JP6701661B2 - Liquid crystal aligning agent, method for producing liquid crystal element, liquid crystal aligning film and liquid crystal element - Google Patents

Description

The present invention relates to a liquid crystal aligning agent, a method of manufacturing a liquid crystal device, it relates to a liquid crystal alignment film and a liquid crystal element.

  Among liquid crystal elements, an MVA (Multi-Domain Vertical Alignment) type panel, which has been conventionally known as a vertical alignment mode, forms a protrusion in a liquid crystal panel, and thereby controls a tilting direction of liquid crystal molecules to thereby reduce a viewing angle. We are trying to expand. However, according to this method, it is inevitable that the transmittance and contrast due to the protrusions are insufficient, and further, the response speed of the liquid crystal molecules is relatively slow.

  In recent years, a PSA (Polymer Sustained Alignment) mode has been proposed in order to solve the problems of the MVA type panel as described above (see, for example, Patent Document 1). In this PSA technology, a component (photopolymerizable compound) that is polymerized by light irradiation is mixed in the liquid crystal layer of the liquid crystal cell, and the liquid crystal molecule is tilted by voltage application and the liquid crystal cell is irradiated with light. , A technique for controlling the molecular orientation of liquid crystal molecules by polymerizing a photopolymerizable compound. However, when controlling the alignment of liquid crystal molecules by the PSA technique, it is necessary to perform light irradiation with a relatively high irradiation amount. Therefore, in addition to the problem that the liquid crystal molecules decompose, unreacted compounds that did not polymerize due to UV irradiation remain in the liquid crystal layer, which in turn causes display unevenness, voltage holding characteristics and long-term reliability of the panel. There is a concern that this may cause a decrease in sex.

  On the other hand, a liquid crystal element can be obtained in which a desired pretilt angle characteristic can be imparted to a coating film formed by using a liquid crystal aligning agent with a light irradiation amount as small as possible and the response speed of liquid crystal molecules to a voltage change is sufficiently fast. A technique for this has been proposed (see, for example, Patent Document 2). In Patent Document 2, a liquid crystal alignment film containing a polymer having a photopolymerizable group is used to form a liquid crystal alignment film on a substrate, and a liquid crystal cell is formed using the substrate, and a voltage is applied between the substrates. It is disclosed that a liquid crystal element is manufactured by irradiating a liquid crystal cell with light in an applied state.

  Further, in recent years, a liquid crystal dropping method (ODF method) has been adopted as a method of manufacturing a liquid crystal cell that has been adopted with an increase in the size of a substrate. In the ODF method, a required amount of liquid crystal is dropped onto a predetermined number of places on a substrate on which a liquid crystal alignment film is formed, and the liquid crystal is attached to the other substrate in a vacuum and the liquid crystal is spread over the entire surface of the substrate. This is a method of filling the liquid crystal over the entire panel by UV-curing a sealing agent for sealing. This method is a technique capable of significantly shortening the process time of the liquid crystal filling step as compared with the vacuum injection method which has been conventionally performed. In particular, this method is often used in the manufacture of vertical alignment type liquid crystal display elements used for large-sized liquid crystal display elements such as televisions.

JP, 2003-149647, A JP, 2011-118358, A

  While the method of manufacturing a liquid crystal element by the ODF method has the above advantages, display unevenness called "ODF unevenness" is likely to occur, which may affect display quality. Further, with the recent increase in definition of liquid crystal panels, the demand for display quality is becoming more and more stringent, and while shortening the time for the manufacturing process of liquid crystal elements, the response speed of liquid crystal molecules is increased to cause afterimages and display unevenness. A new liquid crystal aligning agent that can obtain a liquid crystal element that is unlikely to occur is required.

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a liquid crystal aligning agent that can obtain a liquid crystal element having good afterimage characteristics and less ODF unevenness.

  When a liquid crystal element is manufactured by the ODF method using a liquid crystal aligning agent containing a photopolymerizable compound as an additive, the cause of the ODF unevenness is that the liquid crystal dropped on the alignment film spreads light in the liquid crystal. It was assumed that elution of the polymerizable compound was one of the reasons. Then, when a photopolymerizable compound having a specific partial structure was contained in a liquid crystal aligning agent, it was found that the above problems could be solved, and the present invention was completed. Specifically, the present invention provides the following means.

[1] A liquid crystal aligning agent containing the following component (A) and component (B).
Component (A): at least one polymer selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane, and a polymer of a monomer having a polymerizable unsaturated bond.
Component (B): A photopolymerizable compound having a specific structure that is at least one of the following (C) structure and (D) structure.
(C) Structure: An intermolecular force weaker than a covalent bond or a reversible covalent bond is formed between the functional group of the component (A) and at least one of the components (B). Partial structure to do.
(D) Structure: A partial structure that forms a covalent bond by heating in at least one of the (A) component and the (B) component.

  According to the liquid crystal aligning agent containing the above-mentioned components (A) and (B), a liquid crystal element having a good display quality with less afterimage and ODF unevenness can be obtained.

  Hereinafter, each component contained in the liquid crystal aligning agent according to the present invention and other components optionally blended as necessary will be described.

<(A) component>
The liquid crystal aligning agent according to the present invention is at least one selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane, and a polymer of a monomer having a polymerizable unsaturated bond (hereinafter also referred to as “specific polymer”). Including).
[Polyamic acid]
The polyamic acid according to the present invention can be obtained by reacting a tetracarboxylic dianhydride and a diamine compound.

(Tetracarboxylic acid dianhydride)
Examples of the tetracarboxylic acid dianhydride used for the synthesis of the polyamic acid include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride and the like. .. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, and 5-(2,5-dicarboxylic acid dianhydride. Oxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8 -Methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro -3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3 ,5,6-Tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4. 6: 8-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8,10- tetraone, cyclohexane tetracarboxylic acid dianhydride and the like; Examples of the aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, and the like; and JP-A 2010-97188. The tetracarboxylic dianhydride described in 1. can be used. In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

（式（Ｅ−１）中、Ｘ^I及びＸ^IIは、それぞれ独立に、単結合、−Ｏ−、＊−ＣＯＯ−又は＊−ＯＣＯ−（ただし、「＊」はＸ^Ｉとの結合手を示す。）であり、Ｒ^Ｉは炭素数１〜３のアルカンジイル基であり、Ｒ^ＩＩは単結合又は炭素数１〜３のアルカンジイル基であり、ａは０又は１であり、ｂは０〜２の整数であり、ｃは１〜２０の整数であり、ｄは０又は１である。但し、ａ及びｂが同時に０になることはない。）
で表される化合物などの配向性基含有ジアミン： (Diamine compound)
Examples of the diamine compound used for synthesizing the polyamic acid include aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane and the like. Specific examples of these diamines include aliphatic diamines such as metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine; and alicyclic diamines such as 1,4. -Diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine) and the like;
As the aromatic diamine, for example, dodecanoxydiaminobenzene, hexadecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, cholesteryloxydiaminobenzene, cholestanyl diaminobenzoate, cholesteryl diaminobenzoate, diaminobenzoic acid. Lanostanyl, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butyl Cyclohexane, the following formula (E-1)

(In formula (E-1), X ^I and X ^II are each independently a single bond, —O—, *—COO— or *—OCO— (where “*” is a bond to 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, and b is 0. Is an integer of 2 to 2, c is an integer of 1 to 20, and d is 0 or 1. However, a and b are not 0 at the same time.)
An orienting group-containing diamine such as a compound represented by:

p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis(4-amino) Phenoxy)pentane, bis[2-(4-aminophenyl)ethyl]hexanedioic 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 '-(Phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl and the like; as diaminoorganosiloxane, for example, 1,3- Examples thereof include bis(3-aminopropyl)-tetramethyldisiloxane; and diamines described in JP 2010-97188 A can be used.

（式（Ｃ−１）中、Ｘ^９は単結合、酸素原子又は炭素数１〜３のアルカンジイル基である。ｍ１及びｍ２は、それぞれ独立に０又は１である。） As the diamine compound used for synthesizing the polyamic acid, a diamine having a carboxyl group (hereinafter, also referred to as “carboxyl group-containing diamine”) can be preferably used. It is preferable to blend a polymer having a partial structure derived from a carboxyl group-containing diamine together with the following component (B) in that the effect of improving display unevenness of the liquid crystal display device can be improved.
As the carboxyl group-containing diamine used in the synthesis, a diamine having an aromatic carboxylic acid structure in which a carboxyl group is bonded to an aromatic ring such as a benzene ring can be preferably used. Specifically, for example, a compound represented by the following formula (C-1) and the like can be mentioned.

(In the formula (C-1), X ⁹ is a single bond, an oxygen atom or an alkanediyl group having 1 to 3 carbon atoms. m1 and m2 are each independently 0 or 1.)

  Specific examples of the compound represented by the above formula (C-1) include, for example, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid and 4,4′-diaminobiphenyl. Monocarboxylic acids such as -3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid; 4,4'-diaminobiphenyl-3,3' -Dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid Acid, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, dicarboxylic acid such as 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid; and the like.

  When synthesizing the polyamic acid, the use ratio of the carboxyl group-containing diamine is 5 mol% or more with respect to the total amount of the diamine used for the synthesis, from the viewpoint of sufficiently obtaining the improvement effect of suppressing ODF unevenness by using the diamine. Is preferable, and more preferably 10 mol% or more, further preferably 20 mol% or more. Further, the upper limit of the use ratio is not particularly limited, but from the viewpoint of the voltage holding ratio, it is preferably 90 mol% or less, and preferably 80 mol% or less, with respect to the total amount of the diamine used in the synthesis. Is more preferable. In addition, the carboxyl group-containing diamine can be used alone or by appropriately selecting two or more of the above.

