CN105567259A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, polymer and compound - Google Patents

Abstract

The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, a polymer and a compound. In the present invention, the polymer (P) having a partial structure represented by the following formula (1) is contained in the liquid crystal aligning agent. In the formula (1), A ¹ is a single bond or a divalent organic group, and R ¹ is a carbon A monovalent organic group whose number is 8 or more. X ¹ is a protecting group. "*" indicates a bonding bond to the main chain of the polymer. The liquid crystal aligning agent of this invention can balance the solubility of a polymer component with respect to a solvent, and the burn-in reduction of a liquid crystal display element.

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer and compound

technical field

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

Background technique

Conventionally, as a liquid crystal display element, various liquid crystal display elements having different driving methods such as electrode structures, physical properties of liquid crystal molecules used, and manufacturing processes have been developed. For example, known twisted nematic (Twisted Nematic, TN) type or super Various liquid crystal display elements such as twisted nematic (SuperTwistedNematic, STN) type, vertical alignment (Vertical Alignment, VA) type, in-plane switching (In-Plane Switching, IPS) type, fringe field switching (fringe field switching, FFS) type, etc. These liquid crystal display elements have a liquid crystal aligning 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 a liquid crystal display element. For example, for the purpose of reducing image retention (image burn-in), it has been proposed to form a liquid crystal alignment film using a liquid crystal alignment agent containing polyimide or a precursor thereof in an imide It has a nitrogen atom other than the group (for example, refer to Patent Document 1 or Patent Document 2).

Patent Document 1 proposes a polyamide obtained by reacting tetracarboxylic dianhydride including 1,2,3,4-cyclobutanetetracarboxylic dianhydride with diamine including diamine having an amide bond. The imidized polymer of polyamic acid obtained by reacting tetracarboxylic dianhydride with diamine is contained in the liquid crystal aligning agent, and the imidized polymer contained in the imidized polymer in the liquid crystal aligning agent is The ratio of the number of amine rings is set within a specific range. In patent document 1, the improvement of voltage retention performance and afterimage characteristic is aimed at by using such a liquid crystal aligning agent.

In addition, Patent Document 2 proposes the use of an aromatic diamine in which an amino group protected by a tertiary butoxycarbonyl group (t-BOC group) is introduced into an ortho position with respect to the primary amino group. The polyamic acid or polyimide obtained from diamine is contained in a liquid crystal aligning agent. It is also described that according to this technique, the protection of the t-BOC group is deprotected by heating at the time of film formation to generate an amino group, and a heterocyclic ring is formed by an intramolecular reaction or an intermolecular reaction (crosslinking reaction) of the generated amino group, This achieves a reduction in the accumulation of residual direct current (DirectCurrent, DC) voltage.

[Prior art literature]

[Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-294274

[Patent Document 2] International Publication No. 2013/115228

Contents of the invention

[Problem to be solved by the invention]

In liquid crystal display elements such as vertical alignment type, TN type, and 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 mesogenic skeleton in a side chain. In this case, in order to improve the burn-in of the liquid crystal display element (especially the burn-in caused by AC voltage), it is considered to make the side chain of the polymer a rigid structure, but on the other hand, if the side chain of the polymer is set to If it is a rigid structure, the solubility of a polymer to a solvent will fall. That is, there is a trade-off relationship between the reduction of burn-in of the liquid crystal display element and the improvement of the solubility of the polymer, and it is difficult to have both characteristics.

In addition, when producing a large liquid crystal panel, after printing the liquid crystal aligning agent on the substrate, it may be temporarily stored until the next pre-baking process, so there will be a storage time between the printing process and the pre-baking process. . At this time, when the solubility of the polymer in the solvent is poor, printing unevenness and pinholes are likely to occur due to standing, and there is a possibility that display quality may decrease or product yield may decrease as a result.

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

[means to solve the problem]

The inventors of the present invention conducted diligent research to solve the problems of the prior art as described above, and found that by including a polymer having a structure protected by a protecting group with "-NH-" in the side chain, the liquid crystal aligning agent , the problem can be solved. Specifically, the present invention can provide the following liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, polymer, and compound.

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

[chemical 1]

(In the formula (1), A ¹ is a single bond or a divalent linking group, and R ¹ is a monovalent organic group with a carbon number of 8 or more. X ¹ is a protecting group. "*" means that it is bonded to the polymer bonds of the main chain)

Moreover, this invention provides the liquid crystal aligning film formed using the said liquid crystal aligning agent in another aspect. Moreover, the liquid crystal display element provided with the said liquid crystal aligning film is provided.

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

[Chem 2]

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

[Chem 3]

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

[Effect of the invention]

When -NH- of a polymer side chain is protected by a protective group and contained in a liquid crystal aligning agent, in the state of a liquid crystal aligning agent, the solubility to a solvent of a polymer can be made favorable. In addition, when a liquid crystal aligning agent is applied to a substrate to form a film, for example, the protective group is detached due to heating during film formation, or acid or alkali, etc., and is converted to -NH-, so that the regenerated orientation after film formation is high. As a result, the reduction of burn-in of the liquid crystal display element (especially the reduction of alternating current (Alternating Current, AC) afterimage) can be realized.

Description of drawings

FIG. 1 is an explanatory diagram showing a pattern of a transparent conductive film in a liquid crystal cell having a patterned transparent conductive film manufactured in Examples and Comparative Examples.

[explanation of the symbol]

A, B: glass substrate

detailed description

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

<Polymer (P)>

The liquid crystal aligning agent of this invention contains the polymer (P) which has a partial structure represented by following formula (1).

[chemical 4]

(In the formula (1), A ¹ is a single bond or a divalent linking group, and R ¹ is a monovalent organic group with a carbon number of 8 or more. X ¹ is a protecting group. "*" means that it is bonded to the polymer bonds of the main chain)

In the above formula ( ¹ ), the divalent linking group of A1 includes, for example: a divalent hydrocarbon group having 1 to 20 carbon atoms; -COO-, -COS-, -NR ^a - or -CO-NR ^a - (where R ^a is a hydrogen atom, a monovalent hydrocarbon group or a protecting group with 1 to 12 carbons) and other substituted divalent A group; a divalent group formed by replacing at least one hydrogen atom of a hydrocarbon group bonded to a carbon atom by a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxyl group, a cyano group, etc.; -CO-, -COO-, -NR ^a -CO-, etc.

Here, the term "hydrocarbon group" in this specification includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" in these refers to a linear hydrocarbon group and a branched hydrocarbon group composed of only a chain structure without a cyclic structure in the main chain. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. Among these, it is not necessary to consist only of the structure of an alicyclic hydrocarbon, and what has a chain structure in part is also included. "Aromatic hydrocarbon group" means a hydrocarbon group including an aromatic ring structure as a ring structure. However, it does not need to consist only of an aromatic ring structure, and may contain a chain structure or an alicyclic hydrocarbon structure in a part thereof. The term "organic group" refers to a group comprising a hydrocarbon group, and may contain heteroatoms in the structure.

Specific examples of divalent hydrocarbon groups having ¹ to 20 carbon atoms in A1 include, for example, methylene, ethylene, propanediyl, butanediyl, and pentanediyl groups as chain hydrocarbon groups. , Hexanediyl, Heptanediyl, Octanediyl, Nonanediyl, Decanediyl, Ethylene, Propylenediyl, Butenediyl, etc.; Examples of alicyclic hydrocarbon groups include Cyclohexylene group etc.; As an aromatic hydrocarbon group, a phenylene group, a biphenylene group etc. are mentioned, for example.

X1 is not particularly limited as long as it is ^a functional group for converting an amino group (-NH-) into an inert functional group in advance, and examples thereof include monovalent organic groups detached by heat, acid, or alkali. X ¹ is preferably a monovalent organic group detached by heat. Specific examples include carbamate-based protecting groups, amide-based protecting groups, imide-based protecting groups, and sulfonamide-based protecting groups. Base etc. Among these, carbamate-based protecting groups are preferable, and specific examples thereof include tert-butoxycarbonyl, benzyloxycarbonyl, 1,1-dimethyl-2-haloethoxy Carbonyl, 1,1-dimethyl-2-cyanoethoxycarbonyl, 9-fluorenylmethylcarbonyl, allyloxycarbonyl, 2-(trimethylsilyl)ethoxycarbonyl, and the like. Among them, tert-butoxy is preferred in terms of the ease ^of thermal deprotection or the ability to discharge the compound derived from X1 detached by heating during film formation to the outside of the film in the form of gas. carbonyl.

R ¹ is a monovalent organic group having 8 or more carbon atoms. ^The carbon number of R1 may be 8 or more, but from the viewpoint of improving the orientation of liquid crystal molecules, it is preferably 10 or more, more preferably 12 or more, still more preferably 15 or more, especially It is preferable to set it as 17 or more. The upper limit of the carbon number is not particularly limited, and may be, for example, 100 or less. ^The structure of R1 is not particularly limited, but a group represented by the following formula (2) can be mentioned as a preferable specific example.

[chemical 5]

*-A ³ -R ³ (2)

(In formula (2), A ³ is a single bond or a divalent linking group, and 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 formula (2) are groups capable of imparting a pretilt angle to liquid crystal molecules. Among these, the photo-alignment group is a group capable of exhibiting the property of controlling the alignment of liquid crystal molecules by light irradiation, and the liquid crystal aligning group is a group capable of exhibiting the property of controlling the alignment of liquid crystal molecules without light irradiation. As the liquid crystal aligning group of ^R3 , specifically, for example, an alkyl group having 8 to 20 carbons, a fluoroalkyl group having 8 to 20 carbons, an alkoxy group having 8 to 20 carbons, an alkoxy group having 17 carbons, A group having a steroid skeleton of ~51, a group in which a plurality of rings are bonded directly or via a linking group, and the like may have a substituent.

Here, examples of the alkyl group having 8 to 20 carbon atoms include octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, Octadecyl, nonadecanyl, eicosyl, etc.; Examples of fluoroalkyl groups having 8 to 20 carbon atoms include perfluorooctyl, perfluorooctylethyl, perfluorodecyl, perfluorodecyl ethyl group, etc.; examples of alkoxy groups having 8 to 20 carbon atoms include octyloxy, nonyloxy, decyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, Pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, eicosyloxy, etc.;

As a group having a steroid skeleton having 17 to 51 carbon atoms, for example, a cholestanyl group, a cholestyl group, a lanosteryl group, etc. are mentioned;

As a group in which a plurality of rings are bonded directly or via a linking group, for example, the following formula (L-1) to formula (L-10) can be mentioned.

