JP2016095488A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, polymer, and compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal alignment agent that can achieve both solubility to a solvent of a polymer component and a reduction of seizure of a liquid crystal display device.SOLUTION: A polymer (P) having a partial structure represented by the following formula (1) is made contained in a liquid crystal alignment agent. In the formula (1), Ais a single bond or a divalent organic group, and Ris a monovalent organic group having 8 or more carbon atoms. Xis a protective group. "*" represents a coupling hand coupled to the main chain of the polymer.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, a polymer, and a compound.

  Conventionally, as a liquid crystal display element, various drive systems having different electrode structures, properties of liquid crystal molecules to be used, manufacturing processes, and the like have been developed. For example, a TN (Twisted Nematic) type and an STN (Super Twisted Nematic) type have been developed. Various liquid crystal display elements such as VA (Vertical Alignment), IPS (In-Plane Switching), and FFS (fringe field switching) are known. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules.

  In recent years, various liquid crystal aligning agents have been proposed in order to further improve the display performance of liquid crystal display elements. For example, for the purpose of reducing afterimage (image burn-in), it has been proposed to form a liquid crystal alignment film using a liquid crystal aligning agent containing a polyimide having a nitrogen atom in addition to an imide group or a precursor thereof (for example, (See Patent Document 1 and Patent Document 2).

  Patent Document 1 discloses a polyamic acid obtained by reacting a tetracarboxylic dianhydride containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride with a diamine containing a diamine having an amide bond, and An imidized polymer of polyamic acid obtained by reacting tetracarboxylic dianhydride and diamine, and a liquid crystal aligning agent, and the number of imide rings of the imidized polymer in the liquid crystal aligning agent It has been proposed that the ratio be in a specific range. In Patent Document 1, such a liquid crystal aligning agent is used to improve voltage holding performance and afterimage characteristics.

  In Patent Document 2, an aromatic diamine in which an amino group protected with a tertiary butoxycarbonyl group (t-BOC group) is introduced in the ortho position with respect to the primary amino group is used. It has been proposed that the liquid crystal aligning agent contains polyamic acid or polyimide obtained in this manner. According to this technique, the t-BOC group is deprotected by heating during film formation to generate an amino group, and a heterocycle is formed by intramolecular reaction or intermolecular reaction (crosslinking reaction) of the generated amino group. It is described to reduce the accumulation of residual DC voltage.

JP 2009-294274 A International Publication No. 2013/115228

  In a liquid crystal display element such as a vertical alignment type, a TN type, and an STN type, a liquid crystal alignment film is formed using a polymer having a liquid crystal alignment group such as a linear structure or a mesogen skeleton in a side chain. In this case, in order to improve the image sticking of the liquid crystal display element (especially, the image sticking by the alternating voltage), it is conceivable to make the side chain of the polymer rigid. On the other hand, the polymer side chain is rigid. If it is made into a simple structure, the solubility with respect to the solvent of a polymer will fall. That is, there is a trade-off between reducing the burn-in of the liquid crystal display element and improving the solubility of the polymer, and it has been difficult to achieve both characteristics.

  Also, when manufacturing a large liquid crystal panel, after the liquid crystal aligning agent is printed on the substrate, it is temporarily stored until the next pre-baking process is performed, so that it can be drawn between the printing process and the pre-baking process. Placement time may occur. At this time, if the solubility of the polymer in the solvent is not good, printing unevenness and pinholes are likely to occur due to the placement, and as a result, the display quality and the product yield may be reduced.

  An object of the present invention is to provide a liquid crystal aligning agent capable of satisfying both solubility of a polymer component in a solvent and reduction in image sticking of a liquid crystal display element.

  The present inventors diligently studied to achieve the above-described problems of the prior art, and by incorporating a polymer having a structure in which “—NH—” is protected with a protecting group in the side chain into the liquid crystal aligning agent, It has been found that the above problems can be solved. Specifically, the following liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, polymer and compound are provided.

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

(In Formula (1), A ¹ is a single bond or a divalent linking group, R ¹ is a monovalent organic group having 8 or more carbon atoms, X ¹ is a protecting group, and “*” represents a heavy group. Shows the bond that binds to the main chain of the coalescence.

  In another aspect, a liquid crystal alignment film formed using the liquid crystal alignment agent is provided. Moreover, a liquid crystal display element provided with the said liquid crystal aligning film is provided.

  In another aspect, the present invention provides a polymer having a partial structure represented by the above formula (1). Moreover, the compound represented by the following formula (3) and the compound represented by the following formula (4) are provided.

(In Formula (3), A ¹ is a single bond or a divalent linking group, R ¹ is a monovalent organic group having 8 or more carbon atoms, and X ¹ is a protecting group.)

(In Formula (4), A ⁴ is a divalent organic group, R ¹ is a monovalent organic group having 8 or more carbon atoms, and X ¹ is a protecting group.)

  By protecting —NH— of the polymer side chain with a protective group and containing it in the liquid crystal aligning agent, the solubility of the polymer in the solvent can be improved in the state of the liquid crystal aligning agent. In addition, when a liquid crystal aligning agent is applied to a substrate to form a film, for example, after the film formation, the protective group is removed by conversion to -NH- by heating at the time of film formation or by acid or base. As a result, a highly oriented structure is regenerated, and as a result, the burn-in of the liquid crystal display element can be reduced (particularly, the reduction of the afterimage).

It is explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell which has the transparent transparent conductive film manufactured in the Example and the comparative example.

Below, each component contained in the liquid crystal aligning agent which concerns on this invention, and the other component arbitrarily mix | blended as needed are demonstrated.
<Polymer (P)>
The liquid crystal aligning agent which concerns on this invention contains the polymer (P) which has a partial structure represented by following formula (1).
(In Formula (1), A ¹ is a single bond or a divalent linking group, R ¹ is a monovalent organic group having 8 or more carbon atoms, X ¹ is a protecting group, and “*” represents a heavy group. Shows the bond that binds to the main chain of the coalescence.

In the above formula (1), the divalent linking group of A ¹ is, for example, a divalent hydrocarbon group having 1 to 20 carbon atoms; a methylene group of the hydrocarbon group is —O—, —S—, —CO—. , —COO—, —COS—, —NR ^a —, or —CO—NR ^a — (wherein R ^a is a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms or a protecting group), and the like. A divalent group formed by replacing at least one hydrogen atom bonded to a carbon atom of a hydrocarbon group with a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, a cyano group, or the like. A divalent group consisting of: —CO—, —COO—, —NR ^a —CO—, and the like.

  Here, in the present specification, the “hydrocarbon group” means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among these, the “chain hydrocarbon group” means a linear hydrocarbon group and a branched hydrocarbon group which are composed only of a chain structure without including a cyclic structure in the main chain. However, it may be saturated or unsaturated. The “alicyclic hydrocarbon group” means a hydrocarbon group that includes only an alicyclic hydrocarbon structure as a ring structure and does not include an aromatic ring structure. However, it is not necessary to be comprised only by the structure of an alicyclic hydrocarbon, The thing which has a chain structure in the part is also included. “Aromatic hydrocarbon group” means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure. “Organic group” means a group containing a hydrocarbon group, and the structure may contain a hetero atom.

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in A ¹ include a chain hydrocarbon group such as methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl. Group, octanediyl group, nonanediyl group, decandiyl group, vinylene group, propenediyl group, butenediyl group, etc .; alicyclic hydrocarbon group, eg cyclohexylene group, etc .; aromatic hydrocarbon group, eg phenylene group, Biphenylene groups and the like can be mentioned respectively.

X ¹ is not particularly limited as long as it is a functional group for converting an amino group (—NH—) into an inactive functional group. For example, a monovalent organic group that is eliminated by heat, acid, or base, etc. Is mentioned. X ¹ is preferably a monovalent organic group that is eliminated by heat, and specific examples thereof include carbamate protecting groups, amide protecting groups, imide protecting groups, sulfonamide protecting groups, and the like. Of these, carbamate protecting groups are preferred, and specific examples thereof include, for example, t-butoxycarbonyl group, benzyloxycarbonyl group, 1,1-dimethyl-2-haloethyloxycarbonyl group, 1,1- Examples thereof include a dimethyl-2-cyanoethyloxycarbonyl group, a 9-fluorenylmethylcarbonyl group, an allyloxycarbonyl group, and a 2- (trimethylsilyl) ethoxycarbonyl group. Among them, a t-butoxycarbonyl group is preferable in that it can be easily deprotected by heat and a compound derived from X ¹ desorbed by heating during film formation can be discharged out of the film as a gas.

