TW202003818A - Liquid crystal orientation agent, liquid crystal orientation film, and liquid crystal element - Google Patents

Abstract

This liquid crystal orientation agent comprises a first polymer, a second polymer, and a compound (A). The first polymer has an acid functional group. The compound (A) has at least one nitrogen-containing structure selected from the group consisting of a partial structure represented by formula (1-1), a partial structure represented by formula (1-2), a partial structure represented by formula (3), and a partial structure represented by formula (1-4) (excluding a nitrogen-containing aromatic heterocycle which has at least one of the partial structure represented by formula (1-2) and the partial structure represented by formula (1-3)), and does not have at least one of an acid functional group and an electron withdrawing group. When the compound (A) has the partial structure represented by formula (1-1), the second polymer has a nitrogen-containing aromatic heterocycle.

Description

Liquid crystal alignment agent and manufacturing method thereof, liquid crystal alignment film and manufacturing method thereof, and liquid crystal element

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

Liquid crystal elements are widely used in televisions, mobile devices, and various monitors. In addition, in the liquid crystal element, a liquid crystal alignment film is used to control the alignment of the liquid crystal molecules in the liquid crystal cell. The liquid crystal alignment film is usually formed using a polymer composition (liquid crystal alignment agent) in which a polymer component is dissolved in a solvent. As a method for obtaining an organic film having a liquid crystal alignment restricting force, a method of rubbing an organic film, a method of oblique evaporation of silicon oxide, a method of forming a monomolecular film having a long-chain alkyl group, and A method of irradiating light to a photosensitive organic film (light alignment method) and the like.

In recent years, in order to further improve the performance of liquid crystal elements, various liquid crystal alignment agents have been proposed by setting the polymer component to two or more blends or improving the monomer structure (for example, refer to the patent Document 1 to Patent Document 3). Patent Document 1 proposes a liquid crystal aligning agent comprising polyamic acid ester and polyamic acid as a polymer component, and the weight average molecular weight of the polyamic acid ester is smaller than the weight average molecular weight of the polyamic acid. According to the liquid crystal alignment agent described in Patent Document 1, it is described that fine irregularities generated on the film surface of the liquid crystal alignment film are reduced, and the liquid crystal alignment and electrical characteristics in the liquid crystal display element can be improved.

In addition, Patent Document 2 proposes to include a polyamic acid or polyimide obtained by using 4,4′-diaminodiphenylamine in the liquid crystal alignment agent, thereby achieving improvement in voltage retention characteristics or afterimages cut back. Patent Document 3 discloses that a liquid crystal alignment agent contains a polyimide precursor or a polyimide obtained by using a diamine having a urea bond, thereby obtaining good liquid crystal alignment, friction resistance, and charge accumulation Less liquid crystal alignment film. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 2011/115078 [Patent Document 2] Japanese Patent No. 4052307 [Patent Document 3] International Publication No. 2013/008906

[Problems to be solved by the invention]

In the case of obtaining a liquid crystal alignment film by optical alignment processing, there is a tendency that the alignment restricting force of liquid crystal molecules is insufficient compared to the rubbing processing, and an afterimage called an alternating current (AC) afterimage is likely to occur shadow. The AC afterimage is an afterimage that is generated due to the direction of the initial alignment deviating from the original direction of manufacture of the liquid crystal element due to the long-term driving of the liquid crystal element. As a liquid crystal element, in order to meet the demand for higher performance in recent years, it is desired to sufficiently reduce AC residual images.

The present invention was made in view of the above-mentioned problems, and one of the objects is to provide a liquid crystal alignment agent that can obtain a liquid crystal element with good liquid crystal alignment and good AC afterimage characteristics. [Means to solve the problem]

The present invention adopts the following means to solve the above-mentioned problems.

（式（1-1）中，關於R¹ 及R² ，R¹ 為藉由氮原子或氧原子而鍵結於吡啶環的一價基團，且R² 為一價有機基，或者R¹ 及R² 表示R¹ （其中，R¹ 藉由氮原子或氧原子而鍵結於吡啶環）與R² 相互結合並與R¹ 及R² 分別所鍵結的碳原子一同構成的環結構。m為1～3的整數，n為0～2的整數，m+n≦3。於m為2或3的情況下，多個R¹ 可相同亦可不同，於n為2的情況下，多個R² 可相同亦可不同。式（1-4）中，R³ 為碳數1～5的烷基。r為0～3的整數。於r為2或3的情況下，多個R³ 可相同亦可不同。式（1-1）～式（1-4）中的「*」表示結合鍵） ＜2＞ 一種液晶配向劑的製造方法，其包括將所述第1聚合體、所述第2聚合體、及所述化合物（A）混合的步驟。 ＜3＞ 一種液晶配向膜的製造方法，其使用所述＜1＞的液晶配向劑於基板上形成塗膜，對所述塗膜進行光照射而賦予液晶配向能力。 ＜4＞ 一種液晶配向膜，其是使用所述＜1＞的液晶配向劑而形成。 ＜5＞ 一種液晶元件，其包括所述＜4＞的液晶配向膜。 [發明的效果]<1> A liquid crystal alignment agent comprising: a first polymer, a second polymer, and a compound (A), and the first polymer has an acidic functional group, and the second polymer is 1 Polymers Different polymers, the compound (A) has a partial structure selected from the following formula (1-1), a partial structure represented by the following formula (1-2), and the following formula ( 1-3) the partial structure represented by, and at least one nitrogen-containing structure in the group consisting of the partial structure represented by the following formula (1-4) (wherein the following formula (1-2) will be included Except for the partial structure represented by and at least any of the partial structures represented by the following formula (1-3) except for the nitrogen-containing aromatic heterocyclic ring), and does not have at least one of an acidic functional group and an electron-withdrawing group Compound (wherein, when the compound (A) has a partial structure represented by the following formula (1-1), the second polymer has a nitrogen-containing aromatic heterocycle). [Chemical 1]

(In formula (1-1), regarding R ¹ and R ² , R ¹ is a monovalent group bonded to a pyridine ring via a nitrogen atom or an oxygen atom, and R ² is a monovalent organic group, or R ¹ And R ² represents R ¹ (wherein R ¹ is bonded to a pyridine ring through a nitrogen atom or an oxygen atom) and R ² are bonded to each other and constitute a ring structure together with the carbon atoms to which R ¹ and R ² are respectively bonded. m is an integer of 1 to 3, n is an integer of 0 to 2, m+n≦3. When m is 2 or 3, a plurality of R ¹ may be the same or different, and when n is 2, Multiple R ² may be the same or different. In formula (1-4), R ³ is an alkyl group having 1 to 5 carbon atoms. r is an integer of 0 to 3. When r is 2 or 3, multiple R ³ may be the same or different. "*" in the formula (1-1) to the formula (1-4) represents a bonding bond) <2> A method for manufacturing a liquid crystal alignment agent, which includes the first polymer Step of mixing the second polymer and the compound (A). <3> A method for manufacturing a liquid crystal alignment film, which uses the liquid crystal alignment agent of <1> to form a coating film on a substrate, and irradiates the coating film with light to impart liquid crystal alignment capability. <4> A liquid crystal alignment film formed using the liquid crystal alignment agent of <1>. <5> A liquid crystal element comprising the liquid crystal alignment film of <4>. [Effect of invention]

According to the liquid crystal alignment agent of the present invention, a liquid crystal alignment agent containing a first polymer having an acidic functional group and a second polymer different from the first polymer contains a specific basic compound, thereby obtaining liquid crystal alignment A liquid crystal element with good performance and afterimage characteristics (especially AC afterimage characteristics).

Hereinafter, each component included in the liquid crystal alignment agent and other components arbitrarily blended as necessary will be described. The liquid crystal alignment agent contains a polymer component and the compound (A). The liquid crystal alignment agent can be obtained by mixing the polymer component and the compound (A), and is preferably a liquid polymer composition obtained by dissolving the polymer component in a solvent.

＜＜Polymer component＞＞ The liquid crystal alignment agent contains a first polymer and a second polymer different from the first polymer as a polymer component. The first polymer has an acidic functional group. The acidic functional group is a functional group capable of releasing hydrogen ions in an aqueous solution. Specific examples thereof include a carboxylic acid group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group, a phosphorous acid group, and a phosphonic acid group. . Among these, a carboxylic acid group is preferable in terms of easy introduction into a polymer and a point in which a liquid crystal alignment effect improvement effect by the addition of the compound (A) is higher. In addition, the second polymer only needs to be a polymer different from the first polymer, and the case where the second polymer has an acidic functional group is not excluded.

The first polymer and the second polymer are preferably polymers having different acidities. Specifically, the first polymer is preferably higher in acidity than the second polymer. In this case, the first polymer with higher acidity (lower alkalinity) tends to exist in the lower layer, and the second polymer with lower acidity (higher alkalinity) tends to exist in the upper layer, which can improve The phase separation of polymer components is preferable in this respect. Examples of the combination of the first polymer and the second polymer include the following aspects 1 and 2. (Aspect 1) The number of acidic functional groups is different from that of the first polymer and the second polymer, and the number of acidic functional groups of the first polymer is larger than that of the second polymer. (Aspect 2) The number of basic functional groups is different from that of the first polymer and the second polymer, and the number of basic functional groups of the second polymer is larger than that of the first polymer.