[chemical 6]

(In formula (L-1) to formula (L-10), X ³ is 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 - (where, R ^b is a hydrogen atom, a hydrocarbon group with a carbon number of 1 to 6, or a monovalent organic group detached by heat. "*1" represents a bond with a ring structure having "*". n is an integer of 0 to 20 , m is an integer of 1 to 20. "*" represents the bond with A3 in the ^formula (2))

Respectively represent the basis and so on. 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 formulas (L-1) to (L-5), the group "C _n H _2n+1 -" is preferably linear. In the formulas (L-6) to (L-10), the group "C _m F _2m+1 -" and the group "-C _n H _2n -" are each preferably linear. n is preferably 2-20, more preferably 3-15. m is preferably 1-15, more preferably 1-10.

Examples of substituents that the liquid crystal aligning group may have include (meth)acryloyloxy groups, styryl groups, maleimide groups, vinyl groups, vinyl ether groups, allyl groups, Photopolymerizable groups such as vinylene groups and the like. Among these, a (meth)acryloyloxy group, a styryl group, or a maleimide group can be preferably used at the point that photoreactivity is high. In addition, "(meth)acryloyloxy" has the meaning including "acryloyloxy" and "methacryloyloxy".

As the divalent linking group ^of A3, for example, a carbonyl group, an alkanediyl group having 1 to 10 carbons, "*2-CO-R ^c -COO-" (where R ^c is a carbon number of 1 to 10 alkanediyl or cyclohexylene. "*2" means the bond with the nitrogen atom), etc.

The photo-orientation group of ^R3 is a group that exhibits an orientation-restricting force by photoisomerization, photodimerization, photolysis, etc., as a specific example, for example: a group containing an azo compound or a derivative thereof as a basic Azo-containing group of skeleton, cinnamic acid-containing group containing cinnamic acid or its derivative as basic skeleton, chalcone-containing group containing chalcone or its derivative as basic skeleton, benzophenone or A benzophenone-containing group containing its derivative as a basic skeleton, a coumarin-containing group containing coumarin or its derivatives as a basic skeleton, a cyclobutane-containing group containing cyclobutane or a derivative thereof as a basic skeleton base etc. Among these, an azo-containing group or a cinnamic acid-containing group is preferable from the viewpoint of good photo-orientability and ease of incorporation into a polymer.

As an azo-containing group, if it has an azo group (-N=N-), it will not specifically limit, For example, the group etc. which are represented by following formula (y-1) are mentioned.

[chemical 7]

R ⁴ -A ⁵ -N=NA ⁴ -*(y-1)

(In the formula (y-1), A ⁴ and A ⁵ are independently divalent organic groups, and R ⁴ is a liquid crystal alignment group)

In formula (y ^{- 1} ), the divalent organic groups of A4 and A5 include, for example: divalent hydrocarbon groups having 1 to 20 carbon atoms; methylene groups of hydrocarbon groups via -O-, -S -, -CO-, -COO-, -COS-, -NR ^a - or -CO-NR ^a - (where R ^a is a hydrogen atom, a monovalent hydrocarbon group or a protecting group with 1 to 12 carbons) etc. The divalent group formed; the divalent group formed by replacing at least one hydrogen atom of the hydrocarbon group bonded to the carbon atom by a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxyl group, cyano group, etc. base etc. Regarding the liquid crystal aligning group of R ⁵ , the description of the liquid crystal aligning group of R ³ in the formula (2) above 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), respectively.

[chemical 8]

(In formula (y-1-1) to formula (y-1-10), X ⁴ is 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 with 1 to 6 carbons or a protecting group. "*3" represents the bond with the azobenzene structure). n is an integer of 0 to 20, m is 1 to 20 Integer. The meaning of ^X3 is the same as that of ^X3 in the 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), a group represented by the following formula (x-2), and the like.

[chemical 9]

(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 carbons, or a fluoroalkyl group having 1 to 20 carbons. X ¹¹ and X ¹³ are each independently a single bond, an oxygen atom, a sulfur atom, *-COO- or *-OCO- (wherein, the bond with "*" is bonded to R ¹¹ or R ¹⁴ respectively). X ¹² is a single bond, an oxygen atom, a sulfur atom, an alkanediyl group with 1 to 3 carbons, *-COO- or *-OCO- (wherein, the bonding bond with "*" is bonded to R ¹² ). R ¹² and R ¹⁵ are independently 1,4-phenylene or 1,4-cyclohexylene. X ¹⁴ is a single bond, an alkanediyl group with 1 to 3 carbons, an oxygen atom, a sulfur atom or -NH-. X ¹⁵ is an oxygen atom, *-COO- or *-OCO- (wherein, the bond with "*" is bonded to R ¹⁶ ). R ¹⁶ is a divalent aromatic group, a divalent alicyclic group, A divalent heterocyclic group or a divalent condensed ring group. R ¹⁷ is a single bond, *-OCO-(CH ₂ ) _h - or *-O-(CH ₂ ) _i - (wherein, with "* "The bonding bond is bonded to R ¹⁶ , h and i are integers from 1 to 10 respectively). R ¹⁶ is *-COO- or *-OCO- (wherein, the bonding bond with "*" is bonded to R ¹⁷ ). R ¹³ and R ¹⁸ are each independently a fluorine atom, a cyano group or a methyl group. R ¹⁹ and R ²⁰ are each independently an alkanediyl or 1,4-cyclohexylene group with 1 to 10 carbon atoms. a, e and d are each independently an integer of 0 to 3, b and f are each independently an integer of 0 or 1, and c and g are each independently an integer of 0 to 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 the formula (x-2) include, for example, compounds represented by the following formulas (x-2-1) to (x-2-2), respectively. In addition, groups described in Japanese Patent Application Laid-Open No. 2011-133825 can be mentioned.

[chemical 10]

(In the formula, R ¹¹ and b have the same meanings as R ¹¹ and b in the formula (x-1))

[chemical 11]

(In the formula, 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-mentioned formula (1) is preferably a group represented by the following formula (1-1) or formula (1-2) from the point that the burn-in reduction effect of the liquid crystal display element is high.

[chemical 12]

(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. The meanings of X ¹ , A ¹ and R ¹ are the same as described The formula (1) is the same. "*" represents the bond bonded to the main chain of the polymer)

For the divalent organic group of A2, the illustrations of A4 and A5 of the above ^- mentioned ^formula (y- ¹ ) can be applied, and for the monovalent organic group of R2, the one of the above-mentioned ^formula (1) can be applied. ^An illustration of the description of R1.

"*" in the above formula (1) represents a bonding bond to the main chain of the polymer. Here, in this specification, the so-called "main chain" of a polymer refers to the part of the "backbone" of the connecting chain containing the longest atom in the polymer, and the so-called "side chain" refers to the part of the polymer from the "backbone" of the connecting chain. Part of the "backbone" branch.

The main skeleton of the polymer (P) is not particularly limited, and examples include polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivatives, poly Skeleton of acetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, etc. Among these, from the viewpoint of heat resistance, mechanical strength, affinity with liquid crystals, etc., those selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane are preferred. At least one polymer of the group. In addition, (meth)acrylate means to include acrylate and methacrylate.

(polyamic acid)

When a polymer (P) is a polyamic acid, this polyamic acid can be obtained by making tetracarboxylic dianhydride and diamine react. The polyamic acid having the partial structure (hereinafter also referred to as "specific partial structure") represented by the formula (1) can be obtained by containing a specific partial structure (wherein "*" in the formula (1)) in the monomer composition. " indicates a bonding bond. It is obtained by polymerization in the case of at least any one of tetracarboxylic dianhydride and diamine having a specific partial structure for monomers (hereinafter the same). It is preferable to use the diamine (henceforth "specific diamine") which has a specific partial structure at the point with high freedom degree of selection of a compound.

(tetracarboxylic dianhydride)

As tetracarboxylic dianhydride used for synthesizing polyamic acid, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride etc. are mentioned, for example. As specific examples of these, as aliphatic tetracarboxylic dianhydride, for example, butane tetracarboxylic dianhydride and the like are mentioned;

Examples of alicyclic tetracarboxylic dianhydride include: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3 , 3a, 4, 5, 9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furyl)-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-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethyl Norbornane-2:3,5:6-dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride, bicyclo[2.2. 1] Heptane-2,3,5,6-tetracarboxylic acid 2:3,5:6-dianhydride, 4,9-dioxatricyclo[ ^5.3.1.02,6 ]undecane-3, 5,8,10-tetraketone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride anhydride, ethylenediaminetetraacetic dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol bis(dehydrated trimellitate), 1,3-propanediol bis(dehydrated trimellitate), etc.;

As an aromatic tetracarboxylic dianhydride, pyromellitic dianhydride etc. are mentioned, for example; In addition, the tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 can be used. In addition, tetracarboxylic dianhydrides can be used alone or in combination of two or more of these tetracarboxylic dianhydrides.

As the tetracarboxylic dianhydride used for synthesizing polyamic acid, it is preferable to contain 1,2,3 , 4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic 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-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-Tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane- 3,5,8,10-tetraketone, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride and pyromellitic dianhydride At least one compound in the group consisting of. The amount of these preferred compounds used (the total amount when two or more are used) is preferably 5 mol% or more, more preferably It is 10 mol% or more, More preferably, it is 20 mol% or more.

(diamine)

Specific diamine will not specifically limit other structures as long as it has the said specific partial structure, For example, the compound etc. which are represented by following formula (3) are mentioned.

[chemical 13]

(In formula (3), the meanings of A ¹ , R ¹ and X ¹ are the same as those in formula (1) above)

Regarding A ¹ , R ¹ and X ¹ of the formula (3), the description of the formula (1) can be applied. As a specific example of specific diamine, the compound etc. which are each represented by following formula (3-1) - a formula (3-19) are mentioned.