R ¹ is a monovalent organic group having 8 or more carbon atoms. The carbon number of R ¹ may be 8 or more, but is preferably 10 or more, more preferably 12 or more, and further preferably 15 or more, from the viewpoint of improving the orientation of liquid crystal molecules. It is particularly preferable that the number be 17 or more. The upper limit of the carbon number is not particularly limited, and can be, for example, 100 or less. The structure of R ¹ is not particularly limited, but a group represented by the following formula (2) can be given as a preferred specific example.
(In Formula (2), A ³ is a single bond or a divalent linking group, R ³ is a liquid crystal alignment group or a photo-alignment group. “*” Represents a bond bonded to a nitrogen atom. )

Both the liquid crystal aligning group and the photo aligning group in R ³ of the above formula (2) are groups capable of imparting a pretilt angle to the liquid crystal molecules. Among these, the photo-alignment group is a group that can exhibit the property of controlling the alignment of liquid crystal molecules by light irradiation, and the liquid crystal alignment group can exhibit the property of controlling the alignment of liquid crystal molecules without light irradiation. It is a group. Specific examples of the liquid crystal alignment group for R ³ include, for example, an alkyl group having 8 to 20 carbon atoms, a fluoroalkyl group having 8 to 20 carbon atoms, an alkoxy group having 8 to 20 carbon atoms, and a steroid skeleton having 17 to 51 carbon atoms. And a group in which a plurality of rings are bonded directly or via a linking group, and the like, and these may have a substituent.
Here, examples of the alkyl group having 8 to 20 carbon atoms include octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group. As the fluoroalkyl group having 8 to 20 carbon atoms, for example, a perfluorooctyl group, a perfluorooctylethyl group, a perfluorodecyl group, a perfluorodecylethyl group, and the like; as an alkoxy group having 8 to 20 carbon atoms, For example, octyloxy, nonyloxy, decyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, eicosyloxy Group etc .;
Examples of the group having a steroid skeleton having 17 to 51 carbon atoms include a cholestanyl group, a cholesteryl group, and a lanostannyl group;

Examples of the group formed by bonding a plurality of rings directly or via a linking group include the following formulas (L-1) to (L-10).
(In Formula (L-1) to Formula (L-10), X ³ represents a single bond, —C ₂ H ₄ —, * 1-COO—, * 1-OCO—, * 1-COS—, * 1. ^{-SCO -, * 1-NR b} CO -, * 1-CONR b -, * 1-CH 2 O -, * 1-OCH 2 -, * 1-CH 2 S- or * 1-SCH ₂ - (provided that , R ^b is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a monovalent organic group that is eliminated by heat, “* 1” indicates a bond with a ring structure having “*”. N is an integer of 0 to 20, m is an integer of 1 to 20. “*” represents a bond with A ³ in the above formula (2).
And groups represented by each of the above. The alkyl group, fluoroalkyl group and alkoxy group having 8 to 20 carbon atoms may be linear or branched, but is preferably linear.

In the above formulas (L-1) to (L-5), the group “C _n H _{2n + 1} —” is preferably linear. In the above formula (L-6) to formula (L-10), the group “C _m F _{2m + 1} —” and the group “—C _n H _2n —” are preferably each linear. n is preferably from 2 to 20, and more preferably from 3 to 15. m is preferably from 1 to 15, and more preferably from 1 to 10.
Examples of the substituent that the liquid crystal aligning group may have include a photopolymerizable group such as a (meth) acryloyloxy group, a styryl group, a maleimide group, a vinyl group, a vinyl ether group, an allyl group, and a vinylidene group. Can be mentioned. Among these, a (meth) acryloxy group, a styryl group, or a maleimide group can be preferably used in terms of high photoreactivity. Note that “(meth) acryloxy” means “acryloxy” and “methacryloxy”.
Examples of the divalent linking group for A ³ include a carbonyl group, an alkanediyl group having 1 to 10 carbon atoms, and “* 2-CO—R ^c —COO—” (where R ^c is an alkane having 1 to 10 carbon atoms). A diyl group or a cyclohexylene group, “* 2” represents a bond to a nitrogen atom.) And the like.

The photo-alignable group of R ³ is a group that expresses alignment regulating force by photoisomerization, photodimerization, photolysis, etc., and specific examples thereof include, for example, an azo-containing compound containing an azo compound or a derivative thereof as a basic skeleton. Group, cinnamic acid-containing group containing cinnamic acid or a derivative thereof as a basic skeleton, chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, coumarin or a derivative thereof And a coumarin-containing group containing cyclobutane or a derivative thereof as a basic skeleton. Among these, an azo-containing group or a cinnamic acid-containing group is preferable from the viewpoint of good photoalignment and ease of introduction into the polymer.

The azo-containing group is not particularly limited as long as it has an azo group (—N═N—), and examples thereof include a group represented by the following formula (y-1).
(In formula (y-1), A ⁴ and A ⁵ are each independently a divalent organic group, and R ⁴ is a liquid crystal alignment group.)

In the formula (y-1), examples of the divalent organic group represented by A ⁴ and A ⁵ include a divalent hydrocarbon group having 1 to 20 carbon atoms; a methylene group of the hydrocarbon group is —O—, —S; —, —CO—, —COO—, —COS—, —NR ^a —, or —CO—NR ^a — (wherein R ^a is a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or a protecting group. A divalent group that is substituted with a hydrocarbon atom, at least one hydrogen atom bonded to a carbon atom of a hydrocarbon group is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxyl group, cyano And a divalent group substituted by a group. Regarding the liquid crystal aligning group of R ⁵ , the description of the liquid crystal aligning group of R ^{3 in} the above formula (2) can be applied.
Specific examples of the group represented by the formula (y-1) include groups represented by the following formulas (y-1-1) to (y-1-10).
(In the formula (y-1-1) to the formula (y-1-10), X ⁴ represents a single bond, —C ₂ H ₄ —, * 3-COO—, * 3-OCO—, * 3-COS. ^{-, * 3-SCO -,} * 3-NR d CO -, * 3-CONR d -, * 3-CH 2 O -, * 3-OCH 2 -, * 3-CH 2 S- or * 3-SCH _2- (wherein R ^d is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a protecting group. “* 3” represents a bond with an azobenzene structure.) N is 0 to 0. 20 is an integer of 20, and m is an integer of 1 to 20. X ³ is synonymous with X ³ in the above formula (L-1) to formula (L-10).

Specific examples of the cinnamic acid-containing group include a group represented by the following formula (x-1) and a group represented by the following formula (x-2).
(In Formula (x-1) and Formula (x-2), R ¹¹ and R ¹⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 20 carbon atoms. X ¹¹ and X ¹³ are each independently a single bond, an oxygen atom, a sulfur atom, * —COO— or * —OCO— (where the bond marked with “*” is R ¹¹ or R ¹⁴ , respectively). X ¹² is a single bond, an oxygen atom, a sulfur atom, an alkanediyl group having 1 to 3 carbon atoms, * —COO— or * —OCO— (where “*” is a bond). binds to R ^12.) a is ^{.R 12} and ^{R 15} are each independently a 1,4-phenylene group or a 1,4-cyclohexylene group ^{.X 14} is a single bond, alkane having 1 to 3 carbon atoms Diyl group, oxygen atom, sulfur atom or -NH- That ^{.X 15} is an oxygen atom, * - COO- or * -OCO- (. However, the bond marked with "*" is bonded to ^{R 16)} is ^{.R 16} is a divalent aromatic group, 2 R ¹⁷ is a single bond, * —OCO— (CH ₂ ) _h — or * —O— (CH ₂ ), which is a divalent alicyclic group, divalent heterocyclic group or divalent condensed cyclic group. _i— (However, the bond marked with “*” is bonded to R ^16, and h and i are each an integer of 1 to 10.) X ¹⁶ is * —COO— or * —OCO— ( However, a bond marked with “*” is bonded to R ^17. ) R ¹³ and R ¹⁸ are each independently a fluorine atom, a cyano group, or a methyl group, and R ¹⁹ and R ²⁰ are each Independently an alkanediyl group having 1 to 10 carbon atoms or a 1,4-cyclohexylene group, a, e and d are Are independently integers of 0 to 3, b and f are each independently 0 or 1, c and g are each independently an integer of 0-4.)

Specific examples of the group represented by the formula (x-1) include, for example, groups represented by the following formulas (x-1-1) to (x-1-13); Specific examples of the group represented by x-2) include compounds represented by the following formulas (x-2-1) to (x-2-2). In addition, groups described in JP 2011-133825 A can be mentioned.
^{(Wherein, R 11} and b have the same meanings as ^{R 11} and b in the formula (x-1).)
^{(Wherein, R 14} and f have the same meanings as ^{R 14} and f in the formula (x-2).)

The partial structure represented by the above formula (1) is preferably a group represented by the following formula (1-1) or formula (1-2) in that the effect of reducing the burn-in of the liquid crystal display element is high. .
(In Formula (1-1) and Formula (1-2), A ² is a single bond or a divalent organic group, and R ² is a monovalent organic group. X ¹ , A ¹ and R ¹ are (It is synonymous with the above formula (1). “*” Represents a bond bonded to the main chain of the polymer.)

