JP6962449B2 - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element - Google Patents

Description

Cross-reference of related applications

This application is based on Japanese Application No. 2018-41168 filed on March 7, 2018, the contents of which are incorporated herein by reference.

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

Liquid crystal elements are used in various applications such as display devices such as televisions, personal computers, and smartphones. These liquid crystal elements include a liquid crystal alignment film having a function of orienting liquid crystal molecules in a certain direction. The liquid crystal alignment film is generally formed on the substrate by applying a liquid crystal alignment agent in which the polymer component is dissolved in an organic solvent onto the substrate and preferably heating the substrate. As the polymer component of the liquid crystal alignment agent, polyamic acid and soluble polyimide are widely used because they are excellent in mechanical strength, liquid crystal orientation, and affinity with liquid crystal. Further, as the solvent component of the liquid crystal alignment agent, a solvent having high solubility in a polymer such as polyamic acid or soluble polyimide (for example, a good solvent such as N-methyl-2-pyrrolidone or γ-butyrolactone) and wetness to the substrate are used. A mixed solvent with a solvent having high spreadability (for example, a poor solvent such as butyl cellosolve) is generally used (see, for example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2017-198975 Japanese Unexamined Patent Publication No. 2016-206645

As for LCD TVs, in recent years, there have been standards for display devices with an increased number of pixels, such as 4K (for example, 3840 pixels x 2160 pixels) and 8K (for example, 7680 pixels x 4320 pixels), in order to obtain a sense of realism by further improving the display quality. It is made. As the number of pixels in the display device increases and the pixel size decreases, the pixel electrodes have a finer structure, and the surface on which the pixel electrodes are formed has a higher uneven density per unit area. In this case, when the liquid crystal alignment agent is applied to the forming surface of the pixel electrode to form the alignment film, the liquid crystal alignment agent is difficult to wet and spread with respect to the fine uneven structure of the pixel electrode, and sufficient coatability to the substrate is ensured. There is concern that it cannot be done. In order to obtain good coatability even when the liquid crystal alignment agent is applied to a fine uneven structure, the solvent component of the liquid crystal alignment agent is a substrate while suppressing a decrease in solubility in a polymer. It is necessary to increase the wettability and spreadability.

Further, from the viewpoint of industrial production, it is possible to suppress the volatilization of the solvent from the printing machine when printing the liquid crystal alignment agent on the substrate, and it is heavy on the printing machine even when printing is continuously performed. It is required that the coalescence is hard to precipitate, that is, the continuous printability is good.

Furthermore, in recent years, large-screen liquid crystal panels have become widespread, and larger lines have come into operation than before, and the size of substrates has been increasing. The merits of increasing the size of the substrate are that it is possible to reduce the process time and cost because multiple panels can be taken from one substrate, and that it is possible to cope with the increase in the size of the liquid crystal panel itself. Be done. On the other hand, when a liquid crystal alignment film is formed on a large substrate, temperature unevenness is more likely to occur during post-baking than in the past, and the pretilt angle of the liquid crystal alignment film varies due to this temperature unevenness, resulting in display quality. There is concern that it will lead to a decline.

While the size of the substrate is increasing, the development of a small touch panel type display panel represented by a smartphone or tablet PC is also underway. Here, in the touch panel type display panel, an attempt is made to narrow the frame in order to make the movable area of the touch panel wider and to make the liquid crystal panel smaller. Further, as the frame of the liquid crystal panel is narrowed, display unevenness may be visually recognized around the sealant due to aging or the like. In order to achieve high definition and long life of the liquid crystal panel, a liquid crystal element is required in which display unevenness around the sealant is hard to be visually recognized for a long period of time (high resistance to bezel unevenness).

The present disclosure has been made in view of the above problems, has good coatability and continuous printability on a fine uneven structure, is not easily affected by temperature unevenness during heating during film formation, and has display unevenness around the sealant. One object of the present invention is to provide a liquid crystal alignment agent capable of obtaining a liquid crystal element having a small amount of water.

The present disclosure employs the following means to solve the above problems.

<1> A liquid crystal alignment agent containing a polymer component and the following [A] compound.
[A] At least selected from the group consisting of a compound [A1] in which a monovalent group having a carbonyl group is bonded to the ring portion of an oxygen-containing heterocycle, and a compound [A2] having a ketone carbonyl group and an oxyorganic group. A kind of compound.
<2> A method for manufacturing a liquid crystal element, which forms a liquid crystal alignment film using the liquid crystal alignment agent of <1> above.
<3> A liquid crystal alignment film formed by using the liquid crystal alignment agent of <1> above.
<4> A liquid crystal element provided with the liquid crystal alignment film of <2> above.

The liquid crystal alignment agent of the present disclosure has good wettability and spreadability even when applied to a substrate surface having a fine uneven structure, and can uniformly form a liquid crystal alignment film on the substrate surface. Further, even when printing is continuously performed for a long time in the manufacturing process, the polymer is unlikely to precipitate on the printing machine. Moreover, the liquid crystal alignment agent of the present invention is not easily affected by temperature unevenness during heating during film formation, and thus a liquid crystal alignment film in which characteristic variation due to temperature unevenness is suppressed can be obtained. Further, it is possible to obtain a liquid crystal element having less display unevenness around the sealant (good bezel unevenness resistance).

1A and 1B are views showing a schematic configuration of an ITO electrode substrate for evaluation, FIG. 1A is a plan view, and FIG. 1B is a partially enlarged cross-sectional view.

Hereinafter, each component contained in the liquid crystal alignment agent of the present disclosure, and other components optionally blended will be described. The liquid crystal alignment agent is a liquid polymer composition containing a polymer component and a solvent component, and the polymer component is dissolved in the solvent component.

≪Polymer component≫
The main skeleton of the polymer component contained in the liquid crystal aligning agent is not particularly limited, but for example, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide, polyamideimide, polybenzoxazole precursor, polybenzo Examples thereof include main skeletons such as oxazole, cellulose derivatives, polyacetals, styrene-maleimide copolymers, and poly (meth) acrylates. In addition, (meth) acrylate means containing acrylate and methacrylate.
From the viewpoint of ensuring sufficient performance of the liquid crystal element, the polymer component is composed of a polymer having a structural unit derived from a polyamic acid, a polyamic acid ester, a polyimide, a polyamide, and a monomer having a polymerizable unsaturated bond. It is preferably at least one polymer selected from the group (hereinafter, also referred to as "polymer [P]"), and particularly at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide. preferable.

<Polyamic acid>
The polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound.

(Tetracarboxylic dianhydride)
Examples of the tetracarboxylic dianhydride used for the synthesis of polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. .. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride;
As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic hydride, 5- (2,5-dioxo tetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1 , 3-Dione, 5- (2,5-dioxo tetrahydrofuran-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'-(Anhydride-2', 5'-dione), 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, cyclopentanetetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, etc .; as aromatic tetracarboxylic acid dianhydride, for example, pyromellitic acid dianhydride, 4,4'-(hexafluoroisopropylidene). Diphthalic anhydride, ethylene glycol bisanhydrotrimate, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, etc .; The tetracarboxylic dianhydride described in JP-A-2010-97188 can be used. The tetracarboxylic dianhydride may be used alone or in combination of two or more.

（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、桂皮酸構造を側鎖に有するジアミンなどの側鎖型ジアミン：(Diamine compound)
Examples of the diamine compound used for the synthesis of the polyamic acid include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, and a diaminoorganosiloxane. Specific examples of these diamines include, for example, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like as aliphatic diamines; for example, 1,4 as alicyclic diamines. -Diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), etc .;
As aromatic diamines, for example, dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, pentadecanoxy-2,5-diamino Benzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2, 4-Diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestan, 3,6- Bis (4-aminophenoxy) cholesterol, 2,4-diamino-N, N-diallylaniline, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis ( 4-((Aminophenyl) methyl) phenyl) -4-butylcyclohexane, 3,5-diaminobenzoic acid = 5ξ-cholestane-3-yl, the following formula (E-1)

(In the formula (E-1), X ^I and X ^II are independently single-bonded, -O-, * -COO- or * -OCO- (where "*" is a bond with ^{X I.} shown.), and, ^{R I} is an alkanediyl group having 1 to 3 carbon ^{atoms, R II} is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is 0 It is an integer of ~ 2, c is an integer of 1 to 20, d is 0 or 1. However, a and b cannot be 0 at the same time.)
Side chain diamines such as compounds represented by, diamines having a cinnamic acid structure in the side chain:

p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 1, 5-bis (4-aminophenoxy) pentane, 1,2-bis (4-aminophenoxy) ethane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,10-bis (4-aminophenoxy) Decane, 1,2-bis (4-aminophenyl) ethane, 1,5-bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,4-bis (4-amino) Phenylsulfanyl) butane, bis [2- (4-aminophenyl) ethyl] hexanedioic acid, N, N-bis (4-aminophenyl) methylamine, 2,6-diaminopyridine, 1,4-bis- (4) -Aminophenyl) -piperazin, 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, 4,4'-[4,4'-propane -1,3-diylbis (piperidin-1,4-diyl)] dianiline, 4,4'-diaminobenzanilide, 4,4'-diaminostillbenzene, 4,4'-diaminodiphenylamine, 1,3-bis ( 4-Aminophenethyl) urea, 1,3-bis (4-aminobenzyl) urea, 1,4-bis (4-aminophenyl) -piperazin, N- (4-aminophenylethyl) -N-methylamine, N , N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine and other main chain diamines; as diaminoorganosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldi Siloxane etc .; In addition to the above, the diamine described in JP-A-2010-97188 can be used.

(Synthesis of polyamic acid)
The polyamic acid can be obtained by reacting the tetracarboxylic dianhydride as described above with a diamine compound, if necessary, with a molecular weight modifier. The ratio of the tetracarboxylic acid dianhydride used in the polyamic acid synthesis reaction to the diamine compound is 0.2 for the acid anhydride group of the tetracarboxylic acid dianhydride with respect to 1 equivalent of the amino group of the diamine compound. A ratio of about 2 equivalents is preferable. Examples of the molecular weight adjusting agent include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenylisocyanate and naphthylisocyanate. Can be mentioned. The ratio of the molecular weight adjusting agent used is preferably 20 parts by mass or less with respect to 100 parts by mass in total of the tetracarboxylic dianhydride and the diamine compound used.

