WO2019106952A1

WO2019106952A1 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal device

Info

Publication number: WO2019106952A1
Application number: PCT/JP2018/037081
Authority: WO
Inventors: 哲平野; 幸志樫下
Original assignee: Jsr株式会社
Priority date: 2017-11-30
Filing date: 2018-10-03
Publication date: 2019-06-06
Also published as: CN111164501A; TWI786195B; KR102341987B1; CN111164501B; JPWO2019106952A1; TW201925183A; JP6897791B2; KR20200046093A

Abstract

This liquid crystal aligning agent contains a polymer component and a solvent component. The solvent component is at least one selected from the group consisting of 5-membered ring lactone, 6-membered ring lactone, and 7-membered ring lactam, and comprises a solvent [A] having at least one partial structure selected from the group consisting of an alkyl group having 2-10 carbon atoms, an alkoxy group having 2-10 carbon atoms, an alkoxy-alkyl group having 2-10 carbon atoms, an alkoxy-alkoxy-alkyl group having 2-10 carbon atoms, an alkoxy-alkoxy group having 2-10 carbon atoms, a group "-COR12" (where, R12 is an alkyl group having 1-3 carbon atoms), and a carbon-carbon double bond forming a part of a ring.

Description

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element

Cross-reference to related applications

This application is based on Japanese Patent Application No. 2017-229974 filed on November 30, 2017, the contents of which are incorporated herein by reference.

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

Liquid crystal elements are used in various applications including display devices such as televisions, personal computers, and smartphones. These liquid crystal elements have a liquid crystal alignment film having a function of aligning liquid crystal molecules in a predetermined direction. The liquid crystal alignment film is generally formed on a substrate by applying a liquid crystal alignment agent in which a polymer component is dissolved in an organic solvent onto the substrate, and preferably by heating. As the polymer component of the liquid crystal aligning agent, polyamic acids and soluble polyimides are widely used because they are excellent in mechanical strength, liquid crystal alignment property, and affinity with liquid crystals. In addition, as the solvent component of the liquid crystal aligning 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 wetting to the substrate A mixed solvent with a solvent having high spreadability (eg, poor solvent such as butyl cellosolve) is generally used (see, for example, Patent Documents 1 and 2).

JP, 2017-198975, A JP, 2016-206645, A

In recent years, in liquid crystal televisions, in order to obtain realism by further improvement of display quality, specifications of display devices with an increased number of pixels, such as 4K (for example, 3840 pixels × 2160 pixels) and 8K (for example, 7680 pixels × 4320 pixels) It is done. When the number of pixels of the display device increases and the pixel size decreases, the pixel electrode has a finer structure. Therefore, on the surface on which the pixel electrode is formed, the concavo-convex density per unit area becomes higher. In such a case, when the liquid crystal alignment agent is applied to the surface on which the pixel electrode is formed to form an alignment film, the liquid crystal alignment agent does not easily wet and spread with respect to the fine uneven structure of the pixel electrode. There is concern that we can not do it. In order to obtain good coatability even when applying a liquid crystal aligning agent to a fine uneven structure, as a solvent component of the liquid crystal aligning agent, it is possible to suppress the decrease in the solubility in the polymer, and the substrate It is necessary to improve the wettability and spreadability.

In addition, from the viewpoint of industrial production, volatilization of the solvent from above the printing machine can be suppressed at the time of printing of the liquid crystal alignment agent on the substrate, and even when printing is performed continuously, it is heavy on the printing machine It is required that coalescence does not easily precipitate, that is, good continuous printability.

Further, in recent years, with the spread of large-screen liquid crystal panels, lines larger than before have come to be operated, and substrates are being made larger. The merits of increasing the size of the substrate include the fact that reduction of process time and cost can be achieved because one panel can take a plurality of panels, and that the liquid crystal panel itself can be increased in size. Be 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 before, and this temperature unevenness causes variation in the pretilt angle of the liquid crystal alignment film. There is concern that it will cause a decline.

In the liquid crystal display device, when residual charge (residual DC) in the liquid crystal alignment film is large, the influence of the image previously displayed after switching the image remains, so-called afterimage (this is also referred to as DC afterimage. Cause) to occur. In addition, when the liquid crystal display device is operated for a long time, when the direction of the initial alignment deviates from the direction from the beginning of the manufacture of the liquid crystal display device, burn-in called AC residual image may occur. In order to ensure display quality, a liquid crystal display device in which such DC residual image and AC residual image are reduced as much as possible is required.

The present disclosure has been made in view of the above problems, and is a liquid crystal which has good coatability and continuous printability with respect to a fine concavo-convex structure, is less susceptible to temperature unevenness at the time of film formation, and has good afterimage characteristics. It aims at providing a liquid crystal aligning agent which can obtain a display element.

The present inventors have intensively studied to solve the above problems, and found that the above problems can be solved by using a specific lactone or lactam as a solvent component of a liquid crystal aligning agent. Specifically, the present disclosure adopts the following means in order to solve the problems.