For the divalent organic group of A ² , the illustrations of A ⁴ and A ^{5 in} the above formula (y-1) can be applied, and for the monovalent organic group of R ² , the above formula (1 The illustration of the description of R ¹ in FIG.
“*” In the above formula (1) indicates a bond that bonds to the main chain of the polymer. Here, in the present specification, the “main chain” of the polymer refers to a “trunk” portion composed of the longest chain of atoms in the polymer, and the “side chain” refers to the “trunk” of the polymer. The branching part.

  The main skeleton of the polymer (P) is not particularly limited. For example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly A skeleton composed of (meth) acrylate and the like can be given. Among these, at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane is preferable from the viewpoint of heat resistance, mechanical strength, affinity with liquid crystal, and the like. In addition, (meth) acrylate means containing an acrylate and a methacrylate.

(Polyamic acid)
When the polymer (P) is a polyamic acid, the polyamic acid can be obtained by reacting a tetracarboxylic dianhydride and a diamine. The polyamic acid having a partial structure represented by the above formula (1) (hereinafter also referred to as “specific partial structure”) has a specific partial structure (however, “*” in formula (1) represents a bond. Monomer) The same shall apply hereinafter for the tetracarboxylic dianhydride having a specific partial structure and a diamine having a specific partial structure. It is preferable to use a diamine having a specific partial structure (hereinafter also referred to as “specific diamine”) in terms of a high degree of freedom in selecting a compound.

(Tetracarboxylic dianhydride)
Examples of tetracarboxylic dianhydrides used for the synthesis of polyamic acid include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. . Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride;

Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4, 5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane -2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- No 1,2-dicarboxylic acid Product, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-dianhydride, 4,9-di Oxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2 ] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), 1 , 3-Propylene glycol bis (am Hydrotrimellitate) etc .;
Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like; respectively, and tetracarboxylic dianhydrides described in JP 2010-97188 A can be used. In addition, tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

As tetracarboxylic dianhydride used for the synthesis of polyamic acid, among the above, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, in that various characteristics of the liquid crystal display element can be improved. 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1 , 3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [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 anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-dianhydride, 4,9-dioxa Tricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride It is preferable to contain at least one compound selected from the group consisting of cyclopentanetetracarboxylic dianhydride and pyromellitic dianhydride. The amount of these preferred compounds used (the total amount when two or more are used) is preferably 5 mol% or more based on the total amount of tetracarboxylic dianhydride used for the synthesis of polyamic acid. It is more preferable to set it as 10 mol% or more, and it is more preferable to set it as 20 mol% or more.

(Diamine)
As long as the specific diamine has the specific partial structure, the remaining structure is not particularly limited, and examples thereof include a compound represented by the following formula (3).
(In the formula ^(3), A 1, ^{R 1} and ^{X 1} are the same as defined for the formula (1).)

The explanation of the above formula (1) can be applied to A ¹ , R ¹ and X ^{1 in the} above formula (3). Specific examples of the specific diamine include compounds represented by the following formulas (3-1) to (3-19).
(In the formula, n is an integer of 0 to 20.)
In addition, in the synthesis | combination of a polyamic acid, specific diamine can be used individually by 1 type or in combination of 2 or more types.

  Although the specific diamine may be sufficient as the diamine used for the synthesis | combination of the polyamic acid as a polymer (P), other diamines other than a specific diamine may be used together.

  Examples of other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. Specific examples of these include aliphatic diamines such as m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and 1,3-bis (aminomethyl) cyclohexane. An alicyclic diamine such as 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine);

Examples of aromatic diamines include dodecanoxydiaminobenzene, tetradecanoxydiaminobenzene, pentadecanoxydiaminobenzene, hexadecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, and cholesteryloxydiaminobenzene. Cholestanyl diaminobenzoate, cholesteryl diaminobenzoate, lanostannyl diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 1,1-bis (4 -((Aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((amino Phenoxy Methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, N- (2,4-diaminophenyl) -4 -(4-heptylcyclohexyl) benzamide, the following formula (E-1) or the following formula (E-2)
(In Formula (E-1) and Formula (E-2), X ^I and X ^II are each independently a single bond, —O—, —COO— or —OCO—, and R ^I has 1 carbon atom. -3 alkanediyl group, R ^II is a single bond or a C 1-3 alkanediyl group, X ^III is a hydrogen atom or a photopolymerizable group, r is 0 or 1, and s is 0 is an integer of 0 to 2, t is an integer of 1 to 20, and u is 0 or 1. However, r and s are not 0 at the same time. R ^II may be the same or different.)
Oriented group-containing diamine such as a compound represented by:

p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 4-aminophenyl-4′-aminobenzoate, 4,4′-diaminoazobenzene, 1,5-bis (4-amino) Phenoxy) pentane, 1,7-bis (4-aminophenoxy) heptane, bis [2- (4-aminophenyl) ethyl] hexanedioic acid, N, N-bis (4-aminophenyl) methylamine, 1,5 -Diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4 ' -Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) Luolene, 2,2-bis [4- (4-aminophenoxy) 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-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole N-phenyl-3,6-diaminocarbazole, N, N′-bis (4-aminophenyl) -benzi Emissions, N, N'-bis (4-aminophenyl) -N, N'-dimethyl-benzidine, 1,4-bis - (4-aminophenyl) - piperazine, 3,5-diaminobenzoic acid; the
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane; and the diamines described in JP-A 2010-97188 can be used.

As the divalent group represented by “—X ^I — (R ^I —X ^II ) _u —” in the above formula (E-1), an alkanediyl group having 1 to 3 carbon atoms, * —O—, * —COO— or * —O—C ₂ H ₄ —O— (however, a bond marked with “*” is bonded to a diaminophenyl group) is preferred. The group “—C _t H _{2t + 1} ” and the group “—C _t H _2t —” are preferably linear.
As the photopolymerizable group X ^III, is preferably a (meth) acryloxy group, a styryl group or a maleimide group. The two amino groups in the diaminophenyl group in the above formulas (E-1) and (E-2) are preferably in the 2,4-position or 3,5-position with respect to the other groups.

Specific examples of the compounds represented by the formula (E-1) and the formula (E-2) include, for example, the following formulas (E-1-1) to (E-1-4) and the formula (E-2- Examples thereof include compounds represented by each of 1).

  As the other diamine, a diamine having a specific functional group can also be used for the purpose of enhancing the improvement effect of reducing the image sticking due to the direct current voltage of the liquid crystal display element. Examples of such a diamine include a diamine having a nitrogen-containing structure that is at least one selected from the group consisting of a nitrogen-containing heterocyclic ring, a secondary amino group, and a tertiary amino group, and a diamine having a carboxyl group.

Examples of the diamine having a nitrogen-containing structure include 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1 , 4-bis- (4-aminophenyl) -piperazine, compounds represented by the following formulas (E-3-1) to (E-3-6), and the like.

Examples of the diamine having a carboxyl group include monocarboxylic acids such as 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, and 2,5-diaminobenzoic acid;
4,4′-diaminobiphenyl-3,3′-dicarboxylic acid, 4,4′-diaminobiphenyl-2,2′-dicarboxylic acid, 3,3′-diaminobiphenyl-4,4′-dicarboxylic acid, 3, 3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, 4,4 And polyvalent carboxylic acids such as' -diaminodiphenyl ether-3,3'-dicarboxylic acid;

The diamine used in the synthesis of the polyamic acid is the ratio of the specific diamine to the total amount of the diamine from the viewpoint of sufficiently obtaining the effect of improving the solubility of the polymer in the solvent and the effect of reducing the burn-in by the alternating voltage of the liquid crystal display element. The amount is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and particularly preferably 10 mol% or more. The upper limit of the use ratio of the specific diamine is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, from the viewpoint of developing an appropriate pretilt angle. .
The proportion of the diamine having a nitrogen-containing structure should be 0.1 mol% or more with respect to the total amount of diamine used in the synthesis from the viewpoint of sufficiently obtaining the effect of reducing the burn-in due to the DC voltage of the liquid crystal display element. Is preferable, it is more preferable to set it as 1-50 mol%, and it is further more preferable to set it as 2-30 mol%. The proportion of the diamine having a carboxyl group is preferably 1 mol% or more, more preferably 2 to 90 mol%, and more preferably 5 to 80 mol% with respect to the total amount of diamine used for synthesis. More preferably. In addition, another diamine can be used individually by 1 type or in combination of 2 or more types.

(Synthesis of specific diamine)
The specific diamine can be synthesized by appropriately combining known methods. As an example, for example, a dinitro intermediate having a nitro group is synthesized in place of the primary amino group in the above formula (3), and then the nitro group of the obtained dinitro intermediate is synthesized using an appropriate reduction system. Examples include amination method. The method for synthesizing the dinitro intermediate can be appropriately selected according to the target compound. For example, by reacting a dinitro compound having “—NH—” with di-tert-butyl dicarbonate in the presence of a strong base such as dimethylaminopyridine, “—NH—” is converted into a t-butoxycarbonyl group. Protected dinitro intermediates can be synthesized. However, the method for synthesizing the specific diamine is not limited to the above.

