KR102096370B1 - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, manufacturing method for the liquid crystal display device, and polymer - Google Patents

Abstract

(식 (1A) 중, R²는 2가의 유기기이며, X¹은 질소 함유 방향족 복소환이고; Q¹은 질소 원자, 탄소 원자 또는 규소 원자이며, Y¹은 수소 원자 또는 탄소수 1∼5의 알킬기이고; Q¹이 질소 원자인 경우에는 t＝2이고 s＝0이며, Q¹이 규소 원자인 경우에는 t＝3이고 s＝0이며, Q¹이 탄소 원자인 경우에는 t가 2 또는 3이고 s＝3-t임).(Task) A highly reliable liquid crystal display device with little deterioration associated with use is obtained.
(Solution) A polymer (P) having a specific structure represented by the following formula (1A) is contained in a liquid crystal aligning agent:

(In formula (1A), R ² is a divalent organic group, X ¹ is a nitrogen-containing aromatic heterocycle; Q ¹ is a nitrogen atom, a carbon atom or a silicon atom, and Y ¹ is a hydrogen atom or 1 to 5 carbon atoms. Alkyl group; t = 2 and s = 0 when Q ¹ is a nitrogen atom, t = 3 and s = 0 when Q ¹ is a silicon atom, and t = 2 or 3 when Q ¹ is a carbon atom And s = 3-t).

Description

LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT FILM, LIQUID CRYSTAL DISPLAY DEVICE, MANUFACTURING METHOD FOR THE LIQUID CRYSTAL DISPLAY DEVICE, AND POLYMER}

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning 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 device includes a liquid crystal layer including a liquid crystal molecule and a liquid crystal alignment film that is disposed so as to sandwich the liquid crystal layer between a pair of substrates facing each other and controls the liquid crystal molecules to a desired alignment state. have. In addition, conventionally, various driving methods having different electrode structures and physical properties of liquid crystal molecules to be used have been developed as liquid crystal display elements. For example, the MVA (Multi-Domain Vertical Alignment) type panel, which is conventionally known as a vertical alignment mode, seeks to increase 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, the lack of transmittance and contrast derived from the projections is inevitable, and there is a problem that the response speed of the liquid crystal molecules is slow.

Recently, in order to solve the problem of the MVA type 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 incorporated by incorporating a photopolymerizable monomer into a liquid crystal material and assembling the liquid crystal cell, followed by light irradiation of the liquid crystal cell with a voltage applied between a pair of electrodes sandwiching the liquid crystal layer. It is a technology to control the molecular orientation of liquid crystal molecules by polymerization. According to this technique, there is an advantage that the viewing angle can be enlarged and high-speed response can be achieved. In addition, in recent years, further high-speed responsiveness of the PSA type liquid crystal panel has been studied, and as such a technique, a monofunctional liquid crystalline compound having one of an alkenyl group and a fluoroalkenyl group (hereinafter referred to as "alkenyl-based liquid crystal"). Has also been attempted to be introduced into the liquid crystal layer (see, for example, Patent Documents 1 to 3).

Japanese Patent Publication No. 2010-285499 Japanese Patent Publication No. Hei 9-104644 Japanese Patent Publication No. Hei 6-108053

In recent years, liquid crystal display elements are used not only for display terminals such as personal computers as in the prior art, but are also used for various types of applications such as, for example, liquid crystal televisions, car navigation systems, mobile phones, smartphones, and information displays. From such versatility, a liquid crystal display element with little deterioration and high reliability associated with use is required, and a material for obtaining such a liquid crystal display element is desired.

In addition, in a liquid crystal display device using an alkenyl-based liquid crystal, it is possible to increase the response speed, whereas by irradiation with light during polymerization of the photopolymerizable monomer, a voltage compared to a liquid crystal cell that does not include an alkenyl-based liquid crystal in the liquid crystal layer. It is evident that the decrease in the maintenance rate increases. From the viewpoint of improving the reliability of the liquid crystal display element, it is necessary to maintain a high voltage retention rate even after light irradiation.

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

As a result of earnest examination to achieve the problems of the prior art as described above, the present inventors have found that the problems can be solved by incorporating a polymer having a specific structure into a liquid crystal aligning agent, and have completed the present invention. Specifically, the following liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, manufacturing method of a liquid crystal display element, a polymer, and a compound are provided by this invention.

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 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 a plurality of X ¹ may be the same or different. Good; 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; when Q ¹ is a nitrogen atom, t = 2, s = 0, and Q ¹ is silicon In the case of an atom, t = 3 and s = 0, and when Q ¹ is a carbon atom, t is 2 or 3 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 have the same meaning as in formula (1A) above; “*” represents a bonding hand).

In another aspect, the present invention provides a liquid crystal alignment film formed using the liquid crystal aligning agent, and a liquid crystal display device comprising the liquid crystal alignment film. Moreover, the process of forming the coating film by apply | coating the said liquid crystal aligning agent on the said conductive film of a pair of board | substrates which have a conductive film respectively, and then heating this, and the pair of board | substrate which formed the said coating film are liquid crystal compounds. And a step of constructing a liquid crystal cell by arranging the coating film so as to face each other via a liquid crystal layer comprising a step, and a step of irradiating light to the liquid crystal cell with a voltage applied between the conductive films of the pair of substrates. A method of manufacturing a liquid crystal display device is provided.

According to the liquid crystal aligning agent of this invention, the liquid crystal aligning film with little deterioration and high reliability accompanying use can be obtained. Moreover, since the liquid crystal display element of this invention and the liquid crystal display element manufactured by the manufacturing method of this invention have the liquid crystal aligning film formed using the said liquid crystal aligning agent, there is little quality deterioration accompanying use, and reliability is high. great.

1 is a view showing an electrode pattern of a transparent electrode film used in Examples and Comparative Examples.
2 is a view showing an electrode pattern of a transparent electrode film used in Examples.
3 is a view showing an electrode pattern of a transparent electrode film used in Examples.

(Form for carrying out the invention)

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

<Polymer (P)>

The polymer (P) of the present invention is a polymer having a structure represented by the following formula (1A):

(In 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 a plurality of X ¹ may be the same or different. Good; 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; when Q ¹ is a nitrogen atom, t = 2, s = 0, and Q ¹ is silicon In the case of an atom, t = 3 and s = 0, and when Q ¹ is a carbon atom, t is 2 or 3 and s = 3-t).

It is preferable that the said polymer (P) is a polymer which has a structure represented by following formula (1):

(In formula (1), R ² and X ¹ have the same meaning as in formula (1A) above; “*” represents a bonding hand).

In the formulas (1A) and (1), as the divalent organic group of R ² when Q ¹ is a nitrogen atom or a carbon atom, for example, a divalent hydrocarbon group or a carbon-carbon in the hydrocarbon group Between bonds, -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- divalent group having a functional group, 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- And a divalent group formed by linkage, a divalent group substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, or a hydroxyl group in a hydrocarbon group. Further, as the divalent organic group of R ² when Q ¹ is a silicon atom, for example, in addition to the specific examples of R ² when Q ¹ is a nitrogen atom or a carbon atom, -O-, -CO-O-, etc. Can be mentioned.