The polyamic acid synthesis reaction is preferably carried out in an organic solvent. The reaction temperature at this time is preferably −20 ° C. to 150 ° C., and the reaction time is preferably 0.1 to 24 hours.
Examples of the organic solvent used in the reaction include aprotonic 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, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol. And one or more selected from the group consisting of halogenated phenol can be used as a solvent, or a mixture of one or more of these with another organic solvent (for example, butyl cellosolve, diethylene glycol diethyl ether, etc.) can be used. preferable. The amount of the organic solvent used (a) shall be such that the total amount (b) of the tetracarboxylic dianhydride and the diamine is 0.1 to 50% by mass with respect to the total amount (a + b) of the reaction solution. Is preferable.
As described above, a reaction solution obtained by dissolving a polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal alignment agent, or the polyamic acid contained in the reaction solution may be isolated and then used for the preparation of the liquid crystal alignment agent.

<Polyamic acid ester>
When the polymer [P] is a polyamic acid ester, the polyamic acid ester is, for example, [I] a method of reacting the polyamic acid obtained by the above synthetic reaction with an esterifying agent, [II] tetracarboxylic acid diester. It can be obtained by a method of reacting with a diamine compound, a method of reacting [III] a tetracarboxylic acid diester dihalide with a diamine compound, or the like. 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 in which the amic acid structure and the amic acid ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester may be used as it is for the preparation of the liquid crystal alignment agent, or the polyamic acid ester contained in the reaction solution may be isolated and then used for the preparation of the liquid crystal alignment agent. good.

<Polyimide>
When the polymer [P] is a polyimide, the polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid synthesized as described above to imidize it. The polyimide may be a completely imidized product obtained by dehydrating and ring-closing all of the amic acid structure possessed by the polyamic acid that is the precursor thereof, or by dehydrating and ring-closing only a part of the amic acid structure, and the amic acid structure and the imide. It may be a partially imidized product in which a ring structure coexists. The polyimide used in the reaction preferably has an imidization ratio of 20 to 99%, more preferably 30 to 90%. This imidization ratio is expressed as a percentage of the ratio of the number of imide ring structures to the total of the number of amic acid structures and the number of 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 carried out by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating as necessary. In this method, as the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the amic acid structure of the polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, colidin, lutidine, and triethylamine can be used. The amount of the dehydration ring closure 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 in the dehydration ring closure reaction include organic solvents exemplified as those used in the synthesis of polyamic acids. The reaction temperature of 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 the preparation of the liquid crystal alignment agent, or the polyimide may be isolated and then used for the preparation of the liquid crystal alignment agent. Polyimide can also be obtained by imidization of polyamic acid esters.

<Polyamide>
When the polymer [P] is a polyamide, the polyamide can be obtained, for example, by a method of reacting a dicarboxylic acid with a diamine compound or the like. Here, it is preferable that the dicarboxylic acid is acid chlorided with an appropriate chlorinating agent such as thionyl chloride and then subjected to a reaction with a diamine compound.

The dicarboxylic acid used for the synthesis of polyamide is not particularly limited, and for example, an aliphatic dicarboxylic acid such as oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, and fumaric acid; cyclobutane. Alicyclic dicarboxylic acids such as dicarboxylic acid, 1-cyclobutenedicarboxylic acid, cyclohexanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 2,5-dimethylterephthalic acid, 4-carboxycatephotic acid, Aromatic dicarboxylic acids such as 3,3'-[4,4'-(methylenedi-p-phenylene)] dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)] dibutyric acid ; Etc. can be mentioned. Examples of the diamine compound used for the synthesis include the diamine compound exemplified in the description of the polyamic acid. One type of each of the dicarboxylic acid and the diamine compound may be used alone, or two or more types may be used in combination.

The reaction of the dicarboxylic acid with the diamine compound is preferably carried out in the presence of a base in an organic solvent. At this time, the ratio of the dicarboxylic acid to the diamine compound is preferably 0.2 to 2 equivalents of the carboxyl group of the dicarboxylic acid with respect to 1 equivalent of the amino group of the diamine compound. The reaction temperature is preferably 0 ° C. to 200 ° C., and the reaction time is preferably 0.5 to 48 hours. As the organic solvent, for example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and the like can be preferably used. As the base, for example, tertiary amines such as pyridine, triethylamine, N-ethyl-N, and N-diisopropylamine can be preferably used. The ratio of the base used is preferably 2 to 4 mol with respect to 1 mol of the diamine compound. The solution obtained by the above reaction may be used as it is for the preparation of the liquid crystal alignment agent, or the polyamide contained in the reaction solution may be isolated and then used for the preparation of the liquid crystal alignment agent.

<Polymer having a structural unit derived from a monomer having a polymerizable unsaturated bond>
When the polymer [P] is a polymer having a structural unit derived from a monomer having a polymerizable unsaturated bond (hereinafter, also referred to as “polymer (Q)”), the monomer having a polymerizable unsaturated bond. Examples thereof include compounds having a (meth) acryloyl group, a vinyl group, a styryl group, a maleimide group and the like. Specific examples of such compounds include unsaturated carboxylic acids such as (meth) acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, and vinyl benzoic acid: alkyl (meth) acrylic acid (meth) cycloacrylate. Alkyl, benzyl (meth) acrylate, -2-ethylhexyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic Unsaturated carboxylic acid esters such as acid 3,4-epoxycyclohexylmethyl, (meth) acrylic acid 3,4-epoxybutyl, and acrylic acid 4-hydroxybutylglycidyl ether: unsaturated polyvalent carboxylic acid anhydrides such as maleic anhydride. : Etc. (meth) acrylic compounds; aromatic vinyl compounds such as styrene, methylstyrene, divinylbenzene; conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene; N-methylmaleimide, Maleimide group-containing compounds such as N-cyclohexylmaleimide and N-phenylmaleimide; and the like. As the monomer having a polymerizable unsaturated bond, one type can be used alone or two or more types can be used in combination.

The polymer (Q) can be obtained, for example, by polymerizing a monomer having a polymerizable 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 other azo compounds are preferred. The ratio 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, and diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate and the like are preferable. 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 should be such that the total amount (b) of the monomers used in the reaction is 0.1 to 60% by mass with respect to the total amount (a + b) of the reaction solution. Is preferable. The polymer solution obtained by the above reaction may be used as it is for the preparation of the liquid crystal alignment agent, or the polymer [Q] contained in the reaction solution may be isolated and then used for the preparation of the liquid crystal alignment agent.

The solution viscosity of the polymer [P] preferably has a solution viscosity of 10 to 800 mPa · s when made into a solution having a concentration of 10% by mass, and has a solution viscosity of 15 to 500 mPa · s. Is more preferable. The solution viscosity (mPa · s) is E for a polymer solution having a concentration of 10% by mass prepared using a good solvent of the polymer (A) (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using a mold rotary viscosity meter.
The polystyrene-equivalent weight average molecular weight (Mw) of the polymer [P] measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. Is. 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 7 or less, more preferably 5 or less. The polymer [P] contained in the liquid crystal alignment agent may be only one type or a combination of two or more types.

The content ratio of the polymer [P] (the total amount when two or more types are contained) is the total amount of the polymer components contained in the liquid crystal aligning agent from the viewpoint of improving the quality of the obtained liquid crystal element. On the other hand, it is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably more than 80% by mass.

≪Solvent component≫
The liquid crystal alignment agent of the present disclosure contains the following compound [A].
[A] At least selected from the group consisting of a compound [A1] in which a monovalent group having a carbonyl group is bonded to the ring portion of an oxygen-containing heterocycle, and a compound [A2] having a ketone carbonyl group and an oxyorganic group. A kind of compound.
According to the compound [A], by having the above structure, the solubility of the polymer component in the solvent can be improved, and the coating property (printability) of the liquid crystal aligning agent on the surface of the substrate having the electrode structure having a fine uneven shape can be improved. Can be improved. Further, by using the compound [A], the boiling point of the solvent component of the liquid crystal alignment agent can be adjusted to an appropriate height, and it is not easily affected by temperature unevenness during heating at the time of film formation. Further, it is preferable in that the effect of suppressing display unevenness around the sealant can be obtained.

<Compound [A1]>
The oxygen-containing heterocycle contained in the compound [A1] is preferably a 5- to 7-membered ring, and more preferably a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring portion of the oxygen-containing heterocycle is preferably 3 to 6, and more preferably 3 to 5.
The oxygen-containing heterocycle may have only an oxygen atom as a heteroatom contained in the ring, or may have other atoms other than the oxygen atom (for example, sulfur atom, nitrogen atom, etc.). .. It is preferable that the hetero atom in the ring is only an oxygen atom in that the effect of improving the coatability and the resistance to bezel unevenness can be preferably obtained.
The number of oxygen atoms in the ring is preferably 1 or 2. Further, the oxygen-containing heterocycle may be saturated or unsaturated. The oxygen-containing heterocycle of compound [A1] has no carbon-carbon in the ring in that it can exhibit the performance of coatability, continuous printability, temperature unevenness resistance during post-baking, and bezel unevenness resistance in a well-balanced manner. It is preferably a heterocycle having no saturated bond.

Specific examples of the oxygen-containing heterocycle contained in compound [A1] include, for example, oxylan, oxetane, tetrahydrofuran, tetrahydropyran, hexamethylene oxide, 1,3-dioxane, 1,4-dioxane, morpholin, 1,3-dioxoran. , Γ-Butylollactone, δ-Valerolactone, furan, 2,3-dihydrofuran, 2,5-dihydrofuran, oxepine, oxazole, pyran, 5,6-dihydropyran, 3,4-dihydropyran, 1,3- Examples thereof include dioxol, 2-furanone, 3-furanone, 1,3-oxathiolane and 1,3-oxathiolan-2-one. Of these, preferred are furan, 2,3-dihydrofuran, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, γ-butyrolactone, 5,6-dihydropyran or It is 3,4-dihydropyran, particularly preferably tetrahydrofuran, 1,3-dioxolane or tetrahydropyran.

The monovalent group having a carbonyl group (hereinafter, also referred to as “carbonyl-containing group T”) contained in the compound [A1] is preferably a carboxyl group, an amide group (-CO-NH ₂ ) or 1 to 1 carbon atoms. It is a monovalent organic group of 6. In addition, in this specification, an "organic group" means a group having a hydrocarbon group. Substituents other than the carbonyl-containing group T (hereinafter, also referred to as "substituent U") may be further introduced into the ring portion of the oxygen-containing heterocycle. Examples of the substituent U include an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms, and a methyl group or an ethyl group is preferable. The number of substituents U is appropriately set according to the number of ring members of the oxygen-containing heterocycle, but is preferably 0 to 3, more preferably 0 to 2.