[chemical 14]

[chemical 15]

[chemical 16]

[chemical 17]

(where n is an integer from 0 to 20)

Moreover, when synthesizing a polyamic acid, specific diamine can be used individually by 1 type or in combination of 2 or more types.

The diamine used for synthesizing the polyamic acid which is a polymer (P) may be only specific diamine, and other diamines other than specific diamine may be used together.

As other diamines, aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane etc. are mentioned, for example. Specific examples of these include, for example, m-xylylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and aliphatic diamines. Amines, 1,3-bis(aminomethyl)cyclohexane, etc.; Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexane Hexylamine), etc.;

Examples of aromatic diamines include dodecyloxydiaminobenzene, tetradecyloxydiaminobenzene, pentadecyloxydiaminobenzene, hexadecyloxydiaminobenzene, octadecane Oxydiaminobenzene, cholestanyloxydiaminobenzene, cholestanyloxydiaminobenzene, cholestanyl diaminobenzoate, cholestyl diaminobenzoate, wool diaminobenzoate stanyl esters, 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-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)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)

[chemical 18]

(In formula (E-1) and formula (E-2), X ^I and X ^II are each independently a single bond, -O-, -COO- or -OCO-, R ^I is an alkane with 1 to 3 carbons Diradical, R ^II is a single bond or an alkanediyl group with 1 to 3 carbons, X ^III is a hydrogen atom or a photopolymerizable group. r is 0 or 1, s is an integer of 0 to 2, and t is an integer of 1 to 20 Integer, u is 0 or 1. Wherein, r and s are not 0 at the same time. Two R ^II in the formula (E-2) can be the same or different)

Diamines containing alignment groups such as the represented compounds;

p-Phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'- Diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, 1,7-bis(4-aminophenoxy)heptane, bis[2-(4-aminophenoxy)ethane base] adipic 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)fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2 , 2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropylidene)bisaniline, 4,4'-(m-phenylene diisopropylidene) Dianiline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine , 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6- Diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)- N, N'-dimethylbenzidine, 1,4-bis-(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid, etc.;

Examples of diaminoorganosiloxane include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, etc.; in addition, Japanese Patent Laid-Open No. 2010-97188 can be used The diamines described in.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _u -" in the formula (E-1) is preferably an alkanediyl group having 1 to 3 carbon atoms, *-O- , *-COO- or *-OC ₂ H ₄ -O- (wherein, the bond with "*" is bonded to diaminophenyl). The group "-C _t H _2t+1 " and the group "-C _t H _2t -" are preferably linear.

The ^{photopolymerizable} group of XIII is preferably a (meth)acryloyloxy group, a styryl group or a maleimide group. The two amino groups in the diaminophenyl group in the formulas (E-1) and (E-2) are preferably located at the 2,4-position or the 3,5-position relative to other groups.

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

[chemical 19]

As another diamine, the diamine which has a specific functional group can also be used further for the purpose of improving the improvement effect of reducing the burn-in of a liquid crystal display element by direct-current voltage. Examples of such diamines include diamines having at least one nitrogen-containing structure selected from the group consisting of nitrogen-containing heterocycles, secondary amino groups, and tertiary amino groups, or diamines having carboxyl groups. Wait.

Examples of diamines having a nitrogen-containing structure include: 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methylpyridine Base-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, represented by the following formula (E-3-1) ~ formula (E-3-6) compounds, etc.

[chemical 20]

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 Polycarboxylic acids such as '-diaminodiphenylethane-3,3'-dicarboxylic acid and 4,4'-diaminodiphenylether-3,3'-dicarboxylic acid, etc.

From the point of view of sufficiently obtaining the effect of improving the solubility of the polymer in the solvent or the effect of reducing the burn-in of the liquid crystal display element caused by the AC voltage, the diamine used in the synthesis of the polyamic acid is relative to the total amount of diamine. As for the amine, the compounding ratio of the specific diamine is preferably 1 mol % or more, more preferably 3 mol % or more, still more preferably 5 mol % or more, and especially preferably 10 mol % or more. From the viewpoint of expressing an appropriate pretilt angle, the upper limit of the usage ratio of the specific diamine is preferably 70 mol % or less, more preferably 60 mol % or less, and still more preferably 50 mol % or less.

From the viewpoint of sufficiently obtaining the effect of reducing burn-in of the liquid crystal display element by direct current voltage, it is preferable to set the usage ratio of diamine having a nitrogen-containing structure to 0.1 relative to the total amount of diamine used for synthesis. mol% or more, more preferably 1 mol% to 50 mol%, still more preferably 2 mol% to 30 mol%. The usage ratio of the diamine having a carboxyl group is preferably 1 mol % or more, more preferably 2 mol % to 90 mol %, and still more preferably 5 mol % to 80 mol % with respect to the total amount of diamines used for synthesis. mol %. In addition, other diamines can be used individually by 1 type or in combination of 2 or more types.

(Synthesis of specific diamines)

Specific diamine can be synthesize|combined by combining well-known methods suitably. As an example, for example, the following method can be mentioned: Synthesizing a dinitro intermediate having a nitro group to replace the primary amino group in the formula (3), and then using an appropriate reducing system to make the resulting dinitro intermediate The method of nitroamination, etc. In addition, the method for synthesizing the dinitro intermediate can be appropriately selected according to the target compound. For example, "-NH-" can be synthesized by reacting a dinitro compound with "-NH-" with di-tert-butyl dicarbonate in the presence of a strong base such as dimethylaminopyridine. A dinitro intermediate protected by a carbonyl group. However, the synthesis method of a specific diamine is not limited to what was mentioned above.

(Synthesis of polyamic acid)

A polyamic acid can be obtained by making the tetracarboxylic dianhydride mentioned above, diamine, and a molecular weight adjuster if necessary react. The ratio of tetracarboxylic dianhydride and diamine used in the synthesis reaction of polyamic acid is preferably such that the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 2 equivalents, more preferably It is set to the ratio of 0.3 equivalent - 1.2 equivalent.

Examples of molecular weight modifiers include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; phenyl isocyanate, Monoisocyanate compounds such as naphthyl isocyanate, etc. It is preferable that the usage ratio of a molecular weight modifier shall be 20 weight part or less with respect to the total 100 weight part of tetracarboxylic dianhydride and diamine used, and it is more preferable to set it as 10 weight part or less.

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

Examples of the organic solvent used for the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Among these organic solvents, it is preferable to use at least one selected from the group consisting of aprotic polar solvents and phenolic solvents (organic solvents of the first group), or an organic solvent selected from the first group A mixture of one or more of these and one or more of them selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (organic solvents of the second group). In the latter case, with respect to the total amount of the organic solvent of the first group and the organic solvent of the second group, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight. % by weight or less, and more preferably 30% by weight or less.

Regarding the particularly preferred organic solvent, it is preferred to use a solvent selected from N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butylene One or more of the group consisting of lactone, tetramethylurea, hexamethylphosphoric triamide, m-cresol, xylenol and halogenated phenol is used as a solvent, or these are used within the range of the stated ratio Mixture of more than one with other organic solvents. It is preferable that the usage-amount (a) of an organic solvent is the quantity which makes the total amount (b) of tetracarboxylic dianhydride and a diamine into 0.1 weight% - 50 weight% with respect to the total amount (a+b) of a reaction solution.

In this way, the reaction solution which melt|dissolved polyamic acid was obtained. This reaction solution can be directly provided to the preparation of liquid crystal aligning agent, and the polyamic acid contained in the reaction solution can also be separated and then provided to the preparation of liquid crystal aligning agent, or the separated polyamic acid can also be purified and then Provided for the preparation of liquid crystal aligning agent. The isolation and purification of polyamic acid can be performed according to a well-known method.

(Polyimide)

The polyimide which is a polymer (P) can be obtained, for example by subjecting the polyamic acid synthesize|combined as mentioned above to dehydration ring closure, and imidating it. When polyamic acid is dehydrated and ring-closed to produce polyimide, the reaction solution of polyamic acid can be directly supplied to the dehydration and ring-closing reaction, or the polyamic acid contained in the reaction solution can be separated and then supplied. for the dehydration ring-closing reaction, or the separated polyamic acid may be purified and then provided for the dehydration ring-closing reaction.

The polyimide may be a complete imide formed by dehydrating and ring-closing all the amic acid structures of the polyamic acid as its precursor, or it may be an amide imidate obtained by dehydrating and ring-closing only a part of the amic acid structure. A partial imide compound in which an acid structure and an imide ring structure coexist. The imidization rate of the polyimide used for reaction is preferably 10% or more, more preferably 20% to 99%, and still more preferably 30% to 99%. This imidization rate represents the ratio of the number of imide ring structures with respect to the total number of the number of amic-acid structures of polyimide, and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.

The dehydration and ring closure of polyamic acid is preferably carried out by the following method: the method of heating the polyamic acid; or dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating if necessary Methods. Among them, the latter method is preferably used.

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

In this manner, a reaction solution containing polyimide is obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or can be provided to the preparation of the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or can be provided to the liquid crystal alignment agent after the polyimide is separated. The preparation of the liquid crystal aligning agent, or the isolated polyimide can also be purified and then provided to the preparation of the liquid crystal aligning agent. These purification operations can be performed according to known methods.

(polyamic acid ester)

Polyamic acid ester as polymer (P), for example, can be obtained by the following methods: [I] reacting polyamic acid having the specific partial structure with an esterifying agent; [II] making tetracarboxylic acid diester A method of reacting with diamine; [III] A method of reacting tetracarboxylic acid diester dihalide with diamine, etc.

Here, examples of the esterification agent used in the method [I] include a hydroxyl group-containing compound, an acetal-based compound, an epoxy group-containing compound, and the like. Specific examples of these include, for example, hydroxyl-containing compounds: alcohols such as methanol, ethanol, and propanol, phenols such as phenol and cresol, and the like; and examples of acetal compounds include: N, N -Dimethylformamide diethyl acetal, N,N-diethylformamide diethyl acetal, etc.; Examples of epoxy group-containing compounds include propylene oxide and the like.

