TWI657115B - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer and compound - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent capable of satisfying both the solubility of a polymer component in a solvent and reduction in burn-in of a liquid crystal display element. The present invention contains a polymer (P) having a partial structure represented by the following formula (1) in a liquid crystal aligning agent.

(In formula (1), A ¹ is a single bond or a divalent organic group, R ¹ is a monovalent organic group having a carbon number of 8 or more. X ¹ is a protecting group. "*" Represents a group bonded to a polymer (The bond of the main chain)

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, poly Compounds and compounds

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

Previously, as liquid crystal display elements, liquid crystal display elements having various driving methods such as electrode structures or physical properties of liquid crystal molecules and manufacturing steps have been developed. For example, Twisted Nematic (TN) type Various liquid crystals such as twisted nematic (STN) type, vertical alignment (VA) type, in-plane switching (IPS), fringe field switching (FFS) type Display element. These liquid crystal display elements include a liquid crystal alignment film for aligning liquid crystal molecules.

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

Patent Document 1 proposes a case where a polycarboxylic acid obtained by reacting a tetracarboxylic dianhydride containing 1,2,3,4-cyclobutane tetracarboxylic dianhydride and a diamine including a diamine having a fluorene bond. Phenylamine and polycarboxylic acid derived from the reaction of tetracarboxylic dianhydride and diamine The aminated polymer is contained in a liquid crystal aligning agent, and the ratio of the number of fluorene imine rings which the fluorene imidized polymer in a liquid crystal aligning agent has is made into a specific range. In Patent Document 1, the use of such a liquid crystal aligning agent can improve the voltage holding performance and the afterimage characteristics.

In addition, Patent Document 2 proposes a case where an amino group protected with a tertiary butoxycarbonyl group (t-BOC group) is introduced to an aromatic diamine which is ortho-positioned with respect to the primary amino group, and this is used. The polyamidoacid or polyamidoimide obtained from a diamine is contained in a liquid crystal aligning agent. In addition, it is described that according to this technology, an amino group is generated by removing the protection of the t-BOC group by heating during film formation, and a heterocycle is formed by an intramolecular reaction or an intermolecular reaction (crosslinking reaction) of the generated amino group, This reduces the accumulation of the residual direct current (DC) voltage.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2009-294274

Patent Document 2: International Publication No. 2013/115228

In a liquid crystal display element such as a vertical alignment type, a TN type, or an STN type, a liquid crystal alignment film is formed using a polymer having a liquid crystal alignment group such as a linear structure or a mesogenic skeleton in a side chain. In this case, in order to improve the burning of the liquid crystal display element (especially the burning caused by the AC voltage), it is considered that the side chain of the polymer has a rigid structure. However, if the side chain of the polymer is set For a rigid structure, the polymer The solubility in solvents is reduced. That is, the reduction in burn-in of the liquid crystal display element and the improvement in the solubility of the polymer have a trade-off relationship, and it is difficult to have both characteristics.

In addition, when manufacturing a large-scale liquid crystal panel, there may be a case where the liquid crystal aligning agent is printed on the substrate and temporarily stored until the next pre-baking step, so a leaving time is generated between the printing step and the pre-baking step. . In this case, when the polymer has poor solubility in a solvent, printing unevenness or pinholes are likely to occur due to being left to stand, and as a result, there is a concern that display quality or product yield may decrease.

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

The present inventors have conducted intensive studies in order to achieve the problems of the conventional technology as described above, and found that a liquid crystal aligning agent is contained in a liquid crystal aligning agent by including a polymer having a "-NH-" protected group-protected structure in the side chain To resolve the issue. Specifically, the present invention can provide the following liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer, and compound.

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

(In formula (1), A ¹ is a single bond or a divalent linking group, R ¹ is a monovalent organic group having a carbon number of 8 or more. X ¹ is a protecting group. "*" Represents a group bonded to a polymer (The bond of the main chain)

In addition, the present invention provides, in another aspect, a liquid crystal alignment film formed using the liquid crystal alignment agent. In addition, a liquid crystal display element including the liquid crystal alignment film is provided.

This invention is another one side, and provides the polymer which has a partial structure represented by said Formula (1). In addition, a compound represented by the following formula (3) and a compound represented by the following formula (4) are provided.

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

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

The -NH- of the polymer side chain is protected by a protective group and is contained in the liquid crystal aligning agent, whereby the solubility of the polymer in a solvent can be made good in the state of the liquid crystal aligning agent. In addition, when a liquid crystal aligning agent is applied to a substrate for film formation, the protective group is converted to -NH- due to, for example, heating during film formation, or due to the removal of a protective group, such as acid or alkali, thereby regenerating a film having high orientation after film formation. As a result, it is possible to reduce the burn-in of the liquid crystal display element (especially the reduction of alternating current (AC) afterimage).

A, B‧‧‧ glass substrate

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

Hereinafter, each component contained in the liquid crystal aligning agent of this invention, and another component arbitrarily mix | 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).

(In formula (1), A ¹ is a single bond or a divalent linking group, R ¹ is a monovalent organic group having a carbon number of 8 or more. X ¹ is a protecting group. "*" Represents a group bonded to a polymer (The bond of the main chain)

Examples of the divalent linking group of A ¹ in the formula (1) include a divalent hydrocarbon group having 1 to 20 carbon atoms, and a methylene group of the hydrocarbon group via -O-, -S-, -CO-, -COO-, -COS-, -NRa-, or -CO-NRa- (where Ra is a hydrogen atom, a monovalent hydrocarbon group or a protecting group having 1 to 12 carbon atoms), and other divalent groups; A divalent group in which at least one hydrogen atom bonded to a carbon atom is substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxyl group, a cyano group, and the like; -CO-, -COO- , -NRa-CO-, etc.

Herein, the "hydrocarbon group" in the present specification means a meaning including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain-like hydrocarbon group" in these refers to a straight-chain hydrocarbon group and a branched hydrocarbon group which are not composed of a cyclic structure in the main chain and are composed only of a chain structure. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only a structure of an alicyclic hydrocarbon as a ring structure and having no aromatic ring structure. However, it does not need to consist only of the structure of an alicyclic hydrocarbon, and it also includes those which have a chain structure in a part. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not need to consist only of an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in part. The "organic group" refers to a group containing a hydrocarbon group, and may include a hetero atom in the structure.

As specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in A ¹ , examples of the chain hydrocarbon group include methylene, ethylene, propanediyl, butanediyl, and pentanediyl. , Hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, vinylidene, propylenediyl, butenediyl, etc. Examples of the alicyclic hydrocarbon group include Cyclohexylene and the like; Examples of the aromatic hydrocarbon group include a phenylene group and a biphenylene group.

X ¹ 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 a monovalent organic group that is removed by heat, acid, or alkali. X ¹ is preferably a monovalent organic group that is removed by heat. Specific examples include a urethane-based protecting group, a fluorenyl-based protecting group, a fluorenimine-based protecting group, and sulfonamide. Department of protection and so on. Among these, a urethane-based protecting group is preferable, and specific examples thereof include a tert-butoxycarbonyl group, a benzyloxycarbonyl group, and 1,1-dimethyl-2-haloethoxy group. Carbonyl, 1,1-dimethyl-2-cyanoethoxycarbonyl, 9-fluorenylmethylcarbonyl, allyloxycarbonyl, 2- (trimethylsilyl) ethoxycarbonyl, and the like. Tert-butoxy is preferred in terms of the ease of deprotection due to heat, or the fact that the compound derived from X ¹ which is released by heating during film formation can be discharged to the outside of the film as a gas. Carbonyl.

R ¹ is a monovalent organic group having a carbon number of 8 or more. The carbon number of R ¹ may be 8 or more, but from the viewpoint of improving the alignment of liquid crystal molecules, it is preferably 10 or more, more preferably 12 or more, and even more preferably 15 or more. It is preferably set to 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 R ¹ is not particularly limited, but examples thereof include a group represented by the following formula (2) as a preferable specific example.

[Chem. 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 bonding bond to a nitrogen atom)

The liquid crystal alignment group and the photo alignment group in R ³ in the formula (2) are both groups capable of imparting a pretilt angle to the liquid crystal molecules. Among these, the photo-alignment group is a group that can exhibit the property of controlling the alignment of liquid crystal molecules by light irradiation, and the liquid-crystal alignment group is a group that can exhibit the property of controlling the alignment of liquid crystal molecules without light irradiation. Specific examples of the liquid crystal alignment group for R3 include an alkyl group having 8 to 20 carbon atoms, a fluoroalkyl group having 8 to 20 carbon atoms, an alkoxy group having 8 to 20 carbon atoms, and 17 to 17 carbon atoms. The group of 51 having a steroid skeleton, 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, heptyl, Octadecyl, 19-decyl, icosyl and the like; Examples of the fluoroalkyl group having 8 to 20 carbon atoms include perfluorooctyl, perfluorooctylethyl, perfluorodecyl, and perfluorodecyl Ethyl and the like; examples of the alkoxy group having 8 to 20 carbon atoms include octyloxy, nonyloxy, decoxy, dodecyloxy, tridecyloxy, tetradecyloxy, Pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecanyloxy, eicosyloxy, etc .; as a group with a steroid skeleton having 17 to 51 carbon atoms, Examples include cholesteryl, cholesteryl, and lanosteryl. Examples of the group in which a plurality of rings are bonded directly or via a linking group include the following formula (L-1) to Formula (L-10) [Chemical 6]

(In formulas (L-1) to (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- (wherein, R ^b is a hydrogen atom, a hydrocarbon group having 1 to 6 carbons, or a monovalent organic group that is detached by heat. "* 1" represents a bonding bond with a ring structure having "*"). N is an integer from 0 to 20 , M is an integer from 1 to 20. "*" represents a bonding bond with A ³ in the formula (2))

Represented bases, etc. The alkyl group, fluoroalkyl group, and alkoxy group having 8 to 20 carbon atoms may be linear or branched, but preferably linear.