（式（4）中，X¹ 為四價有機基，X² 為二價有機基）The main skeleton of the first polymer and the second polymer is not particularly limited, and examples thereof include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide, Polyamidimide, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, styrene-maleimide copolymer, poly(methyl) Polymers such as acrylic esters as the main skeleton. In addition, (meth)acrylate is meant to include acrylate and methacrylate. Among these, the first polymer is preferably selected from having a partial structure represented by the following formula (4) in terms of higher improvement effect of liquid crystal alignment and reduction of afterimage in the obtained liquid crystal element Composed of polymers (including polyamic acid, polyamic acid ester, and polyimide), polyorganosiloxanes, and polymers having structural units derived from monomers having polymerizable unsaturated bonds At least one of the groups of is more preferably a polymer having a partial structure represented by the following formula (4). Among these, the first polymer is preferably at least one kind selected from the group consisting of polyamic acid and polyimide having an imidization ratio of 80% or less, and particularly preferably polyamic acid. [Chem 2]

(In formula (4), X ¹ is a tetravalent organic group, X ² is a divalent organic group)

On the other hand, in terms of sufficiently improving various properties of the obtained liquid crystal element, the second polymer is preferably selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyorganosilicon At least one polymer from the group consisting of an oxane and a polymer having a structural unit derived from a monomer having a polymerizable unsaturated bond is particularly preferably selected from the group consisting of polyamic acid, polyamic acid ester, At least one of the group consisting of polyimide and polyorganosiloxane.

(Polyamide) When the first polymer and the second polymer are polyamic acid, the polyamic acid can be obtained by reacting tetracarboxylic dianhydride and a diamine compound. In addition, in the formula (4), X ¹ is a tetravalent group derived from tetracarboxylic dianhydride, and X ² is a divalent group derived from a diamine compound.

(Tetracarboxylic dianhydride) Examples of the tetracarboxylic dianhydride used in the synthesis of polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. . As specific examples of these, aliphatic tetracarboxylic dianhydrides include, for example, 1,2,3,4-butane tetracarboxylic dianhydride and the like; and alicyclic tetracarboxylic dianhydrides include, for example: 1,2 ,3,4-Cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl Acetic 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), 2,4,6,8-tetracarboxybicyclic [3.3.0] Octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraone , Cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc.; for example, aromatic tetracarboxylic dianhydride: pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene ) Diphthalic anhydride, ethylene glycol bistrimellitic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'-carbonyl diphthalic anhydride, etc. In addition to this, the tetracarboxylic dianhydride and the like described in Japanese Patent Laid-Open No. 2010-97188 can also be used. Furthermore, the tetracarboxylic dianhydride can be used alone or in combination of two or more.

（式（E-1）中，X^I 及X^II 分別獨立地為單鍵、-O-、*-COO-或*-OCO-（其中，「*」表示與X^I 的結合鍵），R^I 為碳數1～3的烷二基，R^II 為單鍵或碳數1～3的烷二基，a為0或1，b為0～2的整數，c為1～20的整數，d為0或1。其中，a及b不會同時成為0）；(Diamine compound) Examples of the diamine compound used in the synthesis of polyamic acid include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamine-based organosiloxanes. As specific examples of these diamine compounds, aliphatic diamines include, for example, m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylene Diamines, etc.; alicyclic diamines, for example: 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), etc.; aromatic diamines, for example: twelve Alkoxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2 ,4-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholesteryloxy-3,5-diamine Benzene, cholestenyloxy-3,5-diaminobenzene, cholestoxy-2,4-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, 3, 5-Diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lansteryl alkyl ester, 3,6-bis(4 -Aminobenzyloxy)cholesterane, 3,6-bis(4-aminophenoxy)cholestane, 2,4-diamino-N,N-diallylaniline, 4-(4'-trifluoromethoxybenzyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl) Phenyl)-4-butylcyclohexane, 3,5-diaminobenzoic acid=5ξ-cholestan-3-yl, the compound represented by the following formula (E-1), the side chain has cinnamic acid Structured diamines and other side chain diamines: [Chem 3]

(In formula (E-1), X ^I and X ^II are independently a single bond, -O-, *-COO- or *-OCO- (where "*" represents a bond with X ^I ), R ^I is an alkanediyl group having 1 to 3 carbon atoms, R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, and c is an integer of 1 to 20, d is 0 or 1. Among them, a and b will not become 0 at the same time;

P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4-aminobenzoate, 4, 4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy) ) Ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,6-bis(4-aminophenoxy) ) Hexane, 1,7-bis(4-aminophenoxy)heptane, 1,10-bis(4-aminophenoxy)decane, 1,2-bis(4-aminophenyl) ) Ethane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1,4-bis(4-aminophenylsulfonamide) Group) butane, bis[2-(4-aminophenyl)ethyl]adipic acid, N,N-bis(4-aminophenyl)methylamine, 2,6-diaminopyridine, 1,4-bis-(4-aminophenyl)-piperazine, N,N'-bis(4-aminophenyl)-benzidine, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4 -(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylene diisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-[4,4'-propane-1,3 -Diylbis(piperidine-1,4-diyl)] diphenylamine, 4,4'-diaminobenzylanilide, 4,4'-diaminodiphenylamine, 1,3-bis (4-Aminophenethyl)urea, 1,3-bis(4-aminobenzyl)urea, 1,4-bis(4-aminophenyl)-piperazine, N-(4-amino Phenylethyl)-N-methylamine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine and other main chain diamines, etc.; diamine-based silicone Examples of the oxane include 1,3-bis(3-aminopropyl)-tetramethyldisilaxane, etc. In addition, the diamine described in Japanese Patent Laid-Open No. 2010-97188 can also be used .

When synthesizing a polyamic acid, by using a diamine containing a carboxylic acid group, a kind obtained by the condensation reaction of a tetracarboxylic dianhydride and a diamine compound can be obtained A polymer of different carboxylic acid groups. Specific examples of the carboxylic acid group-containing diamine include, for example, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, and 4,4' -Diaminobiphenyl-2,2'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl ether -3,3'-dicarboxylic acid, etc. When synthesizing polyamic acid, in the case of using a carboxylic acid group-containing diamine, the use ratio thereof is preferably set to 1 mole relative to the total amount of the diamine compound used in the synthesis of polyamic acid % Or more, more preferably 10 mol% to 60 mol%. Furthermore, the carboxylic acid group-containing diamine may be used alone or in combination of two or more.

(Synthesis of Polyamide) Polyamic acid can be obtained by reacting the tetracarboxylic dianhydride and the diamine compound as described above together with a molecular weight modifier as needed. The use ratio of the tetracarboxylic dianhydride and the diamine compound used for the synthesis reaction of the polyamic acid is preferably 1 equivalent to the amine group of the diamine compound and the acid anhydride group of the tetracarboxylic dianhydride becomes 0.2 equivalent to 2 Equivalent ratio. Examples of the molecular weight regulator include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; phenyl isocyanate and isocyanic acid Monoisocyanate compounds such as naphthyl ester and the like. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less based on 100 parts by mass of the total of the tetracarboxylic dianhydride and the diamine compound used.

The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours. Examples of the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. A particularly preferred organic solvent is preferably selected from N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, One or more of the group consisting of γ-butyrolactone, tetramethylurea, hexamethylphosphoryltriamine, m-cresol, xylenol, and halogenated phenol as a solvent, or use one or more of these and other A mixture of organic solvents (for example, butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount of use of the organic solvent (a) is preferably the total amount of the tetracarboxylic dianhydride and the diamine compound (b) relative to the total amount of the reaction solution (a+b) to be 0.1% by mass to 50% by mass the amount. In this way, a reaction solution obtained by dissolving polyamide acid can be obtained. The reaction solution can be directly used for the preparation of the liquid crystal alignment agent, or the polyamic acid contained in the reaction solution can be separated and then used for the preparation of the liquid crystal alignment agent.

(Polyimide) When the first polymer and the second polymer are polyimide, the polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid synthesized as described above and subjecting it to imidization. The polyimide contained in the liquid crystal alignment agent of the present invention is, for example, a partial imidate obtained by dehydrating and ring-closing a part of the amic acid structure possessed by the polyamic acid as a precursor thereof. In the case where the first polymer is polyimide, the imidate ratio is preferably 30% to 80%, and more preferably 50% to 75%. In the case where the second polymer is polyimide, the imidate ratio is preferably 30% to 99%, and more preferably 50% to 90%. The imidate ratio is expressed as a percentage of the ratio of the number of amide imide ring structures of the polyimide to the total of the number of amide acid structures and the number of amide imine ring structures. Here, a part of the amide imide ring may be an amide imide ring.

The dehydration and ring closure of the polyamic acid is preferably performed by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating if necessary. In this method, as the dehydrating agent, for example, anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The use amount of the dehydrating agent is preferably 0.01 mol to 20 mol relative to 1 mol of the amide structure of the polyamic acid. For the dehydration ring-closure catalyst, for example, tertiary amines such as pyridine, tripicoline, lutidine, and triethylamine can be used. The use amount of the dehydration closed-loop catalyst is preferably 0.01 mol to 10 mol relative to 1 mol of the dehydration agent used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified as users used in the synthesis of polyamide. The reaction temperature of the dehydration ring-closure reaction is preferably 0°C to 180°C. The reaction time is preferably 1.0 hour to 120 hours. The reaction solution containing polyimide can be directly used for the preparation of the liquid crystal alignment agent, or the polyimide can be separated and then used for the preparation of the liquid crystal alignment agent.

(A polymer having a structural unit derived from a monomer having a polymerizable unsaturated bond) When the first polymer and the second polymer are polymers having a structural unit derived from a monomer having a polymerizable unsaturated bond (hereinafter, also referred to as "polymer (M)"), the polymer has Examples of the monomer having a unsaturated bond include a compound having a polymerizable unsaturated bonding group such as (meth)acryloyl group, vinyl group, styryl group, and maleimide group, and an acidic functional group (hereinafter , Also known as "monomer (m1)"). Specific examples of such compounds include, for example, unsaturated carboxylic acids such as (meth)acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, and vinylbenzoic acid; (E)-3-(4 -((3-((meth)acryloyloxy)propyl)oxy)phenyl)acrylic acid, (E)-3-(4-((6-((meth)acryloyloxy) )Hexyl)oxy)phenyl)acrylic acid, (E)-3-(4-((8-((meth)acryloyloxy)octyl)oxy)phenyl)acrylic acid, etc. Group based unsaturated carboxylic acid; aromatic vinyl compounds such as p-vinylphenol, m-vinylphenol, etc. One type of monomer may be used alone or two or more types may be used in combination.