(Synthesis of polyamic acid)
The polyamic acid can be obtained by reacting the above-mentioned tetracarboxylic acid dianhydride and a diamine compound together with a molecular weight modifier, if necessary. The ratio of the tetracarboxylic dianhydride and the diamine compound used for the synthesis reaction of the polyamic acid is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 with respect to 1 equivalent of the amino group of the diamine compound. A ratio of about 2 equivalents is preferable. As the molecular weight modifier, for example, acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate, etc. Can be mentioned. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less with respect to 100 parts by mass of the total tetracarboxylic dianhydride and 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 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. Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol. And at least one selected from the group consisting of halogenated phenols as a solvent, or a mixture of at least one of these with other organic solvents (eg butyl cellosolve, diethylene glycol diethyl ether, etc.) preferable. The amount (a) of the organic solvent used is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine becomes 0.1 to 50% by mass with respect to the total amount (a+b) of the reaction solution. Is preferred.
As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution.

[Polyamic acid ester]
The polyamic acid ester according to the present invention is, for example, [I] a method of reacting the polyamic acid obtained by the above synthetic reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine compound, III] Tetracarboxylic acid diester dihalide and diamine compound may be reacted. The polyamic acid ester contained in the liquid crystal aligning agent may have only an amic acid ester structure, or may be a partial esterified product having both an amic acid structure and an amic acid ester structure. The reaction solution obtained by dissolving the polyamic acid ester may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid ester contained in the reaction solution. Good.

[Polyimide]
The polyimide can be obtained, for example, by subjecting the polyamic acid synthesized as described above to dehydration ring closure to imidize. The polyimide may be a completely imidized product obtained by dehydration ring closure of all of the amic acid structure of the precursor polyamic acid, dehydration ring closure of only a portion of the amic acid structure, amic acid structure and imide It may be a partial imidized compound having a ring structure. The imidization ratio of the polyimide used in the reaction is preferably 20 to 99%, more preferably 30 to 90%. The imidization ratio is a percentage of the ratio of the number of imide ring structures to the total number of amic acid structures and imide ring structures of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably performed by a method of heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, and by adding a dehydrating agent and a dehydration ring-closing catalyst in this solution and heating as necessary. . Of these, the latter method is preferable.
In the method of adding the dehydrating agent and the dehydration ring-closing catalyst to the solution of polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 mol per 1 mol of the amic acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent used for the dehydration ring closure reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature for the dehydration ring closure reaction is preferably 0 to 180°C. The reaction time is preferably 1.0 to 120 hours.
In this way, a reaction solution containing polyimide is obtained. This reaction solution may be used as it is for preparing a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after isolation of polyimide. Polyimide can also be obtained by imidization of polyamic acid ester.

  The polyamic acid, the polyamic acid ester, and the polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa·s when the solution has a concentration of 10% by mass, and preferably 15 to 500 mPas. More preferably, it has a solution viscosity of s. The solution viscosity (mPa·s) of polyamic acid, polyamic acid ester and polyimide is 10% by mass prepared using a good solvent for these polymers (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25° C. using the E-type rotational viscometer for the polymer solution of

  The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to. It is 300,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, and more preferably 10 or less. Within such a molecular weight range, good alignment and stability of the liquid crystal display device can be secured.

[Polyorganosiloxane]
The polyorganosiloxane according to the present invention can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound.
Examples of the silane compound used in the synthesis of polyorganosiloxane include alkoxysilane compounds such as tetramethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and dimethyldiethoxysilane; 3-mercaptopropyltriethoxy. Nitrogen/sulfur-containing alkoxysilane compounds such as silane, mercaptomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(3-cyclohexylamino)propyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3- Epoxy group-containing silane compounds such as glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; 3-(meth)acryloxypropyltrimethoxy Unsaturated bond-containing alkoxysilane compounds such as silane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, vinyltriethoxysilane; trimethoxysilylpropylsuccinic anhydride and the like. Can be mentioned. As the hydrolyzable silane compound, one of these compounds may be used alone or two or more thereof may be used in combination. In addition, "(meth)acryloxy" is meant to include "acryloxy" and "methacryloxy".

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

  The above hydrolysis/condensation reaction is preferably carried out, for example, by heating with an oil bath or the like. At that time, the heating temperature is preferably 130° C. or lower, and the heating time is preferably 0.5 to 12 hours. After completion of the reaction, the organic solvent layer separated from the reaction solution is dried with a desiccant, if necessary, and then the solvent is removed to obtain the target polyorganosiloxane. The method for synthesizing the polyorganosiloxane is not limited to the above-mentioned hydrolysis/condensation reaction, and may be, for example, a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol.

The polyorganosiloxane as the component (A) may be a polyorganosiloxane having a liquid crystal aligning group in its side chain (hereinafter, also referred to as “aligning group-containing polysiloxane”). The method of synthesizing the oriented group-containing polysiloxane is not particularly limited, but a polyorganosiloxane having an epoxy group in a side chain by using an epoxy group-containing silane compound as at least a part of the raw material (hereinafter, referred to as “epoxy group-containing polysiloxane”). ).), and then reacting an epoxy group-containing polysiloxane with a carboxylic acid having a liquid crystal aligning group. This method is preferable because it is simple and the introduction rate of the liquid crystal aligning group can be increased. Alternatively, the orientation group-containing polysiloxane may be synthesized by a reaction containing a hydrolyzable silane compound having a liquid crystal orientation group as a monomer.
With respect to the polyorganosiloxane as the component (A), the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably in the range of 100 to 50,000, and more preferably in the range of 200 to 10,000. More preferable.

[Polymer of monomer having polymerizable unsaturated bond]
In a polymer of a monomer having a polymerizable unsaturated bond (hereinafter, also referred to as “polymer (PAc)”), the polymerizable unsaturated bond contained in the monomer is, for example, a (meth)acryloyl group, a vinyl group or a styryl group. , Maleimide groups, and the like. Specific examples of the monomer having a polymerizable unsaturated bond include, for example, unsaturated carboxylic acids such as (meth)acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, and vinylbenzoic acid: (meth)acrylic acid. Cycloalkyl alkyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, trimethoxysilylpropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic Unsaturated carboxylic acid esters such as glycidyl acid salt, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4-hydroxybutyl glycidyl ether acrylate: maleic anhydride and the like (Meth)acrylic compounds such as saturated polycarboxylic acid anhydrides; aromatic vinyl compounds such as styrene, methylstyrene and divinylbenzene; conjugated dienes such as 1,3-butadiene and 2-methyl-1,3-butadiene Compounds; maleimide group-containing compounds such as N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide; and the like. In addition, the monomer which has a polymerizable group unsaturated bond can be used individually by 1 type or in combination of 2 or more types.

  From the viewpoint of transparency and material strength, the polymer (PAc) is preferably a polymer of a monomer containing a (meth)acrylic compound among the above. When synthesizing the polymer (PAc), the proportion of the (meth)acrylic compound used is preferably 50 mol% or more, and more preferably 60 mol% or more, based on the total amount of the monomers used in the synthesis. More preferably, it is more preferably 70 mol or more.

  The polymer (PAc) can be obtained, for example, by polymerizing a monomer having a polymerizable group unsaturated bond in the presence of a polymerization initiator. Examples of the polymerization initiator used include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile) and 2,2′-azobis(4-methoxy-2). , 4-dimethylvaleronitrile) and the like are preferable. The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of all the 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, hydrocarbon compounds and the like, with diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate being preferred. The reaction temperature is preferably 30°C to 120°C, and the reaction time is preferably 1 to 36 hours. The amount (a) of the organic solvent used is such that the total amount (b) of the monomers used in the reaction is 0.1 to 60 mass% with respect to the total amount (a+b) of the reaction solution. Is preferred.

The polymer (PAc) as the component (A) may be a polymer having a liquid crystal aligning group in its side chain (hereinafter, also referred to as “aligning group-containing polymer (PAc)”). The method for synthesizing the oriented group-containing polymer (PAc) is not particularly limited. For example, a compound having an epoxy group in a side chain is synthesized by using an epoxy group-containing compound as at least a part of the raw material, and then a liquid crystal. Examples thereof include a method of reacting with a carboxylic acid having an oriented group.
The polystyrene-equivalent weight average molecular weight (Mw) of the polymer (PAc) measured by GPC is preferably 250 to 500,000, more preferably 500 to 100,000, and 1,000 to 50. More preferably, it is 1,000.

  Among these, the component (A) preferably contains at least one selected from the group consisting of polyimide, polyamic acid and polyamic acid ester. The carboxyl group of these polymers (corresponding to the functional group of the component (A)) enhances the interaction with the component (B). The specific polymer contained in the liquid crystal aligning agent may be used alone or in combination of two or more. As a preferred embodiment of the component (A), <1> The component (A) is at least one selected from the group consisting of polyimide, polyamic acid and polyamic acid ester, <2> The component (A) is polyimide, At least one selected from the group consisting of polyamic acid and polyamic acid ester, and an embodiment that is a polyorganosiloxane, <3> (A) component is at least one selected from the group consisting of polyimide, polyamic acid and polyamic acid ester, The aspect which is a polymer (PAc), etc. are mentioned.

<(B) component>
The liquid crystal aligning agent according to the present invention, together with the component (A), is a photopolymerizable compound having a specific structure that is at least one of the following (C) structure and the following (D) structure (hereinafter also referred to as “compound (B)”). .) is included. In addition, in this specification, a "photopolymerizable compound" means a compound having at least one photopolymerizable group.
(C) Structure: A moiety that generates an intermolecular force weaker than a covalent bond or forms a reversible covalent bond between the functional group of the component (A) and/or the component (B). Construction.
(D) Structure: A partial structure that forms a covalent bond by heating in at least one of the (A) component and the (B) component.