In the formulae (L-1) to (L-5), the group "C _n H _{2n + 1-} " is preferably linear. In the formulae (L-6) to (L-10), each of the groups "C _m F _{2m + 1-} " and "-C _n H _2n- " is preferably linear. n is preferably 2 to 20, and more preferably 3 to 15. m is preferably 1 to 15, and more preferably 1 to 10.

Examples of the substituent that the liquid crystal alignment group may have include (meth) acrylic acid. Photopolymerizable groups such as allyloxy, styryl, maleimide, iminyl, vinyl, vinyl ether, allyl, and vinylidene. Among these, in terms of high photoreactivity, a (meth) acrylfluorenyl group, a styryl group, or a maleimide group may be preferably used. In addition, "(meth) acrylfluorenyloxy" has a meaning including "acrylfluorenyloxy" and "methacrylfluorenyloxy".

Examples of the divalent linking group of A ³ include a carbonyl group, an alkanediyl group having 1 to 10 carbon atoms, and "* 2-CO-R ^c -COO-" (wherein R ^c is 1 to 10 carbon atoms) Alkanediyl or cyclohexylene. "* 2" represents a bond to a nitrogen atom) and the like.

The photo-alignment group of R ^{3 is} a group that exhibits an orientation-limiting force by photoisomerization, photodimerization, photodecomposition, and the like. Specific examples thereof include an azo compound or a derivative thereof as a basic group. Azo-containing group of the skeleton, cinnamic acid-containing group containing cinnamic acid or its derivative as the basic skeleton, chalcone-containing group of chalcone or its derivative as the basic skeleton, benzophenone-containing or A derivative containing a benzophenone-containing group as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, and a cyclobutane-containing group containing cyclobutane or a derivative thereof as a basic skeleton The base and so on. Among these, an azo-containing group or a cinnamic acid-containing group is preferred from the viewpoint of good photo-alignment properties and the ease of introduction into a polymer.

The azo-containing group is not particularly limited as long as it has an azo group (-N = N-), and examples thereof include a group represented by the following formula (y-1).

[Chemical 7] R ⁴ -A ⁵ -N = NA ^4- * (y-1)

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

Examples of the divalent organic group of A ⁴ and A ⁵ in the formula (y-1) include a divalent hydrocarbon group having 1 to 20 carbon atoms, and a methylene group of the hydrocarbon group via -O-, -S. -, -CO-, -COO-, -COS-, -NR ^a -or -CO-NR ^a- (where Ra is ^a hydrogen atom, a monovalent hydrocarbon group or a protecting group having 1 to 12 carbon atoms), etc. A divalent radical formed by a hydrocarbon; at least one hydrogen atom bonded to a carbon atom of a hydrocarbon group is substituted by a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, a cyano group, and the like The base and so on. Regarding the liquid crystal alignment group for R ⁵ , the description of the liquid crystal alignment group for R ³ in the formula (2) can be applied.

Specific examples of the group represented by the formula (y-1) include a group represented by the following formula (y-1-1) to formula (y-1-10).

[Chemical 8]

(In formulas (y-1-1) to (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 -(Where R ^d is a hydrogen atom, a hydrocarbon group having 1 to 6 carbons or a protecting group. "* 3" represents a bonding bond with an azobenzene structure). N is an integer of 0 to 20, and m is 1 to 20 an integer of ³ .X same meaning as in the formula - (L-10) X of the formula (L-1) ³⁾

Specific examples of the cinnamic acid-containing group include a group represented by the following formula (x-1) and a group represented by the following formula (x-2).

[Chemical 9]

(In formulae (x-1) and (x-2), R ¹¹ and R ¹⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 20 carbon atoms. X ¹¹ and X ¹³ are each independently a single bond, an oxygen atom, a sulfur atom, * -COO- or * -OCO- (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 having 1 to 3 carbon atoms, * -COO- or * -OCO- (wherein, the bond with "*" is bonded to R ¹² ). R ¹² And R ¹⁵ are each independently 1,4-phenylene or 1,4-cyclohexylene. X ¹⁴ is a single bond, an alkanediyl group having 1 to 3 carbon atoms, 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 bivalent heterocyclic group or a divalent fused ring group. R ¹⁷ is a single bond, * -OCO- (CH ₂ ) _h -or * -O- (CH ₂ ) _i- (wherein, "* "And R ^{16 are} bonded, and h and i are integers from 1 to 10 respectively. X ¹⁶ is * -COO- or * -OCO- (where the 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 R ²⁰ are each independently alkanediyl group having a carbon number of 1 to 10 or 1,4-cyclohexylene group .a, e and d are each independently an integer of 0 to 3, b, and f are each independently 0 or 1, (c and g are each independently an integer of 0 to 4)

Specific examples of the group represented by the formula (x-1) include a group represented by the following formula (x-1-1) to formula (x-1-13), and the like; Specific examples of the group represented by the formula (x-2) include, for example, the following formula (x-2-1) to formulas (x-2-2) Compounds and the like represented by each. In addition, the bases described in Japanese Patent Application Laid-Open No. 2011-133825 can be mentioned.

(Wherein, R ¹¹ b, and the meanings and R (x-1) of the same and of formula ¹¹ b)

[Chemical 11]

(Wherein, R ¹⁴ and f is the meaning of R (x-2) and ¹⁴ of the same formula f)

It is preferable that the partial structure represented by the said formula (1) is a group represented by the following formula (1-1) or a formula (1-2) from the point which the burn-in reduction effect of a liquid crystal display element is high.

(In formulas (1-1) and (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 as described above. The formula (1) is the same. "*" Represents a bonding bond bonded to the main chain of the polymer)

For the divalent organic group of A ² , the illustrations of the description of A ⁴ and A ⁵ in the formula (y-1) can be applied, and for the monovalent organic group of R ² , the formula (1) can be applied. Illustrative illustration of R ¹ .

"*" In the formula (1) represents a bonding bond bonded to the main chain of the polymer. Here, in the book of this Exchange, the "main chain" of a polymer refers to the "backbone" part of the polymer that contains the longest atomic link chain, and the "side chain" refers to the "backbone" from the polymer. Backbone "branch.

The main skeleton of the polymer (P) is not particularly limited, and examples thereof include Polyamic acid, polyimide, polyamidate, polyorganosiloxane, polyester, polyamine, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-benzene Skeletons such as cis butene diimide) derivatives, poly (meth) acrylates, and the like. Among these, from the viewpoints of heat resistance, mechanical strength, and affinity with liquid crystal, it is preferably selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyorganosiloxane. At least one polymer in the group. In addition, (meth) acrylate means including an acrylate and a methacrylate.

(Polyamic acid)

When the polymer (P) is a polyamic acid, the polyamino acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine. A polyamic acid having a partial structure represented by the formula (1) (hereinafter also referred to as a “specific partial structure”) can have a monomer composition containing a specific partial structure (wherein “ "*" Indicates a bonding bond. It is obtained by polymerization of at least any one of a tetracarboxylic dianhydride and a diamine having a specific partial structure. In terms of a high degree of freedom in selecting a compound, it is preferable to use a diamine (hereinafter also referred to as a "specific diamine") having a specific partial structure.

(Tetracarboxylic dianhydride)

Examples of the tetracarboxylic dianhydride used for synthesizing polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. As specific examples of these, examples of the aliphatic tetracarboxylic dianhydride include butanetetracarboxylic dianhydride; and examples of the alicyclic tetracarboxylic dianhydride include: 1, 2, 3, 4 -Cyclobutane tetracarboxylic 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 anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0] octane Alkane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride, bicyclic [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic acid Acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, ethylenediamine tetraacetic dianhydride, cyclopentanetetracarboxylic dianhydride, ethylene glycol Bis (dehydrated trimellitate), 1,3-propane Bis (dehydrated trimellitic acid ester), etc .; as the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride; etc .; in addition, those described in Japanese Patent Laid-Open No. 2010-97188 can be used. Tetracarboxylic dianhydride. The tetracarboxylic dianhydride may be used singly or in combination of two or more kinds.

As a tetracarboxylic dianhydride for synthesizing a polyamic acid, it is preferable that the tetracarboxylic dianhydride contains 1,2,3 selected from the tetracarboxylic dianhydride from the point which can make various characteristics of a liquid crystal display element more favorable. , 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-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-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. The used amount of these preferred compounds (the total amount in the case of using two or more kinds) is preferably 5 mol% or more with respect to the total amount of the tetracarboxylic dianhydride used for synthesizing polyamic acid. It is preferably 10 mol% or more, and more preferably 20 mol% or more.