Here, the "hydrocarbon group" in the present specification may be saturated or unsaturated, and is meant to include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. In addition, the term "chain hydrocarbon group" means a straight chain hydrocarbon group and a branched hydrocarbon group which do not have a cyclic structure in the main chain and are composed only of a chain structure. The alicyclic hydrocarbon group means a hydrocarbon group having only an alicyclic hydrocarbon structure and no aromatic ring structure as the ring structure. However, it is not necessary to consist only of the structure of alicyclic hydrocarbon, and it also includes what has a chain structure in a part. The "aromatic hydrocarbon group" means a hydrocarbon group having an aromatic ring structure as a ring structure. However, it is not necessary to consist only of an aromatic ring structure, and a part of the structure may have a chain structure or an alicyclic hydrocarbon structure.

The divalent hydrocarbon group for R ² is preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms. As a specific example of the said hydrocarbon group, As a chain hydrocarbon group, For example, alkanediyl groups, such as methylene group, ethylene group, propane diyl group, butane diyl group, pentane diyl group, hexane diyl group, vinylene group, propenyl group My back; As an alicyclic hydrocarbon group, a cyclohexylene group etc. are mentioned, for example; As an aromatic hydrocarbon group, a phenylene group etc. are mentioned, for example; Each can be lifted. Especially, it is preferable that it is a chain hydrocarbon group or an alicyclic hydrocarbon group, and it is more preferable that it is an alkanediyl group.

The nitrogen-containing aromatic heterocycle of X ¹ may be an aromatic ring containing one or more nitrogen atoms in the ring skeleton. Therefore, the ring skeleton may contain only a nitrogen atom as a hetero atom, and may contain a nitrogen atom and a hetero atom (oxygen atom, sulfur atom, etc.) other than the nitrogen atom. Specific examples of the nitrogen-containing aromatic heterocycle for X ¹ include, for example, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, indole ring, benzoimida Sol ring, 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. In addition, X ¹ may be one in which a substituent is introduced into a carbon atom constituting the above-mentioned ring. As said substituent, a halogen atom, an alkyl group, an alkoxy group, etc. are mentioned, for example.

As X ¹ , among these, the ring skeleton has a pyrrole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, benzoimidazole ring, naphthyridine ring, phthalazine ring, It is preferably a quinoxaline ring, a triazine ring, an azepine ring, a diazepine ring, or a phenazine ring, and more preferably a pyrrole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridazine ring or pyrazine ring Do.

In addition, in the nitrogen-containing aromatic heterocycle, the bonding position with R ² is not particularly limited. For example, if the nitrogen-containing aromatic heterocyclic ring as X ¹ is a 5-membered ring, 1-position, 2-position or 3-position can be mentioned, and if it is a 6-membered ring, 1-position, 2-position, 3-position or 4-position.

Q ¹ in the formula (1A) is preferably a nitrogen atom from the viewpoint of 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 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, or a single bond or 1 to 5 carbon atoms when Q ¹ is a silicon atom) An alkanediyl group; R ⁴ is a single bond or an alkanediyl group having 1 to 5 carbon atoms, and A ¹ is a single bond, -O-, -CO-, * ¹ -COO-, * ¹ -OCO-, * ¹ -CONH- or * ¹ -NHCO- ("* ¹ " represents a bond with R ³ ); provided that when R ³ is a single bond, A ¹ is -O- or * ¹ -OCO- And a plurality of R ³ in the formula may be the same or different, a plurality of R ⁴ may be the same or different, and a plurality of A ¹ may be the same or different; X ¹ , Q ¹ , Y ¹ , t and s are It has the same meaning as in the formula (1A); &quot; * &quot; represents a bonding hand).

The structure represented by the formula (1) is preferably a structure represented by the following formula (1-1):

(In formula (1-1), R ³ , R ⁴ , and A ¹ have the same meaning as in formula (1-1A), respectively; X ¹ has the same meaning as in formula (1); `` * '' is a bond Indicates).

In the formulas (1-1A) and (1-1), as the alkanediyl group having 1 to 5 carbon atoms in R ³ and R ⁴ , for example, a methylene group, an ethylene group, a propanediyl group, butanediyl group And pentadiyl groups, which may be straight or branched. In addition, R ³ and R ⁴ may be the same or different from each other.

As R ³ , when Q ¹ is a nitrogen atom or a carbon atom, it is 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, more preferably a single bond. R ⁴ is preferably a single bond or 1 to 3 carbon atoms, more preferably a single bond or 1 to 2 carbon atoms.

A ¹ is a single bond, -O-, -CO-, * ¹ -COO-, * ¹ -OCO-, * ¹ -CONH- or * ¹ -NHCO- ("* ¹ " is a bond with R ³ Represents). Especially, it is preferable that it is a single bond, -O-, * ¹ -CONH-, * ¹ -COO- or * ¹ -OCO-.

As the main skeleton of the polymer (P), for example, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, poly (meth) acrylate, polyester, polyamide, cellulose derivative, polyacetal derivative, polystyrene derivative And a skeleton formed of a poly (styrene-phenylmaleimide) derivative or the like. Which of these to be applied may be appropriately selected depending on the driving mode or use of the liquid crystal display device, among others, it is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and polyamic acid. And it is more preferably at least one member selected from the group consisting of polyimide.

<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 tetracarboxylic acid anhydride with diamine. Since it is easy to introduce the structure represented by said formula (1A) into a polymer side chain, when synthesize | combining polyamic acid (P), it is preferable to use the diamine which has a structure represented by said formula (1A).

[Tetracarboxylic acid 2 anhydride]

Examples of the tetracarboxylic acid anhydride used for the synthesis of the polyamic acid in the present invention include aliphatic tetracarboxylic acid anhydride, alicyclic tetracarboxylic acid anhydride, aromatic tetracarboxylic acid anhydride, and the like. As a specific example of these, as aliphatic tetracarboxylic acid dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride etc. are mentioned, for example;

As an alicyclic tetracarboxylic acid anhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid anhydride, 2,3,5-tricarboxylic cyclopentyl acetic anhydride, 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-tricarbox-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3 , 5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic acid anhydride (1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid anhydride, 1S , 2S, 4R, 5R-cyclohexanetetracarboxylic acid anhydride, etc.), 1,2,3,4-cyclopentanetetracarboxylic acid anhydride (1R, 2R, 3R, 4R-cyclopentanetetracarboxylic acid anhydride, etc.) My back;

As aromatic tetracarboxylic acid anhydride, for example, pyromellitic acid anhydride, etc .; In addition to those listed above, tetracarboxylic acid dianhydride described in JP 2010-97188 A can be used. In addition, the tetracarboxylic acid dianhydride can be used alone or in combination of two or more.

As a tetracarboxylic dianhydride used for synthesis, it is preferable to include an alicyclic tetracarboxylic dianhydride from the viewpoint of transparency and solubility in a solvent. Further, as the alicyclic tetracarboxylic acid anhydride, 2,3,5-tricarboxycyclopentyl acetic anhydride, 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: 8-2 anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid anhydride, 1,2,3,4 It is preferable to include at least 1 sort (s) selected from the group which consists of cyclopentane tetracarboxylic acid dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid 2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] Octane-2: 4,6: 8-2 anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid anhydride and , 1,2,3,4-cycle Pentane tetracarboxylic acid 2 (hereinafter also referred to as a specific tetracarboxylic acid dianhydride) anhydride at least one type of tetracarboxylic acid dianhydride of a member selected from the group consisting of is more preferable to include.