（式（４）中、Ｒ^１は酸素原子、硫黄原子又は−ＮＨ−である。Ｘ^１〜Ｘ^３は、それぞれ独立に水素原子、ハロゲン原子又は１価の有機基である。ただし、Ｒ^１が酸素原子の場合、Ｘ^３は他の基と結合して−ＣＯ−Ｒ^１−と共に環を形成していてもよい「＊」は結合手を示す。） The photopolymerizable group contained in the compound (B) may be any functional group that can be polymerized by irradiation with light, and examples thereof include a group having a polymerizable carbon-carbon unsaturated bond. Specific examples thereof include (meth)acryloyl group, vinyl group, styryl group, and maleimide group. The number of photopolymerizable groups contained in the compound (B) is not particularly limited and may be one or plural. From the viewpoint of suitably controlling the pretilt angle of the coating film and increasing the response speed of the liquid crystal molecules, the number is preferably 2 or more, and more preferably 2 to 4.
The compound (B) is preferably a compound having a group represented by the following formula (4) as a photopolymerizable group from the viewpoint of sufficiently enhancing the alignment regulating force in the alignment film and reducing the afterimage. A compound having two or more groups represented by formula (4) is more preferred.

(In the formula (4), ^{R 1} is ^.X 1 to X ³ oxygen atom, a sulfur atom or -NH- are each independently a hydrogen atom, a halogen atom or a monovalent organic group. However, ^{R 1} Is an oxygen atom, X ³ may be bonded to another group to form a ring with —CO—R ¹ —, “*” represents a bond.

（式（４−１）中、Ｒ^１は酸素原子、硫黄原子又は−ＮＨ−である。Ｘ^７は水素原子、メチル基又はパーフルオロメチル基である。） Examples of the monovalent organic group represented by X ^{1 to} X ³ in the above formula (4) include a monovalent chain hydrocarbon group having 1 to 12 carbon atoms and a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms. And a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and the like, and the hydrogen atom of these hydrocarbon groups may be substituted with a halogen atom or the like. X ¹ and X ² are preferably hydrogen atoms, and X ³ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, or a monovalent group having 6 to 12 carbon atoms. The aromatic ring group is preferably. When X ³ is an aromatic ring group, specific examples thereof include a phenyl group and a tolyl group.
Specific preferred examples of the partial structure represented by the above formula (4) include structures represented by the following formulas (4-1) and (4-2).

(In the formula (4-1), R ¹ is an oxygen atom, a sulfur atom or —NH—. X ⁷ is a hydrogen atom, a methyl group or a perfluoromethyl group.)

（式（１）中、Ｘ^４は酸素原子又は硫黄原子であり、Ｒ^２は酸素原子、硫黄原子、アルカンジイル基、芳香環基、シクロヘキシレン基、又は−ＮＲ^３２−（Ｒ^３２は水素原子又は保護基である。）であり、Ｒ^３０は水素原子又は保護基である。ただし、Ｒ^２が芳香環基又はシクロヘキシレン基の場合、Ｒ^３０は保護基である。式（２）中、Ｘ^５は２価の炭化水素基又は−ＮＲ^３３−（Ｒ^３３は水素原子又は保護基である。）である。「＊」は結合手を示す。） The specific structure is not particularly limited as long as it exhibits the above characteristics, and can be appropriately selected depending on the functional group of the component (A). Here, the (C) structure "intermolecular force weaker than covalent bond" means, for example, ion-dipole interaction, dipole-dipole interaction, hydrogen bond, coordination bond, van der Waals force, etc. It means the electromagnetic force that acts between molecules. Examples of the structure (C) include a partial structure represented by the following formula (1), a partial structure represented by the following formula (2), a partial structure represented by the following formula (3), a tertiary amine structure, nitrogen-containing heterocyclic ^{structure, -NR 31 X 10, -NHX 10} ( provided ^{that, R 31} is a monovalent hydrocarbon ^{group, X 10} is a protecting group.), a hydroxyl group, a carboxyl group, _-NH 2, - Examples thereof include NHR ⁴¹ (R ⁴¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms), a thiol group, a phosphoric acid group and the like. The structure (C) includes, among others, a partial structure represented by the following formula (1), a partial structure represented by the following formula (2), a partial structure represented by the following formula (3), a tertiary amine structure, and a nitrogen-containing structure. It is preferably at least one selected from the group consisting of a heterocyclic structure and —NR ³¹ X ¹⁰ .

(In the formula (1), X ⁴ is an oxygen atom or a sulfur atom, R ² is an oxygen atom, a sulfur atom, an alkanediyl group, an aromatic ring group, a cyclohexylene group, or —NR ³² — (R ³² is a hydrogen atom. R ³⁰ is a hydrogen atom or a protecting group, provided that when R ² is an aromatic ring group or a cyclohexylene group, R ³⁰ is a protecting group. X ⁵ is a divalent hydrocarbon group or —NR ³³ — (R ³³ is a hydrogen atom or a protective group. “*” represents a bond)

（式（８−１）〜式（８−５）中、Ａｒ^１１は炭素数６〜１０の１価の芳香環基であり、Ｒ^２１は炭素数１〜１２のアルキル基であり、Ｒ^２３はメチレン基又はエチレン基である。「＊」は窒素原子に結合する結合手を示す。） In the above formula (1), examples of the alkanediyl group of R ² include a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, and the like, which may be linear or branched. Examples of the aromatic ring group include a phenylene group, a biphenylene group, a naphthalene group and the like, which may have a substituent in the ring portion. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom and the like. The protective group for R ³⁰ and R ³² is preferably a group capable of leaving by heat, and examples thereof include a carbamate-based protective group, an amide-based protective group, an imide-based protective group, a sulfonamide-based protective group, and the following formula (8-1) ) To groups represented by formulas (8-5) and the like. Among them, a tert-butoxycarbonyl group is preferable because it has a high releasability by heat and reduces the amount of the deprotected portion remaining in the film.

(In formula (8-1) to formula (8-5), Ar ¹¹ is a monovalent aromatic ring group having 6 to 10 carbon atoms, R ²¹ is an alkyl group having 1 to 12 carbon atoms, and R ^{23 is} Is a methylene group or an ethylene group. "*" represents a bond that bonds to a nitrogen atom.)

In the formula (1), R ² is preferably an oxygen atom, a sulfur atom, an alkanediyl group or —NR ³² —, more preferably —NR ³² —, and —NH— in terms of a high effect of improving ODF unevenness suppression. More preferable. X ⁴ is preferably a sulfur atom from the viewpoint of suppressing ODF unevenness, and is preferably an oxygen atom from the viewpoint of ease of compound synthesis and cost. R ³⁰ is preferably a hydrogen atom.
In the above formula (2), examples of the divalent hydrocarbon group for X ⁵ include a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group and a divalent aromatic hydrocarbon group. As for the protecting group for R ³³ , the description of the examples and preferred specific examples of the protecting group for R ³⁰ and R ³² are applicable. R ³³ is preferably a hydrogen atom. In addition, the nitrogen atom of "-C=N-" in the formula (2) may be bonded to a monovalent group such as a hydrogen atom or an alkyl group, and by bonding to X ⁵ , a ring structure is formed. It may have been done.

（式中、「＊」は結合手であることを示す。） Specific preferred examples of the partial structure represented by the above formula (1) include structures represented by the following formulas (1-1) and (1-2), and the above formula (2). Specific preferred examples of the partial structure represented by are, for example, structures represented by the following formulas (2-1) and (2-2).

(In the formula, "*" indicates a bond.)

（式（Ｎ−１）中、Ｒ^６は置換又は無置換の１価の炭化水素基である。「＊」は炭化水素基に結合する結合手である。） The tertiary amine structure of the above (C) is a structure in which three hydrocarbon groups are directly bonded to the nitrogen atom, and is represented by, for example, the following formula (N-1).

(In the formula (N-1), R ⁶ is a substituted or unsubstituted monovalent hydrocarbon group. “*” is a bond bonded to the hydrocarbon group.)

In the above formula (N-1), the monovalent hydrocarbon group of R ⁶ preferably has 1 to 10 carbon atoms, and specifically, for example, a linear group such as a methyl group, an ethyl group, a propyl group, a butyl group or the like. Examples thereof include branched alkyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups and methylphenyl; aralkyl groups such as benzyl groups. Examples of the substituent that R ⁶ may have include a halogen atom, a cyano group, an alkylsilyl group, an alkoxysilyl group, a group represented by the following formula (4), and the like. R ⁶ is preferably an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group, a phenyl group, or a benzyl group, and has a high effect of improving ODF unevenness suppression, and is an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group, or benzyl. Groups are more preferred. Examples of the hydrocarbon group to which “*” in the above formula (N-1) is bonded include an alkanediyl group, a cyclohexylene group, a phenylene group and the like.

Examples of the nitrogen-containing heterocyclic structure (C) include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, 1H-pyrrolo[2,3-b]pyridine, purine, quinoline. , Isoquinoline, naphthyridine, phenazine, quinoxaline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine and hexamethyleneimine, etc. Be done. Here, examples of the substituent that the nitrogen-containing heterocycle has include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and the like. The nitrogen-containing heterocycle is preferably at least one selected from the group consisting of pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, imidazole, 1H-pyrrolo[2,3-b]pyridine and acridine. The nitrogen-containing heterocyclic structure is preferably in the main chain of the compound (B) from the viewpoint of response speed.
In "-NR ³¹ X ¹⁰ ", the monovalent hydrocarbon group for R ³¹ is preferably an alkyl group having 1 to 5 carbon atoms. For X ¹⁰ , the examples of the protecting groups for R ³⁰ and R ³² and the description of the preferred specific examples are applied.