The tetracarboxylic-acid diester used by the method [II] can be obtained by ring-opening the tetracarboxylic-acid dianhydride illustrated in the synthesis|combination of the said polyamic acid using alcohols, such as methanol and ethanol, for example. Moreover, as a diamine used by the method [II], the diamine illustrated in the synthesis|combination of a polyamic acid is mentioned, It is preferable that a 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, what was illustrated as an organic solvent for synthesizing a polyamic acid is mentioned. Examples of dehydration catalysts include: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine halide, carbonylimidazole, phosphorus Mixture etc.

The tetracarboxylic-acid diester dihalide used by method [III] can be obtained by making the tetracarboxylic-acid diester obtained above react with suitable chlorinating agents, such as thionyl chloride, for example. Moreover, as a diamine used by the method [III], the diamine illustrated in the synthesis|combination of a polyamic acid is mentioned, It is preferable that a specific diamine is contained. The reaction of method [III] is preferably performed in an organic solvent in the presence of a suitable base. As an organic solvent, what was illustrated as an organic solvent for synthesizing a polyamic acid is mentioned. As the base, for example, tertiary amines such as pyridine and triethylamine can be preferably used.

In this way, the reaction solution which melt|dissolved polyamic acid ester was obtained. This reaction solution can be directly provided to the preparation of liquid crystal aligning agent, also can provide the preparation of liquid crystal aligning agent after the polyamic acid ester contained in the reaction solution is separated, or can also be separated after the polyamic acid ester purification Provided to the preparation of the liquid crystal aligning agent. The isolation|separation and purification of polyamic acid ester can be performed according to a well-known method. Moreover, the polyamic acid ester contained in a liquid crystal aligning agent may have only an amic acid ester structure, and may be the partial esterification thing 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) is preferably a solution viscosity of 10 mPa·s to 800 mPa·s when it is made into a solution with a concentration of 10% by weight. , and more preferably have a solution viscosity of 15 mPa·s to 500 mPa·s. In addition, the solution viscosity (mPa·s) of the polymer is prepared by using an E-type rotational viscometer at 25°C using a good solvent for the polymer (such as γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) The concentration is 10% by weight of the polymer solution to measure the value.

In addition, 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. Also, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.

(polyorganosiloxane)

Examples of methods for synthesizing polyorganosiloxane (hereinafter also referred to as "specific group-containing polyorganosiloxane") as the polymer (P) include:

[1] Reaction of the following polymer (hereinafter also referred to as "epoxy group-containing polyorganosiloxane") with a carboxylic acid having the above-mentioned specific partial structure (hereinafter also referred to as "specific carboxylic acid") The method, the polymer is obtained by hydrolyzing and condensing a hydrolyzable silane compound (ms-1) having an epoxy group or a mixture of the silane compound (ms-1) and other silane compounds;

[2] A method of hydrolyzing and condensing a hydrolyzable silane compound having the above-mentioned specific partial structure or a mixture of the silane compound and another silane compound.

Among these, the method of [1] above is preferable in that a specific partial structure can be introduced with high efficiency.

Specific examples of the silane compound (ms-1) used in the synthesis of epoxy group-containing polyorganosiloxane include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxy Propyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-glycidoxyethyltrimethoxysilane 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethyldimethylmethoxysilane, 2-glycidyloxyethyldimethylethoxysilane , 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldiethoxysilane, 4-glycidyloxybutyl Dimethylmethoxysilane, 4-glycidoxybutyldimethylethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4- Epoxycyclohexyl)ethyltriethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and the like. As the silane compound (ms-1), one of these may be used alone or two or more of them may 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 drive mode of the liquid crystal display element and the like. Specific examples of other silane compounds include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane, Ethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and other alkoxysilane compounds;

3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3 -Alkoxysilane compounds containing nitrogen and sulfur such as aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(3-cyclohexylamino)propyltrimethoxysilane, etc.;

3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane Methoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, etc. Alkoxysilane compounds with unsaturated bonds;

Trimethoxysilylpropyl succinic anhydride, alkoxysilane compounds having a silicon-silicon bond, and the like. Other silane compounds These can be used individually by 1 type or in combination of 2 or more types.

The epoxy equivalent of the epoxy group-containing polyorganosiloxane is preferably 80 g/mol to 10,000 g/mol, more preferably 100 g/mol to 1,000 g/mol. Therefore, when synthesizing an epoxy group-containing polyorganosiloxane, it is preferable that the use ratio of the silane compound (ms-1) and other silane compounds be within the above-mentioned range in terms of the epoxy equivalent of the polyorganosiloxane obtained. way to adjust.

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

As a catalyst used at the time of a hydrolysis/condensation reaction, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. are mentioned, for example. The organic base is preferably a tertiary organic amine like triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene; Quaternary organic amines such as ammonium.

As the catalyst, among these, alkali metal compounds or organic bases are preferred, more preferably For organic bases.

The amount of the organic base used varies depending on the type of organic base, reaction conditions such as temperature, etc., and should be appropriately set. It is preferably 0.01 times mole to 3 times moles, more preferably 0.05 times moles to 1 times the amount of all silane compounds. Moore.

Examples of the organic solvent used in the hydrolysis/condensation reaction include hydrocarbons, ketones, esters, ethers, alcohols and the like. Specific examples of these include, for example, toluene, xylene, etc. as hydrocarbons; and examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone, cyclopentanone, etc.; Examples of esters include: ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl ethyl acetate, esters, ethyl lactate, etc.; as ethers, for example: ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc.; as alcohols, for example: 1-hexanol, 4 -Methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n- Propyl ether etc. It is preferable to use a water-insoluble organic solvent among these. In addition, these organic solvents can be used individually by 1 type or in combination of 2 or more types.

The proportion of the organic solvent used in the hydrolytic condensation reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of all the silane compounds used for the reaction.

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

In the method of [1] above, the epoxy group-containing polyorganosiloxane obtained by the reaction is then reacted with a specific carboxylic acid. Thereby, the epoxy group which the epoxy group-containing polyorganosiloxane has reacts with a carboxylic acid, and the polyorganosiloxane which has the said specific partial structure in a side chain can be obtained.

The specific carboxylic acid used for synthesis is not particularly limited as long as it has the specific partial structure, and the remaining structure is not particularly limited, and examples thereof include compounds represented by the following formula (4).

[chem 21]

(In formula (4), A ⁴ is a divalent organic group; R ¹ and X ¹ have the same meaning as the formula (1))

A ⁴ of the formula (4) can apply the description of the divalent organic group of A ¹ of the formula (1), and is preferably a divalent hydrocarbon group. Regarding 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), respectively.

[chem 22]

[chem 23]

[chem 24]

[chem 25]

(where n is an integer from 0 to 20)

In addition, specific carboxylic acids may be used alone or in combination of two or more.

The synthesis method of the specific carboxylic acid is not particularly limited, and conventionally known methods can be combined for synthesis. As an example of the synthesis method, for example, the method of synthesizing by reacting a halide having "-NHR ¹ " and di-tert-butyl dicarbonate in the presence of a strong base such as dimethylaminopyridine "-NH-" a compound protected by a tert-butoxycarbonyl group, followed by a method of reacting the resulting compound with a carboxylic acid having a functional group reactive with a halogen atom, and the like. However, the synthesis method of the specific carboxylic acid is not limited to the above.

The carboxylic acid used for the reaction with the epoxy group-containing polyorganosiloxane may be only a specific carboxylic acid, or other carboxylic acids other than the specific carboxylic acid may be used in combination.

Other carboxylic acids may be carboxylic acids as long as they do not have the above-mentioned specific partial structure. Specific examples thereof include caproic acid, lauric acid, pentadecanoic acid, palmitic acid, stearic acid, oleic acid, iso Fatty acids with 6 to 20 carbon atoms such as oleic acid, linoleic acid, linolenic acid, and arachidic acid, compounds represented by the following formulas (5-1) to (5-9), respectively Wait.

[chem 26]

(wherein, i is an integer from 0 to 12, and h is an integer from 1 to 20)

In addition, as other carboxylic acids, one selected from these may be used alone or in combination of two or more.

The use ratio of the carboxylic acid reacted with the epoxy group-containing polyorganosiloxane is preferably 0.001 mol to 1.5 mol, more preferably It is 0.01 mol to 1.0 mol.

Moreover, it is preferable that the usage ratio of a specific carboxylic acid shall be 0.01 mol - 0.8 mol with respect to 1 mol of total epoxy groups which polyorganosiloxane has. If the usage ratio is less than 0.01 mol, the introduction amount of the specific partial structure will be small, and it will be difficult to obtain improvement effects such as liquid crystal orientation, burn-in reduction, and solubility. On the other hand, when it exceeds 0.8 mol, there exists a tendency for the solubility of a polymer to deteriorate. Preferably it is 0.03 mol - 0.6 mol, More preferably, it is 0.05 mol - 0.4 mol.

The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid is preferably performed in the presence of a catalyst and an organic solvent.

As a catalyst used for reaction of epoxy group containing polyorganosiloxane and carboxylic acid, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. are mentioned, for example. Of these, organic bases are preferable. The proportion 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, based on 100 parts by weight of the polyorganosiloxane reacted with the carboxylic acid.

Examples of the organic solvent used in the reaction include hydrocarbons, ethers, esters, ketones, amides, alcohols and the like. From the viewpoint of the solubility of raw materials and products and the ease of purification of products, ethers, esters, and ketones are preferred among these, and specific examples of particularly preferred solvents include: 2-butanone, 2-hexyl Ketone, methyl isobutyl ketone and butyl acetate, etc. The organic solvent is preferably used in such a manner 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) becomes 0.1% by weight or more, more preferably 5% by weight. % to 50% by weight.

The reaction temperature in the reaction is preferably 0°C to 200°C, more preferably 50°C to 150°C. The reaction time is preferably 0.1 hour to 50 hours, more preferably 0.5 hour to 20 hours. In addition, after completion of the reaction, it is preferable to wash the organic solvent layer separated from the reaction liquid with water. After washing with water, if necessary, the organic solvent layer is dried with a suitable desiccant, and then the solvent is removed to obtain a polyorganosiloxane having the above-mentioned specific partial structure in a side chain.