(Diamine)

The specific diamine is not particularly limited as long as it has the specific partial structure, and examples thereof include compounds represented by the following formula (3).

(In formula (3), A ¹ , R ¹ and X ^{1 have} the same meaning as in formula (1))

Regarding A ¹ , R ¹ and X ¹ in the formula (3), the description of the formula (1) can be applied. Specific examples of the specific diamine include compounds represented by the following formulae (3-1) to (3-19).

[Chemical 14]

[Chemical 15]

[Chemical 17]

(Where n is an integer from 0 to 20)

Moreover, when synthesizing a polyamidic acid, a specific diamine may be used individually by 1 type, and may use 2 or more types together.

The diamine used to synthesize the polyamidic acid as the polymer (P) may be only a specific diamine, or a diamine other than the specific diamine may be used in combination.

Examples of other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. Specific examples of these include, as examples of the aliphatic diamine, m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. Amine, 1,3-bis (aminomethyl) cyclohexane, etc .; Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclo Hexylamine) and the like; Examples of the aromatic diamine include dodecyloxydiaminobenzene, tetradecyloxydiaminobenzene, pentadecyloxydiaminobenzene, and hexadecyloxydiamino Benzene, stearyloxydiaminobenzene, cholestanyloxy diaminobenzene, cholesterolyloxydiaminobenzene, cholesteryl diaminobenzoate, cholesterolyl diaminobenzoate Lanosteryl diaminobenzoate, 3,6-bis (4-aminobenzyloxy) 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-((aminophenyl) A Phenyl) -4- (4-heptylcyclohexyl) cyclohexane, N- (2,4-diaminophenyl) -4- (4-heptylcyclohexyl) benzamide, the following Formula (E-1) or the following formula (E-2)

(In formulae (E-1) and (E-2), X ^I and X ^II are each independently a single bond, -O-, -COO-, or -OCO-, and R ^I is an alkane having 1 to 3 carbon atoms. Diyl, R ^II is a single bond or an alkane diyl having 1 to 3 carbon atoms, 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 1 to 20 Integer, u is 0 or 1. Among them, r and s are not both 0. The two R ^II in formula (E-2) may be the same or different)

Diamines including oriented compounds such as 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-aminophenyl) Ethyl] adipate, 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) ) Bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diamino Pyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminooxazole, N-methyl-3,6-diaminooxazole, N-ethyl-3,6 -Diaminooxazole, N-phenyl-3,6-diaminooxazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -pyrazine, 3,5-diaminobenzoic acid, etc .; as the diaminoorganosiloxane, for example, Output: 1,3-bis (3-aminopropyl) -tetramethyldisilazane, etc .; in addition, Laid-Open Japanese Patent Application Publication No. 2010-97188 diamine described.

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 the diaminophenyl group). The group "-C _t H _{2t + 1} " and the group "-C _t H _2t- " are preferably linear.

The photopolymerizable group of X ^III is preferably a (meth) acrylfluorenyl group, a styryl group, or a maleimide group. The two amino groups in the diaminophenyl group in the formula (E-1) and the formula (E-2) are preferably located at the 2,4-position or the 3,5-position with respect to the other groups.

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

As another diamine, a diamine having a specific functional group may be further used for the purpose of improving the improvement effect of reducing the burn-in of a liquid crystal display element caused by a DC voltage. Examples of such a diamine include a diamine having a nitrogen-containing structure selected from the group consisting of a nitrogen-containing heterocyclic ring, a secondary amino group, and a tertiary amino group, or a diamine having a carboxyl group. .

Examples of the diamine having a nitrogen-containing structure include 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminopyrazole, and N-formyl -3,6-diaminooxazole, 1,4-bis- (4-aminophenyl) -pyrazine, and the following formulae (E-3-1) to (E-3-6) Compounds.

[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'-diamino Biphenyl-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'-diaminodiphenyl Polycarboxylic acids such as ethane-3,3'-dicarboxylic acid and 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid.

From the viewpoint of sufficiently obtaining the effect of improving the solubility of a polymer on a solvent or the effect of reducing the burn-in of a liquid crystal display element caused by an alternating voltage, it is used in synthesizing polyamic acid with respect to the total amount of diamine. The diamine is preferably a molar ratio of a specific diamine of 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and particularly preferably 10 mol. %the above. From the viewpoint of showing an appropriate pretilt angle, the upper limit of the proportion of the specific diamine used is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. .

The effect of reducing the burn-in of the liquid crystal display element caused by the DC voltage is fully obtained. From a fruit standpoint, the use ratio of the diamine having a nitrogen-containing structure is preferably 0.1 mol% or more, and more preferably 1 mol% to 50 mol, relative to the total amount of diamine used in the synthesis. %, And more preferably 2 mol% to 30 mol%. The use 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 relative to the total amount of diamine used in the synthesis. Ear% ~ 80 mole%. In addition, other diamines may be used alone or in combination of two or more.

(Synthesis of specific diamines)

The specific diamine can be synthesized by appropriately combining known methods. As an example, the following method can be mentioned: synthesizing a dinitro intermediate having a nitro group in place of the primary amino group in the formula (3), and then using an appropriate reduction system to make the obtained dinitro intermediate intermediate Methods for nitro amination and the like. The method for synthesizing the dinitro intermediate can be appropriately selected depending on the intended compound. For example, "-NH-" can be synthesized by tert-butoxy by reacting a dinitro compound having "-NH-" with di-tert-butyl dicarbonate in the presence of a strong base such as dimethylaminopyridine. Carbonyl protected dinitro intermediate. However, the synthesis method of a specific diamine is not limited to the said.

(Synthesis of Polyamic Acid)

Polyamic acid can be obtained by reacting a tetracarboxylic dianhydride as described above with a diamine and, if necessary, a molecular weight modifier. The use ratio of the tetracarboxylic dianhydride and diamine supplied to the synthesis reaction of the polyamic acid is preferably 1 equivalent to the amino group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride becomes a ratio of 0.2 to 2 equivalents, and more The ratio is preferably 0.3 to 1.2 equivalents.

Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; phenyl isocyanate; Monoisocyanate compounds such as naphthalene isocyanate. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used.

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

Examples of the organic solvent used for the reaction include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenol-based solvent (organic solvent of the first group) or an organic solvent selected from the group of the first group is preferably used. A mixture of one or more species with one or more species selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (organic solvent of the second group). In the latter case, the use ratio of the organic solvent in the second group is preferably 50% by weight or less, and more preferably 40% by weight relative to the total amount of the organic solvent in the first group and the organic solvent in the second group. % Or less, and more preferably 30% by weight or less.

As a particularly preferred organic solvent, it is preferable to use a solvent selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylmethylene, and γ. -One or more of the group consisting of butyrolactone, tetramethylurea, hexamethylphosphonium triamine, m-cresol, xylenol and halogenated phenol as a solvent, or in the proportion of A mixture of one or more of these and other organic solvents is used within the scope. The used amount (a) of the organic solvent is preferably an amount of 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution and the total amount (b) of the tetracarboxylic dianhydride and diamine.

In this way, a reaction solution obtained by dissolving polyamidic acid was obtained. The reaction solution may be directly provided to the preparation of the liquid crystal aligning agent, or the polyamidic acid contained in the reaction solution may be separated and then provided to the preparation of the liquid crystal aligning agent, or the separated polyamidic acid may be purified. It is then provided to the preparation of the liquid crystal aligning agent. Isolation and purification of a polyamic acid can be performed according to a well-known method.

(Polyimide)

The polyfluorene imine as the polymer (P) can be obtained, for example, by dehydrating and ring-closing a polyfluorinated acid synthesized as described above, and then fluorinating. In the case where the polyamidic acid is subjected to dehydration and ring closure to prepare polyimide, the reaction solution of the polyamidic acid may be directly provided to the dehydration ring-closure reaction, and the polyamidic acid contained in the reaction solution may be separated. It is then provided to the dehydration ring closure reaction, or the isolated polyamidic acid may be purified and then provided to the dehydration ring closure reaction.

The polyfluorene imide may be a complete fluorinated imide obtained by dehydrating and closing all the fluorinated amino acids of the polyfluorinated acid as a precursor thereof, or may be dehydrated and closed only by a part of the fluorinated acid structure. In addition, a part of the sulfonium imide compound in which the sulfonium acid structure and the sulfonium ring structure coexist. The fluorene imidization rate of the polyfluorene imine used for the reaction is preferably 10% or more, more preferably 20% to 00%, and still more preferably 30% to 99%. The fluorene imidization ratio is a percentage expressed as a percentage of the number of fluorene imine ring structures relative to the total number of fluorene imine structures and the number of fluorene imine rings relative to the polyfluorene imine. example. Here, a part of the fluorene imine ring may be an isofluorene ring.

The dehydration ring closure of the polyamic acid is preferably performed by a method of heating the polyamic acid; or the polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring closure catalyst are added to the solution. A method of heating is required. Among these, the latter method is preferably used.

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

In this way, a polyimide-containing reaction solution was obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the dehydrating agent and the dehydration ring-closing catalyst can be removed from the reaction solution and then provided to the preparation of the liquid crystal alignment agent, or the polyfluorene imide can be separated and then provided to the liquid crystal alignment agent. Preparation of the agent, or the isolated polyfluorene imide may be purified and then provided to the preparation of the liquid crystal aligning agent. These purification operations can be performed according to a known method.