When synthesizing the polymer (M), the monomer (m1) may be used together with other monomers other than the monomer (m1) as long as the effect of the present invention is not impaired. Specific examples of this other monomer include, for example, alkyl (meth)acrylate, cycloalkyl (meth)acrylate, benzyl (meth)acrylate, and 2-ethyl (meth)acrylate Hexyl ester, trimethoxysilylpropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate Unsaturated carboxylic acid esters such as methyl ester, 3,4-epoxybutyl (meth)acrylate, 4-hydroxybutyl glycidyl acrylate; unsaturated polycarboxylic acid anhydrides such as maleic anhydride; (meth)acrylic Compounds; aromatic vinyl compounds such as styrene, methylstyrene, divinylbenzene; conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene; N- Methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, compounds represented by the following formula (m2-1) to formula (m2-3), etc. contain Maleimide-based compounds, etc. Other monomers may be used alone or in combination of two or more. [Chemical 4]

The polymer (M) can be obtained, for example, by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a polymerization initiator. As the polymerization initiator used, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2 are preferred Azo compounds such as'-azobis(4-methoxy-2,4-dimethylvaleronitrile). The use ratio of the polymerization initiator is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of all monomers used in the reaction. The polymerization reaction is preferably carried out in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, and hydrocarbon compounds. Diethylene glycol ethyl ether and propylene glycol monomethyl ether acetate are preferred. The reaction temperature is preferably 30°C to 120°C, and the reaction time is preferably 1 hour to 36 hours. The amount of use of the organic solvent (a) is preferably such that the total amount of monomers used in the reaction (b) is 0.1% by mass to 60% by mass relative to the total amount of the reaction solution (a+b). . The polymer solution obtained by the reaction can be directly supplied to the preparation of the liquid crystal alignment agent, or the polymer (M) contained in the reaction solution can be separated and then supplied to the preparation of the liquid crystal alignment agent.

(Polyorganosiloxane) The polyorganosiloxane can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound. Examples of silane compounds used in the synthesis of polyorganosiloxanes include tetramethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and dimethyl Alkoxysilane compounds such as diethoxysilane; 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(3-cyclo Nitrogen and sulfur-containing alkoxysilane compounds such as hexylamino)propyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and other epoxy-containing silane compounds; 3-(meth)propene Acetyloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, Vinyl triethoxy silane, p-styryl trimethoxy silane and other unsaturated bond-containing alkoxy silane compounds; trimethoxy silane propyl succinic anhydride, etc. These hydrolyzable silane compounds can be used alone or in combination of two or more.

The hydrolysis/condensation reaction is carried out by reacting one or more of the silane compounds with water, preferably in the presence of a suitable catalyst and organic solvent. When the reaction is carried out, the proportion of water used is 1 mole relative to the silane compound (total amount), preferably 1 mole to 30 moles. Examples of the catalyst used include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. The amount of catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and should be appropriately set. For example, it is preferably 0.01 times to 3 times the molar amount relative to the total amount of the silane compound. Examples of the organic solvent used include hydrocarbons, ketones, esters, ethers, and alcohols. Among these, it is preferable to use an insoluble or poorly water-soluble organic solvent. The use ratio of the organic solvent is preferably 10 parts by mass to 10,000 parts by mass with respect to the total of 100 parts by mass of the silane compound used in the reaction.

For example, the hydrolysis/condensation reaction is preferably carried out by heating in an oil bath or the like. At this time, the heating temperature is preferably set to 130° C. or lower, and the heating time is preferably set to 0.5 to 12 hours. After the reaction is completed, the organic solvent layer separated from the reaction solution is dried with a desiccant as needed, and then the solvent is removed, thereby obtaining the target polyorganosiloxane. In addition, the synthesis method of polyorganosiloxane is not limited to the hydrolysis and condensation reaction, for example, it can also be performed by a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol.

The amount of acidic functional groups (mmol/g) possessed by the first polymer is relatively high in view of sufficiently obtaining the effects of improving the polymer solubility, liquid crystal alignment, and afterimage characteristics due to the compound (A). It is preferably 0.1 mmol/g to 10 mmol/g, more preferably 1 mmol/g to 10 mmol/g, and still more preferably 2 mmol/g to 5 mmol/g. In the aspect 1, the amount of acidic functional groups possessed by the second polymer is not particularly limited as long as the amount of acidic functional groups possessed by the first polymer is smaller. From the viewpoint of sufficiently obtaining the effect of improving the liquid crystal alignment and afterimage characteristics caused by the compound (A), the acidic functional group of the second polymer relative to the amount of the acidic functional group of the first polymer The amount is preferably 0.7 mole equivalent or less, more preferably 0.5 mole equivalent or less, and further preferably 0.3 mole equivalent or less. In addition, the term "the amount of acidic functional groups in the second polymer is less than the amount of acidic functional groups in the first polymer" means that the second polymer does not have an acidic functional group. In the case of the above aspect 2, if the basicity of the second polymer is higher than that of the first polymer, the amount of acidic functional groups of the second polymer may be more or less than that of the first polymer Or may be the same as the first polymer.

In the case of the above aspect 2, the amount of basic functional groups (mmol/g) possessed by the second polymer is not particularly limited if it is greater than the amount of basic functional groups possessed by the first polymer, preferably It is 1.5 molar equivalent or more with respect to the amount of the basic functional group which a 1st polymer has, more preferably 1.8 molar equivalent or more, and further preferably 2.0 molar equivalent or more. Here, examples of the basic functional group include amine groups, groups containing nitrogen-containing heterocycles (for example, aromatic heterocycles such as pyridine ring and imidazole ring; aliphatic heterocycles such as piperidine ring and pyrrolidine ring), Guanidine and so on. From the viewpoint of more sufficiently inducing the phase separation of the first polymer and the second polymer, the second polymer preferably has a functional group containing a nitrogen-containing aromatic heterocyclic ring as a basic functional group, and more preferably has Functional group containing pyridine ring. Especially in the case where the compound (A) is a compound having a nitrogen-containing structure represented by the formula (1-1), the second polymer has a functional group containing a nitrogen-containing aromatic heterocyclic ring, thereby inducing the first The effect of phase separation between the first polymer and the second polymer is high, which is preferable.

Specific examples of the combination of polymer components in the case of the aspect 1 include, for example, the following aspects (1-1) to (1-5), and the case of the aspect 2 Specific examples include, for example, the following aspects (2-1) to (2-2), but not limited to these aspects. (1-1) The first polymer is polyamic acid, and the second polymer is polyimide. (1-2) The first polymer is a polyamic acid, and the second polymer is a polyamic acid ester. (1-3) The first polymer is polyamic acid, and the second polymer is polyorganosiloxane. (1-4) The first polymer is polyamic acid, and the second polymer is (meth)acrylate. (1-5) The first polymer and the second polymer are polyamic acid, and the first polymer has more acidic functional groups than the second polymer. (2-1) The first polymer and the second polymer are polyamides, the second polymer has a nitrogen-containing aromatic heterocycle, and the first polymer does not have a nitrogen-containing aromatic heterocycle. (2-2) The first polymer and the second polymer are polyamic acid, the first polymer and the second polymer have an amine group (secondary amine group or tertiary amine group), and the second polymer It has more amine groups than the first polymer.

In addition, the method of obtaining a polymer having a basic functional group is not particularly limited, and as an example, a method of polymerizing using a monomer having a basic functional group may be mentioned. For example, in the case of obtaining a polyamic acid having a basic functional group, it is preferable to use a diamine having a basic functional group from the viewpoint of a high degree of freedom of selectivity of monomers. Specific examples of the diamine having a basic functional group include bis(4-aminophenyl)amine, N,N-bis(4-aminophenyl)-N-methylamine, N, N'-bis(4-aminophenyl)-1,4-phenylenediamine, N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-benzene Diamine, N,N'-bis(4-aminophenyl)-biphenyl-4,4'-diamine, N,N'-bis(4-aminophenyl)-N,N'-di Methylbiphenyl-4,4'-diamine, N,N'-bis(4-aminophenyl)-ethylenediamine, N,N'-bis(4-aminophenyl)-N,N '-Dimethylethylenediamine, N,N'-bis(4-aminophenyl)-piperazine, bis(5-amino-2-pyridyl)amine, N,N-bis(5-amine Yl-2-pyridyl)-N-methylamine, N,N'-bis(5-amino-2-pyridyl)-1,4-phenylenediamine, N,N'-bis(5-amine Yl-2-pyridyl)-N,N'-dimethyl-1,4-phenylenediamine, N,N'-bis(5-amino-2-pyridyl)-biphenyl-4,4' -Diamine, N,N'-bis(5-amino-2-pyridyl)-N,N'-dimethylbiphenyl-4,4'-diamine, N,N'-bis(5- (Amino-2-pyridyl)-ethylenediamine, N,N'-bis(5-amino-2-pyridyl)-N,N'-dimethylethylenediamine, N,N'-di( 5-amino-2-pyridyl)-piperazine and the like. When synthesizing polyamic acid, in the case of using a diamine having a basic functional group, the use ratio thereof is preferably 20 mol relative to the total amount of the diamine compound used in the synthesis of polyamic acid Ear% or more, more preferably 40 mole% or more.

The mixing ratio of the first polymer in the liquid crystal alignment agent is preferably 30% by mass or more, and more preferably 40% by mass or more with respect to the amount of the second polymer contained in the liquid crystal alignment agent. Furthermore, it is preferably 50% by mass or more. Furthermore, the liquid crystal alignment agent may contain one kind of second polymer alone or two or more kinds of second polymers.