(Synthesis of polyamic acid)
The polyamic acid can be obtained by reacting the tetracarboxylic dianhydride and diamine as described above with a molecular weight modifier as necessary. The ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction is 0.2 to 2 for the tetracarboxylic dianhydride acid anhydride group to 1 equivalent of the amino group of the diamine. The ratio which becomes an equivalent is preferable, and the ratio which becomes 0.3-1.2 equivalent is more preferable.

  Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. Can be mentioned. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and diamine used.

  The polyamic acid synthesis reaction is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

  Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (first group organic solvent), or one or more selected from the first group of organic solvents And a mixture of at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second-group organic solvent). In the latter case, the proportion of the second group organic solvent used is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the first group organic solvent and the second group organic solvent. Or less, more preferably 30% by weight or less.

  Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol. And at least one selected from the group consisting of halogenated phenols is used as a solvent, or a mixture of one or more of these and another organic solvent is preferably used in the above range. The amount of organic solvent used (a) is such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution. Is preferred.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. Isolation and purification of the polyamic acid can be performed according to known methods.

(Polyimide)
The polyimide as the polymer (P) can be obtained, for example, by dehydrating and ring-closing the polyamic acid synthesized as described above to imidize. When polyamic acid is dehydrated and cyclized into polyimide, the polyamic acid reaction solution may be subjected to dehydration and cyclization reaction as it is, or after the polyamic acid contained in the reaction solution is isolated and subjected to dehydration and cyclization reaction. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration cyclization reaction.

  The polyimide may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure possessed by the polyamic acid that is the precursor, and only a part of the amic acid structure may be dehydrated and cyclized. It may be a partially imidized product in which a ring structure coexists. The polyimide used for the reaction preferably has an imidization ratio of 10% or more, more preferably 20 to 99%, and still more preferably 30 to 99%. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.

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

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

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

(Polyamic acid ester)
The polyamic acid ester as the polymer (P) is, for example, [I] a method of reacting the polyamic acid having the specific partial structure and an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester and a diamine, [III] It can be obtained by a method of reacting a tetracarboxylic acid diester dihalide with a diamine.

  Here, examples of the esterifying agent used in the method [I] include a hydroxyl group-containing compound, an acetal compound, an epoxy group-containing compound, and the like. Specific examples thereof include hydroxyl group-containing compounds such as alcohols such as methanol, ethanol and propanol; phenols such as phenol and cresol; and acetal compounds such as N, N-dimethylformamide diethyl acetal, N, N-diethylformamide diethyl acetal and the like; Examples of the epoxy group-containing compound include propylene oxide and the like.

  The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by opening the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid with an alcohol such as methanol or ethanol. Moreover, as a diamine used by method [II], the diamine illustrated by the synthesis | combination of polyamic acid can be mentioned, It is preferable that specific diamine is included. The reaction of Method [II] is preferably performed in an organic solvent in the presence of a suitable dehydration catalyst. As an organic solvent, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. Examples of the dehydration catalyst include 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, a phosphorus condensing agent, and the like.

  The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. Moreover, as diamine used by method [III], the diamine illustrated by the synthesis | combination of polyamic acid can be mentioned, It is preferable that specific diamine is included. The reaction of Method [III] is preferably carried out in an organic solvent in the presence of a suitable base. As an organic solvent, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. As the base, for example, tertiary amines such as pyridine and triethylamine can be preferably used.

  Thus, a reaction solution obtained by dissolving the polyamic acid ester is obtained. This reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid ester contained in the reaction solution, or the isolated polyamic acid ester You may use for preparation of a liquid crystal aligning agent, after refine | purifying. Isolation and purification of the polyamic acid ester can be performed according to a known method. In addition, the polyamic acid ester contained in the liquid crystal aligning agent may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.

The solution viscosity of the polyamic acid, polyamic acid ester and polyimide as the polymer (P) preferably has a solution viscosity of 10 to 800 mPa · s when this is a 10% by weight solution, More preferably, it has a solution viscosity of 15 to 500 mPa · s. In addition, the solution viscosity (mPa · s) of the polymer is E for a polymer solution having a concentration of 10% by weight prepared using a good polymer solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using a mold rotational viscometer.
The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. Moreover, the molecular weight distribution (Mw / Mn) represented by the ratio between Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.

(Polyorganosiloxane)
The polyorganosiloxane (hereinafter also referred to as “specific group-containing polyorganosiloxane”) as the polymer (P) is, for example,
[1] Hydrolyzable silane compound having an epoxy group (ms-1) or a polymer obtained by hydrolytic condensation of a mixture of the silane compound (ms-1) and another silane compound (hereinafter referred to as “ A method of reacting an epoxy group-containing polyorganosiloxane ”with a carboxylic acid having the specific partial structure (hereinafter also referred to as“ specific carboxylic acid ”);
[2] A method of hydrolyzing and condensing a hydrolyzable silane compound having the specific partial structure or a mixture of the silane compound and another silane compound;
And so on. Among these, the method [1] is preferable in that the specific partial structure can be introduced with high efficiency.

  Specific examples of the silane compound (ms-1) used for the synthesis of the epoxy group-containing polyorganosiloxane include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxy Propylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethyldimethylmethoxysilane, 2-glycid Xylethyldimethylethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutylmethyldimethoxysilane, 4-glycidoxybutylmethyldiethoxysilane, 4-glycidoxybutyldimethylmethoxysilane, 4-glycidyl Sidoxybutyl Methylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, etc. Can be mentioned. As the silane compound (ms-1), one of these can be used alone, or two or more can be used in combination.

Other silane compounds are not particularly limited as long as they are hydrolyzable silane compounds, and can be appropriately selected according to the driving mode of the liquid crystal display element. Specific examples of other silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and the like. Alkoxysilane compounds;
3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Nitrogen / sulfur-containing alkoxysilane compounds such as silane and N- (3-cyclohexylamino) propyltrimethoxysilane;
3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyl Unsaturated-silane-containing alkoxysilane compounds such as trimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane;
Examples include trimethoxysilylpropyl succinic anhydride, alkoxysilane compounds having a silicon-silicon bond, and the like. Other silane compounds may be used alone or in combination of two or more.

  From the viewpoint of suppressing side reactions caused by an excessive amount of epoxy groups while allowing the specific partial structure to be sufficiently introduced into the side chain of the polymer, the epoxy equivalent of the epoxy group-containing polyorganosiloxane is 80 to 10,000 g / mol, more preferably 100 to 1,000 g / mol. Therefore, when synthesizing an epoxy group-containing polyorganosiloxane, the use ratio of the silane compound (ms-1) and other silane compounds should be adjusted so that the epoxy equivalent of the resulting polyorganosiloxane is within the above range. Is preferred.

  The hydrolysis / condensation reaction of the silane compound is carried out by reacting one or more of the above silane compounds with water, preferably in the presence of an appropriate catalyst and an organic solvent. In the hydrolysis / condensation reaction, the proportion of water used is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, per 1 mol of the silane compound (total amount).

Examples of the catalyst used in the hydrolysis / condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds and the like. Organic bases are tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene: quaternary organic amines such as tetramethylammonium hydroxide. Organic amines are preferred.
Examples of the catalyst include alkali metal compounds or organic bases, in that side reactions such as ring opening of epoxy groups can be suppressed, hydrolysis condensation rate can be increased, and storage stability is excellent. Preferably, an organic base is more preferable.
The amount of the organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and should be set as appropriate. More preferably, it is 0.05-1 times mole.

Examples of the organic solvent used in the hydrolysis / condensation reaction include hydrocarbons, ketones, esters, ethers, alcohols and the like. Specific examples thereof include hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone and cyclopentanone; esters such as ethyl acetate. N-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; alcohols; For example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Glycol mono -n- propyl ether, ethylene glycol monobutyl -n- butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -n- propyl ether and the like; may be mentioned, respectively. Of these, it is preferable to use a water-insoluble organic solvent. In addition, these organic solvents can be used individually by 1 type or in mixture of 2 or more types.
The use ratio of the organic solvent in the hydrolytic condensation reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight with respect to 100 parts by weight of the total silane compounds used in the reaction. .

  The hydrolysis / condensation reaction is preferably carried out by dissolving the silane compound as described above in an organic solvent, mixing this solution with an organic base and water, and heating the solution with, for example, an oil bath. In the hydrolysis / condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C. The heating time is preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux. After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this washing, washing with water containing a small amount of salt (for example, an aqueous ammonium nitrate solution of about 0.2% by weight) is preferable in that the washing operation is facilitated. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve as necessary, and then the solvent is removed to remove the solvent. The polyorganosiloxane can be obtained.

  In the method [1] above, the epoxy group-containing polyorganosiloxane obtained by the above reaction is then reacted with a specific carboxylic acid. As a result, the epoxy group of the epoxy group-containing polyorganosiloxane reacts with the carboxylic acid to obtain a polyorganosiloxane having the specific partial structure in the side chain.

The specific carboxylic acid used for the synthesis is not particularly limited as long as it has the specific partial structure, and examples thereof include a compound represented by the following formula (4).
(In Formula (4), A ⁴ is a divalent organic group. R ¹ and X ¹ have the same meanings as in Formula (1) above.)