(Polyurethane)

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

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

The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid with an alcohol such as methanol or ethanol. Examples of the diamine used in the method [II] include diamines exemplified in the synthesis of polyamic acid, and it is preferable to include a specific diamine. The reaction of the method [II] is preferably performed in an organic solvent and in the presence of a suitable dehydration catalyst. Examples of the organic solvent include organic solvents exemplified as organic solvents for synthesizing polyamic acid. Examples of the dehydration catalyst include 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholine halide, carbonylimidazole, and phosphorus-based condensation. Agent.

The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. Examples of the diamine used in the method [III] include polyamic acid. The diamine exemplified in the synthesis is preferably a specific diamine. The reaction of the method [III] is preferably performed in an organic solvent and in the presence of a suitable base. Examples of the organic solvent include organic solvents exemplified as organic solvents for synthesizing polyamic acid. As the base, for example, a tertiary amine such as pyridine or triethylamine can be preferably used.

In this way, a reaction solution obtained by dissolving polyamidate was obtained. The reaction solution may be directly provided to the preparation of the liquid crystal aligning agent, or the polyamidate contained in the reaction solution may be separated and then provided to the preparation of the liquid crystal aligning agent, or the separated polyamidate After purification, it is provided to the preparation of the liquid crystal aligning agent. Isolation and purification of polyamidate can be performed according to a known method. In addition, the polyamidate contained in the liquid crystal aligning agent may have only a pseudoamidate structure, or may be a partial esterified product in which a pseudoamidate structure and a pseudoamidate structure coexist.

The solution viscosity of the polyamidic acid, polyamidate, and polyimide as the polymer (P) is preferably 10 mPa when the solution is made into a solution having a concentration of 10% by weight. s ~ 800mPa. The solution viscosity of s is more preferably 15 mPa. s ~ 500mPa. Solution viscosity of s. In addition, the solution viscosity (mPa.s) of the polymer is prepared using a E-type rotational viscometer at 25 ° C for a good solvent (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer. The polymer solution was measured at a concentration of 10% by weight.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. In addition, the fraction represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC The molecular weight distribution (Mw / Mn) is preferably 15 or less, and more preferably 10 or less.

(Polyorganosiloxane)

Examples of the polyorganosiloxane (hereinafter also referred to as a "polyorganosiloxane containing a specific group") as the polymer (P) include [1] the following polymer (hereinafter, also referred to as " A method for reacting an epoxy-group-containing polyorganosiloxane "with a carboxylic acid having a specific partial structure (hereinafter also referred to as a" specific carboxylic acid "), wherein the polymer is made by hydrolyzing an epoxy group The silane compound (ms-1) or a mixture of the silane compound (ms-1) and other silane compounds is obtained by hydrolytic condensation; [2] a hydrolyzable silane compound having the specific partial structure or the silane compound A method for hydrolytic condensation with a mixture of other silane compounds. Among these, the method of [1] is preferable in that a specific partial structure can be introduced with high efficiency.

Specific examples of the silane compound (ms-1) for synthesizing an epoxy-containing polyorganosiloxane include 3-glycidyloxypropyltrimethoxysilane and 3-glycidyloxy Propyl triethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-glycidyloxyethyltrimethoxy Silane, 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethyldimethylmethoxysilane, 2-glycidyloxyethyldimethylethoxysilane , 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldiethoxysilane, 4-glycidyloxybutyl Dimethylmethoxysilane, 4-glycidyloxy Butyl dimethyl ethoxysilane, 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 kind of these may be used alone or two or more kinds may be used in combination.

The other silane compounds are not particularly limited as long as they are hydrolyzable silane compounds, and can be appropriately selected depending on the driving mode of the liquid crystal display element and the like. Specific examples of other silane compounds include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltrisilane. Alkoxysilane compounds such as ethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, Mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N -(3-Cyclohexylamino) propyltrimethoxysilane and other nitrogen-containing materials. Sulfur alkoxysilane compounds; 3- (meth) propenyloxypropyltrimethoxysilane, 3- (meth) propenyloxypropyltriethoxysilane, 3- (meth) propylene Ethoxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-benzene Unsaturated bond-containing alkoxysilane compounds such as vinyltrimethoxysilane; trimethoxysilylpropylsuccinic anhydride; alkoxysilane compounds having silicon-silicon bonds; and the like. Other silane compounds can be used alone or in combination. More than that.

From the viewpoint that the specific partial structure can be sufficiently introduced into the side chain of the polymer and the side reactions caused by excessive epoxy groups are suppressed, the epoxy equivalent of the polyorganosiloxane containing epoxy group 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-containing polyorganosiloxane, it is preferred that the ratio of the use of the silane compound (ms-1) to other silane compounds is such that the epoxy equivalent of the obtained polyorganosiloxane is within the above range. Way to adjust.

Hydrolysis of silane compounds. The condensation reaction is performed by reacting one or two or more kinds of silane compounds as described above with water, preferably in the presence of a suitable catalyst and an organic solvent. hydrolysis. In the condensation reaction, the use ratio of water is preferably 0.5 mol to 100 mol, and more preferably 1 mol to 30 mol relative to 1 mol of the silane compound (total amount).

As hydrolysis. Examples of the catalyst used in the condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. The organic base is preferably a tertiary organic amine such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene; tetramethyl hydroxide Quaternary organic amines such as ammonium.

As the catalyst, an alkali metal compound or an organic base is preferable among these, in terms of suppressing side reactions such as ring opening of an epoxy group, in terms of improving hydrolysis and condensation speed, and in terms of excellent storage stability, and the like. For organic bases.

The amount of organic base used varies according to the type of organic base, reaction conditions such as temperature, etc. It should be suitably set, and it is preferably 0.01 to 3 times mole, more preferably 0.05 to 1 mole, relative to all the silane compounds.

As hydrolysis. Examples of the organic solvent used in the condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Specific examples of these include, for example, hydrocarbons such as toluene and xylene, and examples of the ketones include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, and diethyl. Ketone, cyclohexanone, cyclopentanone, etc .; Examples of the ester include ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl ethyl. Acid ester, ethyl lactate, etc .; examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc .; examples of the alcohol include 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-butyl ether Propyl ether and so on. Among these, a water-insoluble organic solvent is preferably used. These organic solvents may be used alone or in combination of two or more.

The use ratio of the organic solvent in the hydrolysis condensation reaction is preferably 10 to 10,000 parts by weight, and more preferably 50 to 1,000 parts by weight, with respect to 100 parts by weight of all the silane compounds used for the reaction.

About hydrolysis. The condensation reaction is preferably carried out by dissolving a silane compound as described above in an organic solvent, mixing the solution with an organic base and water, and heating the solution with an oil bath or the like, for example. hydrolysis. In the condensation reaction, the heating temperature is preferably 130 ° C or lower, and more preferably 40 ° C to 100 ° C. The heating time is preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. During heating, The mixed solution 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 is performed by using water containing a small amount of salt (for example, about 0.2% by weight of an ammonium nitrate aqueous solution or the like), so that the washing operation is facilitated, and this is preferable. The washing is performed until the water layer becomes neutral after the washing, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieve, and the solvent is removed to obtain the target polymer. Organic silicone.

In the method of [1], the epoxy-containing polyorganosiloxane obtained by the reaction is then reacted with a specific carboxylic acid. Thereby, the epoxy group which the polyorganosiloxane containing an epoxy group 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 the synthesis is not particularly limited as long as it has the specific partial structure, and examples thereof include compounds represented by the following formula (4).

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

The description of A ^{4 in} the formula (4) can be applied to the description of the divalent organic group of A ¹ in the formula (1), and is preferably a divalent hydrocarbon group. Regarding R ¹ and X ¹ , the description of the formula (1) can be applied. Specific examples of the specific carboxylic acid include compounds represented by the following formulae (4-1) to (4-19).

[Chemical 23]

[Chemical 24]

[Chemical 25]

(In the formula, n is an integer of 0 to 20.) In addition, a specific carboxylic acid may be used individually by 1 type, and may use 2 or more types together.

The method for synthesizing the specific carboxylic acid is not particularly limited, and it can be synthesized by combining conventionally known methods. As an example of the synthesis method, for example, the following method can be used: Synthesis by reacting a halide having "-NHR ¹ " with di-tert-butyl dicarbonate in the presence of a strong base such as dimethylaminopyridine. "-NH-" A compound protected with a tert-butoxycarbonyl group, and a method of reacting the obtained compound with a carboxylic acid having a functional group capable of reacting with a halogen atom, and the like. However, the synthesis method of a specific carboxylic acid is not limited to the said.

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

The other carboxylic acid may be any carboxylic acid that does not have the specific partial structure, and specific examples thereof include hexanoic acid, lauric acid, pentadecanoic acid, palmitic acid, stearic acid, oleic acid, isopropyl Fatty acids with 6 to 20 carbon atoms such as vaccenic acid, linoleic acid, linolenic acid, and arachidic acid, and the following formulas (5-1) to (5-9) Represented compounds.