（式（１）中、Ａ^１は、酸素含有複素環の環部分から１個の水素原子を取り除いた基であり、環部分にさらに置換基を有していてもよい。Ｒ^１は、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、炭素数２〜５のアルケニル基、炭素数２〜５のアルケニルオキシ基、炭素原子に結合する水素原子が水酸基、シアノ基若しくはアルコキシ基で置換された炭素数５以下の置換アルキル基、炭素原子に結合する水素原子が水酸基、シアノ基若しくはアルコキシ基で置換された炭素数５以下の置換アルコキシ基、炭素原子に結合する水素原子が水酸基、シアノ基若しくはアルコキシ基で置換された炭素数５以下の置換アルケニル基、炭素原子に結合する水素原子が水酸基、シアノ基若しくはアルコキシ基で置換された炭素数５以下の置換アルケニルオキシ基、水酸基、アミノ基又はシアノ基である。Ｒ^２は、単結合、炭素数１〜３のアルカンジイル基、又は炭素数２若しくは３のアルケンジイル基である。Ｒ^３は、炭素数１〜３のアルカンジイル基、又は炭素数２若しくは３のアルケンジイル基である。ａは０〜２の整数であり、ｂは０又は１である。１分子中に複数のＲ^３を有する場合、複数のＲ^３は、互いに同じでも異なっていてもよい。）Of these, the compound [A1] is preferably a compound represented by the following formula (1).

(In the formula (1), A ¹ is a group obtained by removing one hydrogen atom from the ring portion of the oxygen-containing heterocycle, and the ring portion may further have a substituent. R ¹ is carbon. An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkenyloxy group having 2 to 5 carbon atoms, and a hydrogen atom bonded to a carbon atom being a hydroxyl group, a cyano group or an alkoxy group. A substituted alkyl group having 5 or less carbon atoms substituted with a group, a substituted alkoxy group having 5 or less carbon atoms in which a hydrogen atom bonded to a carbon atom is substituted with a hydroxyl group, a cyano group or an alkoxy group, and a hydrogen atom bonded to a carbon atom. Substituent alkenyl group having 5 or less carbon atoms substituted with a hydroxyl group, cyano group or alkoxy group, substituted alkenyloxy group having 5 or less carbon atoms in which a hydrogen atom bonded to a carbon atom is substituted with a hydroxyl group, cyano group or alkoxy group, hydroxyl group , Amino group or cyano group. R ² is a single bond, an alcandiyl group having 1 to 3 carbon atoms, or an arcendyl group having 2 or 3 ^{carbon atoms. R 3} is an alkandiyl group having 1 to 3 carbon atoms. group, or an alkenediyl group having a carbon number of 2 or 3 .a is an integer from 0 to 2, when b is having a plurality of R ³ in .1 molecule is 0 or 1, more R ³ is They may be the same or different from each other.)

In the formula (1), the above description is applied to specific examples and preferable examples of the oxygen-containing heterocycle contained ^{in A 1 (oxygen-containing heterocyclic group).} A ¹ may further have a substituent on the ring portion different from that of "-R ^2- (OR ³ ) _a- (O) _b- ^{COR 1".}
The hydrocarbon moiety of the alkyl group, alkoxy group, alkenyl group, substituted alkyl group, substituted alkoxy group, substituted alkenyl group, and substituted alkenyloxy group of R ^{1 may be linear or branched.} Specific examples of R ¹ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and 3-methylbutyl group. , 1-Methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentoxy group, vinyl group, 1-propenyl group, allyl Examples thereof include a group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, and a group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a hydroxyl group, a cyano group or an alkoxy group.
The ^{alkanediyl group and the arcendyl group of R 2} and R ³ may be linear or branched, but are preferably linear.
a is preferably 0 or 1.
The remaining portion except ^{A 1 (-R 2- (OR 3} ) _a- (O) _b- CO-R ¹ ), that is, the carbon number of the carbonyl-containing group T improves coatability and long-term printability. In terms of higher effect, it is preferably 1 to 6, more preferably 1 to 4, and even more preferably 2 to 4.

（式（１−Ａ）中、Ｘ^１は、単結合、酸素原子、炭素数１〜３のアルカンジイル基、炭素数２又は３のアルケンジイル基、＊^１−（Ｏ−Ｒ^４）_ｃ−、＊^１−（Ｒ^４−Ｏ）_ｃ−、又は＊^１−（Ｏ−Ｒ^４）_ｃ−Ｏ−（ただし、Ｒ^４は炭素数１〜３のアルカンジイル基であり、ｃは１又は２であり、「＊^１」はＡ^１に結合する結合手であることを示す。）である。Ｒ^５は、アルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基、水酸基、アミノ基又はシアノ基である。ただし、Ｘ^１が酸素原子又は＊^１−（Ｒ^４−Ｏ）_ｃ−である場合、Ｒ^５は、アルキル基又はアルケニル基である。Ａ^１を除いた残りの部分の炭素数は１〜６の整数である。Ａ^１は、上記式（１）と同義である。）The compound [A1] is preferably a compound represented by the following formula (1-A).

(In the formula (1-A), X ¹ is a single bond, an oxygen atom, an alkanediyl group having 1 to 3 carbon atoms, an alkanediyl group having 2 or 3 carbon atoms, * ¹ − ( ^{OR 4} ) _c −, * ^1- (R ^4- O) _c- or * ^1- ( ^{OR 4} ) _c- O- (where R ⁴ is an alkanediyl group with 1-3 carbon atoms and c is 1 or 2 Yes, "* ¹ " indicates that it is a bond that binds to ^{A 1. ) R 5} is an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, a hydroxyl group, an amino group or a cyano group. However, when X ¹ is an oxygen atom or * ^1- (R ^4- O) _c- , R ⁵ is an alkyl group or an alkenyl group. The carbon number of the remaining portion excluding ^{A 1 is 1 to 1.} It is an integer of 6. A ¹ is synonymous with the above equation (1).)

In formula (1-A), X ¹ is preferably a single bond, an oxygen atom or an alkanediyl group having 1-3 carbon atoms. R ⁵ is preferably an alkyl group, an alkoxy group, an alkenyl group or an alkenyloxy group, and more preferably an alkyl group or an alkoxy group.
The carbon number of the remaining portion (-X ^1- CO-R ⁵ ) excluding A ¹ is preferably 2 to 6, and more preferably 2 to 4.

<Compound [A2]>
The "ketonic carbonyl group" contained in the compound [A2] refers to a carbonyl group (-C (= O)-) in which two carbon atoms are bonded to a carbon atom constituting the carbonyl group. .. The "oxyorganic group" means a group represented by "-O-organic group". The carbon number of the oxyorganic group is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and particularly preferably 1 to 6.

In the oxyorganic group, the organic group having 1 to 20 carbon atoms includes, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms and a divalent heteroatom-containing group between the carbon-carbon bonds of the hydrocarbon group. Examples thereof include a group in which a part or all of the hydrogen atoms of the group containing the above-mentioned hydrocarbon group and divalent heteroatom-containing group are replaced with a monovalent heteroatom-containing group.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 carbon atoms. Examples thereof include monovalent aromatic hydrocarbon groups of ~ 20. Specific examples of these include alkyl groups such as methyl group, ethyl group, n-propyl group and i-propyl group as monovalent chain hydrocarbon groups having 1 to 20 carbon atoms; ethenyl group, propenyl group, etc. Alkenyl groups such as butenyl groups; alkynyl groups such as ethynyl groups, propynyl groups, butynyl groups and the like can be mentioned.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a monocyclic alicyclic saturated hydrocarbon group such as a cyclopentyl group and a cyclohexyl group; and a monocyclic ring such as a cyclopentenyl group and a cyclohexenyl group. Alicyclic unsaturated hydrocarbon group; polycyclic alicyclic saturated hydrocarbon group such as norbornyl group, adamantyl group, tricyclodecyl group; polycyclic alicyclic such as norbornenyl group and tricyclodecenyl group Examples include unsaturated hydrocarbon groups.
Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include an aryl group such as a phenyl group, a tolyl group, a xsilyl group, a naphthyl group and an anthryl group; a benzyl group, a phenethyl group, a naphthylmethyl group and an anthrylmethyl group. Examples include an aralkyl group such as a group.
Examples of the hetero atom constituting the monovalent and divalent hetero atom-containing groups include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a halogen atom and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the divalent heteroatom-containing group include -O-, -CO-, -S-, -CS-, -NR'-, a group in which two or more of these are combined, and the like. R'is a hydrogen atom or a monovalent hydrocarbon group.

Of the above, the monovalent oxyorganic group having 1 to 20 carbon atoms is preferably an oxyhydrocarbon group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. A group is more preferable, and an alkoxy group having 1 to 3 carbon atoms is particularly preferable.

The number of ketonic carbonyl groups contained in the compound [A2] is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. Is particularly preferred. The number of oxyorganic groups contained in the compound [A2] is preferably 1 to 10, more preferably 1 to 6, further preferably 2 to 4, and 2 It is particularly preferable to have.

（式（３）中、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立して、水素原子又は炭素数１〜２０の１価の有機基である。Ｒ^１０及びＲ^１１は、それぞれ独立して、炭素数１〜２０の１価の有機基である。）In the compound [A2], the ketonic carbonyl group and the oxyorganic group can be present in one molecule, for example, via a carbon atom chain having 1 to 20 carbon atoms. The carbon number of the carbon atom chain is preferably 1 to 10, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1. A preferable specific example of the compound [A2] is a compound represented by the following formula (3).

(In formula (3), R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms. R ¹⁰ and R ¹¹ are respectively. Independently, it is a monovalent organic group having 1 to 20 carbon atoms.)

Specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ^{6 to} R ¹¹ include a group exemplified as an organic group in the oxy organic group possessed by the compound [A2].
R ⁶ and R ⁸ are preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and an alkyl having a hydrogen atom or 1 to 3 carbon atoms. Groups are more preferred, and hydrogen atoms or methyl groups are particularly preferred.
As R ⁷ and R ⁹ , a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferable, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is preferable. Alkyl groups are more preferred, and hydrogen atoms or methyl groups are particularly preferred.
As R ¹⁰ and R ¹¹ , a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is further preferable.

The compound [A] preferably has a melting point of 25 ° C. or lower and a boiling point of 150 ° C. or higher at 1 atm from the viewpoint of sufficiently obtaining the effects of the present disclosure when used as a solvent for a liquid crystal alignment agent. .. The boiling point of compound [A] at 1 atm is preferably 160 ° C. or higher, more preferably 165 to 250 ° C., and even more preferably 170 to 245 ° C. The melting point of compound [A] at 1 atm is preferably 20 ° C. or lower, more preferably 10 ° C. or lower.

Specific examples of the compound [A] include compounds represented by the following formulas (1-1) to (1-122). As the compound [A], one type may be used alone, or two or more types may be used in combination. In the following formula, "Ac" represents an acetyl group (-COCH ₃ ).