(Optical alignment base) In the case where the polymer component of the liquid crystal alignment agent contains a polymer having a photo-alignment group, the organic film formed using the liquid crystal alignment agent can be provided with a liquid crystal alignment capability by a photo alignment method, which is preferable in this respect . Here, the photo-alignment group means that the film can be imparted to each film by a photo reaction such as a photo-isomerization reaction, a photo-dimerization reaction, a photo Fries rearrangement reaction, or a photo-decomposition reaction irradiated with light. Anisotropic functional group. In the polymer blend of the first polymer and the second polymer, in terms of the effect of sufficiently improving the liquid crystal alignment of the obtained liquid crystal element and the improvement effect of the reduction of AC afterimage, The polymer containing a photo-alignment group is preferably used as the second polymer. In this case, it is not excluded that the first polymer has a photo-alignment group.

Specific examples of the photo-alignment group include, for example, azobenzene-containing groups containing azobenzene or its derivatives as the basic skeleton, and those containing cinnamic acid or its derivatives (cinnamic acid structure) as the basic skeleton. A cinnamic acid structure group, a chalcone-containing group containing chalcone or its derivative as a basic skeleton, a benzophenone-containing group containing benzophenone or its derivative as a basic skeleton, containing Coumarin-containing groups with coumarin or its derivatives as the basic skeleton, cyclobutane-containing structures containing cyclobutane or its derivatives as the basic skeleton, those with stilbene or its derivatives as the basic skeleton A styrene-containing group, a phenyl benzoate-containing group containing phenyl benzoate or a derivative thereof as a basic skeleton, and the like. Among these, the photo-alignment group is preferably selected from the group consisting of azobenzene-containing groups, cinnamic acid structure-containing groups, chalcone-containing groups, stilbene-containing groups, and cyclobutane-containing groups. At least one of the structure and the group consisting of a phenyl benzoate-containing group is preferably a cinnamic acid-containing structure in terms of high sensitivity to light and easy introduction into a polymer. Groups or structures containing cyclobutane.

The polymer having a photo-alignment group can be obtained, for example, by polymerizing using a monomer having a photo-alignment group. In addition, when polyorganosiloxane is used as the polyorganosiloxane having a photoalignment group in the side chain, the following method may be used: at least a part of the raw material uses an epoxy group-containing silane compound to synthesize the side chain Epoxy-based polyorganosiloxane (hereinafter, also referred to as "epoxy-containing polysiloxane"), in turn, reacts epoxy-containing polysiloxane with a photo-alignment group carboxylic acid. This method is simple, and is preferable in that it can increase the introduction rate of the photo-alignment group.

The content ratio of the photo-alignment group is appropriately set according to the type of the photo-alignment group in such a way as to impart the required liquid crystal alignment ability to the coating film, for example, in the case of a group containing a cinnamic acid structure, the photo-alignment group It is preferable to set the content ratio of the photo-alignment group to 5 mol% or more for all the structural units of the radical polymer, and more preferably to 10 mol% to 60 mol%. In the case where the photo-alignment group is a cyclobutane-containing structure, it is preferable to set the content ratio of the photo-alignment group to 50 mol% or more with respect to all the constituent units of the polymer having the photo-alignment group. More preferably, it is set to 80 mol% or more.

When a solution having a concentration of 10% by mass is prepared, the solution viscosity of the polymer used in the preparation of the liquid crystal alignment agent is preferably 10 mPa·s to 800 mPa·s, and more preferably 15 mPa·s～ Solution viscosity of 500 mPa·s. In addition, the solution viscosity (mPa·s) is a good solvent for the use of polymers (for example, in the case of polyamic acid, polyamic acid ester and polyimide in the case of γ-butyrolactone, N-methyl Yl-2-pyrrolidone, etc.) The polymer solution prepared at a concentration of 10% by mass was measured at 25°C using an E-type viscometer.

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer measured by gel permeation chromatography (GPC) is appropriately set according to the type of polymer. For example, in the case of polyamic acid, polyamic acid ester, and polyimide, it is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 7 or less, more preferably 5 or less. In the case of polyorganosiloxane, the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is preferably in the range of 100 to 50,000, more preferably in the range of 200 to 20,000. In the case of the polymer (M), the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is preferably 250 to 500,000, more preferably 500 to 100,000.

＜＜Compound[A]＞＞ The liquid crystal alignment agent contains a polymer component and a compound (A) different from the first polymer and the second polymer. Compound (A) is a compound that does not have an acidic functional group (for example, carboxylic acid group, phenolic hydroxyl group, sulfonic acid group, phosphoric acid group, phosphorous acid group, phosphonic acid group), and does not have an electron withdrawing group (for example, carbonyl group, ester group , Nitro, nitrile, halogen), or compounds without acidic functional groups and electron-withdrawing groups.

Regarding R ¹ and R ² of the formula (1-1), when R ¹ is a monovalent group bonded to a pyridine ring via a nitrogen atom or an oxygen atom, and R ² is a monovalent organic group (Hereinafter, expressed as "requirement a"), R ^{1 is} preferably "-NR ²⁶ R ²⁷ "or "-OR ²⁸ " (wherein R ²⁶ and R ²⁷ are independently hydrogen atom or carbon number 1~ A monovalent organic group of 10, or a ring structure formed by combining R ²⁶ and R ²⁷ with each other and the carbon atoms bonded to R ²⁶ and R ^27. R ²⁸ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms base). The monovalent organic group of R ²⁶ , R ²⁷ and R ²⁸ is preferably a C 1-5 alkyl group or a monovalent group having -O- between carbon-carbon bonds of the alkyl group.

Among these, R ^{1 is} preferably a group bonded to a pyridine ring via a nitrogen atom in terms of high solubility in solvents and further improvement of the effect of improving the liquid crystal alignment of the obtained liquid crystal element. group. Preferred specific examples of R ¹ include: "-NR ²⁶ R ²⁷ "where R ²⁶ and R ²⁷ are hydrogen atoms, methyl or ethyl groups, and "-OR ²⁸ " R ²⁸ is a hydrogen atom , Methyl or ethyl group, 1-pyrrolidinyl group, 1-piperidinyl group, and 4-morpholinyl group, among these, a group bonded to a pyridine ring by a nitrogen atom is particularly preferable.

When R ¹ and R ² satisfy the requirement a, the monovalent organic group of R ² is preferably an alkyl group having 1 to 5 carbon atoms, or a monovalent of -O- between carbon-carbon bonds of the alkyl group The group is more preferably an alkyl group having 1 to 3 carbon atoms. In this case, m is preferably 1 or 2, more preferably 1. n is preferably 0 or 1, more preferably 0.

Regarding R ¹ and R ² , R represents R ¹ (where R ¹ is bonded to a pyridine ring through a nitrogen atom or an oxygen atom) and R ² are bonded to each other and together with the carbon atoms to which R ¹ and R ² are respectively bonded In the case of a constituted ring structure (hereinafter referred to as "requirement b"), R ^{1 is} preferably bonded to a pyridine ring via a nitrogen atom. m is preferably 1, and n is preferably 1 or 2. In the formula (1-4), R ^{3 is} preferably methyl or ethyl, and more preferably methyl. r is preferably 0 or 1, more preferably 0.

（式（2-1）中，R¹¹ 為「-NR²⁶ R²⁷ 」或「-OR²⁸ 」，R¹² 為碳數1～10的一價有機基。R²⁶ 、R²⁷ 及R²⁸ 分別獨立地為氫原子或碳數1～10的一價有機基。其中，R²⁶ 與R²⁷ 亦可相互結合並與R²⁶ 及R²⁷ 所鍵結的氮原子一同形成環結構。式（2-2）中，R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 分別獨立地為氫原子或碳數1～10的一價有機基，R¹³ 、R¹⁴ 、R¹⁵ 及R¹⁶ 中的兩個以上的有機基亦可鍵結而形成環結構（其中，將含氮芳香族雜環除外）。式（2-3）中，R¹⁷ 、R¹⁸ 、R¹⁹ 及R²⁰ 分別獨立地為氫原子、胺基或碳數1～10的一價有機基，R²¹ 為氫原子或碳數1～10的一價有機基，R¹⁷ 、R¹⁸ 、R¹⁹ 、R²⁰ 及R²¹ 中的兩個以上的有機基亦可鍵結而形成環結構（其中，將含氮芳香族雜環除外）。式（2-4）中，R²² 、R²³ 、R²⁴ 及R²⁵ 分別獨立地為氫原子或碳數1～10的一價有機基。其中，R¹¹ ～R²⁵ 不具有酸性官能基及拉電子性基中的至少一者。m及n與所述式（1-1）為相同含義，R³ 及r與所述式（1-4）為相同含義）Specific examples of the compound (A) include compounds selected from compounds represented by the following formula (2-1), compounds represented by the following formula (2-2), and compounds represented by the following formula (2-3) At least one of the group consisting of a compound and a compound represented by the following formula (2-4). However, when the compound represented by the following formula (2-2) is a nitrogen-containing heterocyclic compound, and the compound represented by the following formula (2-3) is a nitrogen-containing heterocyclic compound, the compound (A) Except medium. [Chem 5]

(In formula (2-1), R ¹¹ is "-NR ²⁶ R ²⁷ "or "-OR ²⁸ ", and R ¹² is a monovalent organic group having 1 to 10 carbon atoms. R ²⁶ , R ²⁷ and R ²⁸ are independently The ground is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Among them, R ²⁶ and R ²⁷ may also be combined with each other and form a ring structure together with the nitrogen atom bonded to R ²⁶ and R ^27. Formula (2-2 ), R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a C 1-10 monovalent organic group, and two or more of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are organic The group may also be bonded to form a ring structure (excluding nitrogen-containing aromatic heterocycles). In formula (2-3), R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom and an amine group Or a monovalent organic group having 1 to 10 carbon atoms, R ²¹ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and two or more of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are organic The group may also be bonded to form a ring structure (wherein nitrogen-containing aromatic heterocycles are excluded). In formula (2-4), R ²² , R ²³ , R ²⁴ and R ²⁵ are each independently a hydrogen atom or a carbon number A monovalent organic group of 1 to 10. Among them, R ¹¹ to R ²⁵ do not have at least one of an acidic functional group and an electron-withdrawing group. m and n have the same meaning as the above formula (1-1), R ³ And r has the same meaning as the above formula (1-4))

In the above formula (2-2), the monovalent organic groups of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are preferably alkyl groups having 1 to 10 carbon atoms, and more preferably alkyl groups having 1 to 3 carbon atoms. In the formula (2-3), the monovalent organic group of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms. alkyl. In the formula (2-4), the monovalent organic groups of R ²² , R ²³ , R ²⁴ and R ²⁵ are preferably C 1-3 alkyl groups, more preferably methyl groups.