When synthesizing the polyamic acid (P), when the specific tetracarboxylic acid anhydride is used, the use ratio (total amount) is based on the total amount of the tetracarboxylic acid anhydride used for the synthesis of the polyamic acid (P). It is preferably 10 mol% or more, more preferably 20-100 mol%, and even more preferably 50-100 mol%.

[Diamine]

As a diamine used for synthesis of the polyamic acid (P) in the present invention, it is preferable to include a diamine having a structure represented by the formula (1A). As a specific example of the diamine which has the structure represented by said formula (1A), the compound etc. which are represented by following formula (d-1A) are mentioned, for example, Preferably it is a compound represented by following formula (d-1):

(In 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 have the same meaning as in the 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)).

As a divalent organic group of R ¹ in the formula (d-1A) and the formula (d-1), -CO-, * ² -OCO- ("* ² " represents a bonding hand that is bonded to a diaminophenyl group. Shown) and the groups exemplified as the divalent organic group of R ² . Preferable specific examples of R ¹ include, for example, groups represented by the following formula (r-1):

(In formula (r-1), A ² is a single bond, -O-, -CO-, * ³ -OCO- or * ³ -COO-, A ³ is a single bond, -CO- or -OCO- * ⁴ and R ⁵ is a divalent group having -O-, -CO-O-, -CO-NH- or -CO- between a single bond, an alkanediyl group or a carbon-carbon bond of an alkanediyl group; * ³ ″ and “* ⁴ ” represent a bonding hand; provided that “* ³ ” is bonded to a diaminophenyl group).

The alkanediyl group for R ⁵ in the formula (r-1) may be linear or branched, preferably 1 to 8 carbon atoms, and more preferably 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, more preferably a single bond, a methylene group, or an ethylene group. A ² is preferably a single bond, -CO- or * ³ -OCO-. Note that the description of the above formula (1) can be applied to the description of a preferred specific example of the group "-N- (R ² -X ¹ ) ₂ ".

Preferred 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):

Moreover, as a preferable specific example of the compound whose Q <^1> of said formula (d-1A) is a carbon atom or a silicon atom, the compound etc. which are represented by following formula (da-69)-(da-80), etc. are mentioned, for example. have.

As the diamine used for the synthesis of the polyamic acid (P), a diamine having a structure represented by the formula (1) (hereinafter also referred to as "specific diamine") may be used alone, but together with the specific diamine, a specific diamine Other diamines (hereinafter also referred to as "other diamines") may be used.

Here, as other diamine, aliphatic diamine, alicyclic diamine, aromatic diamine, diamino organosiloxane, etc. are mentioned, for example. Specific examples of these diamines include aliphatic diamines, such as m-xylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine; As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, etc .;

As an aromatic diamine, for example, 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'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) Si) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 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, 3, 4-diaminopyrazine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl -3,6-diaminocarbazole, N-phenyl -3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4- Bis- (4-aminophenyl) -piperazine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1- (4-amino Phenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholestenyl Oxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5 -Diaminobenzoic acid cholesteryl, 3,5-diaminobenzoic acid ranstanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4 -(4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1 , 1-bis (4-((aminofe Neil) 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, 1,3-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 1 to 1 carbon atoms. Alkanediyl group of 3, a is 0 or 1, b is an integer from 0 to 2, c is an integer from 1 to 20, m is 0 or 1, n is 0 or 1, provided that a and b is never 0 at the same time)

Compounds represented by;

As the diamino organosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like can be mentioned, and the diamine described in JP 2010-97188 A can be used. You can.

As the divalent group represented by "-X ^I- (R ^I -X ^II ) _n- " in the formula (Y-1), an alkanediyl group having 1 to 3 carbon atoms, * -O-, * -COO- Or * -OC ₂ H ₄ -O- (However, it is preferable that the bonding hand to which "*" is attached to a diaminophenyl group).

As a specific example of the group "-C _c H _{2c +1} ", for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, 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-octade group And a real group, an n-nonadecil group, and an n-acyl group. It is preferable that two amino groups in a diaminophenyl group are in the 2,4-position or 3,5-position with respect to another group.

Specific examples of the compound represented by the formula (Y-1) include, for example, compounds represented by the following formulas (Y-1-1) to (Y-1-4):

Moreover, these diamine can be used individually by 1 type or in combination of 2 or more type.

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

[Molecular weight regulator]

When synthesizing polyamic acid, it is good also as what synthesize | combines the terminal modified type polymer | macromolecule using an appropriate molecular weight modifier together with the above tetracarboxylic acid anhydride and diamine. By using such a terminal-modified polymer, the coating property (printability) of the liquid crystal aligning agent can be further improved without impairing the effect of the present invention.

Examples of the molecular weight regulator include an acid anhydride, a monoamine compound, and a monoisocyanate compound. As specific examples of these, as an acid anhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride My back; As a monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-dodecylamine, n-octadecylamine My back; Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate; Each can be lifted. The proportion of the molecular weight modifier used is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total of tetracarboxylic anhydride and diamine used.

<Synthesis of a specific diamine>

The compound represented by the formula (d-1A) and the compound represented by the formula (d-1) can be synthesized by appropriately combining organic chemical methods. As an example, a dinitro intermediate having a nitro group is synthesized in place of the primary amino group in the formula (d-1A) or the formula (d-1), and thereafter, an appropriate reducing system of the nitro group of the intermediate is obtained. And a method of amination using the same.

The method for synthesizing the intermediate with the above-mentioned dinitni can be appropriately selected depending on the target compound. As an example, in the case of the compound represented by the formula (d-1), for example, [1] a secondary amine compound having a structure represented by the formula (1) and a secondary amino group in the secondary amine compound A method capable of reacting with and further reacting a compound having R ¹ and a dinitrophenyl group (for example, acid chloride or carbonic acid); [2] A bifunctional compound having a group represented by "R ^N -R ¹ -N-" (R ^N represents a dinitrophenyl group) and having two functional groups, and can react with the bifunctional compound, Also, a method of reacting a compound having X ¹ ; And the like.

The reduction reaction of the intermediate with dinitro can be preferably carried out in an organic solvent using, for example, catalysts such as palladium carbon, platinum oxide, zinc, iron, tin, and nickel. Examples of the organic solvent used here include ethyl acetate, toluene, tetrahydrofuran and alcohol. However, the order of synthesis of the compound represented by the formula (d-1A) and the compound represented by the formula (d-1) is not limited to the above method.

<Synthesis of polyamic acid>

The ratio of the tetracarboxylic acid anhydride and the diamine used in the synthesis reaction of the polyamic acid in the present invention is 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic acid anhydride relative to the amino group equivalent of the diamine. It is preferable, and the ratio which becomes 0.3 to 1.2 equivalent is more preferable. Moreover, 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, and more preferably 0 to 100 ° C. Further, the reaction time is preferably 0.1 to 24 hours, and more preferably 0.5 to 12 hours.