(In the formula, j is an integer of 0 to 12, and h is an integer of 1 to 20.) As other carboxylic acids, one kind selected from these may be used alone or two or more kinds may be used in combination.

The use ratio of the carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane is preferably set to 1 mol of the total epoxy groups of the polyorganosiloxane. 0.001 to 1.5 mol, and more preferably 0.01 to 1.0 mol.

In addition, the use ratio of the specific carboxylic acid is preferably set to 0.01 mol to 0.8 mol with respect to a total of 1 mol of epoxy groups in the polyorganosiloxane. If the use ratio is set to less than 0.01 mol, the amount of introduction of a specific partial structure will be small, and it will be difficult to obtain effects such as improvement in liquid crystal alignment, reduction in burnout, and solubility. On the other hand, if it exceeds 0.8 mol, the solubility of the polymer tends to deteriorate. It is preferably 0.03 to 0.6 mol, and more preferably 0.05 to 0.4 mol.

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

Examples of the catalyst used in the reaction of the epoxy-containing polyorganosiloxane with a carboxylic acid include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound. Among these, an organic base is preferable. The use ratio of the catalyst is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane that reacts with the carboxylic acid.

Examples of the organic solvent used in the reaction include hydrocarbons, ethers, esters, ketones, amidines, and alcohols. From the viewpoints of solubility of raw materials and products and ease of product purification, among these, ethers, esters, and ketones are preferred. Specific examples of particularly preferred solvents include 2-butanone and 2-hexanone. Ketones, methyl isobutyl ketones, and butyl acetate. The organic solvent is preferably used at a solid content concentration (a ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) of 0.1% by weight or more, and more preferably 5% by weight. % ~ 50 weight The amount of% to use.

The reaction temperature in the reaction is preferably 0 ° C to 200 ° C, and more preferably 50 ° C to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, and more preferably from 0.5 to 20 hours. After the reaction is completed, it is preferable to wash the organic solvent layer separated from the reaction solution with water. After washing with water, if necessary, the organic solvent layer is dried with an appropriate desiccant, and then the solvent is removed, thereby obtaining a polyorganosiloxane having the specific partial structure in the side chain.

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

The polyorganosiloxane containing a specific group is measured by gel permeation chromatography from the viewpoints of improving the liquid crystal alignment of the formed liquid crystal alignment film and ensuring the stability of the liquid crystal alignment over time. The polystyrene-equivalent weight average molecular weight (Mw) is preferably 1,000 to 50,000, and more preferably 3,000 to 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 the other components include polymers other than the polymer (P), compounds having at least one epoxy group in the molecule (hereinafter, referred to as "epoxy-containing compounds"), and functional silanes. Compounds etc.

[Other polymers]

The other polymers can be used for improving various characteristics such as solution characteristics and electrical characteristics. The other polymer is a polymer which does not have the specific partial structure, and examples thereof include polyamic acid, polyimide, polyamidate, polyorganosiloxane, polyester, and polyamidoamine. , Cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylcis butylene diimide) derivative, or polymer with poly (meth) acrylate as the main skeleton, and the like. As other polymers, at least one polymer selected from the group consisting of polyamidic acid, polyamidoimide, polyamidate, and polyorganosiloxane can be preferably used among these polymers.

When blending other polymers in the liquid crystal aligning agent, the blending ratio of the other polymers is preferred to 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent (total of the polymer (P) and other polymers). It is 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and even more preferably 0.2 to 30 parts by weight.

[Epoxy-containing compound]

The epoxy group-containing compound can be used in order to improve the adhesion to the substrate surface or electrical characteristics in the liquid crystal alignment film. 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-xylylene Amine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane , N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, and the like. In addition, as an example of the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used.

When the epoxy group-containing compound is blended into the liquid crystal aligning agent, the blending ratio of the epoxy group-containing compound is preferably 40 parts by weight or less with respect to 100 parts by weight of the total polymer contained in the liquid crystal aligning agent. It is more preferably set to 0.1 to 30 parts by weight.

[Functional silane compound]

The functional silane compound can be used in order to improve the printability of a liquid crystal aligning agent. Examples of such a functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyltrimethoxysilane. Ethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3- Ureapropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilanepropyltriethyl 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, etc.

When blending other functional silane compounds into the liquid crystal aligning agent, the blending ratio of the other functional silane compounds is preferably 2 parts by weight or less with respect to 100 parts by weight of the total polymer contained in the liquid crystal aligning agent. It is preferably set to 0.02 to 0.2 parts by weight.

In addition, as other components, in addition to the above, a compound or an antioxidant having at least one oxetanyl group in the molecule, a metal chelate compound, a hardening accelerator, a surfactant, a filler, and a dispersant may be mentioned. , Light sensitizers, etc.

The liquid crystal aligning agent of the present invention may contain only one polymer as a polymer component, or may contain two or more polymers as a polymer component. As a preferable aspect of a polymer component, the following [1]-[5] etc. are mentioned, for example.

[1] A form containing only polymer (P) as a polymer component, and polymer (P) is at least one selected from the group consisting of polyamic acid, polyamidate, and polyimide .

[2] A form containing only the polymer (P) as a polymer component, and the polymer (P) is a polyorganosiloxane.

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

[5] Containing polymer (P) and other polymers as polymer components and polymerizing The substance (P) is at least one selected from the group consisting of polyamidic acid, polyamidate, and polyimide, and the other polymer is in the form of a polyorganosiloxane.

Among these [4] and [5], it is presumed that the hydrophobicity of the polymer (P) is increased due to the effect of the introduction of the protective group, and the polarity difference between the polymer (P) and the polymer without the protective group is increased. In the liquid crystal alignment 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 another polymer, in order to improve the effect of reducing the burn-in of a liquid crystal display element caused by a DC voltage, it is preferable to use a polymer selected from One or two or more of a polymer having a nitrogen-containing structure, a polymer having a carboxyl group, and a polymer having a nitrogen-containing structure and a carboxyl group in at least one of the group consisting of a primary amino group and a tertiary amino group.

The blending ratio of the polymer (P) with respect 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 with respect to 100 parts by weight of the total weight of the solid content. It is 50 weight part or more, More preferably, it is 60 weight part or more.

<Solvent>

The liquid crystal aligning agent of the present invention is prepared in the form of a liquid composition obtained by dispersing or dissolving a polymer (P) and other components used as necessary in an appropriate solvent. .

Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamidine, and N, N-dimethyl Methylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, Methyl methoxypropionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellulose Agent), ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl ether Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, and subcarbonate Propyl ester, etc. These can be used alone or in combination of two or more.

The solid content concentration in the liquid crystal aligning agent (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1% by weight Range of ~ 10% by weight. That is, it is preferable to apply a liquid crystal aligning agent on a substrate surface as described later, and to form a coating film as a liquid crystal alignment film or a coating film as a liquid crystal alignment film by heating. 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 is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, and it is difficult to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent tends to increase and the coatability tends to decrease.

The range of a particularly preferable solid content concentration differs according to the method used when apply | coating a liquid crystal aligning agent on a board | substrate. For example, when applied to a substrate by a spinner method, the solid content concentration (the ratio of the total weight of all components except the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is particularly preferably 1.5. The range is from% by weight to 4.5% by weight. In the case of printing, It is particularly preferable to set the solid content concentration to a range of 3% to 9% by weight, thereby setting the solution viscosity to 12 mPa. s ~ 50mPa. The range of s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1 to 5% by weight, and thereby set the solution viscosity to 3 mPa. s ~ 15mPa. The range of s. The temperature at the time of preparing the liquid crystal aligning agent is preferably 10 ° C to 50 ° C, and more preferably 20 ° C to 30 ° C.

<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, and VA type (including Vertical Alignment-Multi-domain Vertical Alignment (VA-MVA) type, vertical alignment). -Various alignment modes (Vertical Alignment-Patterned Vertical Alignment (VA-PVA) type), IPS type, FFS type, Optically Compensated Bend (OCB) type and other working modes.

The liquid crystal display element can be manufactured, for example, by the following steps (1) to (3). In step (1), different substrates are used according to the required operation mode. The working modes in steps (2) and (3) are the same.

[Step (1): Formation of Coating Film]

First, a liquid crystal aligning agent is coated on a substrate, and then the coated surface is heated to form a coating film on the substrate.

(1-A) For example, when manufacturing a TN-type, STN-type, or VA-type liquid crystal display element, first, two substrates provided with a patterned transparent conductive film are used as a pair of substrates, and transparency is formed on each substrate. The surface of the conductive film is preferably coated with a liquid crystal aligning agent by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method, respectively. As the substrate, for example, glass such as float glass and soda glass, and polyethylene terephthalate, polybutylene terephthalate, polyether fluorene, polycarbonate, and poly (ester) can be used. Cyclic olefin) and other plastic transparent substrates. As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG Corporation) including tin oxide (SnO ₂ ), and indium oxide-tin oxide (In ₂ O _3- SnO ₂ ) Indium Tin Oxide (ITO) film and the like. In order to obtain a patterned transparent conductive film, for example, the following methods can be used: a method of forming a pattern without using a patterned transparent conductive film and then photoetching; and forming a transparent conductive film using a desired pattern Mask method. When the liquid crystal aligning agent is applied, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a surface on which the coating film is formed on the substrate surface may be coated with a functional silane compound, a functional titanium compound, or the like in advance. Before processing.