The boiling point of the compound (A) at 1 atm is preferably 60°C or higher, and more preferably 80°C or higher. In this case, even after heating during the pre-baking, a sufficient amount of the compound (A) can remain in the alignment film, and the improvement effect due to the compound (A) can be further improved. Words are better. In addition, in order to sufficiently remove the compound (A) from the alignment film by heating during post-baking, the boiling point of the compound (A) at 1 atm is preferably 300° C. or lower, more preferably 250° C. or lower, and It is preferably below 230°C.

As preferable specific examples of the compound (A), the compound represented by the formula (2-1) includes, for example, the following formula (3-1-1) to formula (3-1-9) Compounds, etc. The compounds represented by the formula (2-2) include, for example, compounds represented by the following formulas (3-2-1) and (3-2-2), respectively; the formula (2- 3) The compound represented by, for example, the compounds represented by the following formula (3-3-1) to formula (3-3-8), etc.; the compound represented by the formula (2-4), for example, can be exemplified Compounds represented by the following formula (3-4-1), etc. [化6]

Regarding the compounding ratio of the compound (A), from the viewpoint of sufficiently obtaining the effects of improving polymer solubility, liquid crystal alignment, and afterimage characteristics, the ratio of the first polymer and the second polymer contained in the liquid crystal alignment agent The total number of acidic functional groups is preferably adjusted at a ratio of 0.1 molar equivalent to 15 molar equivalent, more preferably at a ratio of 0.2 molar equivalent to 12 molar equivalent, and further preferably at 0.5 molar equivalent to 10 molar equivalent. Ear equivalent ratio deployment. Furthermore, the compound (A) may be used alone or in combination of two or more.

Here, in the liquid crystal alignment agent of the polymer blend of the first polymer and the second polymer, the first polymer is compatible with the second polymer, whereby the liquid crystal alignment of the obtained liquid crystal element may be Sex is not sufficient. Especially in the case of a polymer blend of a polymer having an acidic functional group (first polymer) and a polymer having a lower acidity than the polymer (second polymer), the first polymer and the second The compatibility of the polymer is high, and there is a concern that the phase separation may be reduced. In this respect, by compounding the compound (A) as a basic compound in the liquid crystal alignment agent, the first polymer is more likely to be biased in the lower layer of the alignment film, and the phase separation from the second polymer can be improved As a result, it is speculated that the performance of the liquid crystal alignment film can be improved.

＜＜Other Ingredients＞＞ The liquid crystal alignment agent contains a polymer component and a compound (A), and may contain other components as necessary.

<Solvent> The liquid crystal alignment agent preferably dissolves the polymer component in the solvent. Examples of the solvent used include solvents with high solubility and leveling properties of polymers (hereinafter, also referred to as "first solvents"), and solvents with good wettability (hereinafter, also referred to as "second "Solvent"), and these mixed solvents. As specific examples of the solvent, for example, the first solvent may include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, diisobutyl ketone, ethyl carbonate, propyl carbonate, N-ethyl-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-(third butyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, 1,3-dimethyl -2-imidazolidinone, 3-butoxy-N,N-dimethylpropylamide, 3-methoxy-N,N-dimethylpropylamide, etc.; Examples of the second solvent include ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diacetone alcohol, and diethylene glycol dimethyl ether. , Diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, cyclopentanone, butyl lactate, butyl acetate , Methyl methoxy propionate, ethyl ethoxy propionate, isoamyl propionate, isoamyl isobutyrate, propylene glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol monobutyl ether, di Isoamyl ether and so on. In addition, as the solvent, one kind of these may be used alone, or two or more kinds may be used in combination.

When a mixed solvent of the first solvent and the second solvent is used as the solvent component, the use ratio of the first solvent is preferably 10% by mass to the total amount of the solvent components used in the preparation of the liquid crystal alignment agent 95% by mass, more preferably 15% to 80% by mass. The use ratio of the second solvent is preferably 5% by mass to 90% by mass, and more preferably 20% by mass to 85% by mass relative to the total amount of solvent components used in the preparation of the liquid crystal alignment agent.

In the liquid crystal alignment agent of the present disclosure, it is also possible to prepare an aqueous polymer composition by using water as a solvent component. In this case, the amount of organic solvent used can be reduced, and a liquid crystal alignment agent that is more excellent in terms of environment or safety can be produced, which is preferable in this respect. As the solvent component, water can be used alone, but from the viewpoint of improving the solubility of the polymer in the solvent and the viewpoint of improving the applicability to the substrate, it is preferably water-soluble and surface tension A mixed solvent of a solvent lower than water and water is particularly preferably a mixed solvent of water and alcohol. Examples of the alcohol used include ethanol, propanol, isopropanol, 1-methoxy-2-propanol, diacetone alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and butyl cellosolve ( Ethylene glycol monobutyl ether), propylene glycol monoethyl ether, ethyl lactate, 1-hexanol, 4-methyl-2-pentanol, etc. In this case, the use ratio of water is preferably 20% by mass or more relative to the total amount of the solvent contained in the liquid crystal alignment agent, more preferably 40% to 95% by mass, and further preferably 60% by mass to 90% by mass.

As other components contained in the liquid crystal alignment agent, in addition to the solvent, for example, an epoxy group-containing compound (for example, N,N,N',N'-tetraglycidyl-m-xylenediamine, N,N ,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc.), functional silane compounds (such as 3-aminopropyltriethoxysilane, N-(2- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, etc.), antioxidants, metal chelating compounds, hardening catalysts, hardening accelerators, surfactants, fillers, dispersants, light enhancers Sensitive agent, etc. The blending ratio of other components can be appropriately selected according to each compound within a range that does not impair the effects of the present invention.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., preferably 1 mass % To 10% by mass. When the solid content concentration is less than 1% by mass, the film thickness of the coating film is 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 mass, the film thickness of the coating film is too large, and it is difficult to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent increases and the coating property tends to decrease.

＜＜Liquid crystal alignment film and liquid crystal element＞＞ The liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The liquid crystal element can be effectively used in various applications, such as clocks, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (PDA), digital Various display devices such as cameras, mobile phones, smart phones, various monitors, LCD TVs, and information displays, or dimming films and retardation films. When used as a liquid crystal display device, the operation mode of the liquid crystal is not particularly limited, for example, it can be applied to twisted nematic (TN) type, super twisted nematic (STN) type, vertical alignment type (Including vertical alignment-multi-domain vertical alignment (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) type, vertical alignment-pattern vertical alignment (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type, etc.), coplanar switching (In-Plane Switching (IPS) type, Fringe Field Switching (FFS) type, Optically Compensated Bend (OCB) type and other operation modes.

The manufacturing method of a liquid crystal element is demonstrated using an example of a liquid crystal display element. The liquid crystal display element can be manufactured by the method including the following steps 1 to 3, for example. In step 1, the substrate used differs depending on the required operation mode. Steps 2 and 3 are common to each operation mode.

(Step 1: Formation of coating film) First, the liquid crystal alignment agent is applied on the substrate, preferably the application surface is heated, thereby forming a coating film on the substrate. As the substrate, for example, a transparent substrate containing the following materials: glass such as float glass, soda glass, polyethylene terephthalate, polybutylene terephthalate, polyether tartar, polycarbonate, poly( Alicyclic olefins) and other plastics. As a transparent conductive film provided on one side of the substrate, a NESA film (registered trademark of PPG Corporation) containing tin oxide (SnO ₂ ) and indium oxide-tin oxide (In ₂ O ₃ -SnO) ₂ ) Indium tin oxide (ITO) film, etc. In the case of manufacturing a TN type, STN type, or VA type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, in the case of manufacturing an IPS-type or FFS-type liquid crystal element, a substrate provided with electrodes including a transparent conductive film or metal film patterned into a comb-teeth type, and a counter substrate not provided with electrodes are used. For the metal film, for example, a film containing metal such as chromium can be used. The application of the liquid crystal alignment agent to the substrate is preferably carried out by the lithography method, spin coating method, roll coater method, flexographic printing method, or inkjet printing method on the electrode forming surface.

After applying the liquid crystal alignment agent, for the purpose of preventing dripping of the applied liquid crystal alignment agent and the like, it is preferable to perform pre-heating (pre-baking). The pre-baking temperature is preferably 30°C to 200°C, and the pre-baking time is preferably 0.25 minutes to 10 minutes. Thereafter, for the purpose of completely removing the solvent and, if necessary, thermally imidizing the amide acid structure possessed by the polymer, a calcination (post-baking) step is performed. The calcination temperature (post-baking temperature) is preferably 80°C to 300°C, and the post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the film thus formed is preferably 0.001 μm to 1 μm. After the liquid crystal alignment agent is applied on the substrate, the organic solvent is removed, thereby forming a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film.