Here, examples of the organic solvent used for the reaction include non-protonic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons. As specific examples of these organic solvents, as aprotic polar solvents, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-buty Lauractone, tetramethylurea, hexamethylphosphotriamide, and the like; As the phenolic solvent, for example, phenol, m-cresol, xylenol, halogenated phenol, and the like;

Examples of the alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, and the like; As the ketone, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; As the ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methylmethoxypropionate, ethylethoxypropionate, diethyl oxalate, diethyl malonate, isoamylpropionate Nate, isoamyl isobutyrate, etc .; As ether, for example, diethyl ether, diisopentyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether Acetate, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, tetrahydrofuran, and the like; As the halogenated hydrocarbon, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like; As the hydrocarbon, for example, hexane, heptane, octane, benzene, toluene, xylene, etc .; Each can be lifted.

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

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be provided as it is to the preparation of a liquid crystal aligning agent as it is, or may be provided to the preparation of a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the liquid crystal aligning agent may be prepared after purifying the isolated polyamic acid. You may provide to. When the polyamic acid is dehydrated and cyclized to form a polyimide, the reaction solution may be provided as it is to a dehydration cyclization reaction, or may be provided to a dehydration cyclization reaction after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid. After purification, it may be provided in a dehydration ring closure reaction. The polyamic acid can be isolated and purified according to a known method.

<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 synthetic reaction, and a hydroxyl group-containing compound, It can be obtained by a method of reacting a halide, an epoxy group-containing compound or the like, [II] a method of reacting a tetracarboxylic acid diester with diamine, and a method of [III] a method of reacting a tetracarboxylic acid diester dihalide with diamine.

Here, examples of the hydroxyl group-containing compound used in method [I] include alcohols such as methanol, ethanol, and propanol; And phenols such as phenol and cresol. In addition, 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 epoxy group-containing compounds. As this, propylene oxide etc. are mentioned, for example. The tetracarboxylic acid diester used in the method [II] can be obtained by, for example, opening the tetracarboxylic acid anhydride exemplified in the synthesis of the polyamic acid using the alcohols. The tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride. As the diamine used in the methods [II] and [III], diamine having a structure represented by the formula (1A), other diamines and the like can be used. Further, the polyamic acid ester may have only a carboxylic acid ester structure, or may be a partial esterified product in which a carboxylic acid structure and a carboxylic 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 obtained by imidizing the polyamic acid (P) synthesized as described above by dehydration and ring closure. You can.

The polyimide (P) may be a complete imide product of dehydration-closure of all the acidic structures possessed by the precursor polyamic acid (P), or a part of the acidic structure may be dehydrated and closed to form a cancerous acid structure and an imide ring structure. The partial imide cargo which exists together may be sufficient. From the viewpoint of improving the electrical properties of the liquid crystal display element, the polyimide in the present invention preferably has an imidation ratio of 30% or more, more preferably 40-99%, and 50-99%. It is more preferable. This imidation rate is a percentage of the ratio of the number of imide ring structures to the total of the number of the maleic acid structures of the polyimide and the number of imide ring structures. Here, a part of the imide ring may be an isoimide ring.

The dehydration cyclization of the polyamic acid is preferably carried out by a method of heating the polyamic acid or by dissolving the polyamic acid in an organic solvent and adding a dehydrating agent and a dehydration cyclization catalyst to the solution to heat it as necessary. . Among these, it is preferable to use the latter method.

In the method of imidizing by adding a dehydrating agent and a dehydrating ring-closure catalyst in a solution of polyamic acid, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably 0.01 to 20 mol per 1 mol of the rock acid structure of the polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, rutidine and triethylamine can be used. The amount of the dehydration ring-closed catalyst is preferably 0.01 to 10 mol per 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closure reaction include 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, and more preferably 2.0 to 30 hours.

In this way, a reaction solution containing polyimide (P) is obtained. This reaction solution may be provided to the preparation of a liquid crystal aligning agent as it is, or may be provided to the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, or after isolating the polyimide (P), the liquid crystal aligning agent It may be provided in the preparation, or may be provided in the preparation of the liquid crystal aligning agent after purification of the isolated polyimide (P). These purification operations can be performed according to a known method.

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

Moreover, 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 chemical methods. As an example of this, the polymer (P) having a polyorganosiloxane as the main skeleton can be obtained, for example, by reacting a polyorganosiloxane having an epoxy group with a carbon acid having a structure represented by the formula (1A).

From the viewpoint of suitably obtaining the effect of the present invention, the content ratio of the polymer (P) in the liquid crystal aligning agent is preferably 5% by weight or more, and 10% by weight, based on the total amount of the polymer components contained in the liquid crystal aligning agent. It is more preferable to set it as% or more. In addition, the upper limit is not particularly limited, and can be arbitrarily set within a range of 100% by weight or less.

Polymer (P) having the above specific structure is, in terms of obtaining the effects of the present invention as appropriate, based on the total amount of the polymer components contained in the liquid crystal aligning ^{agent, 1 × 10 -5 ~1 × 10} - 2 mol / g it is preferably set to ³ mol / g ^- and preferably, 5 × 10 ^-5 ~5 × 10 according to. Therefore, it is preferable 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 of the polymer (P) 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 a polymer (P), photopolymerization of a photopolymerizable compound (photopolymerizable monomer) upon light irradiation to the liquid crystal cell It is assumed that it is possible to assist from the side of the liquid crystal alignment film so that the reaction is not inhibited, and as a result, the polymerization reaction of the photopolymerizable compound proceeds sufficiently to obtain an effect of improving reliability.

<Other ingredients>

The liquid crystal aligning agent of this invention may contain other components as needed. Examples of such other components include polymers other than the polymer (P), compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compounds"), functional silane compounds, and the like. have.

[Other polymers]

The above-mentioned other polymers can be used to improve solution properties and electrical properties. Examples of such other polymers include polymers not having the above-mentioned specific structure, and examples of the main skeleton include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide, and cellulose derivatives. And polyacetal, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, and poly (meth) acrylates.

When other polymers are added to the liquid crystal aligning agent, the blending ratio is preferably 95 parts by weight or less, more preferably 0.1 to 90 parts by weight, based on 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent, It is more preferably 0.1 to 85 parts by weight.

[Epoxy group-containing compound]

The epoxy group-containing compound can be used to improve the adhesion to the substrate surface and electrical properties in the liquid crystal alignment film. Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl Diether, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N' , N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N- Diglycidyl-cyclohexylamine etc. are mentioned as a preferable thing. 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, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent.

[Functional silane compound]

The said functional silane compound can be used for the purpose of improving the printability of a liquid crystal aligning agent. Examples of the functional silane compound include 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, and N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 9-tri Methoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl-3,6-diazanonanoate methyl, N-benzyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. Can.

When these functional silane compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the total polymer contained in the liquid crystal aligning agent. .

In addition, as the other components, besides 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 this invention is prepared as a liquid composition which the said polymer (P) and other components mix | blended arbitrarily as needed are preferably disperse | distributed or dissolved in an organic solvent.

Here, examples of the solvent used in the preparation of 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, methylmethoxypropionate, ethylethoxypropionate, 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, di Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Tate, di, and the like, propylene glycol monomethyl ether, di-isobutyl ketone, isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate. These can be used individually by 1 type or in mixture of 2 or more types.