<Solvent [B]>
The solvent component is composed of an alcohol-based solvent, a chain ester-based solvent, an ether-based solvent, and a ketone-based solvent together with the compound [A] in that a liquid crystal aligning agent having better wet spreadability can be obtained. It is preferable to further contain a solvent (hereinafter, also referred to as “solvent [B]”) which is at least one selected and is different from the compound [A].

Specific examples of the solvent [B] include, as alcohol-based solvents, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, 3 −methoxy-1-butanol, 3-methoxy-3-methylbutanol, benzyl alcohol, etc.;
Examples of the chain ester solvent include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, isoamyl propionate, and the like. Isoamyl isobutyrate, etc.;
Examples of ether-based solvents include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, and ethylene glycol ethyl. Ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA) ), Diethyl, diisopentyl ether, etc .;
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cycloheptanone, cyclopentanone, 3-methylcyclohexanone, 4-methylcyclohexanone, diisobutyl ketone and the like.

The solvent [B] is preferably at least one selected from the group consisting of alcohol-based solvents, chain ester-based solvents, and ether-based solvents, because it has a higher effect of improving coatability. It is more preferable that it is at least one selected from the group consisting of alcohol-based solvents and ether-based solvents, and it is more preferably ethylene glycol monobutyl ether (butyl cellosolve), diacetone alcohol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether. , Propylene glycol monomethyl ether acetate, and 3-methoxy-1-butanol are more preferably one selected from the group. As the solvent [B], one type can be used alone or two or more types can be used in combination.

<Solvent [C]>
The solvent component, together with compound [A], has a boiling point of 200 ° C. or higher at 1 atm for the purpose of ensuring the solubility of the polymer in the solvent component and suppressing the decrease in product yield due to the precipitation of the polymer in the coating step. However, it is preferable that a solvent different from that of the compound [A] (hereinafter, also referred to as “solvent [C]”) is further contained.

（式（２）中、Ｒ^２１及びＲ^２２は、それぞれ独立に、水素原子若しくはエーテル結合を有していてもよい炭素数１〜６の１価の炭化水素基であるか、又は、Ｒ^２１とＲ^２２とが互いに合わせられてＲ^２１及びＲ^２２が結合する窒素原子と共に構成される環構造を表す。Ｒ^２３は、炭素数１〜４のアルキル基である。）The solvent [C] is preferably at least one selected from the group consisting of an aprotic polar solvent and phenols, and more preferably an aprotic polar solvent. Specifically, from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, gamma-butyrolactone, propylene carbonate and the compound represented by the following formula (2). It is particularly preferable that it is at least one selected from the group.

(In the formula (2), R ²¹ and R ²² are monovalent hydrocarbon groups having 1 to 6 carbon atoms, which may independently have a hydrogen atom or an ether bond, or R ^21. And R ²² are combined with each other to represent a ring structure composed of a nitrogen atom ^{to which R 21} and R ^{22 are bonded. R 23} is an alkyl group having 1 to 4 carbon atoms.

(Compound represented by formula (2))
In the above formula (2), the ^{monovalent hydrocarbon group having 1 to 6 carbon atoms of R 21} and R ²² is, for example, a chain hydrocarbon group having 1 to 6 carbon atoms and an alicyclic group having 3 to 6 carbon atoms. Examples include hydrocarbon groups and aromatic hydrocarbon groups having 5 or 6 carbon atoms. Further, examples of the monovalent group having "-O-" between the carbon-carbon bonds of the hydrocarbon group include an alkoxyalkyl group having 2 to 6 carbon atoms.
R ²¹ and R ²² may form a ring together with the nitrogen atom to which ^{R 21} and R ²² are bonded by bonding to each other. Examples of the ring formed by bonding R ²¹ and R ²² to each other include a pyrrolidine ring and a piperidine ring, and a monovalent chain hydrocarbon group such as a methyl group is bonded to these rings. May be.
R ²¹ and R ²² are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and further preferably a hydrogen atom or a methyl group. ..
The alkyl group having 1 to 4 carbon atoms of R ^{23 may be linear or branched.} R ²³ is preferably a methyl group or an ethyl group.

Specific examples of the compound represented by the above formula (2) include 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-. Examples thereof include dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide and the like. As the solvent [C], one type can be used alone or two or more types can be used in combination.

The content ratio of the compound [A] among the solvent components is preferably 10% by mass or more with respect to the total amount of the solvent components contained in the liquid crystal alignment agent. When it is less than 10% by mass, it tends to be difficult to sufficiently obtain the effect of improving the coatability of the liquid crystal alignment agent. The content ratio of the compound [A] is more preferably 15% by mass or more, still more preferably 20% by mass, in that the balance between the solubility of the polymer component and the wettability of the liquid crystal alignment agent can be improved. That is all. The content of the compound [A] is preferably 85% by mass or less, more preferably 75% by mass or less, and particularly preferably 70% by mass or less.

The content ratio of the solvent [B] is preferably 10% by mass or more, preferably 15% by mass, based on the total amount of the solvent components contained in the liquid crystal alignment agent, in that the wet spreadability of the liquid crystal alignment agent can be further increased. % Or more, more preferably 20% by mass or more. The content ratio of the solvent [B] is preferably 90% by mass or less, more preferably 80% by mass or less, and 70% by mass, based on the total amount of the solvent components contained in the liquid crystal alignment agent. It is more preferably less than or equal to, and particularly preferably 50 or less by mass.

The content ratio of the solvent [C] is preferably 70% by mass or less in that the heating temperature at the time of film formation can be lowered. The content ratio is more preferably 65% by mass or less, still more preferably 60% by mass or less. Further, from the viewpoint of ensuring the solubility of the polymer component in the solvent, the content ratio of the solvent [C] is preferably 1% by mass or more with respect to the total amount of the solvent component contained in the liquid crystal aligning agent. It is more preferably 5% by mass or more, and further preferably 10% by mass or more.

The liquid crystal alignment agent may contain only the compound [A] as the solvent component, but the solvent component is composed of the compound [A] and the solvent [B], or the solvent [A] and the solvent [B]. It is particularly preferably composed of the solvent [C]. However, in the present specification, "the solvent component is composed of the compound [A] and the solvent [B]" and "the solvent component is composed of the compound [A], the solvent [B] and the solvent [C]". , Compound [A], solvent [B] and other solvents other than solvent [C] are allowed to be contained to the extent that they do not interfere with the effects of the present invention.
Examples of other solvents include halogenated hydrocarbon solvents and hydrocarbon solvents. Specific examples of these include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene and the like as hydrocarbon-based solvents; hexane, heptane, octane and the like as hydrocarbon solvents. , Benzene, toluene, xylene and the like, respectively. The content ratio of the other solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and 0.2% by mass, based on the total amount of the solvent components contained in the liquid crystal alignment agent. It is more preferably% or less.

≪Other ingredients≫
The liquid crystal alignment agent contains a polymer component and a solvent component, but may contain other components if necessary. Such other components include, for example, epoxy group-containing compounds (eg, N, N, N', N'-tetraglycidyl-m-xylene diamine, N, N, N', N'-tetraglycidyl-4,4. '-Diaminodiphenylmethane, etc.), functional silane compounds (eg, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, etc.), antioxidants, metal chelate compounds, curing Examples thereof include catalysts, curing accelerators, surfactants, fillers, dispersants, photosensitizers and the like. The blending ratio of the other components can be appropriately selected according to each compound as long as the effects of the present invention are not impaired.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferable. It is in the range of 1 to 10% by mass. 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 excessive and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coatability deteriorates. There is a tendency.

≪Liquid crystal alignment film and liquid crystal element≫
The liquid crystal element of the present disclosure includes a liquid crystal alignment film formed by using the liquid crystal alignment agent described above. The liquid crystal element can be effectively applied to various applications, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, a smartphone, various monitors, and a liquid crystal television. , It can be used as various display devices such as information displays, dimming films, retardation films, and the like. When used as a liquid crystal display device, the operation mode of the liquid crystal is not particularly limited, and for example, TN type, STN type, vertically oriented type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB. It can be applied to various operation modes such as (Optically Compensated Bend) type.

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

(Step 1: Formation of coating film)
First, a liquid crystal alignment agent is applied onto the substrate, and preferably the coated surface is heated to form a coating film on the substrate. As the substrate, for example, glass such as float glass and soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (aliphatic olefin) can be used. As the transparent conductive film provided on one surface of the substrate, NESA film (US PPG registered trademark) made of tin oxide (SnO _2), indium oxide - ITO made of tin oxide _{(In 2} O 3 -SnO ₂₎ film Etc. can be used. When manufacturing a TN type, STN type or VA type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, in the case of manufacturing an IPS type or FFS type liquid crystal element, a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb-teeth shape and an opposing substrate not provided with an electrode. Is used. As the metal film, a film made of a metal such as chromium can be used. The liquid crystal alignment agent is applied to the substrate by an offset printing method, a spin coating method, a roll coater method, a flexographic printing method or an inkjet printing method, preferably on the electrode forming surface.

After the liquid crystal alignment agent is applied, preheating is preferably performed for the purpose of preventing the applied liquid crystal alignment agent from dripping. The pre-baking temperature is preferably 30 to 200 ° C., and the pre-baking time is preferably 0.25 to 10 minutes. Then, a firing (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally imidizing the amic acid structure of the polymer. The firing temperature (post-baking temperature) is preferably 80 to 300 ° C., and the post-baking time is preferably 5 to 200 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 μm. By applying the liquid crystal alignment agent on the substrate and then removing the organic solvent, a liquid crystal alignment film or a coating film to be a liquid crystal alignment film is formed.

(Step 2: Orientation treatment)
When manufacturing a TN type, STN type, IPS type or FFS type liquid crystal display element, a treatment (alignment treatment) for imparting a liquid crystal alignment ability to the coating film formed in the above step 1 is performed. As a result, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. As the orientation treatment, for example, a rubbing treatment in which the coating film is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, and cotton, or a coating film formed on a substrate using a liquid crystal alignment agent is irradiated with light. Examples thereof include a photo-alignment treatment for imparting a liquid crystal alignment ability to the coating film. On the other hand, in the case of manufacturing a vertically oriented liquid crystal element, the coating film formed in the above step 1 can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an orientation treatment. A liquid crystal alignment agent suitable for a vertically oriented liquid crystal display element can also be suitably used for a PSA (Polymer sustained alignment) type liquid crystal display element.