(Step 2: Alignment processing) In the case of manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal display element, the coating film formed in the above step 1 is subjected to a process (alignment process) to impart liquid crystal alignment capability. By this, the alignment ability of liquid crystal molecules is given to the coating film to become a liquid crystal alignment film. Examples of the alignment treatment include the following treatments: rubbing the coating film in a certain direction by using a roll wrapped with a cloth containing fibers such as nylon, rayon, cotton, or cotton, or A light alignment treatment using a liquid crystal alignment agent formed on a substrate to irradiate light to give liquid crystal alignment capability to the coating film. On the other hand, in the case of manufacturing a vertical alignment type liquid crystal element, the coating film formed in the above step 1 may be directly used as a liquid crystal alignment film, but the coating film may also be subjected to alignment treatment (rubbing treatment, optical alignment) Processing, etc.). The liquid crystal alignment agent suitable for a vertical alignment type liquid crystal display element can also be suitably used for a polymer sustained alignment (Polymer sustained alignment, PSA) type liquid crystal display element.

When the liquid crystal alignment agent contains a polymer having a photo-alignment group, the liquid crystal alignment film is preferably formed by a photo-alignment method. In this case, the generation of static electricity and dust can be suppressed, the uniform organic liquid crystal alignment can be provided to the photosensitive organic film, and the liquid crystal alignment direction can be precisely controlled, which is preferable in this respect. The light irradiation for light alignment can be performed by the following methods: a method of irradiating the coating film after the post-baking step, a method of irradiating the coating film after the pre-baking step and before the post-baking step, A method of irradiating a coating film during heating of the coating film in at least any one of the pre-baking step and the post-baking step. As the radiation irradiated to the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. It is preferably ultraviolet light containing light having a wavelength of 200 nm to 400 nm. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. In the case where the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed in a direction perpendicular to the substrate surface, or in an oblique direction, or a combination of these directions. In the case of unpolarized radiation, the irradiation direction is set to an oblique direction.

Examples of the light source used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, and excimer lasers. The radiation dose is preferably 400 J/m ² to 50,000 J/m ² , and more preferably 1,000 J/m ² to 20,000 J/m ² . After the light for aligning ability is irradiated, the surface of the substrate may be used with water, organic solvent (for example, methanol, isopropanol, 1-methoxy-2-propanol acetate, butyl cellosolve, Ethyl lactate, etc.) or these mixtures are subjected to cleaning treatment, or heating the substrate.

(Step 3: Construction of liquid crystal cell) Then, two substrates having a liquid crystal alignment film formed as described above are prepared, and liquid crystal is arranged between the two substrates arranged opposite to each other, thereby manufacturing a liquid crystal cell. Examples of manufacturing liquid crystal cells include: (1) The two substrates are arranged facing each other with a gap (spacer) so that the liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded using a sealant to Liquid crystal injection is filled in the cell gap defined by the substrate surface and the sealant, and then the injection hole is sealed, (2) the sealant is applied to a predetermined position on one of the substrates on which the liquid crystal alignment film is formed, and A method of dropping liquid crystal on the liquid crystal alignment film on a predetermined number of places, bonding another substrate so that the liquid crystal alignment film faces each other, and diffusing liquid crystal over the entire surface of the substrate (liquid crystal drop (one drop filling) , ODF) way) etc. Ideally, the manufactured liquid crystal cell is further heated until the temperature of the liquid crystal used becomes an isotropic phase, and then slowly cooled to room temperature, thereby eliminating the flow alignment during liquid crystal filling.

As the sealant, for example, an epoxy resin containing a hardener and alumina balls as spacers can be used. As the spacer, a photo spacer, a beads spacer, or the like can be used. Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal, and nematic liquid crystal is preferred. In addition, for example, cholesteric liquid crystal (cholesteric liquid crystal), chiral reagent, ferroelectric liquid crystal (ferroelectric liquid crystal), etc. can be added to nematic liquid crystal or smectic liquid crystal.

Next, if necessary, a polarizing plate is attached to the outer surface of the liquid crystal cell. Examples of the polarizing plate include a polarizing plate called a "H film" formed by aligning polyvinyl alcohol with a cellulose acetate protective film extending on one side and absorbing iodine, or a film containing the H film itself. Polarizer. In this way, a liquid crystal display element is obtained. [Example]

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

The structures and abbreviations of the main compounds used in the following examples are as follows. (Tetracarboxylic acid derivative) TA-1: 2,3,5-tricarboxycyclopentylacetic acid dianhydride TA-2: 1,2,3,4-cyclobutane tetracarboxylic dianhydride TA-3: ( 1R, 2R, 3S, 4S)-1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride TA-4: dimethylallyl (2r, 4r)-2 ,4-bis(chlorocarbonyl)-2,4-dimethylcyclobutane-1,3-dicarboxylic acid ester TA-5: pyromellitic anhydride TA-6: 4,4'-oxydiphthalene Dicarboxylic anhydride TA-7: Propane-1,3-diylbis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) [化7]

(Diamine compound) DA-1: p-phenylenediamine DA-2: 2,2'-dimethylbenzidine DA-3: N,N'-bis(4-aminophenyl)-N,N'-Dimethylbiphenyl-4,4'-diamine DA-4: N,N'-bis(5-amino-2-pyridyl)-N,N'-dimethylethylenediamine DA-5 : 1,4-phenylene bis(4-aminobenzoate) DA-6: 4-aminophenyl (E)-3-(4-aminophenyl)-2-methacrylate DA-7: 1,5-bis(4-(2-(4-aminophenyl)ethyl)phenoxy)pentane [Chem 8]

(Basic compound) BA-1: 4-dimethylaminopyridine BA-2: 4-hydroxypyridine BA-3: diazabicycloundecene BA-4: 1,1,3,3-tetramethyl Guanidine BA-5: 1,5,7-triazabicyclo[4.4.0]dec-5-ene BA-6: 1,8-bis(dimethylamino)naphthalene BB-1: dimethyl Aniline BB-2: pyridine BB-3: imidazole BB-4: N,N-diisopropylethylamine BB-5: tetramethylammonium hydroxide

(Solvent) NMP: N-methyl-2-pyrrolidone γBL: γ-butyrolactone BC: butyl cellosolve

<Synthesis of Polymer> [Synthesis Example 1] Diamine (DA-2) and (DA-3) were dissolved in NMP at a molar ratio of 70:30, and 0.9 equivalents of tetracarboxylic acid derivative (TA -1) The reaction was carried out at room temperature for 6 hours to obtain a 15% by mass solution of polyamide (PA-1). [Synthesis Example 2 to Synthesis Example 8] In the same manner as in Synthesis Example 1, except that the types and molar ratios of tetracarboxylic acid derivatives and diamine compounds were changed as described in Table 1 below, respectively. Polyamide acid (PA-2～PA-8). [Synthesis Example 9] The 15% by mass solution of the polyamic acid (PA-4) obtained in Synthesis Example 4 was diluted to 10% by mass with NMP, relative to the polyamide of the polyamic acid (PA-4) 0.7 equivalents of 1-methylpiperidine and acetic anhydride were added, and the mixture was heated and stirred at 60°C for 3 hours. The obtained solution was repeatedly concentrated under reduced pressure and diluted with NMP to obtain a 15% by mass solution of polyimide (PI-1). Determination of ¹ H-nuclear magnetic resonance (NMR) spectrum (DMSO-d ⁶ , 400 MHz) of polyimide (PI-1) based on aromatic protons (δ6.0 ppm～9.0 ppm) and main chain The ratio of amide protons (δ 9.8 ppm to 10.3 ppm) and acetamide terminal amide protons (δ 9.6 ppm to 9.8 ppm) was used to calculate the amide imidization rate. As a result, the amide imidization rate was 70% .

[Synthesis Example 10] Put a tetracarboxylic acid derivative (TA-4) (8.11 g, 20.0 mmol), pyridine (3.80 g, 48.0 mmol), γBL 22 g, and NMP 11 g in a 50 mL three-necked flask equipped with a nitrogen introduction tube and a thermometer , Cooled to about 10 ℃, thereby preparing an acetyl chloride solution. Here, a diamine solution prepared by dissolving diamine (DA-1) (1.95 g, 18.0 mmol) in 11 g of γBL in advance was added, and reacted at 10° C. for 4 hours under a nitrogen flow. The obtained polymerization solution was diluted with 58 g of methanol, and it was slowly poured into the mixed solvent of water/isopropanol=1/1 (mass ratio) while stirring and solidified. The precipitated solid was recovered, stirred and washed in water and isopropyl alcohol, and vacuum-dried at 60°C, thereby obtaining a white powder. The obtained powder was dissolved in γBL to obtain a 15% by mass solution of polyamide (PAE-1). [Synthesis Example 11] The polyorganosiloxane (SQ-1) having a cinnamate structure in the side chain was synthesized according to the method described in Synthesis Example S1 of paragraph [0104] of Japanese Patent Laid-Open No. 2010-217868.

[Table 1]

Regarding the numerical values in Table 1, for the tetracarboxylic acid derivatives, it represents the use ratio (mole parts) of each compound relative to the total amount of 100 mol parts of the tetracarboxylic acid derivatives used in the synthesis. For the diamine The compound refers to the use ratio (mole parts) of each compound relative to the total amount of 100 mol parts of the diamine compound used in the synthesis.

[Example 1: Optical alignment FFS type liquid crystal display element] (1) Preparation of liquid crystal alignment agent Using polyamic acid (PA-1), polyimide (PI-1) and basic compound (BA-1) and diluting with NMP and BC, the solid content concentration becomes 3.5% by mass and the solvent composition ratio Become a solution of NMP:BC=80:20 (mass ratio). The solution was filtered by a filter with a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (R-1). Furthermore, the two polymers were formulated at a ratio of polyamic acid (PA-1): polyimide (PI-1) = 60:40 (solid content conversion mass ratio), so that the liquid crystal alignment agent was relatively The carboxylic acid group (-COOH) in all polymers contains a basic compound at a ratio of 1.0 molar equivalent.