A ^{4 in the} above formula (4) can apply the description of the divalent organic group of A ^{1 in} the above formula (1), and is preferably a divalent hydrocarbon group. For R ¹ and X ^{1, the} description of the above formula (1) can be applied. Specific examples of the specific carboxylic acid include compounds represented by the following formulas (4-1) to (4-19).
(In the formula, n is an integer of 0 to 20.)
In addition, specific carboxylic acid can be used individually by 1 type or in combination of 2 or more types.

The method for synthesizing the specific carboxylic acid is not particularly limited, and it can be synthesized by combining conventionally known methods. As an example of the synthesis method, for example, by reacting a halide having “—NHR ¹ ” with di-tert-butyl dicarbonate in the presence of a strong base such as dimethylaminopyridine, “—NH—” And a method in which a compound protected with a t-butoxycarbonyl group is synthesized, and then the obtained compound is reacted with a carboxylic acid having a functional group capable of reacting with a halogen atom. However, the method for synthesizing the specific carboxylic acid is not limited to the above.

Only the specific carboxylic acid may be used for the reaction with the epoxy group-containing polyorganosiloxane, but other carboxylic acids other than the specific carboxylic acid may be used in combination.
The other carboxylic acid may be a carboxylic acid having no specific partial structure, and specific examples thereof include, for example, caproic acid, lauric acid, pentadecylic acid, palmitic acid, stearic acid, oleic acid, vaccenic acid, linol. Examples thereof include fatty acids having 6 to 20 carbon atoms such as acid, linolenic acid and arachidic acid, and compounds represented by the following formulas (5-1) to (5-9).
(In the formula, j is an integer of 0 to 12, and h is an integer of 1 to 20.)
In addition, as another carboxylic acid, 1 type selected from these can be used individually or in combination of 2 or more types.

The proportion of the carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane is preferably 0.001 to 1.5 mol, based on 1 mol of the total epoxy groups of the polyorganosiloxane, 0.01 to 1 More preferably, it is 0.0 mol.
Moreover, it is preferable that the usage-amount of specific carboxylic acid shall be 0.01-0.8 mol with respect to a total of 1 mol of the epoxy group which polyorganosiloxane has. When the use ratio is less than 0.01 mol, the amount of the specific partial structure introduced is small, and it is difficult to obtain improvement effects such as liquid crystal alignment, burn-in reduction, and solubility. On the other hand, when it exceeds 0.8 mol, the solubility of the polymer tends to be inferior. Preferably it is 0.03-0.6 mol, More preferably, it is 0.05-0.4 mol.

The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent.
Examples of the catalyst used in the reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds and the like. Of these, organic bases are preferred. The ratio of the catalyst used is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane to be reacted with the carboxylic acid. is there.

  Examples of the organic solvent used in the above reaction include hydrocarbons, ethers, esters, ketones, amides, alcohols and the like. Of these, ethers, esters, and ketones are preferred from the viewpoints of solubility of raw materials and products, and ease of purification of the products. Specific examples of particularly preferred solvents include 2-butanone, 2-hexanone, and methylisobutyl. Examples thereof include ketones and butyl acetate. The organic solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, It is more preferable to use it at a ratio of 5 to 50% by weight.

  The reaction temperature in the above reaction is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. Moreover, after completion | finish of reaction, it is preferable to wash | clean the organic-solvent layer fractionated from the reaction liquid with water. After washing with water, the organic solvent layer is dried with an appropriate desiccant as necessary, and then the solvent is removed to obtain a polyorganosiloxane having the specific partial structure in the side chain.

The specific group-containing polyorganosiloxane obtained as described above preferably has a solution viscosity of 1 to 500 mPa · s when it is made into a solution having a concentration of 10% by weight, and 3 to 200 mPa · s. It is more preferable to have a solution viscosity of In addition, the solution viscosity (mPa · s) of the above polymer is an E-type rotation with respect to a polymer solution having a concentration of 10% by weight prepared using a good solvent (for example, N-methyl-2-pyrrolidone) of the polymer. It is a value measured at 25 ° C. using a viscometer.
For the specific group-containing polyorganosiloxane, the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography improves the liquid crystal alignment of the liquid crystal alignment film to be formed, and the liquid crystal alignment over time. From the viewpoint of ensuring stability, it is preferably 1,000 to 50,000, and more preferably 3,000 to 30,000.

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

[Other polymers]
The above other polymers can be used for the purpose of improving various properties such as solution properties and electrical properties. Such other polymers are polymers having no specific partial structure, such as polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenyl). Maleimide) derivatives or polymers having poly (meth) acrylate as the main skeleton. Among these, at least one polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, and polyorganosiloxane can be preferably used.
When other polymers are blended in the liquid crystal aligning agent, the blending ratio is 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent (the sum of the polymer (P) and the other polymer). 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, still more preferably 0.2 to 30 parts by weight.

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

[Functional silane compounds]
The functional silane compound can be used for the purpose of improving the printability of the liquid crystal aligning agent. Examples of such functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl -3,6- Methyl azananoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycid And xylpropyltrimethoxysilane.
When other functional silane compounds are blended in the liquid crystal aligning agent, the blending ratio is preferably 2 parts by weight or less with respect to a total of 100 parts by weight of the polymer contained in the liquid crystal aligning agent. It is more preferable to set it as 02-0.2 weight part.

  As other components, in addition to the above, compounds having at least one oxetanyl group in the molecule, antioxidants, metal chelate compounds, curing accelerators, surfactants, fillers, dispersants, photosensitizers And so on.

The liquid crystal aligning agent which concerns on this invention may contain only 1 type of polymer as a polymer component, and may contain 2 or more types of polymers. As a preferable aspect of a polymer component, the following [1]-[5] etc. are mentioned, for example.
[1] An embodiment containing only the polymer (P) as a polymer component, and the polymer (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide.
[2] An embodiment in which only the polymer (P) is contained as a polymer component, and the polymer (P) is a polyorganosiloxane.
[3] An embodiment containing only the polymer (P) as the polymer component, and containing, as the polymer (P), at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and polyorganosiloxane .
[4] At least selected from the group consisting of a polyamic acid, a polyamic acid ester, and a polyimide, wherein the polymer (P) and the other polymer are contained as a polymer component, and the polymer (P) and the other polymer are included. One aspect.
[5] The polymer (P) and other polymers are contained as a polymer component, and the polymer (P) is a kind selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, An embodiment in which the polymer is a polyorganosiloxane.

Among these, in [4] and [5], the hydrophobicity of the polymer (P) increases due to the introduction effect of the protecting group, and the polarity difference between the polymer and the polymer having no protecting group increases. It is presumed that the polymer (P) can be unevenly distributed in the upper layer and other polymers can be unevenly distributed in the lower layer in the liquid crystal alignment film. In [4] and [5], the other polymer is selected from the group consisting of a nitrogen-containing heterocyclic ring, a secondary amino group, and a tertiary amino group in that the effect of reducing the burn-in due to direct current voltage of the liquid crystal display element can be increased. One or two or more of polymers having a nitrogen-containing structure, a polymer having a carboxyl group, and a polymer having a nitrogen-containing structure and a carboxyl group can be preferably used. .
The blending ratio of the polymer (P) with respect to the solid content of the liquid crystal aligning agent (component other than the solvent of the liquid crystal aligning agent) is preferably 40 parts by weight or more with respect to 100 parts by weight of the total weight of the solid content. The amount is preferably at least part by weight, more preferably at least 60 parts by weight.

<Solvent>
The liquid crystal aligning agent according to the present invention is prepared as a liquid composition in which the polymer (P) and other components used as necessary are preferably dispersed or dissolved in an appropriate solvent.

  Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, Ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether , Ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Recall diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. be able to. These can be used alone or in admixture of two or more.

  The solid content concentration in the liquid crystal aligning agent (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc. It is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent is applied to the substrate surface as will be described later, and preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive, and the viscosity of the liquid crystal aligning agent increases and the applicability decreases. There is a tendency.

  The particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, when applied to a substrate by the spinner method, the solid content concentration (the ratio of the total weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is 1.5 to 4.5% by weight. It is particularly preferable that the range is In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s. The temperature when preparing the liquid crystal aligning agent is preferably 10 to 50 ° C, more preferably 20 to 30 ° C.

<Liquid crystal display element>
The liquid crystal display element according to the present invention includes a liquid crystal alignment film formed using the liquid crystal aligning agent described above. The operation mode of the liquid crystal display element is not particularly limited, and for example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB (Optically Compensated Bend) type. It can be applied to various operation modes.

  A liquid crystal display element can be manufactured by the process containing the following processes (1)-(3), for example. In step (1), the substrate to be used varies depending on the desired operation mode. Step (2) and step (3) are common to each operation mode.