The (D) structure, for example, an epoxy group (including an oxetanyl group and an oxiranyl group.), Isocyanate group, blocked isocyanate ^{group, -NHX} 10 ^{(X 10} is a protecting group.), A hydroxyl group, a carboxyl group, -NH ₂ , Thiol groups and the like.
The blocked isocyanate group (D) is not particularly limited as long as it is a group that regenerates an isocyanate group by deprotection by heat. The blocking agent for blocking the isocyanate group is not particularly limited, for example, alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, pyrazole compounds, Examples thereof include urea compounds, oxime compounds, amine compounds, imine compounds, pyridine compounds and the like.
Among them, the structure (D) is preferably at least one selected from the group consisting of epoxy groups, isocyanate groups and blocked isocyanate groups, and more preferably at least one selected from the group consisting of isocyanate groups and blocked isocyanate groups.

The specific structure contained in the compound (B) is, among the above, a partial structure represented by the above formula (1), a partial structure represented by the above formula (2), a partial structure represented by the above formula (3), It is preferably at least one selected from the group consisting of a tertiary amine structure, a nitrogen-containing heterocyclic structure, —NR ³¹ X ¹⁰ , an epoxy group, an isocyanate group and a blocked isocyanate group. Among them, the structure (C) is preferable because the effect of improving the response speed of liquid crystal molecules is high. Specifically, the partial structure represented by the above formula (1), the partial structure represented by the above formula (2), the partial structure represented by the above formula (3), a tertiary amine structure, a nitrogen-containing heterocycle. It is preferably at least one selected from the group consisting of a structure and —NR ³¹ X ¹⁰ and at least selected from the group consisting of a partial structure represented by the above formula (2), a tertiary amine structure and a nitrogen-containing heterocyclic structure. Particularly preferred is one.

（式（６）中、Ａｒ^３及びＡｒ^４は、各々独立に１，４−フェニレン基又は１，４−シクロヘキシレン基であり、Ｘ^８は単結合又は−ＣＯＯ−である。ｎ２は１又は２である。ｎ２＝２のとき、Ａｒ^４，Ｘ^８は各々独立に上記定義を有する。「＊」は結合手を示す。） From the viewpoint of improving the affinity with liquid crystals and increasing the response speed of liquid crystal molecules, the compound (B) preferably further has a partial structure represented by the following formula (6) in the molecule.

(In formula (6), Ar ³ and Ar ⁴ are each independently a 1,4-phenylene group or a 1,4-cyclohexylene group, and X ⁸ is a single bond or —COO—. n2 is 1 or 2. When n2=2, Ar ⁴ and X ⁸ each independently have the above definition. “*” represents a bond.)

（式中、「＊」は結合手を示す。） Specific examples of the partial structure represented by the above formula (6) include, for example, 4,4′-biphenylene group, 4,4′-bicyclohexylene group, and the following formulas (6-1) to (6-4) ) And the like.

(In the formula, "*" indicates a bond.)

（式（５）中、Ｘ^６は水素原子、フッ素原子、炭素数１〜６のアルキル基、炭素数１〜６のフルオロアルキル基又は炭素数６〜１２の１価の芳香族基であり、Ｒ^３は酸素原子、硫黄原子又は−ＮＨ−であり、Ａｒ^１及びＡｒ^２は、各々独立に、１，４−フェニレン基、１，４−シクロヘキシレン基、ピペリジン−１，４−ジイル基、ピペリジン−２，５−ジイル基、ピペラジン−１，４−ジイル基、ピペラジン−２，５−ジイル基、ピリミジン−２，５−ジイル基、ピリダジン−３，６−ジイル基、ピラジン−２，５−ジイル基、ピリジン−２，５−ジイル基、ナフチレン基、テトラヒドロナフタレンジイル基、又はデカヒドロナフタレンジイル基であり、環部分に置換基を有していてもよい。Ｒ^４は単結合、エステル結合、アミド結合、エーテル結合、又は−ＣＯ−ＮＲ^３４−（Ｒ^３４は保護基である。）であり、Ｒ^５はエステル結合、アミド結合、エーテル結合、又は−ＣＯ−ＮＲ^３５−（Ｒ^３５は保護基である。）である。ｎ１は０〜２の整数である。ｎ１＝２のとき、Ｒ^４，Ａｒ^２は各々独立に上記定義を有する。「＊」は結合手を示す。） The compound (B) is preferably a compound having a partial structure represented by the following formula (5) from the viewpoint of improving the affinity with the liquid crystal.

(In the formula (5), X ⁶ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, or a monovalent aromatic group having 6 to 12 carbon atoms, R ³ is an oxygen atom, a sulfur atom or —NH—, Ar ¹ and Ar ² are each independently a 1,4-phenylene group, a 1,4-cyclohexylene group, a piperidine-1,4-diyl group, Piperidine-2,5-diyl group, piperazine-1,4-diyl group, piperazine-2,5-diyl group, pyrimidine-2,5-diyl group, pyridazine-3,6-diyl group, pyrazine-2,5 A diyl group, a pyridine-2,5-diyl group, a naphthylene group, a tetrahydronaphthalenediyl group, or a decahydronaphthalenediyl group, which may have a substituent in the ring portion, R ⁴ is a single bond or an ester. bond, an amide bond, an ether bond, or ^{-CO-NR 34} - ^(R 34 is a protecting group.) a, ^{R 5} is an ester bond, an amide bond, an ether bond, or ^{-CO-NR 35} - ^(R 35 Is a protecting group.) n1 is an integer of 0 to 2. When n1=2, R ⁴ and Ar ² each independently have the above definition. “*” indicates a bond.

In formula (5), X ⁶ is preferably a hydrogen atom, a fluorine atom, a methyl group or a fluoromethyl group, and more preferably a hydrogen atom or a methyl group. Examples of the substituent that the ring of Ar ¹ and Ar ² may have include a halogen atom, a cyano group, an alkylsilyl group, an alkoxysilyl group, a group represented by the above formula (4), and the like. Ar ¹ and Ar ² are preferably 1,4-phenylene group, 1,4-cyclohexylene group, naphthylene group, tetrahydronaphthalenediyl group, or decahydronaphthalenediyl group, and 1,4-phenylene group or 1 More preferably, it is a 4-cyclohexylene group. A substituent may be introduced into the ring portion of the 1,4-phenylene group and the 1,4-cyclohexylene group, but it is preferably unsubstituted.
At least one of Ar ¹ and Ar ² is a piperidine-1,4-diyl group, a piperidine-2,5-diyl group, a piperazine-1,4-diyl group, a piperazine-2,5-diyl group, a pyrimidine. When it is a -2,5-diyl group, a pyridazine-3,6-diyl group, a pyrazine-2,5-diyl group or a pyridine-2,5-diyl group, the compound (B) having the above formula (5) is Corresponds to a compound having a nitrogen-containing heterocyclic structure as the specific structure.
As for the protecting groups for R ³⁴ and R ³⁵ , the explanation of the protecting groups for R ³⁰ and R ³² and the description of the preferred specific examples are applied. R ⁴ and R ⁵ are preferably a single bond or an ester bond from the viewpoint of enhancing the affinity with liquid crystal. The partial structure represented by the formula (6) may be introduced into the compound (B) as the group “—Ar ¹ —(R ⁴ —Ar ² ) _n ¹ —” in the formula (5). Of course, it may be introduced into the compound (B) separately from the group. The former is preferable.

（式（Ｄ−１）中、Ｙ^１は、上記式（１）で表される部分構造、上記式（２）で表される部分構造、上記式（３）で表される部分構造、三級アミン構造、窒素含有複素環構造及び−ＮＲ^３１Ｘ^１０よりなる群から選ばれる少なくとも一種を含む２価の基である。Ｒ^７は単結合、エステル結合、アミド結合、エーテル結合、又は−ＣＯ−ＮＲ^３６−（Ｒ^３６は保護基である。）である。Ｒ^８は単結合、アルカンジイル基、フェニレン基、シクロヘキシレン基、又は上記式（６）で表される２価の基である。Ｘ^６、Ｒ^３、Ａｒ^１、Ａｒ^２、Ｒ^４、Ｒ^５、及びｎ１は、それぞれ上記式（５）と同義である。複数のＸ^６及び複数のＲ^３は独立して上記定義を有する。） Specific preferred examples of the compound (B) include compounds represented by the following formula (D-1).

(In the formula (D-1), Y ¹ represents a partial structure represented by the formula (1), a partial structure represented by the formula (2), a partial structure represented by the formula (3), or three. Is a divalent group containing at least one selected from the group consisting of a primary amine structure, a nitrogen-containing heterocyclic structure, and —NR ³¹ X ^10. R ⁷ is a single bond, an ester bond, an amide bond, an ether bond, or —CO. —NR ³⁶ — (R ³⁶ is a protecting group.) R ⁸ is a single bond, an alkanediyl group, a phenylene group, a cyclohexylene group, or a divalent group represented by the above formula (6). X ⁶ , R ³ , Ar ¹ , Ar ² , R ⁴ , R ⁵ and n1 have the same meanings as in the above formula (5), and a plurality of X ⁶ and a plurality of R ³ independently have the above definitions. Have.)

（式（ＤＭ−５０）及び式（ＤＭ−５１）中、Ｒ^１１は水素原子又はメチル基であり、Ｒ^１２及びＲ^１３は各々独立に２価の炭化水素基である。ただし、式中の複数のＲ^１１は同じでも異なってもよく、複数のＲ^１３は同じでも異なってもよい。） Specific examples of the compound (B) include compounds represented by the following formulas (DM-1) to (DM-79). The compound (B) may be used alone or in combination of two or more.

(In formula (DM-50) and formula (DM-51), R ¹¹ is a hydrogen atom or a methyl group, and R ¹² and R ¹³ are each independently a divalent hydrocarbon group. A plurality of R ¹¹ may be the same or different, and a plurality of R ¹³ may be the same or different.)

（式（ＤＭ−６６）〜式（ＤＭ−７１）中、ｎは１〜１０の整数である。）

(In formula (DM-66) to formula (DM-71), n is an integer of 1 to 10.)