The specific group-containing polyorganosiloxane obtained in the above manner preferably has a solution viscosity of 1 mPa·s to 500 mPa·s, more preferably 3 mPa·s when it is made into a solution with a concentration of 10% by weight. s～200mPa·s solution viscosity. In addition, the solution viscosity (mPa·s) of the polymer is the concentration prepared by using an E-type rotational viscometer at 25°C for a good solvent (such as N-methyl-2-pyrrolidone, etc.) using the polymer. 10% by weight polymer solution measured value.

Regarding the polyorganosiloxane containing a specific group, from the viewpoint of making the liquid crystal orientation of the formed liquid crystal alignment film good and ensuring the stability of its liquid crystal orientation over time, the value measured by gel permeation chromatography The weight average molecular weight (Mw) of polystyrene conversion becomes like this. Preferably it is 1,000-50,000, More preferably, it is 3,000-30,000.

<other ingredients>

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

[Other polymers]

These other polymers can be used to improve various properties such as solution properties and electrical properties. The other polymer is a polymer that does not have the specific partial structure, for example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose Derivatives, polyacetal, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives or polymers with poly(meth)acrylate as the main backbone, etc. As other polymers, 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 mixed in a liquid crystal aligning agent, the compounding ratio of other polymers is preferable with respect to 100 weight part of total polymers contained in a liquid crystal aligning agent (polymer (P) and other polymer total) In order to be 50 weight part or less, it is more preferable to set it as 0.1 weight part - 40 weight part, and it is still more preferable to set it as 0.2 weight part - 30 weight part.

[Epoxy group-containing compound]

An epoxy group-containing compound can be used for the purpose of improving the adhesiveness with the board|substrate surface in a liquid crystal aligning film, or an electrical characteristic. As such an epoxy group-containing compound, for example, the following compounds can be cited as preferred compounds: 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, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo Neopentyl glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexyl Alkane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl -aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine and the like. In addition, as an example of an epoxy group-containing compound, epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used.

When compounding an epoxy group-containing compound in a liquid crystal aligning agent, it is preferable that the compounding ratio of an epoxy group containing compound shall be 40 weight part or less with respect to 100 weight part of polymers contained in the liquid crystal aligning agent in total , It is more preferable to set it as 0.1 weight part - 30 weight part.

[Functional silane compound]

A functional silane compound can be used for the printability improvement of a liquid crystal aligning agent. Examples of such functional silane compounds include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, Ethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3- Ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethoxysilane Triamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilane Methyl-3,6-diazanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidyloxymethyl Trimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and the like.

When other functional silane compounds are blended into a liquid crystal aligning agent, the compounding ratio of other functional silane compounds is preferably 2 parts by weight or less with respect to a total of 100 parts by weight of polymers contained in the liquid crystal aligning agent. It is preferable to set it as 0.02 weight part - 0.2 weight part.

In addition, as other components, in addition to the above, compounds having at least one oxetanyl group in the molecule, antioxidants, metal chelate compounds, hardening accelerators, surfactants, fillers, dispersants , Photosensitizer, etc.

The liquid crystal aligning agent of this invention may contain only 1 type of polymer as a polymer component, and may contain 2 or more types of polymer as a polymer component. As a preferable aspect of a polymer component, following [1]-[5] etc. are mentioned, for example.

[1] A form in which only the polymer (P) is contained 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] Only the polymer (P) is contained as a polymer component, and the polymer (P) is in the form of polyorganosiloxane.

[3] Containing only polymer (P) as a polymer component, and at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide and polyorganosiloxane as a polymer The shape of the thing (P).

[4] Containing polymer (P) and other polymers as polymer components, and the polymer (P) and other polymers are selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide at least one form of .

[5] Containing polymer (P) and other polymers as polymer components, and the polymer (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide , other polymers are in the form of polyorganosiloxane.

Among these [4] and [5], it is presumed that the hydrophobicity of the polymer (P) increases due to the effect of introducing the protective group, and the polarity difference between the polymer without the protective group becomes large, so that it can be used in In the liquid crystal aligning film, the polymer (P) is biased to exist in the upper layer, and other polymers are biased to exist in the lower layer. In [4] and [5], as other polymers, those having nitrogen-containing heterocycles, di At least one nitrogen-containing polymer in the group consisting of secondary amino and tertiary amino groups, a polymer with carboxyl groups, and one or more than two of the polymers with the nitrogen-containing structure and carboxyl group .

The compounding ratio of the polymer (P) to the solid content of the liquid crystal aligning agent (components other than the solvent of the liquid crystal aligning agent) is preferably 40 parts by weight or more, more preferably 100 parts by weight of the total solid content. Preferably it is 50 weight part or more, More preferably, it is 60 weight part or more.

<solvent>

The liquid crystal aligning agent of this invention is prepared as a liquid composition which preferably disperse|distributes or dissolves a polymer (P) and other components used as needed in an appropriate solvent.

Examples of organic solvents used include: N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethyl Acetamide, 4-Hydroxy-4-methyl-2-pentanone, Ethylene Glycol Monomethyl Ether, Butyl Lactate, Butyl Acetate, Methyl Methoxy Propionate, Ethyl Ethoxy Propionate, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate , Diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, etc. These can be used individually or in mixture of 2 or more types.

The solid content concentration in the liquid crystal aligning agent (the ratio of the total weight of the components of the liquid crystal aligning agent except the solvent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1% by weight ~10% by weight range. That is, a liquid crystal aligning agent is apply|coated on the board|substrate surface as mentioned later, and it is preferable to heat it, and forms the coating film which becomes a liquid crystal aligning film or the coating film which becomes a liquid crystal aligning 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 favorable liquid crystal aligning film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, making it difficult to obtain a good liquid crystal aligning film, and the viscosity of the liquid crystal aligning agent increases to reduce the applicability. tendency.

The range of the especially preferable solid content concentration differs with the method used when apply|coating a liquid crystal aligning agent on a board|substrate. For example, in the case of coating on the substrate by the spinner method, it is particularly preferable that the solid content concentration (the ratio of the total weight of all components in the liquid crystal aligning agent except the solvent to the total weight of the liquid crystal aligning agent) is 1.5% by weight to 4.5% by weight. In the case of using the printing method, it is particularly preferable to set the solid content concentration in a range of 3% by weight to 9% by weight, whereby the solution viscosity is in a range of 12mPa·s to 50mPa·s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration in a range of 1% by weight to 5% by weight, whereby the solution viscosity is in a range of 3 mPa·s to 15 mPa·s. The temperature at the time of preparing a liquid crystal aligning agent becomes like this. Preferably it is 10 degreeC - 50 degreeC, More preferably, it is 20 degreeC - 30 degreeC.

<Liquid crystal display element>

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film formed using the liquid crystal aligning agent demonstrated above. The working mode of the liquid crystal display element is not particularly limited, for example, it can be applied to TN type, STN type, VA type (including vertical alignment-multi-domain vertical alignment (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) type, vertical alignment-pattern type Vertical Alignment (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type, etc.), IPS type, FFS type, Optically Compensated Bend (Optically Compensated Bend, OCB) type and other working modes.

A liquid crystal display element can be manufactured by the process including the following process (1) - process (3), for example. In step (1), different substrates are used depending on the desired operation mode. Each operation mode in process (2) and process (3) is the same.

[Step (1): Formation of coating film]

First, a liquid crystal aligning agent is apply|coated on a board|substrate, and a coating film is formed on a board|substrate by heating an application surface next.

(1-A) For example, when manufacturing TN-type, STN-type or VA-type liquid crystal display elements, at first two substrates provided with a patterned transparent conductive film are used as a pair of substrates, and a transparent layer is formed on each substrate. It is preferable to coat the liquid crystal aligning agent on the surface of the conductive film by the offset printing method, the spin coating method, the roll coater method, or the inkjet printing method, respectively. As the substrate, for example, glass such as float glass (float glass) and soda glass can be used; polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly(alicyclic Transparent substrates of plastics such as olefins). As the transparent conductive film provided on one surface of the substrate, Nesser (NESA) film (registered trademark of PPG Corporation of the United States) containing tin oxide (SnO ₂ ), a film containing indium oxide-tin oxide (In ₂ O ₃ - SnO ₂ ) indium tin oxide (IndiumTinOxide, ITO) film, etc. In order to obtain a patterned transparent conductive film, for example, the following methods can be used: after forming a transparent conductive film without a pattern, using photoetching (photoetching) to form a pattern; The mask method. When coating the liquid crystal aligning agent, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, it is also possible to pre-coat the surface of the substrate surface on which the coating film is formed. A functional silane compound, a functional titanium compound etc. before processing.

After applying a liquid crystal aligning agent, in order to prevent dripping of the applied liquid crystal aligning agent, etc., it is preferable to implement preheating (prebaking). The prebaking temperature is preferably 30°C to 200°C, more preferably 40°C to 150°C, especially preferably 40°C to 100°C. The prebaking time is preferably 0.25 minutes to 10 minutes, more preferably 0.5 minutes to 5 minutes. Then, a calcination (post-baking) process is implemented in order to remove a solvent completely, and to thermally imidize the amic-acid structure which exists in a polymer as needed. The firing temperature (post-baking temperature) at this time is preferably 80°C to 300°C, more preferably 120°C to 250°C. The post-baking time is preferably 5 minutes to 200 minutes, more preferably 10 minutes to 100 minutes. The film thickness of the film thus formed is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

(1-B) When manufacturing an IPS type or FFS type liquid crystal display element, the surface on which the electrode is formed on the substrate provided with the electrode and one surface of the opposite substrate without the electrode are coated with a liquid crystal aligning agent respectively, Next, each coated surface is heated to form a coated film, and the electrode includes a transparent conductive film or a metal film patterned in a comb-tooth shape. Materials of the substrate and transparent conductive film used at this time, coating method, heating conditions after coating, patterning method of the transparent conductive film or metal film, pretreatment of the substrate, and preferred film thickness of the formed coating film , same as (1-A). As the metal film, for example, a film containing metal such as chromium can be used.

In any of the above (1-A) and (1-B), after coating the liquid crystal aligning agent on the substrate, the organic solvent is removed to form a liquid crystal aligning film or a coating film that becomes a liquid crystal aligning film. . At this time, when the polymer contained in the liquid crystal aligning agent is polyamic acid, or polyamic acid ester, or contains an imidized polymer having an imide ring structure and an amic acid structure, the By further heating after coating, a dehydration ring-closing reaction proceeds, and a further imidized coating film is produced.