[Step (1): Formation of coating film]
First, a liquid crystal aligning agent is applied on the substrate, and then the coating surface is heated to form a coating film on the substrate.
(1-A) For example, when manufacturing a TN type, STN type, or VA type liquid crystal display element, first, a pair of two substrates provided with patterned transparent conductive films is formed, and each transparent conductive film is formed. On the surface, a liquid crystal aligning agent is preferably applied by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method, respectively. As the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used. In order to obtain a patterned transparent conductive film, for example, after forming a transparent conductive film without a pattern, a method of forming a pattern by photo-etching; a method of using a mask having a desired pattern when forming a transparent conductive film; And so on. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or a functional titanium compound is formed on the surface of the substrate surface on which the coating film is formed. It is also possible to perform a pretreatment to apply the above in advance.

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

  (1-B) When manufacturing an IPS type or FFS type liquid crystal display element, an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and an electrode are provided. A liquid crystal aligning agent is apply | coated to one surface of the counter substrate which is not formed, respectively, Then, each coating surface is heated, and a coating film is formed. Regarding the material used for the substrate and the transparent conductive film, the coating method, the heating conditions after coating, the patterning method for the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the coating film to be formed Same as (1-A). As the metal film, for example, a film made of a metal such as chromium can be used.

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

[Step (2): Orientation treatment]
When manufacturing a TN type, STN type, IPS type, or FFS type liquid crystal display element, the process (orientation process) which provides liquid crystal aligning ability to the coating film formed at the said process (1) is implemented. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. As the alignment treatment, for example, a rubbing treatment that imparts liquid crystal alignment ability to the coating film by rubbing the coating film in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, cotton, etc., a coating film formed on the substrate And a photo-alignment treatment for imparting liquid crystal alignment ability to the coating film. On the other hand, when manufacturing a vertical alignment type liquid crystal display element, the coating film formed in the above step (1) can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment treatment. .

  The light irradiation in the photo-alignment treatment includes (1a) a method of irradiating a coating film after post-baking, (2a) a method of irradiating a coating film after pre-baking and before post-baking, (3a) pre-baking and It can be performed by a method of irradiating the coating film during heating of the coating film in at least one of post-baking.

The light applied to the coating film can be polarized or non-polarized radiation. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. When the radiation used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof. When non-polarized radiation is irradiated, the irradiation direction is an oblique direction.
As a light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. Ultraviolet rays in a preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter or a diffraction grating. The amount of light irradiation is preferably 100 to 50,000 J / m ² , more preferably 300 to 20,000 J / m ² . Moreover, you may perform light irradiation with respect to a coating film, heating a coating film, in order to improve the reactivity. The temperature at the time of heating is 30-250 degreeC normally, Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC.

  Note that the liquid crystal alignment film after the rubbing treatment is further subjected to a treatment for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film, or a surface of the liquid crystal alignment film. A resist film is formed on the part, and a rubbing process is performed in a direction different from the previous rubbing process, followed by a process of removing the resist film, so that the liquid crystal alignment film has different liquid crystal alignment capabilities for each region. . In this case, it is possible to improve the visibility characteristics of the obtained liquid crystal display element.

  When manufacturing a PSA (Polymer sustained alignment) type liquid crystal display element, the following step (3) may be carried out using the coating film formed in the above step (1) as it is, but the liquid crystal molecules fall down. In order to control the alignment and perform alignment division by a simple method, an alignment process such as a weak rubbing process may be performed. A liquid crystal alignment film suitable for a VA liquid crystal display element can also be suitably used for a PSA liquid crystal display element.

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

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

(3-B) When manufacturing a PSA type liquid crystal display element, a liquid crystal cell is constructed in the same manner as in the above (3-A) except that a photopolymerizable compound is injected or dropped together with a liquid crystal. Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. Moreover, as light to irradiate, the ultraviolet-ray and visible light which contain light with a wavelength of 150-800 nm can be used, for example, However, The ultraviolet-ray containing light with a wavelength of 300-400 nm is preferable. As a light source of irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. In addition, the ultraviolet rays in the above preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter diffraction grating. The irradiation dose of light, preferably less than 1,000 J / ^{m 2} or more 200,000 J / ^{m 2,} more preferably from 1,000~100,000J / ^{m 2.}

  (3-C) When a photopolymerizable group is introduced into the side chain of the polymer (P), or when a photopolymerizable group-containing compound is contained in the liquid crystal aligning agent separately from the polymer (P), the above (3 -A) A liquid crystal cell is constructed in the same manner as described above, and then a method of manufacturing a liquid crystal display element through a process of irradiating the liquid crystal cell with light while applying a voltage between conductive films of a pair of substrates is adopted. May be. According to this method, the PSA mode can be realized with a small amount of light irradiation. The description of (3-B) above can be applied to the voltage to be applied and the conditions of the light to be irradiated.

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

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

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

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

<Synthesis of compounds>
[Synthesis Example 1-1: Synthesis of Compound (a-1)]
Compound (a-1) was synthesized according to the following scheme 1.

-Synthesis | combination of compound (a-1-1) 27.4g of 4- (4-pentyl cyclohexyl) benzoic acid and 18.3g of 3, 5- dinitro anilines are taken to a 2000 mL three necked flask containing a stir bar, and 1200 g of dichloromethane is obtained. Was added and stirred. Thereafter, the mixture was cooled to 0 ° C., 23.0 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 2.44 g of N, N-dimethylaminopyridine were added thereto, and the mixture was stirred at room temperature for 20 hours. . Thereafter, the reaction solution was separated and washed three times with 800 mL of water, and then the organic layer was dried over magnesium sulfate. Then, it concentrated slowly until the internal volume became 200g with a rotary evaporator, and collect | recovered the white solid which precipitated on the way by filtration. This white solid was vacuum-dried to obtain 37.4 g of compound (a-1-1).

-Synthesis | combination of compound (a-1-2) 26.4g of compounds (a-1-1) were taken to the 500 mL three necked flask which put the stirrer, 300 g of acetonitrile was added and stirred. Thereafter, the mixture was cooled to 0 ° C., and 14.4 g of di-tert-butyl dicarbonate and 0.73 g of N, N-dimethylaminopyridine were added thereto, followed by stirring at room temperature for 6 hours. Thereafter, the reaction solution was concentrated by a rotary evaporator until 100 g was reached, poured into 500 g of water, and the precipitated white solid was collected by filtration. This white solid was vacuum-dried to obtain 25.9 g of compound (a-1-2).

-Synthesis | combination of compound (a-1) 21.6g of compound (a-2-1), zinc 52.3g, and ammonium chloride 8.56g were added to the 300 mL three necked flask containing the stirring element, and nitrogen substitution was carried out. 3 times. Thereafter, the reaction vessel was cooled to 0 ° C., 150 g of nitrogen bubbled tetrahydrofuran and 20 g of ethanol were added and stirred, and 10 g of water was further added dropwise, followed by stirring at room temperature. After 3 hours, the reaction solution was filtered through Celite, and 300 g of ethyl acetate was added to the filtrate, followed by separation and washing three times with 200 mL of water. Thereafter, the organic layer was concentrated to dryness by a rotary evaporator. The obtained residue was recrystallized from ethanol to obtain 13.4 g of compound (a-1).

[Synthesis Example 1-2: Synthesis of Compound (a-2)]
Compound (a-2) was synthesized according to the following scheme 2.

Synthesis of Compound (a-2-1) Compound (a-1-1) was synthesized according to the same synthetic formulation as compound (a-1-1) using 4-bromobenzoic acid and 4- (4-pentylcyclohexyl) aniline as starting materials. 2-1) was obtained.
-Synthesis | combination of compound (a-2-2) It replaces with a compound (a-1-1), and a compound (a-2-1) is used, and a compound (a 2-2) was obtained.
-Synthesis | combination of compound (a-2) 21.1g of compounds (a-2-2), 6.63g of 4-carboxyphenyl boronic acid, palladium acetate (II) were put into a 500 mL three necked flask containing a stirrer. 0.225 g, 27.6 g of potassium carbonate, and 0.797 g of 1,2-bis (diphenylphosphino) ethane were added, and nitrogen substitution was performed three times. 80 g of tetrahydrofuran and 80 g of water were bubbled with nitrogen, and the mixture was stirred at 60 ° C. for 3 hours. The reaction solution was filtered through Celite, 200 g of ethyl acetate was added to the filtrate, and the mixture was washed with 150 mL of water three times. Then, it concentrated slowly by concentration by a rotary evaporator until the internal volume became 50g, and collect | recovered the white solid which precipitated in the middle by filtration. This white solid was vacuum-dried to obtain 15.9 g of compound (a-2).

[Synthesis Example 1-3: Synthesis of Compound (a-3)]
Compound (a-3) was synthesized according to the following scheme 3.

  Using 4-bromoaniline and 4- (4-octylcyclohexyl) benzoic acid as starting materials, compound (a-3-1) and compound (a-3-2) were synthesized according to the same synthetic formulation as compound (a-2). ) And compound (a-3) were synthesized.

[Synthesis Example 1-4: Synthesis of Compound (a-4)]
Compound (a-4) was synthesized according to the following scheme 4.