  The compound (B) can be synthesized by appropriately combining conventional methods of organic chemistry. For example, the polyfunctional (meth)acrylate compound having the above-mentioned specific structure is prepared by synthesizing a carboxylic acid having a partial structure represented by the above formula (5) and then reacting with a diol having the above-mentioned specific structure, ) Method of reacting with unsaturated carboxylic acid such as acrylic acid; synthesizing a polyfunctional (meth)acrylate compound having a partial structure represented by the above formula (5) and a hydroxy group, and then reacting with a carboxylic acid having the above specific structure A method of reacting; a method of reacting a benzoyl group-containing compound having a partial structure represented by the above formula (5) with a polyol having the above specific structure; and the like. However, the synthetic method of the compound (B) is not limited to these.

  The reason why the effect of improving the afterimage characteristics and the ODF unevenness can be obtained by using the liquid crystal aligning agent containing the compound (B) is not clear, but one reason is that the compound (B) may have It is presumed that this is due to the change in the bond form between B) or between the specific polymer and the compound (B) due to heat. For example, a photopolymerizable compound having a partial structure that forms an intermolecular force that is weaker than a covalent bond with a specific polymer or the like has a specific structure at a temperature after the dropping of liquid crystal (for example, 80° C. or lower, preferably room temperature). The intermolecular interaction (hydrogen bond or coordination bond) between the polymer and the compound (B) or between the compounds (B) suppresses the elution of the compound (B) into the liquid crystal. On the other hand, it is speculated that the intermolecular interaction is weakened by heating during annealing after the liquid crystal cell is constructed. In this case, the (C) structure preferably has no covalent bond when heated. Further, in the photopolymerizable compound having the partial structure represented by the above formula (3), a reversible covalent bond is formed between the compounds (B) by the Diels-Alder reaction at a temperature after dropping the liquid crystal. On the other hand, it is presumed that this covalent bond is broken by heating during annealing after the liquid crystal cell is constructed. It is speculated that such a change in the bonding mode suppresses the display unevenness due to the elution of the compound (B) into the liquid crystal, while improving the response speed of the liquid crystal molecules. However, the above is only an estimation and does not limit the present invention.

  The content ratio of the compound (B) is preferably 1 part by mass or more, and 5 parts by mass or more based on 100 parts by mass of the total amount of the specific polymer as the component (A) contained in the liquid crystal aligning agent. And more preferably 10 parts by mass or more. If the content ratio of the compound (B) is less than 1 part by mass, the response speed of the liquid crystal molecules in the liquid crystal display element tends to be slow and an afterimage tends to occur. Further, from the viewpoint of suppressing the generation of ODF unevenness due to the addition of an excessive amount of the photopolymerizable compound, the content ratio of the compound (B) is 60 parts by mass or less based on 100 parts by mass of the specific polymer. The amount is preferably 50 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 40 parts by mass or less.

<Other ingredients>
The liquid crystal aligning agent according to the present invention contains the above-mentioned components (A) and (B), but may contain other components as necessary. Examples of the other components include other polymers other than the component (A), compounds having at least one epoxy group in the molecule and having no photopolymerizable group, functional silane compounds, and the above. Examples thereof include photopolymerizable compounds having no specific structure, compounds having at least one oxetanyl group in the molecule, antioxidants, surfactants, and photosensitizers. These compounding ratios can be appropriately selected within a range that does not impair the effects of the present invention.

<Solvent>
The liquid crystal aligning agent according to the present invention is a liquid composition obtained by dispersing or dissolving the above-mentioned components (A) and (B), and optionally other components, in a suitable solvent. It is prepared as a product.

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

  The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferably It is in the range of 1 to 10 mass %. That is, the liquid crystal aligning agent according to the present invention is applied to the surface of a substrate as described below and preferably heated to form a coating film which is a liquid crystal alignment film or a coating film which becomes a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes excessively large, and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coating property deteriorates. There is a tendency.

[Liquid crystal alignment film and liquid crystal element]
The liquid crystal alignment film according to the present invention is formed by the liquid crystal alignment agent prepared as described above. Further, the liquid crystal element according to the present invention comprises a liquid crystal alignment film formed using the above liquid crystal aligning agent. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited and includes, for example, various types such as TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type. It can be applied to operating modes.

  The method for producing a liquid crystal element using the above liquid crystal aligning agent is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, (1) a liquid crystal aligning agent on a pair of substrates having conductive films on the conductive film. And then heating this to form a coating film, (2) a pair of substrates having the coating film formed thereon are arranged so as to face each other so that the coating films face each other through a liquid crystal layer, and a liquid crystal cell And a step of irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates.

[Step (1): Formation of coating film]
As the substrate to which the liquid crystal aligning agent is applied, for example, a glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone or polycarbonate can be used. It is preferable to use a transparent conductive film as the conductive film included in the substrate. For example, a NESA (registered trademark) film made of SnO _{2 or} an ITO film made of In ₂ O ₃ —SnO ₂ can be used.
The liquid crystal aligning agent can be applied onto the conductive film of the substrate by an appropriate applying method such as a roll coater method, a spinner method, an offset printing method, an inkjet printing method or the like. After the application of the liquid crystal aligning agent, preheating (prebaking) is preferably carried out for the purpose of preventing liquid drip of the applied aligning agent. The prebaking temperature is preferably 30 to 200°C. The prebake time is preferably 0.25 to 10 minutes. Then, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, for thermal imidization of the amic acid structure present in the polymer. The firing temperature (post bake temperature) at this time is preferably 80 to 300°C. The post bake time is preferably 5 to 200 minutes. The film thickness of the coating film after post-baking is preferably 0.001 to 1 μm.
The coating film thus formed may be used as it is for manufacturing a liquid crystal cell, or may be subjected to a rubbing treatment and then used for manufacturing a liquid crystal cell. This rubbing treatment can be performed by rubbing the coated surface in a certain direction with a roll around which a cloth made of fibers such as nylon, rayon, and cotton is wound.

[Step (2): Construction of liquid crystal cell]
Next, the pair of substrates having the coating film formed thereon are arranged so as to face each other with the liquid crystal layer interposed therebetween to form a liquid crystal cell. The thickness of the liquid crystal layer is preferably 1 to 5 μm. The liquid crystal contained in the liquid crystal layer is preferably a nematic liquid crystal having negative dielectric anisotropy, and examples thereof include dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal. Can be used.
As a method of manufacturing a liquid crystal cell, for example, an ultraviolet light curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal alignment film surface is further coated. After dropping the liquid crystal, the other substrate is attached so that the liquid crystal alignment films face each other, the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant and thereby the liquid crystal cell. It is preferable to adopt the method of manufacturing the liquid crystal display (ODF method) from the viewpoint that the process time of the liquid crystal filling step can be shortened. It is desirable that the produced liquid crystal cell is further heated to a temperature at which the liquid crystal used has an isotropic phase and then gradually cooled to room temperature to remove the flow orientation at the time of filling the liquid crystal (annealing). The heating temperature at this time is preferably 50 to 150° C., and the heating time is preferably 10 minutes to 2 hours. As the sealant, for example, a curing agent and an epoxy resin containing aluminum oxide spheres as a spacer can be used.

[Step (3): Light irradiation treatment]
Next, the liquid crystal cell manufactured above is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage to be applied can be DC or AC of 5 to 50 V, for example. As the light to be applied, for example, ultraviolet rays and visible rays containing light with a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light with a wavelength of 300 to 400 nm are preferable. As the light source of the irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The irradiation dose of light, preferably 1,000~100,000J / ^{m 2,} more preferably from 1,000~50,000J / ^{m 2.}

  Then, if necessary, a polarizing plate may be attached to the outer surface of the liquid crystal cell that has been subjected to the above-described treatment to obtain a liquid crystal element. Examples of the polarizing plate used here include a polarizing film in which a polarizing film called “H film” in which polyvinyl alcohol is absorbed while absorbing iodine while being stretched and oriented is sandwiched between cellulose acetate protective films, or a polarizing plate formed of the H film itself. Can be mentioned.

  The liquid crystal device according to the present invention can be effectively applied to various uses, for example, watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various types. It can be used for various display devices such as monitors, liquid crystal televisions, information displays, retardation films, light control films, and the like.

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.
In the following examples, the weight average molecular weight of the polymer, the imidization ratio of the polyimide, the solution viscosity of the polymer solution and the epoxy equivalent were measured by the following methods.
[Weight Average Molecular Weight (Mw) of Polymer] This is a polystyrene-equivalent value measured by gel permeation chromatography under the following conditions.
Column: Tosoh Corp., TSKgelGRCXLII
Solvent: Tetrahydrofuran or N,N-dimethylformamide solution containing lithium bromide and phosphoric acid Temperature: 40°C
Pressure: 68 kgf/cm ²
[Imidization rate of polyimide]: A solution containing polyimide was poured into pure water, the obtained precipitate was sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl sulfoxide, using tetramethylsilane as a reference substance. ¹ H-NMR was measured at room temperature. From the obtained ¹ H-NMR spectrum, the imidization ratio [%] was calculated using the following mathematical formula (1).
Imidization rate [%]=(1−A ¹ /A ² ×α)×100 (1)
(In Formula (1), A ¹ is a peak area derived from a proton of an NH group appearing near a chemical shift of 10 ppm, A ² is a peak area derived from another proton, and α is a precursor of a polymer (polyamic acid). The ratio of the number of other protons to one proton of the NH group in ).
[Solution viscosity of polymer solution (mPa·s)]: A solution prepared to have a polymer concentration of 10% by mass using a predetermined solvent was measured at 25° C. using an E-type rotational viscometer.
[Epoxy equivalent]: Measured according to the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.
In the following, the compound represented by the formula X may be simply referred to as “compound X”.