(Step 3: Construction of liquid crystal cell)
A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above and arranging the liquid crystal between the two substrates arranged opposite to each other. In order to manufacture a liquid crystal cell, for example, (1) two substrates are arranged facing each other through a gap (spacer) so that the liquid crystal alignment films face each other, and the peripheral portion of the two substrates is covered with a sealant. A method of sealing the injection holes after laminating, injecting and filling the liquid crystal in the substrate surface and the cell gap partitioned by the sealant, (2) sealing at a predetermined place on one substrate on which the liquid crystal alignment film is formed. A method in which an agent is applied, liquid crystal is dropped onto a predetermined number of places on the liquid crystal alignment film surface, the other substrate is bonded so that the liquid crystal alignment film faces each other, and the liquid crystal is spread over the entire surface of the substrate (ODF method). ) Etc. can be mentioned. It is desirable to remove the flow orientation at the time of filling the liquid crystal by further heating the manufactured liquid crystal cell to a temperature at which the used liquid crystal takes an isotropic phase and then slowly cooling it to room temperature.

As the sealing agent, for example, an epoxy resin containing an aluminum oxide sphere as a curing agent and a spacer can be used. As the spacer, a photo spacer, a bead spacer, or the like can be used. Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal, and among them, the nematic liquid crystal is preferable. Further, for example, a cholesteric liquid crystal, a chiral agent, a ferroelectric liquid crystal or the like may be added to the nematic liquid crystal or the smectic liquid crystal for use.

Subsequently, if necessary, a polarizing plate is attached to the outer surface of the liquid crystal cell. Examples of the polarizing plate include a polarizing plate in which a polarizing film called "H film" in which polyvinyl alcohol is stretch-oriented and iodine is absorbed is sandwiched between a cellulose acetate protective film, or a polarizing plate made of the H film itself. In this way, a liquid crystal display element can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

In the following examples, the weight average molecular weight Mw of the polymer, the imidization ratio of the polyimide in the polymer solution, the solution viscosity of the polymer solution, and the epoxy equivalent were measured by the following methods. The required amounts of the raw material compounds and polymers used in the following examples were secured by repeating the synthesis on the synthetic scale shown in the following synthesis examples as necessary.

[Weight average molecular weight Mw of polymer]
The weight average molecular weight Mw is a polystyrene-equivalent value measured by GPC under the following conditions.
Column: Made by Tosoh Corporation, 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]
The polyimide solution was poured into pure water, the obtained precipitate was sufficiently dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidization rate [%] was determined by the following mathematical formula (1).
Imidization rate [%] = (1- (A ¹ / (A ² x α))) x 100 ... (1)
(In formula (1), A ¹ is the peak area derived from the proton of the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of the polymer (polyamic acid). ) Is the ratio of the number of other protons to one proton of the NH group.)
[Solution viscosity of polymer solution]
The solution viscosity (mPa · s) of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer.
[Epoxy equivalent]
Epoxy equivalents were measured by the hydrochloric acid-methylethylketone method described in JIS C 2105.

The abbreviations of the compounds are as follows. In the following, the compound represented by the formula (DA-X) (where X is an integer of 1 to 8) may be simply referred to as "compound (DA-X)".
(Diamine compound)

(solvent)

<Synthesis of polymer>
[Synthesis Example 1: Synthesis of Polyimide (PI-1)]
22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) as tetracarboxylic dianhydride, and 8.6 g (0.08 mol) of p-phenylenediamine (PDA) as diamine. ) And 10.5 g (0.02 mol) of cholestanyl 3,5-diaminobenzoate (HCDA) were dissolved in 166 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C. for 6 hours to carry out a polyamic acid. Was obtained in an amount of 20% by mass. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 90 mPa · s.
Next, NMP was added to the obtained polyamic acid solution to prepare a solution having a polyamic acid concentration of 7% by mass, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and a dehydration ring closure reaction was carried out at 110 ° C. for 4 hours. .. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP (the pyridine and acetic anhydride used in the dehydration ring closure reaction were removed from the system by this operation. The same applies hereinafter), so that the imidization rate was about 68. A solution containing 26% by mass of% polyimide (PI-1) was obtained. A small amount of the obtained polyimide solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 45 mPa · s. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain polyimide (PI-1).

[Synthesis Example 2: Synthesis of Polyimide (PI-2)]
As tetracarboxylic acid dianhydride, 110 g (0.50 mol) of TCA and 1,3,3a,4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] Furan-1,3-dione 160 g (0.50 mol), PDA 91 g (0.85 mol) as diamine, 1,3-bis (3-aminopropyl) tetramethyldisiloxane 25 g ( 0.10 mol) and 25 g (0.040 mol) of 3,6-bis (4-aminobenzoyloxy) cholesterol, and 1.4 g (0.015 mol) of aniline as a monoamine were dissolved in 960 g of NMP at 60 ° C. The reaction was carried out for 6 hours to obtain a solution containing a polyamic acid. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 60 mPa · s.
Next, 2,700 g of NMP was added to the obtained polyamic acid solution, 390 g of pyridine and 410 g of acetic anhydride were added, and a dehydration ring closure reaction was carried out at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone (GBL) to obtain about 2,500 g of a solution containing 15% by mass of polyimide (PI-2) having an imidization ratio of about 95%. Obtained. A small amount of this solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 70 mPa · s. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain polyimide (PI-2).

[Synthesis Example 3: Synthesis of Polyimide (PI-3)]
Except that the diamine used was changed to 0.08 mol of 3,5-diaminobenzoic acid (3,5 DAB) and 0.02 mol of cholestanyloxy-2,4-diaminobenzene (HCODA), the same as in Synthesis Example 1 above. A polyamic acid solution was obtained by the same method. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 80 mPa · s.
Next, imidization was carried out by the same method as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-3) having an imidization ratio of about 65%. A small amount of the obtained polyimide solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 40 mPa · s. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain polyimide (PI-3).

[Synthesis Example 4: Synthesis of Polyimide (PI-4)]
Except that the diamine used was changed to 0.06 mol of 4,4'-diaminodiphenylmethane, 0.02 mol of compound (DA-1), and 0.02 mol of compound (DA-2), the same as in Synthesis Example 1 above. A polyamic acid solution was obtained by the same method. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 60 mPa · s.
Next, imidization was carried out by the same method as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-4) having an imidization ratio of about 65%. A small amount of the obtained polyimide solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 33 mPa · s. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain polyimide (PI-4).

[Synthesis Example 5: Synthesis of Polyimide (PI-5)]
Except that the diamine used was changed to 0.098 mol of 4-aminophenyl-4-aminobenzoate (compound represented by the above formula (DA-3)) and 0.002 mol of compound (DA-4). A polyamic acid solution was obtained by the same method as in Synthesis Example 1 above. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 70 mPa · s.
Next, imidization was carried out by the same method as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-5) having an imidization ratio of about 60%. A small amount of the obtained polyimide solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by mass was 45 mPa · s. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain polyimide (PI-5).

[Synthesis Example 6: Synthesis of Polyamic Acid (PA-1)]
1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (CB) 200 g (1.0 mol) as tetracarboxylic acid dianhydride, 2,2'-dimethyl-4,4'-diaminobiphenyl 210 g as diamine (1.0 mol) was dissolved in a mixed solvent of 370 g of NMP and 3,300 g of GBL, and the reaction was carried out at 40 ° C. for 3 hours to obtain a polyamic acid solution having a solid content concentration of 10% by mass and a solution viscosity of 160 mPa · s. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain a polyamic acid (PA-1).

[Synthesis Example 7: Synthesis of Polyamic Acid (PA-2)]
7.0 g (0.031 mol) of TCA as tetracarboxylic dianhydride and 13 g of compound (DA-5) as diamine (corresponding to 1 mol with respect to 1 mol of TCA) were dissolved in 80 g of NMP and 4 at 60 ° C. By carrying out a time reaction, a solution containing 20% by mass of polyamic acid (PA-2) was obtained. The solution viscosity of this polyamic acid solution was 2,000 mPa · s. The compound (DA-5) was synthesized according to the description in Japanese Patent Application Laid-Open No. 2011-10099. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain a polyamic acid (PA-2).

[Synthesis Example 8: Synthesis of Polyamic Acid (PA-3)]
The diamine used was changed to 0.7 mol of 1,3-bis (4-aminophenethyl) urea (compound represented by the above formula (DA-6)) and 0.3 mol of compound (DA-7). A polyamic acid solution was obtained by the same method as in Synthesis Example 6 except for the above. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 95 mPa · s. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain a polyamic acid (PA-3).

[Synthesis Example 9: Synthesis of Polyamic Acid (PA-4)]
The tetracarboxylic acid dianhydride used was changed to 1.0 mol of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and the diamine used was p-phenylenediamine 0. Polyamic acid solution by the same method as in Synthesis Example 6 above, except that it was changed to 3 mol, 0.2 mol of compound (DA-7), and 0.5 mol of 1,2-bis (4-aminophenoxy) ethane. Got A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 90 mPa · s. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain a polyamic acid (PA-4).

[Synthesis Example 10: Synthesis of Polyamic Acid (PA-5)]
Except that the diamine used was changed to 0.2 mol of 2,4-diamino-N, N-diallylaniline, 0.2 mol of 4,4'-diaminodiphenylamine, and 0.6 mol of 4,4'-diaminodiphenylmethane. Obtained a polyamic acid solution by the same method as in Synthesis Example 6 above. A small amount of the obtained polyamic acid solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 95 mPa · s. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain a polyamic acid (PA-5).

[Synthesis Example 11: Synthesis of Polyamic Acid Ester (PAE-1)]
0.035 mol of 2,4-bis (methoxycarbonyl) -1,3-dimethylcyclobutane-1,3-dicarboxylic acid was added to 20 ml of thionyl chloride, N, N-dimethylformamide was added in a catalytic amount, and then the temperature was increased to 80 ° C. Stirred for 1 hour. Then, the reaction solution was concentrated, and the residue was dissolved in 113 g of γ-butyrolactone (GBL) (this solution was designated as reaction solution A). Separately, 0.01 mol of p-phenylenediamine, 0.01 mol of 1,2-bis (4-aminophenoxy) ethane, and 0.014 mol of compound (DA-8) were added to 6.9 g of pyridine, 44.5 g of NMP, and GBL33. It was dissolved in addition to 5.5 g and cooled to 0 ° C. Then, the reaction solution A was slowly added dropwise to this solution over 1 hour, and after completion of the addition, the mixture was stirred at room temperature for 4 hours. The obtained solution of polyamic acid ester was added dropwise to 800 ml of pure water with stirring, and the precipitated precipitate was filtered. Subsequently, it was washed 5 times with 400 ml of isopropyl alcohol (IPA) and dried to obtain 15.5 g of polymer powder. The weight average molecular weight Mw of the obtained polyamic acid ester (PAE-1) was 34,000.