The solid content concentration (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) in the liquid crystal aligning agent of the present invention is suitably selected in consideration of viscosity, volatility, and the like, but is preferably Is 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described below, and preferably heated to form a coating film which is a liquid crystal alignment film or a coating film to be a liquid crystal alignment film, but at this time, when the solid content concentration is less than 1% by weight , It is difficult to obtain a good liquid crystal alignment film because the film thickness of this coating film is too small. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes excessive and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent tends to increase and the coating properties tend to be inferior.

The range of particularly preferable solid content concentration differs 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 range of solid content concentration of 1.5 to 4.5% by weight is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thus 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 accordingly, the solution viscosity is in the range of 3 to 15 mPa · s. The temperature when the liquid crystal aligning agent of the present invention is prepared is preferably 10 to 100 ° C, and more preferably 20 to 80 ° C.

<Liquid crystal alignment film and liquid crystal display element>

The liquid crystal aligning film of this invention is formed by the liquid crystal aligning agent prepared as mentioned above. Moreover, the liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention. The driving mode to which the liquid crystal display device of the present invention is applied is not particularly limited, and can be applied to various driving modes such as TN type, STN type, IPS type, FFS type, VA type, MVA type, and PSA type. Especially, it can apply suitably to PSA mode.

In the PSA mode liquid crystal display element of the present invention, for example, the following steps (1) to (3)

(1) A step of applying the liquid crystal aligning agent of the present invention onto the conductive films of a pair of substrates each having a conductive film, and then heating them to form a coating film,

(2) a step of constructing a liquid crystal cell by arranging the pair of substrates on which the coating film is formed so that the coating films face each other via a liquid crystal layer containing a liquid crystal compound;

(3) It can be manufactured by a method including a step of irradiating light to a liquid crystal cell in a state in which a voltage is applied between the conductive films of a pair of substrates.

[Process (1): Formation of coating film]

First, the liquid crystal aligning agent of the present invention is applied onto a substrate, and then a coated film is formed on the substrate by heating the coated surface. As a substrate of a liquid crystal display element, For example, glass, such as float glass and soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. It is preferable to use a transparent conductive film as the conductive film of the substrate, 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₎ ) Can be used. It is preferable that this conductive film is a pattern-shaped conductive film divided into a plurality of regions. When such a conductive film is used, 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 area by applying a different voltage in each area, thereby making it possible to widen the viewing angle characteristic. To obtain a patterned transparent conductive film, for example, after forming a transparent conductive film without a pattern, a method of forming a pattern by photoetching, a method of using a mask having a desired pattern when forming the transparent conductive film, or the like can be used. .

As a method of applying a liquid crystal aligning agent on a substrate, it can be preferably performed by an offset printing method, a spin coating method, a roll coater method or an inkjet printing method. When the liquid crystal aligning agent is applied, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, or the like is applied to the surface on which the coating film is to be formed. You may perform pre-coating beforehand.

After the liquid crystal aligning agent is applied to the substrate, preheating (prebaking) is preferably performed for the purpose of preventing liquid flow 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-baking time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. Thereafter, a sintering (post-baking) process is carried out with the aim of completely removing the solvent and thermally imidizing the acid structure present in the polymer, if necessary. The post-baking temperature is preferably 80 to 300 ° C, and more preferably 120 to 250 ° C. The post-baking time is preferably 5 to 200 minutes, and more preferably 10 to 100 minutes. In this way, the film thickness of the film to be formed is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5 μm.

The coating film used as an alignment film is formed by removing the organic solvent by heating after applying the liquid crystal aligning agent. At this time, in the case where 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 a cancer acid structure, dehydration cyclization reaction proceeds by further heating after forming a coating film, It may be a more imidized coating film. In the case of the PSA mode, the following steps may be performed using the post-baking coating film as it is, but for the purpose of controlling the inclination of the liquid crystal molecules and performing the orientation division in a simple and easy manner, a weak rubbing treatment is performed on the coating film. You may do it. This rubbing treatment can be performed by rubbing the coated film surface in a predetermined direction with a roll of cloth made of fibers such as nylon, rayon, and cotton, for example.

[Process (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 two substrates arranged opposite to each other at predetermined intervals. 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, two substrates are arranged to face 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 portion of the two substrates is sealed with a sealing agent. A liquid crystal cell is manufactured by bonding, filling a liquid crystal composition by injecting it into a cell gap partitioned by a substrate surface and a sealing agent, and sealing the injection port. The second method is a method called ODF (One Drop Fill) method. An ultraviolet light-curable sealing agent is applied to a predetermined position on one of the two substrates on which the coating film is formed, and after further dropping the liquid crystal composition into a predetermined number of places on the coating film surface, the coating film faces each other. A liquid crystal cell is manufactured by bonding the other substrate and spreading the liquid crystal composition on the entire surface of the substrate, and then irradiating ultraviolet light on the entire surface of the substrate to cure the sealing agent. In any case, even if 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, the flow orientation during liquid crystal charging may be removed. good.

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 crystal compound, a nematic liquid crystal having negative dielectric anisotropy can be preferably used, for example, dicyanobenzene liquid crystal, pyridazine liquid crystal, cispbase liquid crystal, sub clock crystal, biphenyl based A liquid crystal, a phenyl cyclohexane liquid crystal, a terphenyl liquid crystal, or the like can be used. Moreover, as a liquid crystalline compound, you may use together alkenyl type liquid crystal from a viewpoint of making the response speed of a PSA mode liquid crystal display element faster. As the alkenyl-based liquid crystal, conventionally known ones can be used, and examples thereof include compounds represented by the following formulas (L1-1) to (L1-9). Moreover, 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, it is preferable to be polyfunctional, and it is more preferable to have two or more of at least any one of acryloyl group and methacryloyl group. In addition, from the viewpoint of stably maintaining the orientation of the liquid crystal molecules, as the photopolymerizable compound, it is preferable to use a compound having at least two or more rings of at least one of a cyclohexane ring and a benzene ring as the liquid crystal skeleton. Moreover, 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 relative to the total amount of the liquid crystal compound used.

Moreover, the liquid crystal composition may contain other components, such as a polymerization initiator, an antioxidant, an ultraviolet absorber, and a stabilizer, other than the said compound. These blending amounts can be appropriately adjusted depending on the other components used. The thickness of the liquid crystal layer is preferably 1 to 5 μm. Moreover, as a sealing agent, for example, an epoxy resin containing an aluminum oxide sphere as a curing agent and a spacer can be used.

[Process (3): Light irradiation process]

After the liquid crystal cell is constructed, 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, DC or AC of 5 to 50V. As the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As the light source of the 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, ultraviolet rays in the above-described preferred wavelength range can be obtained by means of using a light source in combination with, for example, a filter diffraction grating or the like. The light irradiation amount is preferably 1,000 J / m 2 or more and less than 200,000 J / m 2, and more preferably 1,000 to 150,000 J / m 2.

And a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after light irradiation. As a polarizing plate used here, the polarizing plate called the "H film" which absorbed iodine while extending | stretching orientation of polyvinyl alcohol, and the polarizing plate which consists of the cellulose acetate protective film or the polarizing plate which consists of H film itself is mentioned.

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

(Example)

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

In the following examples and comparative examples, the imidation ratio of the 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 method.