<Synthesis of component (A)>
[Synthesis Example 1-1]
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 43 g (0.40 mol) of p-phenylenediamine as a diamine compound and 3-(3,5- 52 g (0.10 mol) of diaminobenzoyloxy)cholestane was dissolved in 830 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60° C. for 6 hours. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10%. The result was 60 mPa·s. Next, 1900 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and dehydration ring closure was performed at 110° C. for 4 hours. After the imidization reaction, the solvent in the system was replaced with new NMP (the pyridine and acetic anhydride used in the imidization reaction were removed to the outside of the system in this operation), and the polyimide (heavy-duty ratio: about 50%) A solution containing about 15% by mass of the combined product (PIm-1) was obtained. A small amount of the obtained polyimide solution was added, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10 mass% was 47 mPa·s.

[Synthesis Example 1-2]
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 22 g (0.20 mol) of p-phenylenediamine as a diamine compound, 3,5-diaminobenzoic acid 30 g (0.20 mol) and 52 g (0.10 mol) of 3-(3,5-diaminobenzoyloxy)cholestane were dissolved in 860 g of NMP and reacted at 60° C. for 6 hours. A small amount of the obtained polyamic acid solution was sampled, NMP was added, and the viscosity was measured with a solution having a solid content concentration of 10%. The result was 58 mPa·s. Next, 1800 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and dehydration ring closure was performed at 110° C. for 4 hours. After the imidization reaction, the solvent in the system was replaced with new NMP to obtain a solution containing about 15% by mass of polyimide (polymer (PIm-2)) having an imidization ratio of about 50%. A small amount of the obtained polyimide solution was added, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 69 mPa·s.

[Synthesis Example 2-1]
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 52 g (0.10 mol) of 3-(3,5-diaminobenzoyloxy)cholestane as a diamine compound , P-phenylenediamine 11 g (0.10 mol) and 2,5-diaminobenzoic acid 45 g (0.30 mol) were dissolved in NMP870 g and reacted at 60° C. for 6 hours. A solution containing polyamic acid (polymer (PAm-1)) was obtained by adding and diluting NMP and adjusting the concentration of polyamic acid to 10% by mass. The solution viscosity of this polyamic acid solution was 120 mPa·s.

[Synthesis example 2-2]
1,2,3,4-cyclobutane tetracarboxylic acid dianhydride 200 g (1.0 mol) as tetracarboxylic acid dianhydride, 3-(3,5-diaminobenzoyloxy)cholestane 52 g (0.1 mol) as diamine compound Mol) and 191 g (0.9 mol) of 2,2′-dimethyl-4,4′-diaminobiphenyl in 3,990 g of NMP, and the reaction was carried out at 40° C. for 3 hours to give a polyamic acid (polymer (PAm- A solution containing 10% by mass of 2)) was obtained. The solution viscosity of this polyamic acid solution was 90 mPa·s.

[Synthesis Example 3-1]
As the diamine compound, 12.69 g of 4,4′-diaminodiphenylmethane (80 parts by mole relative to 100 parts by mole of the total amount of diamine used in the synthesis) and 8.37 g of 3-(3,5-diaminobenzoyloxy)cholestane ( (20 mol parts), 15 ml of pyridine as a base, and 505 ml of N-methyl-2-pyrrolidone (NMP) as a solvent were added and dissolved. Dimethyl-1,3-bis(chlorocarbonyl)cyclobutane-2,4-carboxylate (23.05 g (97 parts by mole)) was added to this solution while stirring with water cooling, and the solid content concentration was 5% by mass. Thus, NMP was added, and the mixture was stirred for 4 hours while cooling with water. This solution was poured into 250 g of water to precipitate a polymer, the polymer was collected by suction filtration, washed again with 250 g of water, washed with 63 g of methanol three times, and dried under reduced pressure at 40° C., 36 g of polyamic acid ester powder was obtained. This polyamic acid ester (polymer (PAE-1)) was adjusted to 10% by mass with NMP.

[Synthesis Example 4-1]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane as a hydrolyzable silane compound and 500 g of methyl isobutyl ketone as a solvent, And 10.0 g of triethylamine as a catalyst were charged and mixed at room temperature. After 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, the mixture was reacted under reflux and reacted at 80° C. for 6 hours. After completion of the reaction, the organic layer is taken out, washed with a 0.2% by mass aqueous ammonium nitrate solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to have an epoxy group. The polyorganosiloxane was obtained as a viscous transparent liquid. When ¹ H-NMR analysis was performed on this polyorganosiloxane having an epoxy group, a peak based on the epoxy group was obtained in the vicinity of the chemical shift (δ)=3.2 ppm according to the theoretical intensity, and during the reaction, the peak of the epoxy group It was confirmed that no side reaction occurred. When the epoxy equivalent of this epoxy group-containing polyorganosiloxane was measured, it was 186 g/equivalent.
Then, in a 200 mL three-necked flask, 10.0 g of the epoxy group-containing polyorganosiloxane obtained above, 30.28 g of methyl isobutyl ketone as a solvent, and 3.87 g of 4-(4-pentylcyclohexyl)benzoic acid as a carboxylic acid (epoxy (Equivalent to 25 mol% based on the epoxy group of the group-containing polyorganosiloxane), and 0.10 g of UCAT18X (trade name, manufactured by San-Apro Co., Ltd.) as a catalyst were charged, and the reaction was carried out at 100° C. for 48 hours with stirring. went. After the reaction was completed, ethyl acetate was added to the reaction mixture, the resulting solution was washed with water three times, and the solvent was distilled off to give a polyorganosiloxane having a liquid crystal aligning group (polymer (PSi-1)). 5 g was obtained. The weight average molecular weight Mw of the obtained polymer (PSi-1) was 5,500.

[Synthesis Example 5-1]
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 3,4-epoxycyclohexylmethylmethacrylate (ECMMA as a polymerizable unsaturated monomer, 60 parts by mole based on 100 parts by weight of the total amount of monomers used for the polymerization) ), 2-hydroxyethylmethacrylate (HEMA, 15 parts by mole), N-cyclohexylmaleimide (CMI, 10 parts by mole), and styrene (ST, 15 parts by mole), and the total amount of polymerizable unsaturated monomers is Diethylene glycol ethyl methyl ether was added and dissolved so as to be 50% by mass.
Here, 2,2′-azobis(2,4-dimethylvaleronitrile) was used as a polymerization initiator in an amount of 3 mol% based on the total number of moles of the polymerizable unsaturated monomer, and α-methylstyrene dimer was used as a chain transfer agent. 0.5 times the mass of the polymerization initiator was added. Then, after bubbling with a nitrogen stream for 10 minutes to replace the nitrogen in the system, a polymerization reaction was performed at 70° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours to obtain a methacrylic acid ester copolymer having an epoxy group.
Then, in a 200 mL three-necked flask, 10.0 g of the epoxy group-containing methacrylic acid ester copolymer obtained above, 30.28 g of methyl isobutyl ketone as a solvent, and 4-(4-pentylcyclohexyl)benzoic acid as a carboxylic acid were used. 01 g (corresponding to 25 mol% based on the epoxy group-containing methacrylic acid ester copolymer used for polymerization) and 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) as a catalyst were charged, and the temperature was 90°C. The reaction was carried out under stirring for 12 hours. After the reaction was completed, ethyl acetate was added to the reaction mixture and the resulting solution was washed with water three times. The organic layer after washing with water was poured into a large excess of methanol to precipitate a polymer, and the recovered precipitate was dried at 40° C. for 12 hours to give a methacrylic polymer having a liquid crystal aligning group as a polymer (PAc). 10.5 g of an acid ester copolymer (polymer (PAc-1)) was obtained. The weight average molecular weight Mw of the obtained polymer (PAc-1) was 16,800.

<Synthesis of component (B)>
[Synthesis Example 6-1]
The compound (DM-1) was synthesized by the following scheme 1.

To a 2 L three-necked flask equipped with a dropping funnel and a thermometer, 4(4 hydroxyphenyl)benzoic acid 42.8 g (0.2 mol), sodium hydroxide 16 g (0.4 mol) and water 1 L were added and uniformly dissolved. After that, it was cooled to 5° C. or lower. Next, 23.4 mL (0.24 mol) of methacryloyl chloride and 300 mL of methylene chloride were added to the dropping funnel, and the mixture was added dropwise at 5° C. over 2 hours, allowed to return to room temperature and further reacted for 3 hours. After completion of the reaction, the white precipitate collected by filtration was dissolved in 1 L of ethyl acetate and 2 L of tetrahydrofuran, and washed once with 1 L of 1M hydrochloric acid aqueous solution and three times with 500 mL of water. Next, the organic layer was dried over magnesium sulfate and then concentrated to about 500 mL, and the obtained white crystals were collected and dried to obtain 56.4 g of compound (DM-1-1) white crystals.
Then, in a 500 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 8.03 g (28.4 mmol) of compound (DM-1-1), 9.89 g (71.1 mmol) of 2,6-pyridinedimethanol, and tetrahydrofuran. 150 mL and 30 mL of N,N-dimethylformamide were added to suspend and ice-cool. Next, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride 8.17 g (42.6 mmol) and N,N-dimethylaminopyridine 0.70 g (5.73 mmol) were added under ice cooling. After stirring for 2 hours, the mixture was returned to room temperature and reacted for 16 hours. After completion of the reaction, 1 L of ethyl acetate was added, and the mixture was separated and washed with water three times, and then dried over magnesium sulfate. A white precipitate of the compound (DM-1-2) was obtained by purifying the resulting precipitate by concentration with a silica column (developing solvent: methylene chloride/hexane/ethyl acetate=1:1:1), concentrating and vacuum drying. 7.82 g was obtained.
Then, to a 200 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 5.46 g (13.5 mmol) of compound (DM-1-2), 1.75 g (20.3 mmol) of methacrylic acid and 50 mL of methylene chloride were added. It was melted and cooled on ice. Next, 3.89 g (20.3 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 330 mg (2.7 mmol) of N,N-dimethylaminopyridine were added, and the mixture was cooled under ice for 2 hours. After stirring, the mixture was returned to room temperature and reacted for 16 hours. After completion of the reaction, the product was purified with a silica column (developing solvent: methylene chloride/ethyl acetate=10:1), concentrated, added with 700 mL of ethyl acetate, washed with water three times, and dried with magnesium sulfate. Next, the white precipitate produced by concentration was filtered and dried to obtain 4.21 g of white crystals of the compound (DM-1).