(2) Formation of liquid crystal alignment film by photo-alignment method The liquid crystal alignment agent (R-1) prepared in (1) above was applied on a single surface in order to be laminated in order so that the film thickness became 0.1 μm using a spinner The surface of the glass substrate with the plate electrode, the insulating layer, and the comb-shaped electrode, and the opposing glass substrate on which the electrode is not provided was dried by a hot plate at 80°C for 1 minute to form a coating film. The surface of the coating film was irradiated with ultraviolet light 2,000 J/m ² containing a bright line of linearly polarized 254 nm from the normal direction of the substrate using an Hg-Xe lamp to perform light alignment treatment. The coating film subjected to the photo-alignment treatment was heated in a 230° C. oven with nitrogen substitution in the cavity for 40 minutes and heat-treated to form a liquid crystal alignment film.

(3) Manufacture of liquid crystal display elements For the pair of substrates having the liquid crystal alignment film prepared in (2) above, the liquid crystal injection port is left at the edge of the surface where the liquid crystal alignment film is formed, and an epoxy resin with an alumina ball with a diameter of 5.5 μm is bonded After the agent screen printing is applied, the substrates are stacked and pressure-bonded so that the projection direction of the polarization axis toward the substrate surface becomes anti-parallel when light is irradiated, and the adhesive is thermally cured at 150°C for 1 hour. Then, after filling the nematic liquid crystal (MLC-7028 manufactured by Merck) between the pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to eliminate the flow alignment at the time of liquid crystal injection, it was heated at 120° C. and then slowly cooled to room temperature. Then, polarizing plates were bonded on both outer sides of the substrate to manufacture FFS-type liquid crystal display elements.

(4) Evaluation of liquid crystal alignment For the liquid crystal display element manufactured in the above (3), the abnormal domain (domain) in the change of light and dark when the voltage of 5 V is turned ON/OFF (applied/released) at a magnification of 50 times is observed by a microscope ). Regarding the evaluation, the case where no abnormal region was observed was set to "good", and the case where an abnormal region was observed was set to "bad". As a result, this example was evaluated as "good".

(5) Evaluation of AC residual image characteristics The FFS type liquid crystal cell was produced except that the polarizing plates were not bonded to both outer sides of the substrate, and the same operation as (3) above was performed. For this FFS type liquid crystal cell, after driving at an alternating voltage of 10 V for 30 hours, the minimum relative value represented by the following formula (1) was measured using a device in which a polarizer and an analyzer were arranged between the light source and the light amount detector Transmittance (%). Minimum relative transmittance (%) = (β-B0)/(B100-B0)×100… (1) (In equation (1), B0 is blank, and is the amount of light transmission under crossed nicols. B100 is blank, and is light under parallel nicols. The amount of transmission. β is the minimum light transmission amount between the polarizer and the analyzer under the crossed Nicols and the liquid crystal cell is minimized) The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal cell. In the FFS type liquid crystal cell, the smaller the black level (minimum relative transmittance) in the dark state, the better the contrast. The minimum relative transmittance is less than 0.2% as "excellent", 0.2% or more and less than 0.5% as "good", 0.5% or more and less than 1.0% as "acceptable", 1.0 % Or more is set to "bad". As a result, this example was evaluated as "excellent".

[Example 2 to Example 10, Comparative Example 1 to Comparative Example 6] In the above Example 1, the polymer and the basic compound contained in the liquid crystal alignment agent were changed as shown in Table 2 below, except that the liquid crystal alignment agent was prepared and formed in the same manner as in Example 1. Liquid crystal alignment film, and FFS type liquid crystal display element and liquid crystal cell were manufactured and evaluated variously. The evaluation results are shown in Table 2 below.

[Example 11] In the above Example 1, "(1) Preparation of liquid crystal alignment agent" and "(2) Formation of liquid crystal alignment film by photo-alignment method" are as follows (1a) and (2a) Except for general changes, the FFS type liquid crystal display element and the liquid crystal cell were manufactured in the same manner as in Example 1, and various evaluations were performed. The evaluation results are shown in Table 2 below. (1a) Preparation of liquid crystal alignment agent Polyamide (PA-1), polyamide (PA-4) and basic compound (BA-1) were used and diluted with NMP and BC to obtain solid content concentration It becomes a solution of 3.5 mass% and a solvent composition ratio of NMP:BC=80:20 (mass ratio). The solution was filtered by a filter with a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (R-11). Furthermore, the two polymers were formulated at a ratio of polyamic acid (PA-1): polyamic acid (PA-4) = 60:40 (solid content conversion mass ratio) to make the liquid crystal alignment agent relatively The basic compound is contained at a ratio of 0.5 mol equivalent to the carboxylic acid groups in all polymers. (2a) Formation of liquid crystal alignment film by photo-alignment method The liquid crystal alignment agent (R-11) prepared in (1a) above is applied to a layered plate electrode, insulating layer and comb layered on one side in sequence using a spinner The surfaces of the glass substrate of the toothed electrode and the opposing glass substrate without electrodes were heated by a hot plate at 80° C. for 1 minute, and then placed in a 230° C. oven with nitrogen substitution in the chamber. After drying for 30 minutes, a coating film having an average film thickness of 0.1 μm was formed. The surface of the coating film was irradiated with ultraviolet light 2,000 J/m ² containing a bright line of linearly polarized 254 nm from the normal direction of the substrate using an Hg-Xe lamp to perform light alignment treatment. The coating film subjected to the photo-alignment treatment was heated in a 230° C. oven with nitrogen substitution in the cavity for 40 minutes and heat-treated to form a liquid crystal alignment film. [Example 12 to Example 13, Comparative Example 7] In the above Example 11, the polymer and the basic compound contained in the liquid crystal alignment agent were changed as shown in Table 2 below, except that A liquid crystal alignment agent was prepared and a liquid crystal alignment film was formed in the same manner as in Example 11, and FFS-type liquid crystal display elements and liquid crystal cells were manufactured and subjected to various evaluations. The evaluation results are shown in Table 2 below.

[Example 14] In Example 11, the "(1) Preparation of liquid crystal alignment agent" was changed as described in (1b) below, and the amount of ultraviolet radiation was changed to 5,000 J/m ² , except that In the same manner as in Example 11, an FFS-type liquid crystal display element and a liquid crystal cell were manufactured and subjected to various evaluations. The evaluation results are shown in Table 2 below. (1b) Preparation of liquid crystal alignment agent Polyamide (PA-1), polyamide (PAE-1) and basic compound (BA-3) were used and diluted with NMP and BC to obtain solid content The concentration became 3.5% by mass, and the solvent composition ratio became NMP:BC=80:20 (mass ratio). The solution was filtered by a filter with a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (R-14). Furthermore, the two polymers were formulated in a ratio of polyamic acid (PA-1): polyamic acid ester (PAE-1) = 90:10 (solid content conversion mass ratio), so that the liquid crystal alignment agent was The basic compound is contained at a ratio of 0.5 molar equivalent to the carboxylic acid groups in all polymers.

[Examples 15 to 16] In Example 11, the polymer and the basic compound contained in the liquid crystal alignment agent were changed as shown in Table 2 below, and the ultraviolet irradiation amount was changed to 5,000 J /m ² , except that a liquid crystal alignment agent was prepared and a liquid crystal alignment film was formed in the same manner as in Example 11, and an FFS-type liquid crystal display element and a liquid crystal cell were manufactured and subjected to various evaluations. The evaluation results are shown in Table 2 below.

[Example 17: Friction alignment FFS type liquid crystal display element] In the above Example 1, "(1) Preparation of liquid crystal alignment agent" and "(2) Formation of liquid crystal alignment film by photo-alignment method" were changed as follows (1c) and (2c) except Other than that, the FFS-type liquid crystal display element and liquid crystal cell were manufactured and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2 below. (1c) Preparation of liquid crystal alignment agent Using polyamide (PA-1), polyamide (PA-8) and basic compound (BA-3) and diluting with NMP and BC, the solid content concentration becomes 3.5% by mass and the solvent composition ratio Become a solution of NMP:BC=80:20 (mass ratio). The solution was filtered by a filter with a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (R-17). Furthermore, the two polymers were formulated at a ratio of polyamic acid (PA-1): polyamic acid (PA-8) = 60:40 (solid content conversion mass ratio) to make the liquid crystal alignment agent relatively The basic compound is contained at a ratio of 0.5 mol equivalent to the carboxylic acid groups in all polymers. (2c) Formation of liquid crystal alignment film by rubbing method Using a spinner, apply the liquid crystal alignment agent (R-17) prepared in (1c) above to a glass substrate on which a flat electrode, an insulating layer, and a comb-shaped electrode are sequentially stacked on one side, facing the surface where no electrode is provided Each surface of the glass substrate was dried on a hot plate at 80°C for 1 minute, and then dried in a 230°C oven with nitrogen substitution in the chamber for 30 minutes to form a coating film having an average film thickness of 0.1 μm. The surface of the coating film was subjected to a rubbing treatment using a rubbing machine having a roller wound with a cloth made of nylon, at a roller rotation speed of 1000 rpm, a platform moving speed of 25 mm/sec, and a wool pressing length of 0.4 mm. After the coating film subjected to the rubbing alignment treatment was ultrasonically cleaned in ultrapure water for 1 minute, it was dried in an oven at 100° C. for 10 minutes to form a liquid crystal alignment film.