[Process (2): Orientation treatment]

When manufacturing a TN-type, STN-type, IPS-type or FFS-type liquid crystal display element, the coating film formed in the above step (1) is subjected to a treatment (orientation treatment) for imparting liquid crystal alignment ability. Thereby, the orientation ability of a liquid crystal molecule is given to a coating film, and it becomes a liquid crystal aligning film. As the orientation treatment, it can be mentioned that the coating film is rubbed in a certain direction with a roller wound with a cloth containing fibers such as nylon (nylon), rayon (rayon), cotton (cotton), etc. Rubbing treatment for liquid crystal alignment ability; photo-alignment treatment for imparting liquid crystal alignment ability to the coating film by irradiating light on the coating film formed on the substrate, etc. On the other hand, when manufacturing a vertical alignment type liquid crystal display element, the coating film formed in the said process (1) may be used as a liquid crystal aligning film as it is, and you may give this coating film an orientation process.

The light irradiation in the photo-alignment treatment can be carried out by the following methods, etc.: (1a) the method of irradiating the coating film after the post-baking, (2a) the method of irradiating the coating film after the pre-baking and before the post-baking The method (3a) is a method of irradiating the coating film during heating of the coating film in at least one of pre-baking and post-baking.

The light irradiated to the coating film may be polarized or non-polarized radiation. As radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. When the radiation is polarized, it may be linearly polarized or partially polarized. In addition, when the radiation used is linearly polarized or partially polarized, it may be irradiated from a direction perpendicular to the substrate surface, may be irradiated from an oblique direction, or may be irradiated from a combination of these directions. In the case of irradiating non-polarized radiation, the irradiating direction is an oblique direction.

As the light source 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 range can be obtained by a method of using a light source together with, for example, a filter, a diffraction grating, and the like. The amount of light irradiation is preferably 100 J/m ² to 50,000 J/m ² , more preferably 300 J/m ² to 20,000 J/m ² . In addition, regarding the light irradiation to the coating film, in order to improve the reactivity, the light irradiation may be performed while heating the coating film. The temperature at the time of heating is usually 30°C to 250°C, preferably 40°C to 200°C, more preferably 50°C to 150°C.

In addition, the liquid crystal aligning film after the rubbing treatment may be further subjected to the following treatment to make the liquid crystal aligning film have different liquid crystal aligning capabilities in each region. Treatment of changing the pretilt angle of a part of the liquid crystal alignment film; or after forming a resist film on a part of the surface of the liquid crystal alignment film, performing rubbing treatment in a direction different from the previous rubbing treatment, and then removing the resist film deal with. In this case, the viewing field characteristics of the obtained liquid crystal display element can be improved.

In the case of manufacturing a polymer sustainable alignment (polymer sustainable alignment, PSA) type liquid crystal display element, the coating film formed in the step (1) can also be directly used to implement the following step (3). In order to control the liquid crystal molecular Collapsing, using a simple method for orientation division, and orientation treatment such as weak friction treatment can also be performed. The liquid crystal aligning film suitable for the liquid crystal display element of VA type can also be used suitably for the liquid crystal display element of PSA type.

[Process (3): Construction of liquid crystal cell]

(3-A) Two board|substrates on which the liquid crystal aligning film was formed as mentioned above were prepared, and liquid crystal was arrange|positioned between the two board|substrates arrange|positioned facing each other, and the liquid crystal cell was manufactured. When manufacturing 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 facing each other with a gap (cell gap) interposed therebetween so that the liquid crystal alignment films face each other, and the peripheral parts of the two substrates are bonded together using a sealant. After injecting and filling liquid crystal into the divided cell gap, the injection hole is sealed to manufacture a liquid crystal cell. In addition, the second method is a method called a liquid crystal drop filling (One Drop Fill, ODF) method. On a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed, for example, a UV-curable sealant is coated, and then liquid crystal is dropped on several predetermined positions on the surface of the liquid crystal alignment film, A liquid crystal cell is manufactured by laminating another substrate so that the liquid crystal aligning film faces it, spreading the liquid crystal over the entire surface of the substrate, and then irradiating the entire surface of the substrate with ultraviolet light to harden the sealant. In the case of using either method, it is desirable to further heat the liquid crystal cell manufactured in the above-mentioned manner to the temperature at which the liquid crystal used acquires an isotropic phase, and then slowly cool it to room temperature to remove the liquid crystal filling. flow orientation.

As the sealing agent, for example, an epoxy resin containing a curing agent and alumina balls as spacers, or the like can be used. In addition, examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferable, and for example, Schiffbase liquid crystals, azoxy liquid crystals, and biphenyl liquid crystals can be used. , phenylcyclohexane-based liquid crystals, ester-based liquid crystals, terphenylcyclohexane-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals, etc. . In addition, the following substances can also be added to these liquid crystals: for example, cholesterol liquid crystals such as cholesterol chloride (cholesterylchloride), cholesterylnonanoate (cholesterylnonanoate), and cholesteryl carbonate; such as trade names "C-15", "CB- 15" (Merck (Merck)) and the sale of chiral agents; p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate methylbutylcinnamate) and other ferroelectric liquid crystals, etc.

(3-B) When manufacturing a PSA type liquid crystal display element, except the point which injects or drips a photopolymerizable compound together with a liquid crystal, it operates similarly to said (3-A) and constructs a liquid crystal cell. Then, the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films included in the pair of substrates. Here, the voltage to be applied can be, for example, a direct current or alternating current of 5V to 50V. In addition, as light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used, preferably ultraviolet rays including light having a wavelength of 300 nm to 400 nm. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. In addition, ultraviolet rays in the above-mentioned preferred wavelength region can be obtained by a method of using a light source together with, for example, a filter, a diffraction grating, and the like. The irradiation amount of light is preferably 1,000 J/m ² to less than 200,000 J/m ² , more preferably 1,000 J/m ² to 100,000 J/m ² .

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

Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell to obtain a liquid crystal display element. Examples of the polarizing plate to be bonded to the outer surface of the liquid crystal cell include a polarizing film called "H film" in which polyvinyl alcohol is stretched and oriented while absorbing iodine with a cellulose acetate protective film. A sandwiched polarizer, or a polarizer that includes the H film itself.

The liquid crystal display element of the present invention can be effectively applied to various devices, for example, can be used for clocks, portable game machines, word processors, notebook computers, car navigation systems (carnavigationsystem), video cameras (camcorder), personal digital assistants (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart phone, various monitors (monitor), LCD TV, information display (information display) and other display devices.

[Example]

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these Examples.

In the following examples, the weight average molecular weight Mw of a polymer, the imidization rate, the solution viscosity of a polymer solution, and epoxy equivalent are measured by the following methods. In addition, the compound represented by formula X may be referred to only as "compound X" below.

[The weight average molecular weight Mw of the polymer]

Mw is a polystyrene conversion value measured by GPC under the following conditions.

Pipe string: manufactured by Tosoh Co., Ltd., TSKgelGRCXLII

Solvent: THF

Temperature: 40°C

Pressure: 68kgf/ ^cm2

[Imidation rate of polymer]

Put the solution containing polyimide into pure water, dry the obtained precipitate under reduced pressure at room temperature, dissolve it in deuterated dimethyl sulfoxide, and use tetramethylsilane as a standard substance at room temperature Measure ¹ H-NMR. From the obtained ¹ H-NMR spectrum, the imidation rate was calculated|required using the following numerical formula (1).

Imidization ratio (%)=(1-A ¹ /A ² ×α)×100...(1)

(In formula (1), A ¹ is the peak area of the proton derived from the NH group that appears near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of the polymer (polyamic acid) The ratio of the number of other protons in the NH group to the number of a proton in the NH group)

[epoxy equivalent]

The epoxy equivalent is measured by the hydrochloric acid-methyl ethyl ketone method described in Japanese Industrial Standards (JIS) C2105.

<Synthesis of Compound>

[Synthesis Example 1-1: Synthesis of Compound (a-1)]

Compound (a-1) was synthesized according to Scheme 1 below.

[chem 27]

・Synthesis of compound (a-1-1)

Take 27.4 g of 4-(4-pentylcyclohexyl)benzoic acid and 18.3 g of 3,5-dinitroaniline into a 2000 mL three-necked flask equipped with a stirrer, add 1200 g of dichloromethane and stir. Then, after cooling 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. Stir at room temperature for 20 hours. Then, the reaction liquid was separated and washed three times with 800 mL of water, and then the organic layer was dried with magnesium sulfate. Then, it concentrated slowly by the rotary evaporator until the internal capacity became 200g, and the white solid which precipitated on the way was recovered by filtration. The compound (a-1-1) 37.4g was obtained by vacuum-drying this white solid.

・Synthesis of compound (a-1-2)

Take 26.4 g of compound (a-1-1) into a 500 mL three-necked flask equipped with a stirrer, add 300 g of acetonitrile and stir. Thereafter, it was cooled to 0° C., 14.4 g of di-tert-butyl dicarbonate and 0.73 g of N,N-dimethylaminopyridine were added thereto, and the mixture was stirred at room temperature for 6 hours. Then, after concentrating with a rotary evaporator until the reaction liquid became 100 g, it poured into 500 g of water, and the precipitated white solid was collect|recovered by filtration. This white solid was vacuum-dried to obtain 25.9 g of compound (a-1-2).

· Synthesis of compound (a-1)

21.6 g of compound (a-1-2), 52.3 g of zinc, and 8.56 g of ammonium chloride were added to a 300 mL three-necked flask equipped with a stirrer, and nitrogen replacement was performed three times. Then, the reaction container was cooled to 0° C., 150 g of tetrahydrofuran bubbled with nitrogen 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 liquid was filtered with celite, 300 g of ethyl acetate was added to the filtrate, and 200 mL of water was used to perform liquid separation washing three times. Then, the organic layer was concentrated and dried using a rotary evaporator. The resulting 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 Scheme 2 below.

[chem 28]

・Synthesis of compound (a-2-1)

Compound (a-2-1) was obtained by the same synthesis recipe as compound (a-1-1) using 4-bromobenzoic acid and 4-(4-pentylcyclohexyl)aniline as starting materials.