[Synthesis Example 6-2 to Synthesis Example 6-5]
The same procedure as in Synthesis Example 6-1 was repeated except that the compound shown below was used in place of 2,6-pyridinedimethanol, and was represented by each of the formulas (DM-2) to (DM-5). Was synthesized.
Synthesis Example 6-2 (Synthesis of Compound (DM-2)): 1,3-(Hydroxymethyl)urea Synthesis Example 6-3 (Synthesis of Compound (DM-3)): 1,3-(Hydroxymethyl)thio Urea Synthesis Example 6-4 (Synthesis of Compound (DM-4)): N-Phenyldiethanolamine Synthesis Example 6-5 (Synthesis of Compound (DM-5)): N-Methyldiethanolamine

[Synthesis Example 6-6; Synthesis of compound (DM-6)]
Compound (DM-6) was synthesized by the following scheme 2.

In a 300 mL three-necked flask equipped with a cooling tube, 10 g (35.4 mmol) of compound (DM-1-1), 6.95 g (35.4) of 3,4-epoxycyclohexylmethyl methacrylate, 85 mL of methyl isobutyl ketone as a solvent, Then, 0.24 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) was charged as a catalyst, and the reaction was performed at 70° C. for 12 hours with stirring. After the reaction was completed, ethyl acetate was added to the reaction mixture, the resulting solution was washed with water three times, and then dried over magnesium sulfate. Next, 13.7 g of white crystals of compound (DM-6-1) (mixture of positional isomers) was obtained by filtering and drying the white precipitate produced by concentration.
Then, to a 30 mL eggplant-shaped flask equipped with a reflux tube, 2.78 g (20.3 mmol) of 3-pyridylacetic acid, 2.2 mL (30.5 mmol) of thionyl chloride and 0.1 g of N,N-dimethylformamide were added and added to 1 Reflux for hours. After completion of the reaction, thionyl chloride was distilled off by concentration under reduced pressure, and 20 mL of methylene chloride was added (this solution is referred to as "A1 solution"). On the other hand, to a 200 mL three-necked flask equipped with a thermometer and a nitrogen introducing tube, 6.46 g (13.5 mmol) of the compound (DM-6-1) and 50 mL of methylene chloride as a solvent were added and dissolved, followed by cooling with ice. Next, the previously prepared A1 solution was added dropwise over 3 hours under ice cooling, and the reaction was continued at room temperature for 1 hour. After completion of the reaction, 500 mL of ethyl acetate was added, and liquid separation washing was performed three times with water, followed by drying with magnesium sulfate. Next, the concentrated white precipitate was filtered and dried to obtain 7.34 g of white crystals of compound (DM-6) (mixture of positional isomers).

[Synthesis Example 6-7 to Synthesis Example 6-10]
A compound represented by each of the above formulas (DM-7) to (DM-10) in the same manner as in Synthesis Example 6-6 above except that the following compounds were used instead of 3-pyridylacetic acid. Was synthesized.
Synthesis Example 6-7 (Synthesis of Compound (DM-7)): 1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid Synthesis Example 6-8 (Synthesis of Compound (DM-8)): (2 -Methyl-1H-imidazol-1-yl)acetic acid Synthesis Example 6-9 (synthesis of compound (DM-9)): 3-guanidinopropionic acid Synthesis Example 6-10 (synthesis of compound (DM-10)): 4 -(4,5-Dihydro-1H-imidazol-2-ylamino)butyric acid

[Synthesis Example 6-11]
Compound (DM-52) was synthesized as shown in Scheme 3 below.

  A 200 mL eggplant flask equipped with a cooling tube was charged with 14.1 g (50.0 mmol) of the compound (DM-1-1) and 71.4 g (600 mmol) of thionyl chloride, and reacted at 80° C. for 1 hour with stirring. I went. After the reaction, excess thionyl chloride was distilled off by concentration under reduced pressure to dryness. The obtained solid was washed with hexane and dried to obtain 14.9 g of white crystals of the compound (DM-1-1-Cl). Then, into a 500 mL three-necked flask, 2.22 g (30.0 mmol) of 1-hydroxy-2,3-epoxypropane, 4.75 g (60.0 mmol) of pyridine, and 300 mL of methylene chloride were charged, and the mixture was ice-bathed. A solution prepared by dissolving 9.20 g (30.6 mmol) of compound (DM-1-1-Cl) in 50 mL of methylene chloride was added dropwise thereto, and the reaction was carried out at room temperature with stirring for 5 hours. After the reaction was completed, the reaction solution was washed with water three times. Next, the concentrated residue was purified by silica gel chromatography to obtain 7.95 g of white crystals of compound (DM-52).

[Synthesis Example 6-12]
Compound (DM-56) was synthesized as shown in scheme 4 below.

A 2000 mL three-necked flask was charged with the compound 2,2′-dihydroxydiethylamine 10.5 g (100 mmol), epichlorohydrin 9.25 g (100 mmol), triethylamine 12.1 g (120 mmol), and tetrahydrofuran 1000 mL, and stirred at 40° C. for 10 hours. The reaction was carried out below. The reaction solution was concentrated to remove the resulting solid by filtration, and the filtrate was concentrated to obtain 13.6 g of a yellow oil of compound (EDHA).
Then, into a 1000 mL three-necked flask, 5.64 g (35.0 mmol) of the compound (EDHA), 8.50 g (84.0 mmol) of triethylamine and 350 mL of methylene chloride were charged, and the mixture was ice-bathed. A solution prepared by dissolving 23.2 g (38.5 mmol) of compound (DM-1-1-Cl) in 100 mL of methylene chloride was added dropwise thereto, and the reaction was carried out at room temperature with stirring for 5 hours. After the reaction was completed, the reaction solution was washed with water three times. Next, the concentrated residue was subjected to silica gel chromatography to obtain 22.0 g of a white crystal of compound (DM-56).

[Synthesis Example 6-13 and Synthesis Example 6-14]
Compound (DM-52) was synthesized from compound (DM-1-1-Cl) in Synthesis Example 6-11 above except that the compound shown below was used instead of 1-hydroxy-2,3-epoxypropane. The compound (DM-66) (however, n=3) and the compound (DM-72) were each synthesize|combined by the method similar to what was done.
Synthesis Example 6-13 (Synthesis of Compound (DM-66) (n=3)): 3-(Dimethylamino)-1-propanol Synthesis Example 6-14 (Synthesis of Compound (DM-72)): Methyl carbamate 4-hydroxycyclohexyl

[Synthesis Example 6-15]
Compound (DM-76) was synthesized as shown in Scheme 5 below.

  A 1000 mL three-necked flask was charged with 5.96 g (50.0 mmol) of 3-aminopentane-1,5-diol, 6.07 g (60.0 mmol) of triethylamine, and 500 mL of tetrahydrofuran, and the mixture was ice-bathed. A solution obtained by dissolving 5.20 g (55.0 mmol) of methyl carbonochlorate in 100 mL of methylene chloride was added dropwise thereto, and the reaction was carried out at room temperature with stirring for 5 hours. After the reaction was completed, the reaction solution was washed with water three times. The reaction solution was concentrated to remove the resulting solid by filtration, and the filtrate was concentrated to obtain 17.2 g of a yellow oil of compound (BIDHA). The subsequent reaction was carried out in the same manner as the method for synthesizing the compound (DM-55) from the compound (EDHA) in the above Synthesis Example 6-12 except that the compound (BIDHA) was used in place of the compound (EDHA). (DM-76) was synthesized.

[Synthesis Example 6-15]
A compound represented by the above formula (DM-78) was produced by the same method as in Synthesis Example 6-1 except that acrylic acid was reacted with the compound (DM-1-2) in place of methacrylic acid in the above scheme 1. Synthesized.

[Example 1]
(1) Preparation of liquid crystal aligning agent 80 parts by mass of the polymer (PIm-1) obtained in Synthesis Example 1-1 as the component (A), and the compound (DM- obtained in Synthesis Example 6-1 as the component (B)). 1) NMP and butyl cellosolve (BC) were added to 20 parts by mass to prepare a solution having a solid content concentration of 6.5% by mass and a solvent mixing ratio of NMP:BC=50:50 (mass ratio). After sufficiently stirring this solution, a liquid crystal aligning agent was prepared by filtering with a filter having a pore size of 0.2 μm.

(2) Production of liquid crystal cell Using the liquid crystal aligning agent prepared in (1) above, a glass substrate with a transparent electrode having a fine slit ITO electrode structure, using a liquid crystal alignment film printer (manufactured by Nissha Printing Co., Ltd.), And a patterned ITO electrode structure on the transparent electrode surface of the glass substrate with a transparent electrode. Then, after heating on a hot plate at 80°C for 1 minute (pre-baking) to remove the solvent, heating on a hot plate at 200°C for 10 minutes (post-baking) to form a coating film having an average film thickness of 800Å. .. Each substrate after the coating film was formed was subjected to ultrasonic cleaning in ultrapure water for 1 minute and then dried in a 100° C. clean oven for 10 minutes. As a result, a pair (two) of substrates having a liquid crystal alignment film was obtained.
Next, after applying a photocurable epoxy acrylic resin adhesive containing a 3.5 μm diameter aluminum oxide spacer to the outer edge of the coating film forming substrate having a fine slit ITO electrode structure, a liquid crystal (MLC-6608, manufactured by Merck & Co., Inc. ) Was added dropwise in the required amount. At this time, the liquid crystal was dropped on a plurality of locations on the coating film forming substrate. The total amount of liquid crystal dropped is 0.98 to 1.0 times the volume obtained by multiplying the area where the adhesive is applied and the spacer diameter, and the amount of one drop is 0.2 to 1.0 g. Adjusted between. Next, the substrate on which the liquid crystal was dropped was placed in a vacuum bonding apparatus, a coating film forming substrate having a patterned ITO electrode structure was placed on the opposite side of the substrate, and then bonding was performed under vacuum. The operation up to this point was performed at room temperature. After the bonding was completed, the adhesive part was cured using UV light of 365 nm, and then annealed in an oven at 120° C. for 1 hour to obtain a liquid crystal cell.
Then, with the liquid crystal cell obtained above, an alternating current of 10 V with a frequency of 60 Hz was applied between the electrodes, and while the liquid crystal was driven, an ultraviolet irradiation device using a metal halide lamp as a light source was used to emit 50 Irradiation was performed at an irradiation dose of 000 J/m ² . Note that this irradiation amount is a value measured using a photometer that measures the wavelength of 365 nm. The following evaluation was performed using the liquid crystal cell after light irradiation.