[Example 18] In the above Example 1, "(1) Preparation of liquid crystal alignment agent" and "(2) Formation of liquid crystal alignment film by photo-alignment method" are as follows (1d) and (2d) Except for general changes, the FFS type liquid crystal display element and the liquid crystal cell were manufactured in the same manner as in Example 1, and various evaluations were performed. The evaluation results are shown in Table 2 below. (1d) Preparation of liquid crystal alignment agent Polyamide (PA-1), polyorganosiloxane (SQ-1) and basic compound (BA-3) were used and diluted with NMP and BC to obtain solid content The concentration became 3.5% by mass, and the solvent composition ratio became NMP:BC=80:20 (mass ratio). The solution was filtered by a filter with a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent (R-18). Furthermore, the two polymers were formulated at a ratio of polyamic acid (PA-1): polyorganosiloxane (SQ-1) = 90:10 (mass ratio converted to solid content), so that the liquid crystal alignment agent The basic compound is contained at a ratio of 0.5 molar equivalent to the carboxylic acid groups in all polymers. (2d) Formation of liquid crystal alignment film by photo-alignment method The liquid crystal alignment agent (R-18) prepared in (1d) above was applied to a layered plate electrode, insulating layer and comb sequentially stacked on one side using a spinner The surfaces of the glass substrate of the tooth electrode and the opposing glass substrate on which the electrode is not provided were heated by a hot plate at 80° C. for 1 minute, and then placed in a 200° C. oven with nitrogen substitution in the chamber After drying for 30 minutes, a coating film having an average film thickness of 0.1 μm was formed. The surface of the coating film was irradiated with ultraviolet light 300 J/m ² including a bright line of 313 nm linearly polarized from the substrate normal direction using an Hg-Xe lamp to perform an optical alignment treatment, thereby forming a liquid crystal alignment film.

[Table 2]

In Examples 1 to 6 and Comparative Examples 1 to 6, the first polymer was used (PA-1) and the second polymer was used (PI-1). The type of basic compound was changed and evaluated. In Examples 1 to 6, the polymer solubility is improved compared to Comparative Example 1. Even if the liquid crystal alignment agent absorbs moisture, the polymer hardly precipitates, and the coating property on the substrate is good. Furthermore, the liquid crystal alignment and the AC afterimage characteristics are "good", "acceptable", or "excellent" in Examples 1 to 6, and any of Comparative Examples 1 to 6 is " bad". It is considered that by adding the compound (A) to the liquid crystal alignment agent, a salt is formed with the polymer having an acidic functional group, and the polarity of the polymer changes greatly. In addition, in Examples 1 to 6, the mechanism for improving the liquid crystal alignment and the AC afterimage characteristics is uncertain, but it is believed that by using the compound (A) as a basic compound, the first polymer tends to be biased in In the lower layer of the alignment film, as a result, the polymer (second polymer) having a photo-alignment group is layer-separated in the upper layer of the alignment film, thereby improving the characteristics. On the other hand, in Comparative Examples 1 to 6, it is considered that the basicity, polarity, non-nucleophilicity, volatility, etc. of the basic compound are not suitable, and the desired characteristics are not exhibited.

In Example 7 and Example 8, the type of the first polymer was changed and evaluated. As a result, the liquid crystal alignment and the AC afterimage characteristics were "good" and "excellent", respectively. In Example 9 and Example 10, the addition amount of the basic compound was changed and evaluated. As a result, both the liquid crystal alignment and the AC residual image characteristics were "good" or "acceptable". In Examples 11 to 13 and Comparative Example 7, the types of the second polymer and the basic compound were changed and evaluated. The liquid crystal alignment properties are all “good”, and the AC afterimage characteristics are “excellent” or “achievable” in Examples 11 to 13, and the comparative examples are “bad” in Comparative Example 7. In Examples 14 to 18, the type and alignment treatment method of the second polymer were changed and evaluated. As a result, the liquid crystal alignment was "good", and the AC afterimage characteristics were "excellent" or "acceptable".

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Claims (9)

A liquid crystal alignment agent comprising: a first polymer; a second polymer; and a compound (A), and the first polymer has an acidic functional group, and the second polymer is a compound with the first polymer Different polymers, the compound (A) has a partial structure selected from the following formula (1-1), a partial structure represented by the following formula (1-2), and the following formula (1-3) ) And at least one nitrogen-containing structure in the group consisting of the partial structure represented by the following formula (1-4) (wherein, the part represented by the following formula (1-2) will be included Compounds other than nitrogen-containing aromatic heterocycles of at least any one of the structure and the partial structure represented by the following formula (1-3), and do not have at least one of an acidic functional group and an electron-withdrawing group ( However, when the compound (A) has a partial structure represented by the following formula (1-1), the second polymer has a nitrogen-containing aromatic heterocycle),

(In formula (1-1), regarding R ¹ and R ² , R ¹ is a monovalent group bonded to a pyridine ring via a nitrogen atom or an oxygen atom, and R ² is a monovalent organic group, or R ¹ And R ² represents R ¹ (wherein R ¹ is bonded to a pyridine ring through a nitrogen atom or an oxygen atom) and R ^{2 is} combined with each other and formed together with the carbon atoms to which R ¹ and R ² are bonded; m is an integer of 1 to 3, n is an integer of 0 to 2, m+n≦3; when m is 2 or 3, a plurality of R ¹ may be the same or different, and when n is 2, Multiple R ² may be the same or different; in formula (1-4), R ³ is a C 1-5 alkyl group; r is an integer from 0 to 3; when r is 2 or 3, multiple R ³ may be the same or different; "*" in formula (1-1) to formula (1-4) represents a bond). The liquid crystal alignment agent according to item 1 of the patent application range, wherein the compound (A) is selected from a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), At least one compound in the group consisting of the compound represented by the following formula (2-3) and the compound represented by the following formula (2-4) (wherein, the following formula (2-2) Except that the compound is a nitrogen-containing heterocyclic compound and the compound represented by the following formula (2-3) is a nitrogen-containing heterocyclic compound),

(In formula (2-1), R ¹¹ is "-NR ²⁶ R ²⁷ "or "-OR ²⁸ ", R ¹² is a monovalent organic group having 1 to 10 carbon atoms; R ²⁶ , R ²⁷ and R ²⁸ are independently The ground is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; wherein, R ²⁶ and R ²⁷ may also be combined with each other and form a ring structure together with the nitrogen atom to which R ²⁶ and R ²⁷ are bonded; formula (2-2 ), R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a C 1-10 monovalent organic group, and two or more of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are organic Groups can also be bonded to form a ring structure (including nitrogen-containing aromatic heterocycles); in formula (2-3), R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independently a hydrogen atom and an amine group Or a monovalent organic group having 1 to 10 carbon atoms, R ²¹ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and two or more of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are organic The group can also be bonded to form a ring structure (wherein the nitrogen-containing aromatic heterocycle is excluded); in formula (2-4), R ²² , R ²³ , R ²⁴ and R ²⁵ are each independently a hydrogen atom or a carbon number 1 to 10 monovalent organic groups; wherein, R ¹¹ to R ²⁵ do not have at least one of an acidic functional group and an electron-withdrawing group; m and n have the same meaning as the above formula (1-1), R ³ And r have the same meaning as the above formula (1-4)). The liquid crystal alignment agent according to item 1 or 2 of the patent application, wherein the first polymer is a polymer having a partial structure represented by the following formula (4),

(In formula (4), X ¹ is a tetravalent organic group, and X ² is a divalent organic group). The liquid crystal alignment agent according to item 1 or item 2 of the patent application scope, wherein the second polymer is selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, At least one of the group consisting of a polymer having a structural unit derived from a monomer having a polymerizable unsaturated bond. The liquid crystal alignment agent according to item 1 or 2 of the patent application, wherein the second polymer has a photo-alignment group. A method for manufacturing a liquid crystal alignment agent, comprising: a step of mixing a first polymer, a second polymer, and a compound (A), and the first polymer has an acidic functional group, and the second polymer is Unlike the first polymer, the compound (A) has a partial structure selected from the following formula (1-1), a partial structure represented by the following formula (1-2), At least one nitrogen-containing structure in the group consisting of the partial structure represented by the following formula (1-3) and the partial structure represented by the following formula (1-4) (wherein, the following formula (1 -2) Except at least one of the partial structure represented by and the partial structure represented by the following formula (1-3) except the nitrogen-containing aromatic heterocyclic ring), and does not have an acidic functional group and an electron-withdrawing group A compound of at least one of (wherein the second polymer has a nitrogen-containing aromatic heterocyclic ring when the compound (A) has a partial structure represented by the following formula (1-1),

(In formula (1-1), regarding R ¹ and R ² , R ¹ is a monovalent group bonded to a pyridine ring via a nitrogen atom or an oxygen atom, and R ² is a monovalent organic group, or R ¹ And R ² represents R ¹ (wherein R ¹ is bonded to a pyridine ring through a nitrogen atom or an oxygen atom) and R ^{2 is} combined with each other and formed together with the carbon atoms to which R ¹ and R ² are bonded; m is an integer of 1 to 3, n is an integer of 0 to 2, m+n≦3; when m is 2 or 3, a plurality of R ¹ may be the same or different, and when n is 2, Multiple R ² may be the same or different; in formula (1-4), R ³ is a C 1-5 alkyl group; r is an integer from 0 to 3; when r is 2 or 3, multiple R ³ may be the same or different; "*" in formula (1-1) to formula (1-4) represents a bond). A method for manufacturing a liquid crystal alignment film, which uses the liquid crystal alignment agent as described in any one of claims 1 to 5 to form a coating film on a substrate, and irradiates the coating film with light to give the liquid crystal alignment ability. A liquid crystal alignment film is formed using the liquid crystal alignment agent as described in any one of claims 1 to 5 in the patent application. A liquid crystal element including the liquid crystal alignment film as described in item 8 of the patent application.