[Synthesis Example 12: Synthesis of Polyorganosiloxane (APS-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 (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed. It was charged and mixed at room temperature. Then, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and then the reaction was carried out at 80 ° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out, washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a reactive polyorganosiloxane. (EPS-1) was obtained as a viscous transparent liquid. ^{When 1} H-NMR analysis was performed on this reactive polyorganosiloxane (EPS-1), a peak based on an epoxy group was obtained near chemical shift (δ) = 3.2 ppm according to the theoretical intensity, and during the reaction. It was confirmed that no side reaction of the epoxy group occurred. The weight average molecular weight Mw of the obtained reactive polyorganosiloxane was 3,500, and the epoxy equivalent was 180 g / mol.
Next, 10.0 g of reactive polyorganosiloxane (EPS-1), 30.28 g of methyl isobutyl ketone as a solvent, 3.98 g of 4-dodecyloxybenzoic acid as a reactive compound, and UCAT as a catalyst were placed in a 200 mL three-necked flask. 0.10 g of 18X (trade name, manufactured by Sun Appro Co., Ltd.) was charged, and the reaction was carried out at 100 ° C. for 48 hours with stirring. After completion of the reaction, the solution obtained by adding ethyl acetate to the reaction mixture was washed with water three times, the organic layer was dried over magnesium sulfate, and then the solvent was distilled off to obtain a liquid crystal oriented polyorganosiloxane (APS-). 1) was obtained in 9.0 g. The weight average molecular weight Mw of the obtained polymer was 9,900.

[Example 1]
1. 1. Preparation of liquid crystal alignment agent To the polyimide (PI-1) obtained in Synthesis Example 1 above, 2-acetylmethylfuran (AcMeF), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added as solvents. A solution having a solid content concentration of 6.5% by mass and a solvent mixing ratio of AcMeF: NMP: BC = 10: 60: 30 (mass ratio) was prepared. After sufficiently stirring this solution, a liquid crystal alignment agent (S-1) was prepared by filtering through a filter having a pore size of 1 μm. The liquid crystal alignment agent (S-1) is mainly for manufacturing a vertically oriented liquid crystal display element.

2. Evaluation of surface unevenness (printability) 1. The liquid crystal alignment agent (S-1) prepared in the above was applied onto a glass substrate using a spinner, prebaked on a hot plate at 80 ° C. for 1 minute, and then the inside of the refrigerator was replaced with nitrogen in an oven at 200 ° C. 1 A coating film having an average film thickness of 0.1 μm was formed by heating (post-baking) for a time. The surface of the obtained coating film was observed with an atomic force microscope (AFM), and the center average roughness (Ra) was measured. When Ra was 5 nm or less, the printability was evaluated as “good (◯)”, when it was larger than 5 nm and less than 10 nm, it was evaluated as “possible (Δ)”, and when it was 10 nm or more, it was evaluated as “poor (×)”. As a result, in this example, the printability was evaluated as "good".

3. 3. Evaluation of Continuous Printability The liquid crystal alignment agent (S-1) prepared above was evaluated for printability (continuous printability) when printing on a substrate was continuously performed. The evaluation was performed as follows. First, using a liquid crystal alignment film printing machine (manufactured by Nissha Printing Machine Co., Ltd., ongstromer type "S40L-532"), the amount of the liquid crystal alignment agent (S-1) dropped onto the anilox roll is 20 drops reciprocating. Under the condition of (about 0.2 g), printing was performed on the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film. Printing on the substrate was carried out 20 times using a new substrate at 1-minute intervals.
Subsequently, the liquid crystal alignment agent (S-1) is dispensed (one way) on the anilox roll at 1-minute intervals, and each time the anilox roll and the printing plate are brought into contact with each other (hereinafter referred to as idle operation), a total of 10 times. It was done (during this time, printing on the glass substrate was not performed). It should be noted that this idle operation is an operation performed in order to intentionally print the liquid crystal alignment agent under harsh conditions.
After 10 idle runs, the main printing was subsequently performed using a glass substrate. In this printing, after idle operation, five substrates are put in at intervals of 30 seconds, and each substrate after printing is heated (prebaked) at 80 ° C. for 1 minute to remove the solvent, and then heated at 200 ° C. for 10 minutes (prebaking). Post-baking) was performed to form a coating film having a film thickness of about 0.08 μm. The printability (continuous printability) was evaluated by observing this coating film with a microscope having a magnification of 20 times. In the evaluation, continuous printability is "good (○)" when no precipitation of the polymer is observed from the first main printing after the idle operation, and precipitation of the polymer is observed in the first main printing after the idle operation. Continuous printability is "possible (Δ)" when the precipitation of the polymer is not observed during the main printing 5 times, and continuous when the precipitation of the polymer is observed even after the main printing is repeated 5 times. Printability was defined as "poor (x)". As a result, the continuous printability was "good (◯)" in this example. It has been experimentally found that with a liquid crystal alignment agent having good printability, the precipitation of the polymer is improved (disappeared) while the substrate is continuously charged. Furthermore, when the number of idle operations was changed to 15, 20, and 25 times, and the printability of the liquid crystal alignment agent was evaluated in the same manner as above for each, in this embodiment, the idle operations were performed 15 times and 20 times. When it was set to 25 times, it was "good (○)", and when it was 25 times, it was "OK (Δ)".

4. Evaluation of Applicability to Fine Concavo-convex Surface Using the evaluation ITO electrode substrate 10 shown in FIG. 1, the applicability of the liquid crystal alignment agent to the fine concavo-convex surface was evaluated. As the evaluation ITO electrode substrate 10, a plurality of striped ITO electrodes 12 were arranged on one surface of the glass substrate 11 at predetermined intervals (see FIG. 1). The electrode width A was 50 μm, the distance between the electrodes B was 2 μm, and the electrode height C was 0.2 μm. A wettability evaluation device LSE-A100T (manufactured by Nick) was used on the electrode forming surface of the evaluation ITO electrode substrate 10, and the above 1. The liquid crystal alignment agent (S-1) prepared in the above was added dropwise, and the ease of adapting to the uneven surface of the substrate was evaluated. At this time, it can be said that the larger the wett spread area S (mm ² / μL) of the droplet with respect to the amount of liquid, the larger the wet spread of the droplet, and the better the applicability of the liquid crystal aligning agent to the fine uneven surface.
Evaluation, if the area S is 15 mm ² / [mu] L or more "good (◎)", when the area S is less than 10 mm ² / [mu] L or more 15 mm ² / [mu] L "good (○)", the area S is 5mm ^When it was larger than ² / μL and less than 10 mm 2 / μL, it was evaluated as “OK (Δ)”, and when the area S was 5 mm ² / μL or less, it was evaluated as “Defective (×)”. As a result, in this example, the area S was 14 mm ² / μL, and the applicability to the fine uneven surface was judged to be “good”.

5. Manufacture of vertically oriented liquid crystal display element The above 1. A liquid crystal alignment agent (S-1) was prepared in the same manner as in the above. The prepared liquid crystal alignment agent (S-1) is applied to a glass substrate with a transparent electrode made of a pair (2 sheets) of ITO films using a spinner, prebaked on a hot plate at 80 ° C. for 1 minute, and then prebaked. A coating film (liquid crystal alignment film) having a film thickness of 0.08 μm was formed by removing the solvent by heating at 200 ° C. for 1 hour in an oven replaced with nitrogen. The coating film was subjected to a rubbing treatment using a rubbing machine having a roll wrapped with rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a fluff pushing length of 0.1 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then the substrate was dried in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film. It should be noted that this rubbing process is a weak rubbing process performed for the purpose of controlling the collapse of the liquid crystal display and performing the orientation division by a simple method.
After applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 μm by screen printing on the outer periphery of the surface of one of the substrates having the liquid crystal alignment film, the liquid crystal alignment film surfaces of the pair of substrates face each other. The adhesive was heat-cured by heating the adhesive at 150 ° C. for 1 hour. Next, after filling the gap between the substrates from the liquid crystal injection port with a negative liquid crystal display (MLC-6608 manufactured by Merck), the liquid crystal injection port is sealed with an epoxy adhesive, and further, in order to eliminate the flow orientation during liquid crystal injection. This was heated at 150 ° C. for 10 minutes and then slowly cooled to room temperature. Further, a liquid crystal display element was manufactured by laminating polarizing plates on both outer sides of the substrate so that the polarization directions of the two polarizing plates were orthogonal to each other.

6. Evaluation of variation characteristics (post-bake margin) of pre-tilt angle with respect to post-bake temperature unevenness 5. Liquid crystal alignment films were prepared at different post-baking temperatures (120 ° C., 180 ° C. and 230 ° C.) according to the above method, and the pretilt angles of the obtained liquid crystal display elements were measured. Then, the measured value at 230 ° C. was set as the reference pretilt angle θp, and the variation characteristic of the pretilt angle with respect to the temperature unevenness of the postbake was evaluated by the difference Δθ (= θp−θa) between the reference pretilt angle θp and the measured value θa. It can be said that the smaller Δθ is, the smaller the variation in the pretilt angle with respect to the temperature unevenness is and the better. The measurement of the pre-tilt angle is performed in accordance with the method described in the non-patent document (TJ Scheffer et. Al. J. Appl. Phys. Vo. 19, p. 2013 (1980)). The value of the inclination angle of the liquid crystal molecule from the substrate surface measured by the crystal rotation method using the above was defined as the pretilt angle [°]. The evaluation was "good (○)" when Δθ was 0.2 ° or less, "possible (Δ)" when it was greater than 0.2 ° and less than 0.5 °, 0.5 °. The case of the above was regarded as "defective (x)". As a result, in this example, the post-bake margin was evaluated as "good" when the post-bake temperature was 180 ° C. and "good" when the post-bake temperature was 120 ° C.

7. Evaluation of bezel unevenness resistance 5. A vertically oriented liquid crystal display element was manufactured using a liquid crystal aligning agent (S-1) having a solid content concentration of 3.5% by mass according to the above method. The obtained vertically oriented liquid crystal display element was stored under the conditions of 25 ° C. and 50% RH for 30 days, and then driven by an AC voltage of 5 V to observe the lighting state. The evaluation is "good (○)" if the brightness difference (more black or more white) is not visible around the sealant, but it is "OK" if the brightness difference disappears within 20 minutes after lighting. Δ) ”, the case where the difference in brightness was visually recognized even after 20 minutes had passed was defined as“ defective (×) ”. As a result, this liquid crystal display element was judged to be "OK".

[Examples 2 to 10 and Comparative Examples 1 to 8]
A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the types and amounts of the polymers and the solvent composition were as shown in Table 1 below. In addition, various evaluations were carried out in the same manner as in Example 1 using the prepared liquid crystal alignment agent. The evaluation results are shown in Table 2 below.