<1> A polymer component and a solvent component, wherein the solvent component is at least one selected from the group consisting of 5-membered ring lactones, 6-membered ring lactones and 7-membered ring lactams, and having 2 carbon atoms An alkyl group of ̃10, an alkoxy group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, a group “—COR ¹² ”(wherein R ¹² is an alkyl group of 1 to 3 carbon atoms) and a solvent having at least one partial structure selected from the group consisting of carbon-carbon double bonds forming part of a ring [A ], The liquid crystal aligning agent.
The manufacturing method of the liquid crystal element which forms a liquid crystal aligning film using the liquid crystal aligning agent of <2> said <1>.
The liquid crystal aligning film formed using the liquid crystal aligning agent of <3> said <1>.
The liquid crystal element which comprises the liquid crystal aligning film of <4> said <2>.

The liquid crystal aligning agent of the present disclosure has good wettability and spreadability even when applied to a substrate surface having a fine uneven structure, and can form a liquid crystal alignment film uniformly on the substrate surface. Moreover, when printing is continuously performed in a manufacturing process, it can be made hard to precipitate a polymer on a printer. In addition, the liquid crystal aligning agent of the present disclosure is not susceptible to temperature unevenness at the time of film formation heating, and thus it is possible to obtain a liquid crystal alignment film in which characteristic variation due to temperature unevenness is suppressed. An excellent liquid crystal display element can be obtained.

FIG. 1 is a view showing a schematic configuration of an ITO electrode substrate for evaluation. (A) is a top view, (b) is a sectional view which expanded a part.

Below, each component contained in the liquid crystal aligning agent of this indication, and the other component arbitrarily mix | blended as needed are demonstrated. The liquid crystal aligning agent is a liquid polymer composition which contains 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. For example, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyamide, polyamide imide, polybenzoxazole precursor, polybenzo Main skeletons such as oxazole, cellulose derivative, polyacetal, styrene-maleimide copolymer, poly (meth) acrylate and the like can be mentioned. In addition, (meth) acrylate is meant to include acrylate and methacrylate. From the viewpoint of sufficiently securing the performance of the liquid crystal element, etc., as the polymer component, at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide among the above (hereinafter referred to as “polymer [P It is preferable to include]].

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

(Tetracarboxylic acid dianhydride)
Examples of tetracarboxylic acid dianhydrides used in the synthesis of polyamic acids include aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aromatic tetracarboxylic acid dianhydrides. . As specific examples of these, as aliphatic tetracarboxylic acid dianhydride, for example, 1,2,3,4-butanetetracarboxylic acid dianhydride etc .;
Examples of alicyclic tetracarboxylic acid dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-Tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1 , 3-dione, 5- (2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 3-Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 2,4,6,8-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, cyclopentane tetracarboxylic Acid dianhydrides, cyclohexane tetracarboxylic acid dianhydrides and the like; as aromatic tetracarboxylic acid dianhydrides, for example, pyromellitic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, ethylene Glycol bisanhydrotrimate, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, etc .; The tetracarboxylic acid dianhydride described in the publication can be used. In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

(Diamine compound)
As a diamine compound used for the synthesis | combination of a polyamic acid, an aliphatic diamine, an alicyclic diamine, aromatic diamine, a diamino organosiloxane etc. can be mentioned, for example. Specific examples of these diamines include, as aliphatic diamines, for example, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like; as alicyclic diamines, for example, 1,4 -Diaminocyclohexane, 4,4'- methylenebis (cyclohexylamine) and the like;
As an aromatic diamine, 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, cholestyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestyloxy-2, 4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6- Bis (4-amino Phenoxy) cholestane, 2,4-diamino-N, N-diallylaniline, 4- (4'-trifluoromethoxybenzyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((amino Phenyl) methyl) phenyl) -4-butylcyclohexane, 3,5-diaminobenzoic acid = 5ξ-cholestan-3-yl, the following formula (E-1)

(In formula (E-1), X ^I and X ^II each independently represent a single bond, -O-, * -COO- or * -OCO- (wherein "*" represents a bond to X ^I R ¹ is an alkanediyl group having 1 to 3 carbon atoms, R ^II is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, and b is 0. And is an integer of to 2, c is an integer of 1 to 20, and d is 0 or 1. However, a and b can not be 0 simultaneously.)
And side chain type diamines such as diamines having a cinnamic acid structure in the side chain:

p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 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 ( -Aminophenyl) hexane, 1,4-bis (4-aminophenylsulfanyl) butane, bis [2- (4-aminophenyl) ethyl] hexanedioic acid, N, N-bis (4-aminophenyl) methylamine, 2,6-Diaminopyridine, 1,4-bis- (4-aminophenyl) -piperazine, N, N'-bis (4-aminophenyl) -benzidine, 2,2'-dimethyl-4,4'-diamino Biphenyl, 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-amino) Phenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4 ′-[4,4′-propane-1,3-diylbis (piperidine-1,4-diyl)] dianiline, 4, 4′-diaminobenzanilide, 4,4′-diaminostilbenzene, 4,4′-diaminodiphenylamine, 1,3-bis (4-aminophenethyl) urea, 1,3-bis (4-aminobenzyl) urea, 1,4-bis (4-aminophenyl) -piperazine, N- (4-aminophenylethyl) -N-methylamine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine etc. Main chain type diamine etc .; as diamino organosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane etc .; In addition to the above, diamines described in JP-A-2010-97188 can be used.