[Imidization rate of polyimide]

The solution of the polyimide was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference material. From the obtained ¹ H-NMR spectrum, the imidation rate [%] was obtained by the following formula (1):

Imidation rate [%] = {(1-A ¹¹ ) / (A ¹² × α)} × 100. (One)

(In Formula (1), A ¹¹ is a peak area derived from a proton of the NH group appearing near 10 ppm of chemical shift, A ¹² is a peak area derived from other protons, and α is a precursor of the polymer (polyamic acid). The ratio of the number of other protons to one proton of the NH group).

[Solution viscosity of polymer solution]

The solution viscosity [m㎩ · s] of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer for a solution prepared at 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 conversion value measured by gel permeation chromatography under the following conditions.

 Column: Tosoh Corporation, TSKgelGRCXLⅡ

 Solvent: tetrahydrofuran

 Temperature: 40 ℃

 Pressure: 68kgf / ㎠

[Epoxy equivalent]

The epoxy equivalent was measured by the hydrochloric acid-methylethylketone method described in JIS C 2105.

<Synthesis of compound>

[Example 1A: Synthesis of Compound (da-5)]

According to the following reaction formula 1, a compound represented by the formula (da-5) (hereinafter also referred to as compound (da-5)) was synthesized.

12.5 g (62.8 mmol) of bis (3-pyridylmethyl) amine, 150 ml of dichloromethane and 15.9 ml (114 mmol) of triethylamine were mixed and cooled in an ice bath, while 13.2 g of 3,5-dinitrobenzoyl chloride ( 57.1 mmol) was added dropwise to 50 ml of dichloromethane, and stirred at room temperature for 3 hours. After the reaction, 500 ml of ethyl acetate and 500 ml of tetrahydrofuran were added, and water was washed four times with 400 ml of distilled water. After drying the organic layer with magnesium sulfate, the solvent was distilled off to filter and dry the precipitated solid, and 17.7 g (45.0 mmol, yield) of brown powder dinitroce (compound represented by the formula (dm-5) above) was obtained. 78.7%).

Subsequently, 17.7 g (45.0 mmol) of the dinitro body, 1.77 g of 5% palladium carbon (containing 50% water), 90 ml of tetrahydrofuran, and 90 ml of ethanol were mixed, and a balloon containing hydrogen gas was attached to the mixture under a hydrogen atmosphere. , And stirred 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 reaction formula 2, a compound represented by the formula (da-6) (hereinafter also referred to as compound (da-6)) was synthesized.

11.3 g (50.0 mmol) of 2,4-dinitrophenylacetic acid, 9.09 g (50.0 mmol) of bis (3-pyridylmethyl) amine, and 200 ml of dichloromethane were mixed and cooled in an ice bath while 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 stirred at room temperature for 2 hours. After the reaction, 800 ml of ethyl acetate was added, and water was washed four times with 400 ml of distilled water. After drying the organic layer with magnesium sulfate, the solvent was distilled off to filter and dry the precipitated solid, and 16.4 g (40.3 mmol, yield) of dinitroce (compound represented by the formula (dm-6)) as a brown powder was obtained. 80.5%).

Subsequently, 16.4 g (40.3 mmol) of the dinitro body, 1.64 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 to the mixture under hydrogen atmosphere. , And stirred 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 the following reaction formula 3, a compound represented by the above formula (da-37) (hereinafter also referred to as compound (da-37)) was synthesized.

12.9 g (96.7 mmol) of imino diacetic acid and 145 ml of a 2M aqueous sodium hydroxide solution were mixed, and 22.3 g (96.7 mmol) of 3,5-dinitrobenzoyl chloride was dissolved in 30 ml of tetrahydrofuran while cooling in an ice bath. Then, it was stirred at room temperature for 4 hours. After the reaction, 300 ml of 1M dilute hydrochloric acid was added while cooling in an ice bath, and the precipitated solid was filtered and dried. Thereafter, recrystallization was performed with 200 ml of ethyl acetate, and the precipitated solid was filtered and dried to yield 15.3 g (46.7 mmol, yield 48.3) of the dicarboxylic acid (compound represented by the formula (dm-37-1)) as a white powder. %) Obtained.

Subsequently, 15.3 g (46.7 mmol) of dicarboxylic acid, 10.6 g (98.1 mmol) of 3-aminomethylpyridine, and 200 ml of dichloromethane were mixed and cooled in an ice bath while 1-ethyl-3- (3-dimethylamino Profile) Carbodiimide hydrochloride 21.5 g (112 mmol) and N, N-dimethyl-4-aminopyridine 2.28 g (18.7 mmol) were added and stirred at room temperature for 3 hours. After the reaction, 800 ml of ethyl acetate was added, and water was washed four times with 400 ml of distilled water. 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 show a brown powder of dinitroce (expressed as the above formula (dm-37-2)). Compound) 17.5 g (34.6 mmol, yield 74.1%) was obtained.

Subsequently, 17.5 g (34.6 mmol) of the dinitro body, 1.75 g of 5% palladium carbon (containing 50% water), 70 ml of tetrahydrofuran, and 70 ml of ethanol were mixed, and a balloon containing hydrogen gas was attached to the mixture under hydrogen atmosphere. , And stirred at room temperature for 4 hours. After the reaction, palladium 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 the following reaction formula 4, 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 m) Mol), and mixed with 200 ml of N, N-dimethylacetamide and stirred at 100 ° C for 5 hours. After the reaction, 600 ml of ethyl acetate was added, and water was washed four times with 600 ml of distilled water. The solid obtained by drying and concentrating the organic layer with magnesium sulfate was recrystallized with 200 ml of ethanol, and the precipitated solid was filtered and dried to obtain 15.7 g of a brown powder dinitroce (compound represented by the formula (dm-67)). 41.4 mmol, yield 82.8%).

Subsequently, 15.7 g (41.4 mmol) of the dinitro body, 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 to the mixture under a hydrogen atmosphere. , And stirred at room temperature for 4 hours. After the reaction, palladium 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 reaction formula 5, a compound represented by the above formula (da-70) (hereinafter also referred to as compound (da-70)) was synthesized.

102 g (750 mmol) of pentaerythritol, 41.8 ml (300 mmol) of triethylamine, and 750 ml of tetrahydrofuran were mixed, and while cooling in an ice bath, 12.8 g (75.0 mmol) of 3,5-dinitrobenzoyl chloride was tetrahydro. After dissolving what was dissolved in 50 ml of furan, it was stirred at room temperature for 5 hours. After the reaction, 1500 ml of ethyl acetate was added, and water was washed four times with 750 ml of distilled water. 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 obtain a triol body (compound represented by the formula (dm-70-1)). ) 18.9 g (57.2 mmol, yield 76.3%) was obtained.

Subsequently, 18.9 g (57.2 mmol) of the triol body, 21.1 g (172 mmol) of nicotinic acid, and 250 ml of dichloromethane were mixed and cooled in an ice bath while 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 39.5 g (206 mmol) and N, N-dimethyl-4-aminopyridine 4.19 g (34.3 mmol) were added and stirred at room temperature for 4 hours. After the reaction, 800 ml of ethyl acetate was added, and water was washed four times with 400 ml of distilled water. The solid obtained by drying and concentrating the organic layer with magnesium sulfate was recrystallized with 200 ml of ethanol, and the precipitated solid was filtered and dried to obtain a brown powder of dinitroce (compound represented by the formula (dm-70-2)) 29.6. g (45.9 mmol, yield 80.4%) was obtained.