・Synthesis of compound (a-2-2)

Compound (a-2-2) was obtained by using compound (a-2-1) instead of compound (a-1-1) and using the same synthesis recipe as compound (a-1-2).

· Synthesis of compound (a-2)

21.1 g of compound (a-2-2), 6.63 g of 4-carboxyphenylboronic acid, 0.225 g of palladium (II) acetate, 27.6 g of potassium carbonate, and 0.797 g of 1,2-bis(diphenylphosphino)ethane were added The mixture was placed in a 500 mL three-necked flask equipped with a stirrer, and replaced with nitrogen three times. 80 g of tetrahydrofuran bubbled with nitrogen and 80 g of water were added thereto, and stirred at 60° C. for 3 hours. The reaction liquid was filtered with celite, 200 g of ethyl acetate was added to the filtrate, and 150 mL of water was used to perform liquid separation washing three times. Then, the concentration by the rotary evaporator was gradually concentrated until the inner volume became 50 g, and the white solid which precipitated on the way was collected 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 Scheme 3 below.

[chem 29]

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

[Synthesis Example 1-4: Synthesis of Compound (a-4)]

Compound (a-4) was synthesized according to Scheme 4 below.

[chem 30]

・Synthesis of compound (a-4-1)

18.3 g of 2,5-dinitroaniline and 10.0 g of succinic anhydride were put into a 500 mL three-neck flask equipped with a stirrer, and 250 g of acetonitrile was added thereto, followed by reflux for 10 hours. Then, the reaction liquid was concentrated and dried by a rotary evaporator to obtain 25.3 g of compound (a-4-1).

・Synthesis of compound (a-4-2)

Compound (a-4-2) was obtained by the same synthesis recipe as compound (a-1-1) using β-cholestanol and compound (a-4-1) as starting materials.

· Synthesis of compound (a-4-3)

26.2 g of compound (a-4-2) was put into a 300 mL three-necked flask equipped with a stirrer, 120 g of tetrahydrofuran was added thereto, and cooled to 0°C. 3.97 g of methyl chloroformate was added dropwise thereto, followed by stirring at room temperature for 3 hours. 200 g of ethyl acetate was added to the reaction liquid, and the organic layer was dried with magnesium sulfate after performing liquid separation and washing three times with 150 mL of 1 mol/L hydrochloric acid and 150 mL of water. Then, by concentrating with a rotary evaporator and drying in a vacuum, 27.1 g of compound (a-4-3) was obtained as a yellow solid.

· Synthesis of compound (a-4)

Compound (a-4) was obtained by the same synthesis recipe as 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 Scheme 5 below.

[chem 31]

・Synthesis of compound (a-5-1)

Add 25.2 g of 4-(4-propylcyclohexyl) cyclohexyl carboxylic acid to a 300 mL eggplant-shaped flask with a stirrer, and add 200 g of thionyl chloride and 0.25 g of dimethylformamide (DimethylFormamide, DMF). , stirred at 80 °C for 2 hours. Then, excess thionyl chloride was removed by an aspirator, and the residue was dissolved in 500 g of dichloromethane. Let this be solution A.

16.4 g of 4-hydroxycinnamic acid and 8 g of sodium hydroxide were put into a 2000 mL three-necked flask equipped with a stirrer, and 500 g of water was added thereto, followed by cooling to 0°C. Solution A was added dropwise thereto over 30 minutes, followed by stirring at room temperature for 5 hours. Then, the reaction liquid was separated and washed three times with 400 mL of water, and then the organic layer was dried with magnesium sulfate. Then, the concentration by the rotary evaporator was gradually concentrated until the inner volume became 50 g, and the white solid which precipitated on the way was collected 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-5-2) was obtained by the same synthesis recipe as compound (a-1-1) using compound (a-5-1) and 3,5-dinitroaniline as starting materials.

・Synthesis of Compound (a-5-3)

Compound (a-5-3) was obtained by the same synthesis recipe as compound (a-1-2) using compound (a-5-2) as a starting material.

· Synthesis of compound (a-5)

Compound (a-5) was obtained by the same synthesis recipe 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 Scheme 6 below.

[chem 32]

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

[Synthesis Example 1-7: Synthesis of Compound (a-7)]

Compound (a-7) was synthesized according to Scheme 7 below.

[chem 33]

・Synthesis of compound (a-7-1)

Take 18.6g of 4-fluoro-1,3-dinitrobenzene and 24.5g of 4-(4-pentylcyclohexyl)aniline into a 2000mL eggplant-shaped flask with a stirrer, and add 1000g of tetrahydrofuran and triethylamine 15.2 g, and refluxed for 10 hours. 1200 g of ethyl acetate was added to the reaction liquid, and liquid separation washing was performed 3 times with 1000 mL of water. Then, the concentration by the rotary evaporator was gradually concentrated until the inner capacity became 200 g, and the yellow solid which precipitated on the way was recovered by filtration. This yellow solid was vacuum-dried to obtain 38.3 g of compound (a-7-1).

· Synthesis of compound (a-7-2)

Compound (a-7-2) was obtained by the same synthesis recipe as compound (a-1-2) using compound (a-7-1) as a starting material.

· Synthesis of compound (a-7)

Compound (a-7) was obtained by the same synthesis recipe as compound (a-1) using compound (a-7-2) as a starting material.

[Synthesis Example 1-8: Synthesis of Compound (a-9)]

Compound (a-9) was obtained by using the compound 4-(4,4,4-trifluorobutyl)cyclohexanecarboxylic acid as a starting material and the same synthesis recipe as compound (a-5) in scheme 5.

[chem 34]

<Synthesis of Polymer>

[Synthesis Example 2-1: Synthesis of Polymer (PA-1)]

Dissolve 100 parts by mole of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic acid dianhydride, 20 parts by mole of compound (a-1) as diamine, and 80 parts by mole of p-phenylenediamine in In N-methyl-2-pyrrolidone (NMP), it reacted at room temperature for 6 hours, and obtained the solution containing 20 weight% of polyamic acids. Here, let the obtained polyamic acid be a polymer (PA-1).

[Synthesis Example 2-2 to Synthesis Example 2-11, Synthesis Example 2-19]

Except having changed the kind and quantity of the tetracarboxylic dianhydride and diamine used like following Table 1, it carried out similarly to the said synthesis example 2-1, and synthesize|combined polyamic acid, respectively. The obtained polyamic acid was made into polymer (PA-2) - polymer (PA-7) and polymer (Ra-1) - polymer (Ra-5), respectively.

[Table 1]

In Table 1, the numerical value in () of a diamine and an acid dianhydride shows the usage ratio [mol part] with respect to the total 100 mol parts of tetracarboxylic dianhydride used for synthesizing a polymer. The abbreviations of acid anhydrides and diamines in Table 1 represent the following compounds, respectively.

<Acid dianhydride>

t-1: 2,3,5-tricarboxycyclopentylacetic 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: a compound represented by the following formula (a-8)

b-1: a compound represented by the following formula (b-1)

b-2: a compound represented by the following formula (b-2)

b-3: a compound represented by the following formula (b-3)

b-5: a compound represented by the following formula (b-5)

b-6: a compound represented by the following formula (b-6)

b-7: a compound represented by the following formula (b-7)

b-8: a compound represented by the following formula (b-8)

b-9: a compound represented by the following formula (b-9)

d-1: p-phenylenediamine

d-2: 3,5-diaminobenzoic acid

d-3: a compound represented by the following formula (d-3)

[chem 35]

[Synthesis Example 2-12: Synthesis of Polymer (PI-1)]

Except having changed the kind and quantity of tetracarboxylic dianhydride and diamine used like Table 1, it carried out similarly to the said synthesis example 2-1, and synthesize|combined a polyamic acid. Next, pyridine and acetic anhydride were added to the obtained polyamic acid solution, and chemical imidation was performed. The reaction solution after chemical imidation was concentrated, and it prepared so that the density|concentration might become 10 weight% using NMP. The imidation rate of the obtained polymer (PI-1) was about 30%.

[Synthesis Example 2-13: Synthesis of Epoxy Group-Containing Polyorganosiloxane (EPS-1)]

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux cooling pipe, add 100.0 g of 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane, 500 g of methyl isobutyl ketone and triethyl 10.0 g of amine, mixed at room temperature. Then, after dropping 100 g of deionized water from the dropping funnel over 30 minutes, it was mixed under reflux and reacted at 80° C. for 6 hours. After the reaction, the organic layer was extracted, washed with a 0.2% by weight ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain polyorganic acid as a viscous transparent liquid. Silicone (EPS-1).

As a result of ¹ H-NMR analysis of this polyorganosiloxane (EPS-1), it was confirmed that a peak based on the oxirane group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm, as in the theoretical intensity, and In the reaction, no side reaction of the epoxy group is caused. The polyorganosiloxane (EPS-1) had a Mw of 2,200 and an epoxy equivalent of 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), 11.1 g of cyclopentanone, and 1.1 g of compound (a-2) (equivalent to relative 30 mol% of silicon atoms contained in the polyorganosiloxane) and 0.03 g of tetrabutylammonium fluoride were reacted at 90° C. for 36 hours. After the reaction, methanol was added to the reaction mixture to form a precipitate, and the solution obtained by dissolving the precipitate in ethyl acetate was washed three times with water, and the solvent was distilled off to obtain polyorganosiloxane (PS -1) White powder. The weight average molecular weight of polyorganosiloxane (PS-1) was 2,700.

[Synthesis Example 2-15 to Synthesis Example 2-18]

The types and amounts of the compounds used are set as in the following Table 2, except that, the polyorganosiloxanes containing specific groups (PS- 2)～Specific group-containing polyorganosiloxane (PS-4) and specific group-containing polyorganosiloxane (Rs-1).

[Table 2]

In Table 2, the numerical value of the compounding amount of a carboxylic acid shows the addition amount [mol%] with respect to the silicon atom which the epoxy group-containing polyorganosiloxane has.