(3) Evaluation of response speed Regarding the liquid crystal cell manufactured in (2) above, first, a visible light lamp was irradiated without applying a voltage, and the brightness of light transmitted through the liquid crystal cell was measured with a photomultimeter. This value was defined as a relative transmittance of 0%. Next, the transmittance when an alternating current of 5 V was applied for 5 seconds between the electrodes of the liquid crystal cell was measured in the same manner as above, and this value was defined as the relative transmittance of 100%. The time required for the relative transmittance to shift from 10% to 90% when an alternating current of 5 V was applied to the liquid crystal cell was measured, and this time was defined as the response speed for evaluation. When the response speed is less than 8 msec, the high-speed response is “excellent”, when it is 8 msec or more and less than 15 msec, the high-speed response is “good”, when it is 15 msec or more and less than 20 msec, the high-speed response is “OK”, and when it is 20 msec or more, the high-speed response is The property was judged to be "poor" and evaluated. As a result, in this example, the response speed of the liquid crystal cell was 5 msec, which was "excellent".

(4) Evaluation of ODF unevenness By applying an alternating voltage of 60 Hz to the liquid crystal cell manufactured in the above (2) at 2.5 V, 2.5 V was observed. When the unevenness does not occur, it is "excellent", and when the unevenness is visually recognized weakly in at least one of the liquid crystal dropping position and the liquid crystal dropping position, it is "good", and at least in the middle of the liquid crystal dropping position and the liquid crystal dropping position. When the liquid crystal cell was evaluated as "poor" when the strong unevenness was observed, the ODF unevenness evaluation of this liquid crystal cell was "good".

[Examples 2-35 and Comparative Examples 1-5]
A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the types and amounts of the components (A), (B) and other components were as shown in Table 1 below. The cell was manufactured and various evaluations were performed. In addition, in Examples 3, 4, 20 to 23, 25, two kinds were used as the component (A), and in Examples 33 to 35, other components were further blended. The evaluation results are shown in Table 1 below.

In Table 1, the numerical values in the columns of (A) component, (B) component and other components are 100 parts by mass of the solid content (all components other than the solvent in the liquid crystal aligning agent) used in the preparation of the liquid crystal aligning agent. The compounding ratio (parts by mass) of each compound is shown. The abbreviations in Table 1 have the following meanings.
DM-55: Compound represented by the above formula (DM-55) dm-1: EO-modified bisphenol A dimethacrylate (trade name FA-321M, manufactured by Hitachi Chemical Co., Ltd.)
dm-2: 4,4'-isopropylidene diphenol dimethacrylate dm-3: compound represented by the following formula (dm-3)

  As shown in Table 1, in Examples 1 to 35 containing the component (B), the ODF unevenness was small and the response speed of the liquid crystal cell was high. In addition, in Examples containing a polymer having a partial structure derived from a carboxyl group-containing diamine, it was observed that the response speed was fast and the ODF unevenness was small. On the other hand, in Comparative Examples 1 to 4 not containing the component (B), the ODF unevenness was evaluated as “poor”, and in Comparative Example 5, the response speed was evaluated as “poor”. From the above results, it was confirmed that the liquid crystal alignment film used in the examples can suppress the ODF unevenness without deteriorating the response speed.

Claims (7)

A liquid crystal aligning agent containing the following component (A) and component (B).
Component (A): at least one polymer selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane, and a polymer of a monomer having a polymerizable unsaturated bond.
Component (B): Partial structure represented by the following formula (1), Partial structure represented by the following formula (2), Partial structure represented by the following formula (3), Tertiary amine structure, Nitrogen-containing heterocycle At least one selected from the group consisting of a structure, —NR ³¹ X ¹⁰ (wherein R ³¹ is a monovalent hydrocarbon group and X ¹⁰ is a protecting group), an epoxy group, an isocyanate group and a blocked isocyanate group. It has a specific structure, and a photopolymerizable compound to have a partial structure represented by the following formula (6) in the molecule.

(In the formula (1), X ⁴ is an oxygen atom or a sulfur atom, R ² is an oxygen atom, a sulfur atom, an alkanediyl group, an aromatic ring group, a cyclohexylene group, or —NR ³² — (R ³² is a hydrogen atom. R ³⁰ is a hydrogen atom or a protecting group, provided that when R ² is an aromatic ring group or a cyclohexylene group, R ³⁰ is a protecting group. X ⁵ is a divalent hydrocarbon group or —NR ³³ — (R ³³ is a hydrogen atom or a protective group. “*” represents a bond)

(In formula (6), Ar ³ and Ar ⁴ are each independently a 1,4-phenylene group or a 1,4-cyclohexylene group, and X ⁸ is a single bond or —COO—. n2 is 1 or 2. When n2=2, Ar ⁴ and X ⁸ each independently have the above definition. “*” represents a bond.) The liquid crystal aligning agent according to claim 1, wherein the photopolymerizable compound is a compound having one or more photopolymerizable groups represented by the following formula (4).

(In the formula (4), ^{R 1} is ^.X 1 to X ³ is an oxygen atom, a sulfur atom or -NH- are each independently a hydrogen atom, a halogen atom or a monovalent organic group. However, ^{R 1} Is an oxygen atom, X ³ may be bonded to another group to form a ring together with —CO—R ¹ — and the carbon atom to which X ³ , X ³ is bonded, and “*” is a bond. Is shown.) A liquid crystal aligning agent containing the following component (A) and component (B).
Component (A): at least one polymer selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane, and a polymer of a monomer having a polymerizable unsaturated bond.
Component (B): a compound represented by the following formula (D-1).

(In the formula (D-1), Y ¹ is a partial structure represented by the following formula (1), a partial structure represented by the following formula (2), a partial structure represented by the following formula (3), or 2 containing at least one selected from the group consisting of a primary amine structure, a nitrogen-containing heterocyclic structure, and —NR ³¹ X ¹⁰ (wherein R ³¹ is a monovalent hydrocarbon group and X ¹⁰ is a protecting group). X ⁶ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms or a monovalent aromatic ring group having 6 to 12 carbon atoms, and R 6 ³ is an oxygen atom, a sulfur atom or —NH—, and Ar ¹ and Ar ² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, naphthylene group, tetrahydronaphthalenediyl group, or decahydro. It is a naphthalenediyl group, which may have a substituent on the ring portion, R ⁴ is a single bond, an ester bond, an amide bond, an ether bond, or —CO—NR ³⁴ — (R ³⁴ is a protecting group. And R ⁵ is an ester bond, an amide bond, an ether bond, or —CO—NR ³⁵ — (R ³⁵ is a protecting group.) R ⁷ is a single bond, an ester bond, an amide bond, or an ether bond. Or —CO—NR ³⁶ — (R ³⁶ is a protecting group.) R ⁸ is a single bond, an alkanediyl group, a phenylene group, a cyclohexylene group, or a divalent group represented by the following formula (6). N1 is an integer of 0 to 2. When n1=2, R ⁴ and Ar ² each independently have the above definition, and a plurality of X ⁶ and a plurality of R ³ are independently the above definitions. Have.)

(In the formula (1), X ⁴ is an oxygen atom or a sulfur atom, R ² is an oxygen atom, a sulfur atom, an alkanediyl group, an aromatic ring group, a cyclohexylene group, or —NR ³² — (R ³² is a hydrogen atom. R ³⁰ is a hydrogen atom or a protecting group, provided that when R ² is an aromatic ring group or a cyclohexylene group, R ³⁰ is a protecting group. X ⁵ is a divalent hydrocarbon group or —NR ³³ — (R ³³ is a hydrogen atom or a protective group. “*” represents a bond)

(In formula (6), Ar ³ and Ar ⁴ are each independently a 1,4-phenylene group or a 1,4-cyclohexylene group, and X ⁸ is a single bond or —COO—. n2 is 1 or 2. When n2=2, Ar ⁴ and X ⁸ each independently have the above definition. “*” represents a bond.) The component (A) is at least one selected from the group consisting of polyimide, polyamic acid, and polyamic acid ester, and contains a polymer having a partial structure derived from a diamine having a carboxyl group. the liquid crystal aligning agent according to any one of 3. A method of manufacturing a liquid crystal element, comprising:
A step of forming a coating film by applying the liquid crystal aligning agent according to any one of claims 1 to 4 on the conductive films of a pair of substrates each having a conductive film,
A step of constructing a liquid crystal cell by arranging a pair of substrates on which the coating film is formed so as to face each other so that the coating film faces each other through a liquid crystal layer,
And a step of irradiating the liquid crystal cell with light with a voltage applied between the conductive films. Liquid crystal alignment film formed by using the liquid crystal aligning agent according to any one of claims 1-4. A liquid crystal device comprising the liquid crystal alignment film according to claim 6 .