Subsequently, 29.6 g (45.9 mmol) of the dinitro body, 2.96 g of 5% palladium carbon (containing 50% water), 100 ml of tetrahydrofuran, and 100 ml of ethanol were mixed, and a balloon containing hydrogen gas was attached to the mixture under a hydrogen atmosphere. , And stirred at room temperature for 4 hours. After the reaction, palladium 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 anhydride (TCA) 100 moles as tetracarboxylic acid anhydride, 70 moles of p-phenylenediamine (PDA) as diamine, cholestanyl 3,5-diaminobenzoate (HCDA) ) 20 mol parts and 10 mol parts of the 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 prepared. Got. A small amount of the obtained polyamic acid solution was fractionated, and NMP was added to obtain a solution having a polyamic acid concentration of 10% by weight.

Subsequently, 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 added at 1.0 fold moles with respect to the total amount of tetracarboxylic acid anhydride used, respectively, at 110 ° C. The dehydration ring closure reaction was performed for 4 hours. After the dehydration cyclization reaction, the solvent in the system is replaced with a new NMP (the pyridine and acetic anhydride used in the dehydration cyclization reaction are removed out of the system by the present operation, the same applies hereinafter) to a polyimide having an imidation ratio of about 60% (PI A solution containing 26% by weight of -1) was obtained.

[Examples 2B to 9B, Synthesis Examples 1 and 2]

The type and amount of tetracarboxylic acid anhydride and diamine used, and the amount of pyridine and acetic anhydride used in imidization were changed as shown in Table 1 below, and polyimide (PI-2) was used in the same manner as in Example 1B. )-(PI-11) were synthesized, respectively. The measurement results of the imidation rate of the obtained polymer were also shown in Table 1 below. Further, in Example 7B, monoamine was used together with tetracarboxylic anhydride and diamine in the synthesis of the polymer.

In Table 1, the numerical value in () of tetracarboxylic dianhydride shows the use ratio [molar part] with respect to 100 mol part of the total tetracarboxylic acid dianhydride used for the synthesis of a polymer. The numerical value in () of diamine and monoamine shows the use ratio [molar part] with respect to 100 mol part of the total of tetracarboxylic acid dianhydride used for the synthesis of a polymer. The abbreviations in Table 1 mean the following, respectively. In addition, "-" in Table 1 means that the compound of the said column was not used.

<Tetracarboxylic acid 2 anhydride>

TCA: 2,3,5-tricaroxycyclopentylacetic acid 2 anhydride

BODA: 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride

CB: 1,2,3,4-cyclobutanetetracarboxylic acid anhydride

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 anhydride

<Diamine>

PDA: p-phenylenediamine

HCDA: 3,5-diaminobenzoic acid cholestanyl

35DAB: 3,5-diaminobenzoic acid

HCODA: cholestanyloxy-2,4-diaminobenzene

LDA: Compound represented by the above formula (Y-1-4)

D-1: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene (formula (Y-1-2) Compounds that appear)

D-2: 1,3-bis (3-aminopropyl) -tetramethyldisiloxane

D-3: 3,6-bis (4-aminobenzoyloxy) cholestane

D-5: 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl

D-6: 4,4'-diaminodiphenylmethane

D-7: 2,2'-dimethyl-4,4'-diaminobiphenyl

D-8: 4,4'-diaminodiphenyl ether

da-x: a compound represented by the following formula (da-x)

<Monoamine>

D-4: aniline

[Synthesis Example 3: Synthesis of polyamic acid (PA-1)]

1,2,3,4-cyclobutane tetracarboxylic acid anhydride (CB) 100 mole parts as tetracarboxylic acid anhydride, 100 mole parts of 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine, NMP And dissolved in a mixed solvent of γ-butyrolactone (γBL) (NMP: γBL = 10: 90 (weight ratio)) and reacted at 40 ° C. for 3 hours to contain 10% by weight of polyamic acid (PA-1). A solution was obtained. The solution viscosity measured by fractionating the obtained polyamic acid solution was 180 mPa · s.

[Synthesis Example 4: Synthesis of polyamic acid (PA-2)]

A solution containing 10% by weight of polyamic acid (PA-2) was obtained by performing the same operation as in Synthesis Example 3, except that the type and amount of tetracarboxylic acid anhydride and diamine used were changed as shown in Table 1 above. A small amount of the obtained polyamic acid solution was aliquoted and the measured solution viscosity was 150 mPa · s.

[Synthesis Example 5: Synthesis of polyorganosiloxane (APS-1)]

In a reaction vessel equipped with a stirrer, hygrometer, dropping funnel and reflux cooling tube, 100.0g 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500g methylisobutylketone and 10.0g triethylamine And mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and then reacted at 80 ° C for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out, washed with 0.2% by weight aqueous ammonium nitrate solution until the water after washing was neutral, and then distilled off the solvent and water under reduced pressure to remove the reactive polyorganosiloxane (EPS-1 ) Was obtained as a viscous transparent liquid. As a result of performing ¹ H-NMR analysis on this reactive polyorganosiloxane, a peak based on an epoxy group was obtained in the vicinity of the chemical shift (δ) = 3.2ppm according to the theoretical strength, and that no side reaction of the epoxy group occurred during the reaction. Was confirmed. The obtained reactive polyorganosiloxane had a weight average molecular weight Mw of 3,500 and an epoxy equivalent of 180 g / mol.

Subsequently, 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 18X (as a catalyst) Product name, manufactured by San-Apro Co., Ltd.) 0.10 g was added, and the mixture was reacted at 100 ° C under stirring for 48 hours. After completion of the reaction, the 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, so that the liquid crystal aligning polyorganosiloxane (APS-1) was 9.0 g. Got. The weight average molecular weight Mw of the obtained polymer was 9,900.

[Examples 10B and 11B]

The type and amount of tetracarboxylic acid anhydride and diamine used, and the amount of pyridine and acetic anhydride used during imidization were changed as shown in Table 2 below, and the same procedure as in Example 1B was carried out to give polyimide (PI- 12) and (PI-13) were synthesized, respectively. The results of measuring the imidation rate of the obtained polymers are also shown in Table 2 below. In addition, description of each numerical value, abbreviation, and "-" in Table 2 is the same as that of Table 1 above.

<Preparation of liquid crystal composition>

[Preparation of liquid crystal composition LC1]

Liquid crystal composition LC1 was obtained by adding and mixing 0.3 wt% of 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., Ltd.).

[Preparation of liquid crystal composition LC2]

With respect to 10 g of nematic liquid crystal (MLC-6608 manufactured by Merck), 5% by weight of the liquid crystal compound represented by the formula (L1-1) and 0.3% by weight of the photopolymerizable compound represented by the following formula (pc-1): Liquid crystal composition LC2 was obtained by adding and mixing.

[Example 1C]

<Preparation of liquid crystal aligning agent>

To the solution containing polyimide (PI-1) obtained in Example 1B above as a polymer, NMP and butyl cellosolve (BC) were added as an organic solvent, and the solvent composition was NMP: BC = 50: 50 (weight ratio), A solution having a solid content concentration of 6.0% by weight was used. A liquid crystal aligning agent (S1) was prepared by filtering this solution using a filter having a pore diameter of 1 µm.