The abbreviations of the compounds in Table 2 are as follows.

b-4: the compound represented by the formula (b-4)

[Example 1]

(1) Preparation of liquid crystal aligning agent

Add NMP and butyl cellosolve (ButylCellosolve, BC) as an organic solvent to the polymer (PA-1) obtained in the above-mentioned Synthesis Example 2-1 as a polymer to make a solvent composition of NMP:BC=50: 50 (weight ratio), a solution having a solid content concentration of 5.0% by weight. The liquid crystal aligning agent (D-1) was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

(2) Manufacture of liquid crystal display elements

Glass substrates having two systems of transparent electrodes (electrodes on the electrode surface of the glass substrate A and electrodes on the electrode surface of the glass substrate B) including an ITO film on one surface were used as a pair of substrates, and the pair was rotated using a rotator. Coating the liquid crystal aligning agent (D-1) prepared in the above on the glass substrate, after carrying out 1 minute prebaking on the heating plate of 80 ℃, after carrying out 10 minutes post-baking on the heating plate of 230 ℃, thereby A coating film with a film thickness of about 0.08 μm was formed. Then, after coating the epoxy resin adhesive with alumina balls with a diameter of 5.5 μm on the outer edge of the surface with the liquid crystal alignment film of any one of the substrates, the two substrates are arranged facing each other through a gap, and the outer edge abut against each other to perform crimping and harden the adhesive. Next, after the nematic liquid crystal (MLC-6608, manufactured by Merck) was filled between the pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an acrylic photocurable adhesive.

(3) Evaluation of burn-in characteristics (AC afterimage characteristics)

Place the liquid crystal display element manufactured above in an environment of 25°C and one atmospheric pressure, apply no voltage to the electrodes on the electrode surface of the glass substrate B, and apply an AC voltage to the electrodes on the electrode surface of the glass substrate A for 2 hours Composite voltage of 3.5V and DC voltage 5V. Immediately thereafter, an AC 4V voltage was applied to both the electrodes on the electrode surface of the glass substrate A and the electrodes on the electrode surface of the glass substrate B. The time until the difference in light transmittance between the electrode on the electrode surface of the glass substrate A and the electrode on the electrode surface of the glass substrate B was not visually recognized was measured from the time when the voltage of AC 4V was started to be applied to both electrodes. The case where the time was less than 20 seconds was evaluated as "good 1 (⊚)" for the burn-in characteristics; The case of 100 seconds was evaluated as "possible 1 (△)" for the burn-in characteristic; the case of 100 seconds or more and less than 150 seconds was evaluated as "possible 2 (△△)"; and the case of more than 150 seconds was evaluated as The burn-in characteristic was "poor (x)", and as a result, the burn-in characteristic of this liquid crystal display element was "good 1 (⊚)".

(4) Evaluation of printability after standing time

Using a liquid crystal alignment film printer (manufactured by Nippon Photo Printing Co., Ltd.), the liquid crystal alignment agent (D-1) prepared in the above is coated on the transparent electrode surface of a glass substrate with a transparent electrode comprising an ITO film . After leaving to stand for 30 minutes, it heated (pre-baked) for 1 minute on the hot plate of 80 degreeC, and removed the solvent. Then, heating was performed on a 200° C. hot plate for 10 minutes (post-baking) to form a coating film with an average film thickness of 0.06 μm. The coating film was observed with a microscope at a magnification of 20 times, and the presence or absence of printing unevenness and pinholes was investigated. In addition, the lower the solubility of the polymer in the solvent, the easier it is for printing unevenness and pinholes to occur during standing time. Regarding the evaluation, after the elapse of the standing time, the case where printing unevenness and pinholes were hardly observed was regarded as "good (○)", and the case where printing unevenness and pinholes were slightly observed was regarded as "printability" Possible (Δ)", and the case where at least one of printing unevenness and pinholes were clearly observed was defined as "poor (x)" in printability. As a result, the result of this Example was "favorable ((circle)) printability.

[Example 2 to Example 9, Example 11 and Comparative Example 1 to Comparative Example 6]

Except having changed the kind and quantity of the polymer to be used into the point described in following Table 3, it carried out similarly to the said Example 1, and prepared the liquid crystal aligning agent, respectively. Moreover, using the prepared liquid crystal aligning agent, it operated similarly to the said Example 1, and performed various evaluation. These results are shown in Table 3 below.

[table 3]

In Table 3, the numerical value of the compounding ratio of a polymer shows the compounding ratio [weight part] of each polymer with respect to the total 100 weight part of polymer components used for preparation of a liquid crystal aligning agent.

[Example 10]

(1) Preparation of liquid crystal aligning agent

Add NMP and butyl cellosolve (BC) as an organic solvent to the polymer (PA-5) obtained in the above-mentioned Synthesis Example 2-5 as a polymer to make a solvent composition of NMP:BC=50:50 ( weight ratio) and a solid content concentration of 5.0% by weight solution. The liquid crystal aligning agent (D-10) was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

(2) Manufacture of liquid crystal display elements

Use a liquid crystal alignment film printer (manufactured by Nippon Photo Printing (Stock)), the liquid crystal alignment agent (D-10) prepared in the above is coated on the ITO electrodes (the electrode faces of the glass substrate A) with two systems respectively. electrode and the electrode on the electrode surface of the glass substrate B) on each electrode surface of a pair of glass substrates, heat (pre-baked) on a hot plate at 80°C for 1 minute to remove the solvent, and then heat it on a hot plate at 200°C 10 minutes of heating (post-baking), resulting in an average film thickness of coating film, the ITO electrodes of the two systems (the electrodes on the electrode surface of the glass substrate A and the electrodes on the electrode surface of the glass substrate B) are patterned into stripes as shown in FIG. 1 and divided into multiple area. Then, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying for 10 minutes in a clean oven at 100° C., thereby obtaining a substrate having a liquid crystal aligning film. This operation was repeated to obtain a pair (two sheets) of substrates having a liquid crystal aligning film.

Next, for one substrate in the pair of substrates, after the epoxy resin adhesive with aluminum oxide balls with a diameter of 5.5 μm is coated on the outer edge of the surface with the liquid crystal alignment film, the pair of substrates are aligned with the liquid crystal. Overlap and crimp the films against each other, and harden the adhesive. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck) was filled between the pair of substrates from the liquid crystal inlet, and the liquid crystal inlet was sealed with an acrylic photocurable adhesive to manufacture a liquid crystal cell. The obtained liquid crystal cell was irradiated with ultraviolet rays at an irradiation dose of 10,000 J/m ² using an ultraviolet irradiation device using a metal halide lamp as a light source while applying AC 10 V at a frequency of 60 Hz between the electrodes to drive the liquid crystal. In addition, this irradiation amount is the value measured using the light meter which measures based on wavelength 365nm.

(3) Evaluation of burn-in characteristics (AC afterimage characteristics)

Place the liquid crystal display element manufactured above in an environment of 25°C and one atmospheric pressure, apply no voltage to the electrodes on the electrode surface of the glass substrate B, and apply an AC voltage to the electrodes on the electrode surface of the glass substrate A for 300 hours 10V. Immediately after 300 hours, an AC voltage of 3 V was applied to both the electrodes on the electrode surface of the glass substrate A and the electrodes on the electrode surface of the glass substrate B, and the difference ΔT [%] in light transmittance between the two electrodes was measured. At this time, the case where ΔT is less than 2% is evaluated as "good 1 (⊚)" for AC afterimage characteristics; the case where 2% or more and less than 3% is evaluated as "good 2 (◯)" for afterimage characteristics; The case of less than 4% was evaluated as "possible (Δ)" in the afterimage characteristic; the case of 4% or more was evaluated as "poor (x)" in the afterimage characteristic. The result was an evaluation of "good 1 (⊚)" in this Example.

(4) Evaluation of printability after standing time

Using the liquid crystal aligning agent (D-10) prepared above, it carried out similarly to the said Example 1, and evaluated the printability after the elapse of leaving time. As a result, in this Example, it was the result of "favorable ((circle)) printability.

From the results of these Examples 1 to 11, in the liquid crystal aligning agent containing the polymer having the above-mentioned specific partial structure, the printability was also good when the substrate was coated and left to stand for 30 minutes. . This suggests that the solubility of the polymer (P) to the solvent is high.

Moreover, the burn-in characteristic (AC afterimage characteristic) of a liquid crystal display element was also favorable. From this result, it can be presumed that the protective group introduced into the polymer is detached by heating during the post-baking, so that the side chain of the polymer after the post-baking has a rigid structure, and the AC of the liquid crystal display element can be sufficiently reduced. afterimage. On the other hand, in the comparative example, any one of the imprinting characteristic and printability was worse than the example.

Claims (8)

1. a liquid crystal aligning agent, is characterized in that: the polymkeric substance (P) containing the part-structure had represented by following formula (1),

In formula (1), A ¹for the concatenating group of singly-bound or divalence, R ¹it is the organic radical of the monovalence of more than 8 for carbon number; X ¹for protecting group; " * " represents the associative key being binding on the main chain of polymkeric substance.

2. liquid crystal aligning agent according to claim 1, is characterized in that: described R ¹for the base represented by following formula (2),

*-A ³-R ³(2)

In formula (2), A ³for the concatenating group of singly-bound or divalence, R ³for liquid crystal aligning base or light orientation base.

3. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: described polymkeric substance (P) is for being selected from least one in the cohort that is made up of polyamic acid, poly amic acid ester, polyimide and organopolysiloxane.

4. a liquid crystal orientation film, is characterized in that: it uses liquid crystal aligning agent according to any one of claim 1 to 3 and is formed.

5. a liquid crystal display device, is characterized in that: possess liquid crystal orientation film according to claim 4.

6. a polymkeric substance, is characterized in that: have the part-structure represented by following formula (1),

In formula (1), A ¹for the concatenating group of singly-bound or divalence, R ¹it is the organic radical of the monovalence of more than 8 for carbon number; X ¹for protecting group; " * " represents the associative key being binding on the main chain of polymkeric substance.

7. a compound, is characterized in that: it is represented by following formula (3),

In formula (3), A ¹for the concatenating group of singly-bound or divalence, R ¹it is the organic radical of the monovalence of more than 8 for carbon number; X ¹for protecting group.

8. a compound, is characterized in that: it is represented by following formula (4),

In formula (4), A ⁴for the organic radical of divalence, R ¹it is the organic radical of the monovalence of more than 8 for carbon number; X ¹for protecting group.