-Synthesis | combination of compound (a-4-1) 2,5-dinitroaniline 18.3g and 10.0g of succinic anhydrides were taken to the 500 mL three necked flask containing the stirring element, 250g of acetonitrile was added, and it recirculate | refluxed for 10 hours. . Thereafter, the reaction solution was concentrated and dried by a rotary evaporator to obtain 25.3 g of compound (a-4-1).
-Synthesis | combination of compound (a-4-2) Compound (a-4) is prepared by the same synthesis formulation as compound (a-1-1) using β-cholestanol and compound (a-4-1) as starting materials. -2) was obtained.
-Synthesis | combination of compound (a-4-3) 26.2g of compounds (a-4-2) were taken to the 300 mL three necked flask which put the stirring element, 120 g of tetrahydrofuran was added there, and it cooled to 0 degreeC. Thereto, 3.97 g of methyl chloroformate was added dropwise and stirred at room temperature for 3 hours. After adding 200 g of ethyl acetate to the reaction solution and separating and washing three times with 150 mL of 1 mol / L hydrochloric acid and 150 mL of water, the organic layer was dried over magnesium sulfate. Then, 27.1g of yellow solid compound (a-4-3) was obtained by concentrating with a rotary evaporator and making it dry by vacuum drying.
-Synthesis | combination of compound (a-4) Compound (a-4) was obtained by the synthetic | combination prescription | regulation similar to compound (a-1) using compound (a-4-3) as a starting material.

[Synthesis Example 1-5: Synthesis of Compound (a-5)]
Compound (a-5) was synthesized according to the following scheme 5.

-Synthesis | combination of compound (a-5-1) 4- (4-propyl cyclohexyl) cyclohexyl carboxylic acid 25.2g is added to a 300 mL eggplant-shaped flask containing a stirrer, 200 g of thionyl chloride and 0.25 g of DMF are added, and 80 ° C is added. For 2 hours. Thereafter, excess thionyl chloride was removed with an aspirator, and the residue was dissolved in 500 g of dichloromethane. This was designated as Solution A.
To a 2000 mL three-necked flask containing a stirrer, 16.4 g of 4-hydroxycinnamic acid and 8 g of sodium hydroxide were taken, 500 g of water was further added, and the mixture was cooled to 0 ° C. The solution A was dripped there over 30 minutes, and it was made to stir at room temperature for 5 hours. Thereafter, the reaction solution was separated and washed with 400 mL of water three times, and then the organic layer was dried over magnesium sulfate. Then, it concentrated slowly by the concentration by a rotary evaporator until the internal volume became 50g, and collect | recovered the white solid which precipitated on the way by filtration. This white solid was vacuum-dried to obtain 31.9 g of compound (a-5-1).
-Synthesis of compound (a-5-2) Compound (a-5-1) and 3,5-dinitroaniline were used as starting materials and compound (a-1-1) was synthesized according to the same synthetic formulation as compound (a-1-1). -5-2) was obtained.
-Synthesis | combination of compound (a-5-3) Compound (a-5-3) is obtained by the same synthesis prescription as compound (a-1-2) using compound (a-5-2) as a starting material. It was.
-Synthesis | combination of compound (a-5) Compound (a-5) was obtained by the same synthesis prescription as compound (a-1) using compound (a-5-3) as a starting material.

[Synthesis Example 1-6: Synthesis of Compound (a-6)]
Compound (a-6) was synthesized according to the following scheme 6.

  Using 4- (4′-pentyl- [1,1′-bis (cyclohexane)]-4-yl) benzoic acid and 4′-hydroxyazobenzene-4-carboxylic acid as starting materials, compound (a-5 The compound (a-6) was obtained by the same synthetic formulation as in (1).

[Synthesis Example 1-7; Synthesis of Compound (a-7)]
Compound (a-7) was synthesized according to the following scheme 7.

Synthesis of compound (a-7-1) Take 18.6 g of 4-fluoro-1,3-dinitrobenzene and 24.5 g of 4- (4-pentylcyclohexyl) aniline in a 2000 mL eggplant flask containing a stir bar, Tetrahydrofuran 1000g and triethylamine 15.2g were added and it recirculate | refluxed for 10 hours. Ethyl acetate 1200g was added to the reaction liquid, and liquid separation washing | cleaning was carried out 3 times with water 1000mL. Then, it concentrated slowly by the concentration by a rotary evaporator until the internal volume became 200g, and the yellow solid which precipitated on the way was collect | recovered by filtration. This yellow solid was vacuum-dried to obtain 38.3 g of compound (a-7-1).
-Synthesis | combination of compound (a-7-2) Compound (a-7-2) is obtained by the synthetic | combination prescription similar to compound (a-1-2) using compound (a-7-1) as a starting material. It was.
-Synthesis | combination of compound (a-7) Compound (a-7) was obtained by the synthetic | combination prescription similar to compound (a-1) using compound (a-7-2) as a starting material.

[Synthesis Example 1-8; Synthesis of Compound (a-9)]
Using compound 4- (4,4,4-trifluorobutyl) cyclohexanecarboxylic acid as a starting material, compound (a-9) was obtained by the same synthetic recipe as compound (a-5) in scheme 5.

<Synthesis of polymer>
[Synthesis Example 2-1: Synthesis of Polymer (PA-1)]
100 mol parts of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 20 mol parts of compound (a-1) as diamine, and 80 mol parts of p-phenylenediamine, N- It was dissolved in methyl-2-pyrrolidone (NMP) and reacted at room temperature for 6 hours to obtain a solution containing 20% by weight of polyamic acid. The polyamic acid obtained here was used as a polymer (PA-1).

[Synthesis Example 2-2 to Synthesis Examples 2-11 and 2-19]
Polyamic acids were synthesized in the same manner as in Synthesis Example 2-1, except that the types and amounts of tetracarboxylic dianhydride and diamine used were changed as shown in Table 1 below. The obtained polyamic acids were referred to as polymers (PA-2) to (PA-7) and (Ra-1) to (Ra-5), respectively.

In Table 1, the numerical values in parentheses for diamine and acid dianhydride represent the usage ratio [mole part] with respect to a total of 100 mole parts of tetracarboxylic dianhydride used for the synthesis of the polymer. Abbreviations of acid anhydride and diamine in Table 1 represent the following compounds, respectively.
<Acid dianhydride>
t-1: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride t-2: bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8- Dianhydride t-3: 1,2,3,4-cyclobutanetetracarboxylic dianhydride t-4: pyromellitic dianhydride <diamine>
a-8: Compound b-1 represented by the following formula (a-8): Compound b-2 represented by the following formula (b-1): Compound b- represented by the following formula (b-2) 3: Compound b-5 represented by the following formula (b-3): Compound b-6 represented by the following formula (b-5): Compound b-7 represented by the following formula (b-6): Compound b-8 represented by the following formula (b-7): Compound b-9 represented by the following formula (b-8): Compound d-1 represented by the following formula (b-9): p- Phenylenediamine d-2: 3,5-diaminobenzoic acid d-3: compound represented by the following formula (d-3)

[Synthesis Example 2-12: Synthesis of Polymer (PI-1)]
A polyamic acid was synthesized in the same manner as in Synthesis Example 2-1, except that the types and amounts of tetracarboxylic dianhydride and diamine used were changed as shown in Table 1 above. Next, pyridine and acetic anhydride were added to the obtained polyamic acid solution to perform chemical imidization. The reaction solution after chemical imidation was concentrated and prepared with NMP so that the concentration was 10% by weight. The imidation ratio of the obtained polymer (PI-1) was about 30%.

[Synthesis Example 2-13: Synthesis of Epoxy Group-Containing Polyorganosiloxane (EPS-1)]
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine, and room temperature. Mixed with. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing became neutral. 1) was obtained as a viscous transparent liquid.
When this polyorganosiloxane (EPS-1) was subjected to ¹ H-NMR analysis, a peak based on the oxiranyl group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction occurred. Mw of the polyorganosiloxane (EPS-1) was 2,200, and the epoxy equivalent was 186 g / mol.

[Synthesis Example 2-14: Synthesis of specific group-containing polyorganosiloxane (PS-1)]
In a 100 mL three-necked flask, 2.3 g of polyorganosiloxane (EPS-1) synthesized in Synthesis Example 2-13, 11.1 g of cyclopentanone, 1.1 g of compound (a-2) (polyorganosiloxane (EPS) -1)), and 0.03 g of tetrabutylammonium fluoride was charged and reacted at 90 ° C. for 36 hours. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate. A solution obtained by dissolving the precipitate in ethyl acetate was washed with water three times, and the solvent was distilled off to remove polyorganosiloxane (PS- A white powder of 1) was obtained. The weight average molecular weight of the polyorganosiloxane (PS-1) was 2,700.

[Synthesis Example 2-15 to Synthesis Example 2-18]
The specific group-containing polyorganosiloxanes (PS-2) to (PS-4) and (PS-4) and (PS-4) were synthesized according to the same synthesis formulation as in Synthesis Example 2-14 except that the types and amounts of the compounds used were as shown in Table 2 below. Rs-1) was synthesized respectively.