After the liquid crystal aligning agent is applied, in order to prevent dripping or the like of the applied liquid crystal aligning agent, it is preferable to perform preheating (prebaking). The pre-baking temperature is preferably 30 ° C to 200 ° C, more preferably 40 ° C to 150 ° C, and particularly preferably 40 ° C to 100 ° C. The pre-baking time is preferably 0.25 minutes to 10 minutes, and more preferably 0.5 minutes to 5 minutes. Then, in order to completely remove the solvent and, if necessary, to thermally imidize the amido acid structure present in the polymer, a calcination (post-baking) step is performed. The calcination temperature (post-baking temperature) at this time is preferably 80 ° C to 300 ° C, and more preferably 120 ° C to 250 ° C. The post-baking time is preferably 5 minutes to 200 minutes, and more preferably 10 minutes to 100 minutes. The film thickness of the film formed in this manner is preferably 0.001 μm to 1 μm, and more preferably 0.005μm ~ 0.5μm.

(1-B) When manufacturing an IPS-type or FFS-type liquid crystal display element, a liquid crystal aligning agent is applied to the electrode-formed surface of the substrate provided with the electrode, and one surface of the substrate opposite to the electrode-less surface, and then Each coating surface is heated to form a coating film, and the electrode includes a transparent conductive film or a metal film patterned in a comb-tooth shape. Regarding the material, coating method, heating conditions after coating, the patterning method of the transparent conductive film or metal film, the substrate pretreatment, and the preferred film thickness of the formed coating film, the substrate and the transparent conductive film used at this time, and The (1-A) is the same. As the metal film, for example, a film containing a metal such as chromium can be used.

In any of the cases (1-A) and (1-B), after the liquid crystal aligning agent is coated on the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film to be a liquid crystal alignment film. In this case, when the polymer contained in the liquid crystal aligning agent is a polyamidic acid or a polyamidate, or a fluorinated polymer containing a fluorinated imine ring structure and a fluorinated acid structure, After the coating film is formed, further heating may be performed to perform a dehydration ring-closing reaction, thereby forming a coating film that is further imidized.

[Step (2): Orientation Processing]

When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal display element, the coating film formed in the step (1) is subjected to a treatment (alignment 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. Examples of the orientation treatment include applying a coating film in a certain direction by rubbing the coating film with a roller wound around a cloth including fibers such as nylon, rayon, and cotton, thereby imparting the coating film. Friction treatment of liquid crystal alignment ability; on substrate The coating film formed thereon is subjected to light irradiation, and a photo-alignment treatment or the like is provided to the coating film to give a liquid crystal alignment ability. On the other hand, in the case of manufacturing a vertical alignment type liquid crystal display element, the coating film formed in the step (1) may be directly used as a liquid crystal alignment film, and an alignment treatment may be performed on the coating film.

The light irradiation in the photo-alignment treatment can be performed by the following methods and the like: (1a) a method of irradiating a coating film after post-baking, and (2a) irradiating a coating film after pre-baking and before post-baking. Method (3a) A method of irradiating a 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 the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. When the radiation is polarized, linearly polarized light or partially polarized light may be used. In addition, when the radiation used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction, or a combination of these directions may be used for irradiation. In the case of irradiating non-polarized light, the direction of irradiation is set to an oblique direction.

As the light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and the like can be used. Ultraviolet rays in a preferred wavelength region can be obtained by a method in which a light source is used in combination with, for example, a filter, a diffraction grating, and the like. Light irradiation amount is preferably ^{100J / m 2 ~ 50,000J / m} 2, and more preferably ^{300J / m 2 ~ 20,000J / m} 2. In addition, as for 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 during heating is usually 30 ° C to 250 ° C, preferably 40 ° C to 200 ° C, and more preferably 50 ° C to 150 ° C.

In addition, the liquid crystal alignment film after the rubbing treatment may be further subjected to the following treatment to make the liquid crystal alignment film have different liquid crystal alignment ability in each region. The processing is: irradiating a part of the liquid crystal alignment film with radiation, thereby making A process for 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, rubbing the resist film in a direction different from the previous rubbing treatment, and then removing the resist film deal with. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved.

When manufacturing a polymer sustained alignment (PSA) type liquid crystal display device, the following step (3) may be performed by directly using the coating film formed in the step (1), in order to control the liquid crystal The molecules can be collapsed, the orientation can be divided by a simple method, and orientation treatments such as weak friction treatment can also be performed. A liquid crystal alignment film suitable for a VA type liquid crystal display element can also be suitably used for a PSA type liquid crystal display element.

[Step (3): Construction of Liquid Crystal Cell]

(3-A) Prepare two liquid crystal alignment film-formed substrates as described above, and arrange liquid crystal between the two substrates disposed opposite to each other, thereby manufacturing a liquid crystal cell. When manufacturing a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, the two substrates are disposed to face each other with a gap (cell gap) facing each other so that the liquid crystal alignment films face each other. The peripheral portions of the two substrates are bonded together with a sealant, and the substrate surface and the substrate are sealed. The liquid crystal cell is manufactured by injecting and filling liquid crystal into the cell gap divided by the agent and sealing the injection hole. In addition, The second method is a method called a One Drop Fill (ODF) method. For example, a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed is coated with a UV-curable sealant, and then liquid crystal is dripped onto predetermined positions on the liquid crystal alignment film surface. The liquid crystal alignment film is bonded to another substrate in such a manner that the liquid crystal is spread on the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, thereby manufacturing a liquid crystal cell. In any case, it is desirable to further heat the liquid crystal cell manufactured as described above to a temperature at which the liquid crystal used obtains an isotropic phase, and then slowly cool to room temperature to remove the liquid crystal filling. Flow orientation.

As the sealant, for example, an epoxy resin containing a hardener and alumina balls as a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azoxy liquid crystals, and biphenyl liquid crystals can be used. Liquid crystal, phenylcyclohexane-based liquid crystal, ester-based liquid crystal, terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, and cubane-based liquid crystal Wait. In addition, these liquid crystals may be added with the following substances: for example, cholesterol liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, and cholesterol carbonate; such as "C-15", "C-15" CB-15 "(manufactured by Merck); chiral agent sold; p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate (p-decyloxybenzylidene-p-amino- 2-methylbutylcinnamate) and other ferroelectric liquid crystals.

(3-B) When manufacturing a PSA liquid crystal display element, a liquid crystal cell is constructed in the same manner as in (3-A) except that a photopolymerizable compound is injected or dropped together with the liquid crystal. Then, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films included in the pair of substrates. Here, the applied voltage can be, for example, 5V to 50V DC or AC. In addition, as the 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, and ultraviolet rays including light having a wavelength of 300 nm to 400 nm can be preferably used. 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. The ultraviolet rays in the preferred wavelength region can be obtained by a method in which a light source is used in combination with, for example, a filter, a diffraction grating, and the like. The irradiation amount of light is preferably 1,000 J / m ² or more and less than 200,000 J / m ² , and more preferably 1,000 J / m ² to 100,000 J / m ² .

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

Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell, thereby obtaining a liquid crystal display element. As a polarizing plate attached to the outer surface of a liquid crystal cell, Examples include a polarizing plate formed by sandwiching a polarizing film called an "H film" using a cellulose acetate protective film while extending the orientation of polyvinyl alcohol while absorbing iodine, or polarizing light including the H film itself. board.

The liquid crystal display element of the present invention can be effectively applied to various devices, such as a clock, a portable game machine, a word processor, a notebook computer, a car navigation system, a camcorder, and a personal digital assistant. (Personal Digital Assistant (PDA)), digital cameras (digital cameras), mobile phones, smartphones, various monitors, LCD TVs, information displays and other display devices.

[Example]

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to these examples.

In the following examples, the weight average molecular weight Mw of the polymer, the fluorenimidization ratio, the solution viscosity of the polymer solution, and the epoxy equivalent were measured by the following methods. In addition, hereinafter, the compound represented by Formula X may be simply referred to as "compound X".

[Polymer average molecular weight Mw]

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

Column: made by Tosoh Co., Ltd., TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / cm ²

[Polyhydrazone imidization rate of polymer]

The solution containing polyfluoreneimide was poured into pure water, and the obtained precipitate was dried under reduced pressure at room temperature, and then dissolved in deuterated dimethylsulfine, and tetramethylsilane was used as a standard substance at room temperature. ¹ H-NMR was measured next. Based on the obtained ¹ H-NMR spectrum, the fluorene imidization ratio was determined using the following formula (1).

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

(In formula (1), A ¹ is the peak area of NH-derived protons occurring near the chemical shift of 10 ppm, A ² is the peak area of other protons, and α is the precursor of the polymer (polyamine The proportion of other protons in the acid) relative to one proton of the NH group)

[Epoxy equivalent]

The epoxy equivalent is measured by the hydrochloric acid-methyl ethyl ketone method described in Japanese Industrial Standards (JIS) C 2105.

<Synthesis of Compound>

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

Compound (a-1) was synthesized according to the following scheme 1.