<Preparation of liquid crystal cell>

The liquid crystal aligning agent (S1) of Example 1C prepared above was patterned in a slit shape as shown in Fig. 1, and on each electrode surface of two glass substrates each having ITO electrodes partitioned into a plurality of regions, a liquid crystal. After coating using an alignment film printer (manufactured by Nippon Shashin Insatsu Co., Ltd.), the solvent is removed by heating (pre-baking) on a hot plate at 80 ° C for 10 minutes, and then heating on a hot plate at 150 ° C for 10 minutes (post-baking). Thus, a coating film having an average film thickness of 600 Pa was formed. This coating film was subjected to ultrasonic cleaning for 1 minute in ultrapure water, and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a coating film serving as a liquid crystal alignment film. By repeating this operation, a pair (two) of substrates having a coating film was obtained. In addition, the pattern of the electrode used is the same pattern as the electrode pattern in PSA mode.

Subsequently, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 µm was applied to each outer edge having a coating film of the pair of substrates, and then pressed against each other so that the coating film surfaces faced each other and cured the adhesive. . Subsequently, the liquid crystal composition LC1 prepared above was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive. Thereafter, light was irradiated with an irradiation amount of 100,000 J / m 2 in a state in which a voltage was applied between the conductive films of the obtained liquid crystal cell.

<Evaluation of reliability>

The reliability of the liquid crystal aligning film (liquid crystal display element) was evaluated using the liquid crystal cell manufactured above (liquid crystal cell after light irradiation). Evaluation was performed as follows. First, a voltage of 5 V was applied to the above liquid crystal cell with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage retention rate (VHR1) 167 milliseconds after the application was released was measured. Subsequently, the liquid crystal cell was allowed to stand for 200 hours in an 80 ° C. oven under LED lamp irradiation, and then left standing at room temperature to naturally cool 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 retention rate (VHR2) 167 milliseconds after the application was released was measured. In addition, "VHR-1" manufactured by Toyo Technica Co., Ltd. was used as the measuring device. At this time, the rate of change (ΔVHR) of VHR was calculated by the following formula (2), and the reliability of the liquid crystal alignment film was evaluated by ΔVHR. In the evaluation, ΔVHR is less than 1.0%, reliability is `` very good (◎) '', reliability is 1.0% or more and less than 1.5% `` good (○) '', and 1.5% or more is less than 2.0%, reliability is `` possible (△) '' In the case of 2.0% or more, reliability was determined as "defect (x)". As a result, reliability was "very good" in Example 1C.

ΔVHR [%] = {(VHR1-VHR2) / (VHR1)} x 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, a liquid crystal cell was produced in the same manner as in Example 1C using each liquid crystal aligning agent, and the produced liquid crystal cell was evaluated. In addition, about Examples 3C and 4C, the liquid crystal composition used was changed from LC1 to LC2. Table 3 shows the results of their evaluation.

As shown in Table 3, in Examples 1C to 9C, the drop in voltage retention was small and the reliability was good even after long exposure (200 hours) under light irradiation and a stress environment of 80 ° C. On the other hand, in Comparative Examples 1 and 2, the voltage preservation rate greatly decreased due to the application of light stress and heat stress.

Further, the liquid crystal aligning agents of Examples 1C to 9C were used, and the same as in Example 1C, except that the pattern of the ITO electrode on the glass substrate was changed to the fishbone-shaped electrode pattern shown in FIGS. 2 and 3, respectively. Then, a liquid crystal cell was produced and evaluated. 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, a liquid crystal cell was produced in the same manner as in Example 1C using each liquid crystal aligning agent, and the produced liquid crystal cell was evaluated. Table 4 shows the results.

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

1: ITO electrode
2: Slit part
3: Light shielding film

Claims (12)

A liquid crystal aligning agent containing a polymer (P) having a specific structure represented by the following formula (1A):

(In 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 a plurality of X ¹ may be the same or different. Good; 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; when Q ¹ is a nitrogen atom, t = 2, s = 0, and Q ¹ is silicon In the case of an atom, t = 3 and s = 0, and in the case where Q ¹ is a carbon atom, t is 2 or 3 and s = 3-t; "*" represents a bonding hand). According to claim 1,
The specific structure is a liquid crystal aligning agent 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, or a single bond or 1 to 5 carbon atoms when Q ¹ is a silicon atom) An alkanediyl group; R ⁴ is a single bond or an alkanediyl group having 1 to 5 carbon atoms, and A ¹ is a single bond, -O-, -CO-, * ¹ -COO-, * ¹ -OCO-, * ¹ -CONH- or * ¹ -NHCO- ("* ¹ " represents a bond with R ³ ); provided that when R ³ is a single bond, A ¹ is -O- or * ¹ -OCO- And a plurality of R ³ in the formula may be the same or different, a plurality of R ⁴ may be the same or different, and a plurality of A ¹ may be the same or different; X ¹ , Q ¹ , Y ¹ , t and s are It has the same meaning as in the formula (1A); &quot; * &quot; represents a bonding hand. According to claim 1,
The polymer (P) is at least one liquid crystal aligning agent selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide. According to claim 3,
The polymer (P) is a polymer obtained by reacting at least one compound selected from the group consisting of tetracarboxylic acid dianhydride, tetracarboxylic acid diester and tetracarboxylic acid diester dihalide, and diamine,
The diamine is a liquid crystal aligning agent containing 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 , X ¹ , Q ¹ , Y ¹ , t and s have the same meanings as in the formula (1A)). The method according to any one of claims 1 to 4,
The Q ¹ is a nitrogen atom, a liquid crystal aligning agent. The method according to any one of claims 1 to 4,
The polymer (P) is 2,3,5-tricarboxycyclocyclopentyl acetic anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride , 1,2,3,4-cyclobutanetetracarboxylic acid anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid anhydride and 1,2,3,4-cyclopentanetetracarboxylic acid anhydride A liquid crystal aligning agent that is a polymer obtained by reacting at least one tetracarboxylic acid anhydride selected from the group consisting of diamine having the specific structure. The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-4. The liquid crystal display element provided with the liquid crystal aligning film of Claim 7. The process of forming the coating film by apply | coating the liquid crystal aligning agent in any one of Claims 1-4 on the said conductive film of a pair of board | substrates which have a conductive film, and then heating this, respectively.
A step of constructing a liquid crystal cell by arranging the pair of substrates on which the coating film is formed so as to face the coating film through a liquid crystal layer containing a liquid crystal compound;
Process of irradiating light to the liquid crystal cell while applying a voltage between the conductive films of the pair of substrates
Method for manufacturing a liquid crystal display device comprising a. The method of claim 9,
The said liquid crystalline compound, The manufacturing method of the liquid crystal display element containing the monofunctional liquid crystalline compound which has any one of an alkenyl group and a fluoroalkenyl group. A polymer having a specific structure represented by the following formula (1A):

(In 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 a plurality of X ¹ may be the same or different. Good; 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; when Q ¹ is a nitrogen atom, t = 2, s = 0, and Q ¹ is silicon In the case of an atom, t = 3 and s = 0, and when Q ¹ is a carbon atom, t is 2 or 3 and s = 3-t). delete

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