[Example 11]
1. 1. Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-11) was prepared in the same manner as in Example 1 except that the polymer components and the solvent composition were changed as shown in Table 1 below. The liquid crystal alignment agent (S-11) is mainly for manufacturing a horizontally oriented liquid crystal display element.
2. Evaluation of Liquid Crystal Aligning Agent The surface unevenness, continuous printability, and applicability to a finely uneven surface were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-11) was used. The results are shown in Table 2 below.

3. 3. Manufacture of rubbing FFS type liquid crystal display element The above 1. A liquid crystal alignment agent (S-11) was prepared in the same manner as in the above. Subsequently, a flat plate electrode (bottom electrode), an insulating layer, and a comb-shaped electrode (top electrode) are laminated on one side in this order on a glass substrate and a counter glass substrate on which no electrode is provided. A liquid crystal aligning agent (S-11) having a solid content concentration of 3.5% by mass was applied using a spinner, and heated (prebaked) on a hot plate at 80 ° C. for 1 minute. Then, the inside of the chamber was dried (post-baked) for 1 hour in a nitrogen-substituted oven at 200 ° C. to form a coating film having an average film thickness of 0.08 μm.
Next, the surface of the coating film was subjected to a rubbing treatment using a rubbing machine having a roll wrapped with rayon cloth at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a fluff pushing length of 0.4 mm. Then, it was ultrasonically cleaned in ultrapure water for 1 minute and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film.
Next, for a pair of substrates having a liquid crystal alignment film, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm was screen-printed and applied, leaving a liquid crystal injection port on the edge of the surface on which the liquid crystal alignment film was formed, and then the substrate was applied. The adhesive was overlapped and crimped, and the adhesive was heat-cured at 150 ° C. for 1 hour. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to eliminate the flow orientation at the time of liquid crystal injection, this was heated at 120 ° C. and then slowly cooled to room temperature to produce a liquid crystal cell. When stacking a pair of substrates, the rubbing method of each substrate was set to be antiparallel. Further, the polarizing plates were attached so that the polarization directions of the two polarizing plates were parallel and orthogonal to the rubbing direction, respectively.
For the top electrode, the line width of the electrode was set to 4 μm, and the distance between the electrodes was set to 6 μm. As the top electrode, four types of driving electrodes, electrode A, electrode B, electrode C, and electrode D, were used. In this case, the bottom electrode acts as a common electrode that acts on all of the four drive electrodes, and each of the regions of the four drive electrodes becomes a pixel region.
4. Evaluation of rubbing FFS type liquid crystal display element 3. The post-bake margin was evaluated in the same manner as in Example 1 except that the rubbing FFS type liquid crystal display element obtained in 1 was used. In addition, the above 3. A rubbing FFS type liquid crystal display element was manufactured according to the method described in the above, and the bezel unevenness resistance was evaluated. The results are shown in Table 2 below.

[Examples 12 and 13]
Liquid crystal alignment agents (S-12) and (S-13) were prepared in the same manner as in Example 1 except that the polymer components and the solvent composition were changed as shown in Table 1 below. In addition, the surface unevenness, continuous printability, and coatability on the finely uneven surface were evaluated and carried out in the same manner as in Example 1 except that the liquid crystal alignment agents (S-12) and (S-13) were used, respectively. A rubbing FFS type liquid crystal display element was manufactured in the same manner as in Example 11 and various evaluations were performed. The results are shown in Table 2 below.

[Example 14]
1. 1. Preparation of liquid crystal alignment agent 1. of Example 1 except that the polymer components and solvent composition were changed as shown in Table 1 below. A liquid crystal alignment agent (S-14) was prepared in the same manner as in the above. The liquid crystal alignment agent (S-14) is mainly used for manufacturing a PSA type liquid crystal display element.
2. Evaluation of Liquid Crystal Aligning Agent The surface unevenness, continuous printability, and applicability to a finely uneven surface were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-14) was used. The results are shown in Table 2 below.

3. 3. Preparation of liquid crystal composition With respect to 10 g of nematic liquid crystal (MLC-6608 manufactured by Merck Co., Ltd.), 5% by mass of the liquid crystal compound represented by the following formula (L1-1) and the following formula (L2-1) are represented. The liquid crystal composition LC1 was obtained by adding 0.3% by mass of the photopolymerizable compound and mixing the compounds.

4. Manufacture of PSA type liquid crystal display element The above 1. The liquid crystal alignment agent (S-14) is prepared in the same manner as in the above, and the prepared liquid crystal alignment agent (S-14) is used to describe in "5. Production of a vertically oriented liquid crystal display element" of Example 1. In the same manner as the method, a pair (two) of substrates having a liquid crystal alignment film was obtained. Next, a liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal composition LC1 prepared above was used instead of MLC-6608 and that the polarizing plate was not bonded.
Next, an AC 10V having a frequency of 60 Hz was applied between the electrodes to the liquid crystal cell obtained above, and in a state where the liquid crystal was driven, 50 ultraviolet rays were emitted using an ultraviolet irradiation device using a metal halide lamp as a light source. The irradiation was performed at an irradiation rate of 000 J / m ^2. The irradiation amount is a value measured using a photometer measured based on a wavelength of 365 nm. Further, a liquid crystal display element was manufactured by laminating polarizing plates on both outer sides of the substrate so that the polarization directions of the two polarizing plates were orthogonal to each other.
5. Evaluation of PSA type liquid crystal display element 4. The post-bake margin was evaluated in the same manner as in Example 1 except that the PSA type liquid crystal display element obtained in 1 was used. In addition, the above 4. A PSA type liquid crystal display element was manufactured according to the method described in 1 and the bezel unevenness resistance was evaluated. The results are shown in Table 2 below.

[Examples 15 to 17, 27, 28, and Comparative Example 9]
Liquid crystal alignment agents were prepared in the same manner as in Example 1 except that the polymer components and the solvent composition were changed as shown in Table 1 below. In addition, the surface unevenness, continuous printability, and coatability on the finely uneven surface were evaluated in the same manner as in Example 1 except that each liquid crystal alignment agent was used, and the PSA type liquid crystal cell was formed in the same manner as in Example 14. It was manufactured and evaluated for post-bake margin and bezel unevenness resistance. The results are shown in Table 2 below.

[Example 18]
1. 1. Preparation of liquid crystal alignment agent 1. of Example 1 except that the polymer components and solvent composition were changed as shown in Table 1 below. A liquid crystal alignment agent (S-18) was prepared in the same manner as in the above. The liquid crystal alignment agent (S-18) is mainly for manufacturing an optical vertical alignment type liquid crystal display element.
2. Evaluation of Liquid Crystal Aligning Agent The surface unevenness, continuous printability, and applicability to a finely uneven surface were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-18) was used. The results are shown in Table 2 below.

3. 3. Manufacture of optical vertical alignment type liquid crystal display element The above 1. A liquid crystal alignment agent (S-18) was prepared in the same manner as in the above. In addition, the prepared liquid crystal alignment agent (S-18) was used, and instead of the rubbing treatment, polarized ultraviolet rays were irradiated using an Hg-Xe lamp and a Gran Tailor prism. An optical vertical alignment type liquid crystal display element was manufactured in the same manner as described in "Manufacture of Orientation Type Liquid Crystal Display Element". The irradiation of polarized ultraviolet rays was performed from a direction inclined by 40 ° from the normal of the substrate, the irradiation amount was 200 J / m ² , and the polarization direction was p-polarized light. Further, this irradiation amount is a value measured using a photometer measured based on a wavelength of 313 nm.
4. Evaluation of optical vertical alignment type liquid crystal display element 3. The post-bake margin was evaluated in the same manner as in Example 1 except that the optical vertical alignment type liquid crystal cell obtained in 1 was used. In addition, the above 3. An optical vertical liquid crystal display element was manufactured according to the method described in 1 and the bezel unevenness resistance was evaluated. The results are shown in Table 2 below.

[Examples 19 and 20]
Example 1 1. Except that the polymer components and solvent composition were changed as shown in Table 1 below. The liquid crystal aligning agent was prepared in the same manner as in the above. Further, the surface unevenness, continuous printability, and coatability on the finely uneven surface were evaluated in the same manner as in Example 1 except that each liquid crystal alignment agent was used, and the optical vertical alignment type liquid crystal was evaluated in the same manner as in Example 18. A display element was manufactured to withstand post-bake margin and bezel unevenness. The results are shown in Table 2 below.

[Example 21]
1. 1. Preparation of liquid crystal alignment agent 1. of Example 1 except that the polymer components and solvent composition were changed as shown in Table 1 below. A liquid crystal alignment agent (S-21) was prepared in the same manner as in the above. The liquid crystal alignment agent (S-21) is mainly used for manufacturing an optical FFS type liquid crystal display element.
2. Evaluation of liquid crystal alignment agent 1. The surface unevenness, continuous printability, and applicability to a finely uneven surface were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-21) prepared in 1 was used. The results are shown in Table 2 below.

3. 3. Production of Optical FFS Type Liquid Crystal Cell The above 1. A liquid crystal alignment agent (S-21) was prepared in the same manner as in the above. In addition, the prepared liquid crystal alignment agent (S-21) was used, and instead of the rubbing treatment, polarized ultraviolet rays were irradiated using an Hg-Xe lamp and a Gran Tailor prism. An optical FFS type liquid crystal display element was manufactured in the same manner as described in "Manufacture of FFS type liquid crystal display element". The irradiation of polarized ultraviolet rays was performed from the vertical direction from the substrate, the irradiation amount was 10,000 J / m ² , and the polarization direction was a direction orthogonal to the direction of the rubbing treatment in Example 11. Further, this irradiation amount is a value measured using a photometer measured based on a wavelength of 254 nm.
4. Evaluation of optical FFS type liquid crystal display element 3. The post-bake margin was evaluated in the same manner as in Example 1 except that the optical FFS type liquid crystal display element obtained in 1 was used. In addition, the above 3. An optical FFS type liquid crystal display element was manufactured according to the method described in 1 and the bezel unevenness resistance was evaluated. The results are shown in Table 2 below.

[Examples 22 to 26]
Example 1 1. Except that the polymer components and solvent composition were changed as shown in Table 1 below. The liquid crystal aligning agent was prepared in the same manner as in the above. Further, the surface unevenness, continuous printability, and coatability on the finely uneven surface were evaluated in the same manner as in Example 1 except that each liquid crystal alignment agent was used, and the optical FFS type liquid crystal cell was evaluated in the same manner as in Example 21. Was manufactured and various evaluations were performed. The results are shown in Table 2 below.