[Chemical 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, it was cooled to 0 ° C, and 23.0 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 2.44 g of N, N-dimethylaminopyridine were added thereto. Stir for 20 hours at room temperature. Then, the reaction solution was separated and washed three times with 800 mL of water, and then the organic layer was dried with magnesium sulfate. Then, the content was gradually concentrated by a rotary evaporator until the content became 200 g, and the white solid precipitated in the middle was recovered by filtration. This white solid was vacuum-dried to obtain 37.4 g of a compound (a-1-1).

． Synthesis of compound (a-1-2)

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

． Synthesis of compound (a-1)

21.6 g of compound (a-2-1), 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 by dropwise addition, and the mixture was stirred at room temperature. After 3 hours, the reaction solution was filtered through diatomaceous earth, 300 g of ethyl acetate was added to the filtrate, and the solution was separated and washed three times with 200 mL of water. Then, the organic layer was concentrated and dried using a rotary evaporator. The obtained residue was recrystallized with ethanol to obtain 13.4 g of a compound (a-1).

[Synthesis Example 1-2: Synthesis of Compound (a-2)]

Compound (a-2) was synthesized according to the following scheme 2.

． Synthesis of compound (a-2-1)

Using 4-bromobenzoic acid and 4- (4-pentylcyclohexyl) aniline as the starting materials, compound (a-2-1) was obtained using the same synthetic formula as compound (a-1-1).

． Synthesis of compound (a-2-2)

Compound (a-2-1) was used in place of compound (a-1-1), and compound (a-2-2) was obtained by using the same synthetic formula 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 A 500 mL three-necked flask equipped with a stirrer was replaced with nitrogen three times. 80 g of tetrahydrofuran bubbled with nitrogen and 80 g of water were added thereto, and the mixture was stirred at 60 ° C. for 3 hours. The reaction solution was filtered through diatomaceous earth, 200 g of ethyl acetate was added to the filtrate, and the solution was separated and washed three times with 150 mL of water. Then, the concentration was gradually concentrated using a rotary evaporator until the content became 50 g, and the white solid precipitated in the middle was recovered by filtration. This white solid was vacuum-dried to obtain 15.9 g of a compound (a-2).

[Synthesis Example 1-3: Synthesis of Compound (a-3)]

Compound (a-3) was synthesized according to the following scheme 3.

[Chemical 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 the following scheme 4.

． Synthesis of compound (a-4-1)

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

． Synthesis of compound (a-4-2)

Compound (a-4-2) was obtained using β-cholestanol and compound (a-4-1) as starting materials, and using the same synthetic formula as compound (a-1-1).

． Synthesis of compound (a-4-3)

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

． Synthesis of compound (a-4)

Using compound (a-4-3) as an initial substance, compound (a-4) was obtained using the same synthetic formula as compound (a-1).

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

Compound (a-5) was synthesized according to the following scheme 5.

[Chemical 31]

． Synthesis of compound (a-5-1)

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

Take 16.4 g of 4-hydroxycinnamic acid and 8 g of sodium hydroxide into a 2000 mL three-necked flask equipped with a stirrer, add 500 g of water, and cool to 0 ° C. Solution A was added dropwise thereto over 30 minutes, and stirred at room temperature for 5 hours. Then, the reaction solution was separated and washed three times with 400 mL of water, and then the organic layer was dried with magnesium sulfate. Then, the concentration was gradually concentrated using a rotary evaporator until the content became 50 g, and the white solid precipitated in the middle was recovered by filtration. This white solid was vacuum-dried to obtain 31.9 g of a compound (a-5-1).

． Synthesis of compound (a-5-2)

Using compound (a-5-1) and 3,5-dinitroaniline as starting materials, The compound (a-5-2) was obtained by the same synthetic formula as the compound (a-1-1).

． Synthesis of compound (a-5-3)

Using compound (a-5-2) as an initial substance, compound (a-5-3) was obtained using the same synthetic formula as compound (a-1-2).

． Synthesis of compound (a-5)

Using compound (a-5-3) as an initial substance, compound (a-5) was obtained using the same synthetic formula as compound (a-1).

[Synthesis Example 1-6: Synthesis of compound (a-6)]

Compound (a-6) was synthesized according to the following scheme 6.

Using 4- (4'-pentyl- [1,1'-bis (cyclohexane)]-4-yl) benzoic acid and 4'-hydroxyazobenzene-4-carboxylic acid as the starting materials, (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 the following scheme 7.

． Synthesis of compound (a-7-1)

Take 18.6 g of 4-fluoro-1,3-dinitrobenzene and 24.5 g of 4- (4-pentylcyclohexyl) aniline into a 2000 mL eggplant-shaped flask with a stirrer, and add 1000 g of tetrahydrofuran and triethylamine 15.2 g, refluxed for 10 hours. 1200 g of ethyl acetate was added to the reaction solution, and the solution was separated and washed three times with 1,000 mL of water. Thereafter, the concentration was gradually concentrated by a rotary evaporator until the content became 200 g, and the yellow solid precipitated in the middle was recovered by filtration. This yellow solid was vacuum-dried to obtain 38.3 g of a compound (a-7-1).

． Synthesis of compound (a-7-2)

Using compound (a-7-1) as an initial substance, compound (a-7-2) was obtained using the same synthetic formula as compound (a-1-2).

． Synthesis of compound (a-7)

Using compound (a-7-2) as an initial substance, compound (a-7) was obtained using the same synthetic formula as compound (a-1).

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

Using compound 4- (4,4,4-trifluorobutyl) cyclohexanecarboxylic acid as an initial substance, compound (a-9) was obtained using the same synthetic formula as compound (a-5) of Scheme 5.

<Synthesis of Polymer>

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

100 mol parts of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 20 mol parts of compound (a-1) as diamine, and 80 mol of p-phenylenediamine Parts were dissolved in N-methyl-2-pyrrolidone (NMP) and reacted at room temperature for 6 hours to obtain a solution containing 20% by weight of polyamic acid. Here, the obtained polyamic acid is referred to as a polymer (PA-1).

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

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

In Table 1, the numerical values in () of the diamine and the acid dianhydride represent the use ratio [mole part] with respect to the total 100 mole parts of the tetracarboxylic dianhydride used to synthesize the polymer. The abbreviations of the acid anhydride and diamine 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-cyclobutane tetracarboxylic dianhydride

t-4: pyromellitic dianhydride

<Diamine>

a-8: Compound represented by the following formula (a-8)

b-1: Compound represented by the following formula (b-1)

b-2: Compound represented by the following formula (b-2)

b-3: Compound represented by the following formula (b-3)

b-5: Compound represented by the following formula (b-5)

b-6: Compound represented by the following formula (b-6)

b-7: Compound represented by the following formula (b-7)

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

b-9: Compound represented by the following formula (b-9)

d-1: p-phenylenediamine

d-2: 3,5-diaminobenzoic acid

d-3: Compound represented by the following formula (d-3)

[Chemical 35]

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

A polycarboxylic acid was synthesized in the same manner as in Synthesis Example 2-1 except that the types and amounts of tetracarboxylic dianhydride and diamine used were changed as in Table 1 described above. Next, pyridine and acetic anhydride were added to the obtained polyfluorenic acid solution to perform chemical hydration. The reaction solution after chemical imidization was concentrated and prepared by NMP so that the concentration became 10% by weight. The obtained polymer (PI-1) had a sulfonium imidization ratio of about 30%.

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

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone, and triethyl 10.0 g of amine was mixed at room temperature. Then, 100 g of deionized water was added dropwise from a dropping funnel over 30 minutes, and then mixed under reflux and reacted at 80 ° C. for 6 hours. After the reaction, the organic layer was extracted and 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 a polyorganic organic compound as a thick transparent liquid. Siloxane (EPS-1). As a result of ¹ H-NMR analysis of this polyorganosiloxane (EPS-1), it was confirmed that a peak based on an oxetanyl group was obtained at a chemical shift (δ) = 3.2 ppm in the same manner as the theoretical intensity, and No side reaction of the epoxy group is caused in the reaction. Polyorganosiloxane (EPS-1) had a Mw of 2,200 and an epoxy equivalent of 186 g / mole.

[Synthesis Example 2-14: Synthesis of polyorganosiloxane (PS-1) containing specific group]

In a 100 mL three-necked flask, 2.3 g of polyorganosiloxane (EPS-1) synthesized in Synthesis Example 2-13, 11.1 g of cyclopentanone, and 1.1 g of compound (a-2) (corresponding to the relative 30 mol% of silicon atoms in 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 generate a precipitate. The solution obtained by dissolving the precipitate in ethyl acetate was washed three times with water, and then the solvent was distilled off to obtain a polyorganosiloxane (PS -1) white powder. Weight average of polyorganosiloxane (PS-1) The molecular weight is 2,700.

[Synthesis example 2-15 to synthesis example 2-18]

The types and amounts of the compounds to be used are as shown in Table 2 below, and polyorganosiloxanes containing specific groups (PS- 2) ~ Polyorganosiloxane containing specific groups (PS-4) and Polyorganosiloxane containing specific groups (Rs-1).

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 polyorganosiloxane containing an epoxy group has.

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

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

[Example 1]

(1) Preparation of liquid crystal aligning agent

To the polymer (PA-1) obtained in Synthesis Example 2-1 as a polymer, NMP and butyl cellosolve (BC) as organic solvents were added to prepare The solvent composition was a solution of NMP: BC = 50: 50 (weight ratio) and solid content concentration of 5.0% by weight. This solution was filtered using a sieve with a pore size of 1 μm to prepare a liquid crystal aligning agent (D-1).