In Table 2, the numerical value of the blending amount of carboxylic acid indicates the amount [mol%] charged with respect to the silicon atom of the epoxy group-containing polyorganosiloxane.
Abbreviations of the compounds in Table 2 are as follows.
b-4; a compound represented by the above formula (b-4)

[Example 1]
(1) Preparation of liquid crystal aligning agent NMP and butyl cellosolve (BC) are added as an organic solvent to the polymer (PA-1) obtained in Synthesis Example 2-1 as a polymer, and the solvent composition is NMP: BC = 50: The solution was 50 (weight ratio) and the solid content concentration was 5.0% by weight. A liquid crystal aligning agent (D-1) was prepared by filtering this solution using a filter having a pore size of 1 μm.
(2) Manufacture of liquid crystal display element As a pair of substrates, a glass substrate having two transparent electrodes (electrode A and electrode B) made of ITO film on one side was prepared on the pair of glass substrates as described above. The liquid crystal aligning agent (D-1) was applied by a spinner, pre-baked on a hot plate at 80 ° C. for 1 minute, and then post-baked on a hot plate at 230 ° C. for 10 minutes to obtain a film thickness of about 0.08 μm. The coating film was formed. Subsequently, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edge of the surface of one of the substrates having the liquid crystal alignment film, the two substrates are arranged to face each other with a gap between them. The outer edges were brought into contact with each other and pressed to cure the adhesive. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) 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 photo-curing adhesive.

(3) Evaluation of image sticking characteristics (AC afterimage characteristics) The liquid crystal display device manufactured as described above was placed in an environment of 25 ° C. and 1 atm, no voltage was applied to electrode B, and an AC voltage of 3.5 V was applied to electrode A. A combined voltage of DC voltage 5V was applied for 2 hours. Immediately thereafter, an AC voltage of 4 V was applied to both electrode A and electrode B. The time from when the voltage of 4V AC was started to be applied to both electrodes until the difference in light transmittance between the electrodes A and B could not be visually confirmed was measured. When this time is less than 20 seconds, the image sticking property “good 1 (◎)”, when it is 20 seconds or more and less than 60 seconds, the image sticking property “good 2 (◯)”, when it is 60 seconds or more and less than 100 seconds The seizure property “possible 1 (Δ)”, the seizure property “possible 2 (ΔΔ)” when it is 100 seconds or more and less than 150 seconds, and the seizure property “bad (×)” is evaluated when it exceeds 150 seconds. However, the image sticking characteristic of this liquid crystal display element was “Good 1 (◎)”.

(4) Evaluation of printability after elapse of holding time The liquid crystal aligning agent (D-1) prepared above is transparent made of an ITO film using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.). It apply | coated to the transparent electrode surface of the glass substrate with an electrode. After leaving for 30 minutes, the solvent was removed by heating (prebaking) on an 80 ° C. hot plate for 1 minute. Then, it heated for 10 minutes on a 200 degreeC hotplate (post-baking), and formed the coating film with an average film thickness of 0.06 micrometer. This coating film was observed with a microscope with a magnification of 20 times to examine the presence or absence of printing unevenness and pinholes. Note that the lower the solubility of the polymer in the solvent, the more easily printing unevenness and pinholes occur during the holding time. The evaluation is that the printability is “good (○)” when printing unevenness and pinholes are hardly observed after the lapse of the holding time, and the printability is “good” when printing unevenness and pinholes are slightly observed. (Δ) ”, a case in which at least one of printing unevenness and pinholes was clearly observed was defined as printability“ defect (x) ”. As a result, in this example, the printability was “good (◯)”.

[Examples 2 to 9, 11 and Comparative Examples 1 to 6]
Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the types and amounts of the polymers used were as shown in Table 3 below. Various evaluations were performed in the same manner as in Example 1 using the prepared liquid crystal aligning agent. The results are shown in Table 3 below.

  In Table 3, the numerical value of the blending ratio of the polymer indicates the blending ratio [parts by weight] of each polymer with respect to 100 parts by weight in total of the polymer components used for preparing the liquid crystal aligning agent.

[Example 10]
(1) Preparation of liquid crystal aligning agent As a polymer, NMP and butyl cellosolve (BC) are added as an organic solvent to the polymer (PA-5) obtained in Synthesis Example 2-5, and the solvent composition is NMP: BC = 50: The solution was 50 (weight ratio) and the solid content concentration was 5.0% by weight. A liquid crystal aligning agent (D-10) was prepared by filtering this solution using a filter having a pore size of 1 μm.
(2) Manufacture of liquid crystal display element The liquid crystal aligning agent (D-10) prepared above is patterned into a slit shape as shown in FIG. And a liquid crystal alignment film printer (manufactured by Nissha Printing Co., Ltd.) on each electrode surface of a pair of glass substrates each having an electrode B) and heated on a hot plate at 80 ° C. for 1 minute (pre-baking) Then, after removing the solvent, it was heated (post-baked) for 10 minutes on a 200 ° C. hot plate to form a coating film having an average film thickness of 600 mm. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then drying was performed in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film.
Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edge of the surface having the liquid crystal alignment film for one of the pair of substrates, the liquid crystal alignment film surface is placed on the pair of substrates. The adhesives were cured by overlapping and pressing so as to face each other. Next, after filling nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an acrylic photocuring adhesive to produce a liquid crystal cell. With respect to the obtained liquid crystal cell, an alternating current of 10 Hz is applied between the electrodes and the liquid crystal is driven, and an ultraviolet ray irradiation device using a metal halide lamp as a light source is used to emit ultraviolet rays of 10,000 J / m ^2. Irradiation was performed at a dose of. In addition, this irradiation amount is the value measured using the light meter measured on the basis of wavelength 365nm.

(3) Evaluation of image sticking characteristics (AC afterimage characteristics) The liquid crystal display device manufactured as described above was placed in an environment of 25 ° C. and 1 atm, no voltage was applied to electrode B, and AC voltage 10 V was applied to electrode A for 300 hours. Applied. Immediately after 300 hours, an AC voltage of 3 V was applied to both the electrode A and the electrode B, and the difference ΔT [%] in light transmittance between the electrodes was measured. At this time, when ΔT is less than 2%, the AC afterimage characteristic “good 1 (◎)”, and when it is 2% or more and less than 3%, the afterimage characteristic “good 2 (◯)”, 3% or more and 4% The afterimage characteristic “possible (Δ)” was 4% or more, and the afterimage characteristic “bad (×)” was evaluated. As a result, in this example, the evaluation was “Good 1”.
(4) Evaluation of printability after elapse of holding time Using the liquid crystal aligning agent (D-10) prepared above, the printability after elapse of the holding time was evaluated in the same manner as in Example 1. did. As a result, in this example, the printability was “good (◯)”.

From these results of Examples 1 to 11, in the liquid crystal aligning agent containing the polymer having the specific partial structure, the printability was good even when a holding time of 30 minutes was provided after application to the substrate. . This suggests that the solubility of the polymer (P) in the solvent is high.
Further, the image sticking characteristic (AC afterimage characteristic) of the liquid crystal display element was also good. From this result, the protecting group introduced into the polymer is eliminated by heating during post-baking, so that the polymer side chain has a rigid structure after post-baking, and the AC afterimage of the liquid crystal display element is sufficiently reduced. It is speculated that it was possible. On the other hand, in the comparative example, either the image sticking property or the printability was inferior to that of the example.

  A, B: Glass substrate

Claims (8)

The liquid crystal aligning agent containing the polymer (P) which has a partial structure represented by following formula (1).
(In Formula (1), A ¹ is a single bond or a divalent linking group, R ¹ is a monovalent organic group having 8 or more carbon atoms, X ¹ is a protecting group, and “*” represents a heavy group. Shows the bond that binds to the main chain of the coalescence. The liquid crystal aligning agent according to claim 1, wherein R ¹ is a group represented by the following formula (2).
(In Formula (2), A ³ is a single bond or a divalent linking group, and R ³ is a liquid crystal aligning group or a photo aligning group.)   The liquid crystal aligning agent according to claim 1 or 2, wherein the polymer (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane.   The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-3.   A liquid crystal display device comprising the liquid crystal alignment film according to claim 4. A polymer having a partial structure represented by the following formula (1).
(In Formula (1), A ¹ is a single bond or a divalent linking group, R ¹ is a monovalent organic group having 8 or more carbon atoms, X ¹ is a protecting group, and “*” represents a heavy group. Shows the bond that binds to the main chain of the coalescence. A compound represented by the following formula (3).
(In Formula (3), A ¹ is a single bond or a divalent linking group, R ¹ is a monovalent organic group having 8 or more carbon atoms, and X ¹ is a protecting group.) A compound represented by the following formula (4).
(In Formula (4), A ⁴ is a divalent organic group, R ¹ is a monovalent organic group having 8 or more carbon atoms, and X ¹ is a protecting group.)