliability was “bad (×)”. As a result, in Example 1C, the reliability was “very good”.
ΔVHR [%] = (VHR1−VHR2) / (VHR1) × 100 (2)

<Examples 2C to 9C and Comparative Examples 1 and 2>
A liquid crystal aligning agent was prepared in the same manner as in Example 1C except that the composition of the liquid crystal aligning agent was changed as shown in Table 3 below. Moreover, using each liquid crystal aligning agent, while manufacturing the liquid crystal cell similarly to Example 1C, the manufactured liquid crystal cell was evaluated. In Examples 3C and 4C, the liquid crystal composition used was changed from LC1 to LC2. The evaluation results are shown in Table 3 below.

  As shown in Table 3, in Examples 1C to 9C, even after light irradiation and exposure to a stress environment of 80 ° C. for a long time (200 hours), the decrease in voltage holding ratio is small and the reliability is high. It was good. On the other hand, in Comparative Examples 1 and 2, the voltage holding ratio was greatly reduced by the application of light stress and thermal stress.

  Furthermore, except that the ITO electrode pattern on the glass substrate was changed to a fishbone-like electrode pattern as shown in FIGS. 2 and 3, the liquid crystal aligning agents of Examples 1C to 9C were used, and Example 1C was used. A liquid crystal cell was manufactured and evaluated in the same manner as described above. Also in this case, the same effects as in Examples 1C to 9C were exhibited.

<Examples 10C and 11C>
A liquid crystal aligning agent was prepared in the same manner as in Example 1C except that the composition of the liquid crystal aligning agent was changed as shown in Table 4 below. Moreover, using each liquid crystal aligning agent, while manufacturing the liquid crystal cell similarly to Example 1C, the manufactured liquid crystal cell was evaluated. The results are shown in Table 4 below.

As shown in Table 4, in Example 10C including a polymer synthesized using a diamine in which Q ¹ in the formula (d-1A) is a nitrogen atom, the reliability was “very good”. In Example 11C including a polymer synthesized using a diamine in which Q ¹ is a carbon atom, the reliability was evaluated as “good”. Further, except that the ITO electrode pattern on the glass substrate was changed to the electrode pattern of FIGS. 2 and 3, respectively, the liquid crystal cell was prepared in the same manner as in Example 1C using the liquid crystal aligning agent of Examples 10C and 11C. Manufactured and evaluated. In this case, similar results were obtained.

  DESCRIPTION OF SYMBOLS 1 ... ITO electrode, 2 ... Slit part, 3 ... Light-shielding film

Claims (12)

The liquid crystal aligning agent containing the polymer (P) which has a specific structure represented by a following formula (1A).
(In the formula (1A), R ² is a divalent organic group, and X ¹ is a nitrogen-containing aromatic heterocycle. However, a plurality of R ² in the formula may be the same or different, and X ¹ may be the same or different, Q ¹ is a nitrogen atom, a carbon atom or a silicon atom, Y ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and when Q ¹ is a nitrogen atom Is t = 2 and s = 0, t = 3 and s = 0 when Q ¹ is a silicon atom, t is 2 or 3 when Q ¹ is a carbon atom and s = 3-t.) The liquid crystal aligning agent according to claim 1, wherein the specific structure is represented by the following formula (1-1A).
(In Formula (1-1A), R ³ is an alkanediyl group having 1 to 5 carbon atoms when Q ¹ is a nitrogen atom or a carbon atom, and a single bond or carbon when Q ¹ is a silicon atom. An alkanediyl group having a number of 1 to 5. R ⁴ is a single bond or an alkanediyl group having a carbon number of 1 to 5, and A ¹ is a single bond, —O—, —CO—, * ¹ —COO—. , ^* 1 --OCO ^-, * 1 -CONH- or ^* 1 -NHCO -. (. ^{"* 1",} which indicates a bond to ^{R 3)} is provided that when ^{R 3} is a single bond, ^{a 1} Is —O— or * ¹ —OCO—, wherein a plurality of R ³ may be the same or different, a plurality of R ⁴ may be the same or different, and a plurality of A ¹ are the same or different; which may be ^{.X 1, Q 1, Y 1} , t and s are as defined in the above formula (1A). "*" indicates a bond )   The liquid crystal aligning agent according to claim 1 or 2, wherein the polymer (P) is at least one selected from the group consisting of a polyamic acid, a polyamic acid ester, and a polyimide. The polymer (P) is a polymer obtained by reacting at least one compound selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic diester and tetracarboxylic diester dihalide with diamine. ,
The said diamine is a liquid crystal aligning agent of Claim 3 containing the compound represented by a following formula (d-1A).
(In the formula (d-1A), R ¹ is a single bond or a divalent organic group. R ² , X ¹ , Q ¹ , Y ¹ , t and s are as defined in the above formula (1A). ) The liquid crystal aligning agent according to claim 1, wherein Q ¹ is a nitrogen atom.   The polymer (P) is 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8- Dianhydrides, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride The polymer according to any one of claims 1 to 5, which is a polymer obtained by reacting at least one tetracarboxylic dianhydride selected from the group consisting of an anhydride and a diamine having the specific structure. Liquid crystal aligning agent.   The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-6.   A liquid crystal display device comprising the liquid crystal alignment film according to claim 7. Applying the liquid crystal aligning agent according to any one of claims 1 to 6 on the conductive film of a pair of substrates having a conductive film, and then heating this to form a coating film;
A step of constructing a liquid crystal cell by arranging a pair of substrates on which the coating film is formed, with the coating film facing each other through a liquid crystal layer containing a liquid crystalline compound,
Irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates.   The method for producing a liquid crystal display element according to claim 9, wherein the liquid crystal compound includes a monofunctional liquid crystal compound having one of an alkenyl group and a fluoroalkenyl group. A polymer having a specific structure represented by the following formula (1A).
(In the formula (1A), R ² is a divalent organic group, and X ¹ is a nitrogen-containing aromatic heterocycle. However, a plurality of R ² in the formula may be the same or different, and X ¹ may be the same or different, Q ¹ is a nitrogen atom, a carbon atom or a silicon atom, Y ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and when Q ¹ is a nitrogen atom Is t = 2 and s = 0, t = 3 and s = 0 when Q ¹ is a silicon atom, t is 2 or 3 when Q ¹ is a carbon atom and s = 3-t.) A compound represented by the following formula (d-1A).
(In formula (d-1A), R ¹ is a single bond or a divalent organic group, R ² is a divalent organic group, and X ¹ is a nitrogen-containing aromatic heterocyclic ring, provided that A plurality of R ² may be the same or different, and a plurality of X ¹ may be the same or different, Q ¹ is a nitrogen atom, a carbon atom or a silicon atom, and Y ¹ is a hydrogen atom or a carbon number. An alkyl group of 1 to 5. When Q ¹ is a nitrogen atom, t = 2 and s = 0, and when Q ¹ is a silicon atom, t = 3 and s = 0, and Q ¹ is In the case of a carbon atom, t is 2 or 3, and s = 3-t.