(2) Manufacturing of liquid crystal display elements

A glass substrate having transparent electrodes (electrode A and electrode B) of two systems including an ITO film on one surface was used as a pair of substrates, and the liquid crystal aligning agent prepared in the above was coated on the pair of glass substrates using a spinner ( D-1) After pre-baking on a hot plate at 80 ° C. for 1 minute, post-baking on a hot plate at 230 ° C. for 10 minutes to form a coating film having a film thickness of about 0.08 μm. Next, the outer edge of the surface having the liquid crystal alignment film of any of the substrates was coated with an epoxy resin adhesive in which alumina balls having a diameter of 5.5 μm were added, and the two substrates were arranged to face each other with a gap therebetween, and the outer edge portions were placed on each other. Abutment is performed for crimping and curing the adhesive. Then, a nematic liquid crystal (Merck, MLC-6608, manufactured by Merck) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic light-curing adhesive.

3) Evaluation of burning characteristics (AC afterimage characteristics)

The liquid crystal display element manufactured in the above was placed in an environment of 25 ° C. and one atmospheric pressure, and no voltage was applied to the electrode B, and a combined voltage of an AC voltage of 3.5 V and a DC voltage of 5 V was applied to the electrode A for 2 hours. Immediately thereafter, a voltage of 4 V AC was applied to both the electrode A and the electrode B. The time from the moment when the voltage of 4V AC was applied to both electrodes was measured until the difference in the light transmittance of electrode A and electrode B could not be confirmed visually. A case where the time was less than 20 seconds was evaluated as a "good 1 (◎)" in the burning characteristic; and a case where 20 seconds or more and less than 60 seconds was evaluated as a "good" in the burning characteristic. Good 2 (○) "; the case of 60 seconds or more and less than 100 seconds was evaluated as the burning characteristic" may 1 (△) "; the case of 100 seconds or more and less than 150 seconds was evaluated as the burning characteristic" may 2 (△ Δ) "; Furthermore, the case of exceeding 150 seconds was evaluated as the" bad (x) "in the burning characteristic, and as a result, the burning characteristic of the liquid crystal display element was" good 1 (◎) ".

(4) Evaluation of printability after standing time

The liquid crystal aligning agent (D-1) prepared as described above was applied on a transparent electrode surface of a glass substrate with a transparent electrode including an ITO film using a liquid crystal alignment film printer (manufactured by Japan Photo Printing (Stock)). After standing for 30 minutes, heating (pre-baking) was performed on a hot plate at 80 ° C. for 1 minute to remove the solvent. Then, heating (post-baking) was performed on a hot plate at 200 ° C. for 10 minutes to form a coating film having an average film thickness of 0.06 μm. This coating film was observed with a microscope with a magnification of 20 times to investigate the presence of uneven printing and pinholes. In addition, the lower the solubility of the polymer in the solvent, the more likely it is that printing unevenness and pinholes occur during standing time. Regarding the evaluation, the printability "good (○)" was observed when printing unevenness and pinholes were hardly observed after the elapse of the standing time, and the printability was observed when printing unevenness and pinholes were slightly observed. "(Δ)", and a case where at least any one of uneven printing and pinholes was clearly observed was defined as printability "poor (x)". As a result, the printability of this example was "good (○)".

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

A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the types and amounts of the polymers used were as described in Table 3 below. Moreover, using the prepared liquid crystal aligning agent, it carried out similarly to the said Example 1, and performed various evaluation. These results are shown in Table 3 below.

In Table 3, the numerical value of the blending ratio of the polymer is expressed relative to the liquid crystal aligning agent. The blending ratio [parts by weight] of each polymer in total 100 parts by weight of the polymer components used in the preparation.

[Example 10]

(1) Preparation of liquid crystal aligning agent

NMP and butyl cellosolve (BC) as organic solvents were added to the polymer (PA-5) obtained in Synthesis Example 2-5 as a polymer, and the solvent composition was NMP: BC = 50: 50 ( Weight ratio) and a solid content concentration of 5.0% by weight. This solution was filtered using a sieve with a pore size of 1 μm to prepare a liquid crystal aligning agent (D-10).

(2) Manufacturing of liquid crystal display elements

Using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.), the liquid crystal alignment agent (D-10) prepared in the above was applied to a pair of ITO electrodes (electrode A and electrode B) each having two systems. Each electrode surface of the glass substrate was heated (pre-baked) on a hot plate at 80 ° C for 1 minute to remove the solvent, and then heated (post-baked) on a hot plate at 200 ° C for 10 minutes to form an average film. A coating film having a thickness of 600 Å, the ITO electrodes (electrode A and electrode B) of the two systems were patterned into stripes as shown in FIG. 1 and divided into a plurality of regions. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then, it was dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two sheets) of substrates having a liquid crystal alignment film.

Next, on one of the pair of substrates, an epoxy resin adhesive having alumina balls having a diameter of 5.5 μm was applied to the outer edge of the surface having the liquid crystal alignment film, and then the pair of substrates were aligned with the liquid crystal alignment film. The opposing methods are overlapped and crimped, and the adhesive is hardened. Next, a nematic liquid crystal (Merck, MLC-6608, manufactured by Merck, Inc.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic light-curing adhesive to produce a liquid crystal cell. The obtained liquid crystal cell was irradiated with ultraviolet rays at an irradiation amount of 10,000 J / m ² using an ultraviolet irradiation device using a metal halide lamp as a light source in a state where an alternating current of 10 Hz with a frequency of 60 Hz was applied between the electrodes and the liquid crystal was driven. It should be noted that the irradiation amount is a value obtained by measuring using a light quantity meter that measures with a wavelength of 365 nm as a standard.

(3) Evaluation of burning characteristics (AC afterimage characteristics)

The liquid crystal display element manufactured as described above was placed in an environment of 25 ° C. and one atmospheric pressure, no voltage was applied to the electrode B, and an AC voltage of 10 V was applied to the electrode A for 300 hours. Immediately after 300 hours, a voltage of 3 V AC was applied to both the electrode A and the electrode B, and the difference in light transmittance ΔT [%] between the two electrodes was measured. At this time, the case where ΔT is less than 2% is evaluated as the AC afterimage characteristic "Good 1 (◎)"; the case where 2% or more and less than 3% is evaluated as the afterimage characteristic "Good 2 (○)"; 3 A case where the percentage is more than 4% and less than 4% is evaluated as an afterimage characteristic “OK (Δ)”; a case where 4% or more is evaluated as the afterimage characteristic “bad (×)”. Results In this example, the evaluation was "Good 1 (◎)".

(4) Evaluation of printability after standing time

Using the liquid crystal aligning agent (D-10) prepared as described above, the operation was performed in the same manner as in Example 1, and the printability after the elapse of the standing time was evaluated. As a result, the printability was "good (○)" in this example.

Based on the results of these Examples 1 to 11, it has In the polymer liquid crystal aligning agent having a fixed partial structure, printability is also good when a standing time of 30 minutes is set after coating the substrate. This suggests that the polymer (P) has high solubility in a solvent.

In addition, the burn-in characteristics (AC afterimage characteristics) of the liquid crystal display element were also good. Based on this result, it is presumed that the protective group introduced into the polymer is detached by heating during post-baking, whereby the polymer side chain after 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 burning characteristics and printability was inferior to that in the example.

Claims (8)

A liquid crystal aligning agent comprising a polymer (P) having a partial structure represented by the following formula (1-1) or formula (1-2),

In the formulae (1-1) and (1-2), A ¹ and A ² are a single bond or a divalent linking group, R ¹ and R ² are monovalent organic groups having a carbon number of 10 or more; X ¹ Is a protecting group; "*" indicates a bonding bond to the polymer's main chain. The liquid crystal aligning agent according to item 1 of the scope of patent application, wherein R ¹ and R ² are groups represented by the following formula (2), and * -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. The liquid crystal aligning agent according to claim 1 or claim 2, wherein the polymer (P) is selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyorganosiloxane. At least one of the groups consisting of alkanes. A liquid crystal aligning film, which is formed by using the liquid crystal aligning agent according to any one of claims 1 to 3 of the scope of patent application. A liquid crystal display element comprising the liquid crystal alignment film according to item 4 of the scope of patent application. A polymer characterized by having a partial structure represented by the following formula (1-1) or formula (1-2),

In the formulae (1-1) and (1-2), A ¹ and A ² are a single bond or a divalent linking group, R ¹ and R ² are monovalent organic groups having a carbon number of 10 or more; X ¹ Is a protecting group; "*" indicates a bonding bond to the polymer's main chain. A compound characterized by the following formula (3-1) or (3-2):

In the formulae (3-1) and (3-2), A ¹ and A ² are a single bond or a divalent linking group, R ¹ and R ² are monovalent organic groups having a carbon number of 10 or more; X ¹ Protective group. A compound characterized by the following formula (4-1) or (4-2):

In the formulae (4-1) and (4-2), A ⁴ is a divalent organic group, R ¹ and R ² are monovalent organic groups having a carbon number of 8 or more, and X ¹ is a protecting group.