[Example 29]
1. 1. Preparation of liquid crystal alignment agent 1. of Example 1 except that the polymer components and solvent composition were changed as shown in Table 1 below. A liquid crystal alignment agent (S-29) was prepared in the same manner as in the above. The liquid crystal alignment agent (S-29) is mainly used for manufacturing a TN mode type liquid crystal display element.
2. Evaluation of liquid crystal alignment agent 1. The surface unevenness, continuous printability, and applicability to a finely uneven surface were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-29) prepared in 1 was used. The results are shown in Table 2 below.

3. 3. Manufacture of TN type liquid crystal display element The above 1. A liquid crystal alignment agent (S-29) was prepared in the same manner as in the above. Subsequently, using this liquid crystal alignment agent (S-29), the rubbing process is performed by a rubbing machine having a roll wrapped with rayon cloth, a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a hair-foot pushing length of 0. A pair (two) of substrates having a liquid crystal alignment film was obtained in the same manner as in the method described in "5. Manufacture of a vertically oriented liquid crystal display element" of Example 1 except that the operation was performed under the condition of .4 mm. Next, instead of MLC-6608, a positive liquid crystal display (MLC-6221 made by Merck) was used so that the rubbing methods of the respective substrates were orthogonal to each other when the pair of substrates were overlapped, and the two polarizing plates were used. A TN type liquid crystal display element was manufactured in the same manner as in Example 1 except that the polarization direction was parallel to the rubbing direction of each substrate.
4. Evaluation of TN type liquid crystal display element 3. The post-bake margin was evaluated in the same manner as in Example 1 except that the TN type liquid crystal display element obtained in 1 was used. In addition, the above 3. A TN type liquid crystal display element was manufactured according to the method described in 1 and the bezel unevenness resistance was evaluated. The results are shown in Table 2 below.

In Table 1, the numerical values of the polymer components indicate the blending ratio (parts by mass) of each polymer with respect to the total 100 parts by mass of the polymer components used for preparing the liquid crystal alignment agent. The numerical value of the solvent composition indicates the mixing ratio (parts by mass) of each solvent with respect to the total 100 parts by mass of the solvent components used for preparing the liquid crystal alignment agent. The abbreviations of the compounds are as follows. In each example, two types of liquid crystal alignment agents having different solid content concentrations (solid content concentration 6.5% by mass and 3.5% by mass) were prepared, and the solid content concentration was 6. A liquid crystal alignment agent having a solid content concentration of 3.5% by mass was used in the evaluation of the bake margin and bezel unevenness resistance using a liquid crystal alignment agent having a solid content of 5% by mass (the same applies to Table 3 below).
<Solvent>
a: 2-Acetylmethylfuran b: Methyl 2-furancarboxylic acid c: Flactone d: Tetrahydropyran acetate e: α-Acetyl-γ-butyrolactone f: α-methoxycarbonyl-γ-butyrolactone g: Tetrahydropyran-4- Methyl carboxylate h: Acetic acid = 3-dihydropyranyl i: 4-Acetyl (tetrahydropyran)
j: 2- (acetylmethyl) dioxane k: γ-butyrolactone m: propylene carbonate n: furfuryl alcohol o: tetrahydrofurfuryl alcohol p: tetrahydro-4-pyranol q: Solketal r: N-methyl-2-pyrrolidone s: Butyl cellosolve t: Diacetone alcohol u: Diethylene glycol diethyl ether v: N-ethyl-2-pyrrolidone

As can be seen from Table 2, Examples 1 to 29 containing the compound [A] are "excellent", "good" or "possible" in all of the printability, the continuous printability, and the coatability on the fine uneven surface. It was an evaluation. In addition, the post-bake margin was small, and the bezel unevenness resistance of the obtained liquid crystal display element was evaluated as "good" or "possible". Among these, when the solvents c, d, e, f, g, h, i, and j are used, the continuous printability is superior, and when the solvents c, d, e, f, and g are used, the continuous printability is excellent. Was also excellent in bezel unevenness resistance. Further, when the solvents c, d, and g were used, the uneven coating property was further excellent. Among these, the solvents c and d were particularly excellent in that they were more effective in improving continuous printability, unevenness coating property, post-bak margin and bezel unevenness resistance.
On the other hand, Comparative Examples 1 to 9 containing no compound [A] were inferior in coatability to the fine uneven surface as compared with Examples. Further, in Comparative Examples 1 to 3 and 9, the polymer was easily precipitated and the continuous printability was also inferior.

[Examples 30 to 33]
A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the types and amounts of the polymers and the solvent composition were as shown in Table 3 below. In addition, various evaluations were carried out in the same manner as in Example 1 using the prepared liquid crystal alignment agent. The evaluation results are shown in Table 4 below.

The abbreviations of the compounds are as follows.
w: 2,4-dimethoxy-2,4-dimethylpentane-3-one x: 2,4-diethoxy-2,4-dimethylpentane-3-one y: 2,4-dimethoxypentane-3-one z: 2,4-dimethoxypropane-3-one

As can be seen from Table 4, Examples 30 to 33 containing the compound [A] were evaluated as "good" in all of the printability, the continuous printability, and the coatability on the fine uneven surface. In addition, the post-bake margin was small, and the bezel unevenness resistance of the obtained liquid crystal display element was evaluated as "good".

10 ... Evaluation ITO electrode substrate, 11 ... Glass substrate, 12 ... ITO electrode

Claims (15)

A polymer component, [A] compounds <br/> [A] compounds monovalent group bonded to the ring portion of the oxygen-containing heterocyclic ring having a carbonyl group of the following [A1], and, and ketonic carbonyl group compounds having an oxy organic group of at least one compound selected from the group consisting of [A2]
And, containing,
The compound [A] is a solvent and
The content of [A] compounds, Der Ru 1 0 wt% or more based on the total amount of the solvent component included in the liquid crystal alignment agent, a liquid crystal aligning agent. Further comprising an alcohol solvent, a chain ester solvent, a solvent [B] is at least one selected from the group consisting of ether solvents and ketone solvents, liquid crystal aligning agent of claim 1. Content before Symbol solvent [B] is 20 to 90 wt% based on the total amount of the solvent component included in the liquid crystal alignment agent, a liquid crystal aligning agent of claim 2. The liquid crystal alignment agent according to claim 2 , further containing a solvent [C] having a boiling point of 200 ° C. or higher at 1 atm. Content before Symbol solvent [B] is 20 to 80 wt% based on the total amount of the solvent component included in the liquid crystal alignment agent,
The liquid crystal alignment agent according to claim 4 , wherein the content ratio of the solvent [C] is 10 to 70% by mass with respect to the total amount of the solvent components contained in the liquid crystal alignment agent. Polymer components and the following [A] compound
[A] A compound in which a monovalent group having a carbonyl group is bonded to the ring portion of an oxygen-containing heterocycle [A] 1] and a group consisting of a compound [A2] having a ketone carbonyl group and an oxyorganic group. At least one compound selected from
When,
Group consisting of alcohol solvents, chain ester solvents, ether solvents and ketone solvents Solvent [B], which is at least one selected from
Contains,
The compound [A] is a solvent and
The content ratio of the solvent [B] is 20 with respect to the total amount of the solvent components contained in the liquid crystal alignment agent. A liquid crystal alignment agent in an amount of up to 90% by mass. Polymer components and the following [A] compound
[A] A compound in which a monovalent group having a carbonyl group is bonded to the ring portion of an oxygen-containing heterocycle [A] 1] and a group consisting of a compound [A2] having a ketone carbonyl group and an oxyorganic group. At least one compound selected from
When,
Group consisting of alcohol solvents, chain ester solvents, ether solvents and ketone solvents Solvent [B], which is at least one selected from
A solvent [C] having a boiling point of 200 ° C. or higher at 1 atm and
Contains,
The compound [A] is a solvent and
The content ratio of the solvent [B] is 20 with respect to the total amount of the solvent components contained in the liquid crystal alignment agent. ~ 80% by mass,
The content ratio of the solvent [C] is 10 with respect to the total amount of the solvent components contained in the liquid crystal alignment agent. A liquid crystal alignment agent in an amount of ~ 70% by mass. The liquid crystal alignment agent according to any one of claims 1 to 7, wherein the compound [A] has a melting point of 25 ° C. or lower and a boiling point of 150 ° C. or higher at 1 atm. The liquid crystal alignment agent according to any one of claims 1 to 8, wherein the compound [A1] is a compound represented by the following formula (1).

(In the formula (1), A ¹ is a group obtained by removing one hydrogen atom from the ring portion of the oxygen-containing heterocycle, and the ring portion may further have a substituent. R ¹ is carbon. An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkenyloxy group having 2 to 5 carbon atoms, and a hydrogen atom bonded to a carbon atom being a hydroxyl group, a cyano group or an alkoxy group. A substituted alkyl group having 5 or less carbon atoms substituted with a group, a substituted alkoxy group having 5 or less carbon atoms in which a hydrogen atom bonded to a carbon atom is substituted with a hydroxyl group, a cyano group or an alkoxy group, and a hydrogen atom bonded to a carbon atom. Substituent alkenyl group having 5 or less carbon atoms substituted with a hydroxyl group, cyano group or alkoxy group, substituted alkenyloxy group having 5 or less carbon atoms in which a hydrogen atom bonded to a carbon atom is substituted with a hydroxyl group, cyano group or alkoxy group, hydroxyl group , Amino group or cyano group. R ² is a single bond, an alcandiyl group having 1 to 3 carbon atoms, or an arcendyl group having 2 or 3 ^{carbon atoms. R 3} is an alkandiyl group having 1 to 3 carbon atoms. group, or an alkenediyl group having a carbon number of 2 or 3 .a is an integer from 0 to 2, when b is having a plurality of R ³ in .1 molecule is 0 or 1, more R ³ is They may be the same or different from each other.) The liquid crystal alignment agent according to any one of claims 1 to 9 , wherein the oxygen-containing heterocycle is a heterocycle having no carbon-carbon unsaturated bond in the ring. The liquid crystal alignment agent according to any one of claims 1 to 10 , wherein the compound [A2] is a compound represented by the following formula (3).

(In formula (3), R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms. R ¹⁰ and R ¹¹ are respectively. Independently, it is a monovalent organic group having 1 to 20 carbon atoms.) Claims 1 to 1, wherein the polymer component includes at least one selected from the group consisting of a polymer having a structural unit derived from a polyamic acid, a polyamic acid ester, a polyimide, a polyamide, and a monomer having a polymerizable unsaturated bond. The liquid crystal aligning agent according to any one of 11. A method for manufacturing a liquid crystal element, which forms a liquid crystal alignment film using the liquid crystal alignment agent according to any one of claims 1 to 12. A liquid crystal alignment film formed by using the liquid crystal alignment agent according to any one of claims 1 to 12. A liquid crystal element comprising the liquid crystal alignment film according to claim 14.

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