(Synthesis of polyamic acid)
A polyamic acid can be obtained by reacting the above-described tetracarboxylic acid dianhydride and a diamine compound, as necessary, together with a molecular weight modifier. The use ratio of the tetracarboxylic acid dianhydride and the diamine compound to be subjected to the synthesis reaction of the polyamic acid is such that the acid anhydride group of the tetracarboxylic acid dianhydride is 0.2 with respect to 1 equivalent of the amino group of the diamine compound. A ratio of ̃2 equivalents is preferred. Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. It can be mentioned. The use ratio of the molecular weight modifier is preferably 20 parts by mass or less with respect to 100 parts by mass in total of the tetracarboxylic acid dianhydride used and the diamine compound.

The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and the reaction time is preferably 0.1 to 24 hours.
Examples of the organic solvent used for the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like. Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol And using one or more selected from the group consisting of and halogenated phenols as a solvent, or using a mixture of one or more of these and another organic solvent (eg, butyl cellosolve, diethylene glycol diethyl ether, etc.) preferable. The amount (a) of the organic solvent used is such that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50% by mass with respect to the total amount (a + b) of the reaction solution. Is preferred.
As described above, a reaction solution in which the polyamic acid is dissolved is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, or may be used for preparation of a liquid crystal aligning agent after the polyamic acid contained in the reaction solution is isolated.

<Polyamic acid ester>
When the polymer [P] is a polyamic acid ester, the polyamic acid ester is, for example, [I] a method of reacting a polyamic acid obtained by the above synthesis reaction with an esterifying agent, [II] tetracarboxylic acid diester These compounds can be obtained by a method of reacting a diamine compound with a diamine compound, a method of reacting a [III] tetracarboxylic acid diester dihalide with a diamine compound, or the like. The polyamic acid ester to be contained in the liquid crystal aligning agent may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester may be used as it is for preparation of a liquid crystal aligning agent, or the polyamic acid ester contained in the reaction solution may be isolated and then provided for preparation of a liquid crystal aligning agent. Good.

<Polyimide>
When the polymer [P] is a polyimide, the polyimide can be obtained, for example, by dehydration ring closure and imidization of the polyamic acid synthesized as described above. The polyimide may be a completely imidized product obtained by dehydrating and ring closing all of the amic acid structure of the precursor polyamic acid, and only a part of the amic acid structure may be dehydrating and ring closing, and the amic acid structure and the imide. It may be a partial imidate coexisting with a ring structure. The polyimide used for the reaction preferably has an imidation ratio of 20 to 99%, more preferably 30 to 96%. The imidation ratio is a percentage representing the ratio of the number of imide ring structures to the total number of amic acid structures of polyimide and the number of imide ring structures. Here, 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 this solution, and heating as necessary. In this method, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride and the like can be used. The amount of the dehydrating agent used is preferably 0.01 to 20 moles relative to 1 mole of the polyamic acid's amic acid structure. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydrating ring-closing catalyst used is preferably 0.01 to 10 moles relative to 1 mole of the dehydrating agent used. As an organic solvent used for a dehydration ring-closing reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. 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. Thus, a reaction solution containing a polyimide is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after isolating the polyimide. Polyimides can also be obtained by imidization of polyamic acid esters.

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

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

The content ratio of the polymer [P] (in the case of containing two or more, the total amount thereof) is the total amount of the polymer components contained in the liquid crystal aligning agent from the viewpoint of making the quality of the liquid crystal element obtained better. On the other hand, the content is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more.

«Solvent composition»
The liquid crystal aligning agent of the present disclosure is at least one member selected from the group consisting of 5-membered ring lactones, 6-membered ring lactones and 7-membered ring lactams as at least a part of the solvent component, and an alkyl having 2 to 10 carbon atoms. Group, an alkoxy group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, a group “—COR ¹² ” (wherein , R ¹² is an alkyl group having 1 to 3 carbon atoms) and at least one partial structure selected from the group consisting of carbon-carbon double bonds forming part of a ring (hereinafter also referred to as “specific partial structure”) Containing a solvent [A].

<Solvent [A]>
The solvent [A] has a structure in which one hydrogen atom bonded to the ring of a specific cyclic ester (γ-butyrolactone, δ-valerolactone or ε-caprolactam) is substituted with a group consisting of a chain structure, or a specific It has a structure in which one ethylene group constituting the ring of the cyclic ester is substituted by a group having a carbon-carbon double bond. By using a compound having such a structure as at least a part of the solvent component, the solubility of the polymer component in the solvent and the wetting and spreading properties of the liquid crystal aligning agent are exhibited in a well-balanced manner. Thereby, the coatability (printability) of the liquid crystal aligning agent to the substrate surface which has an electrode structure of fine concavo-convex shape can be improved. In addition, the boiling point of the solvent component of the liquid crystal aligning agent can be adjusted to an appropriate height, and the influence of temperature unevenness can be made less at the time of film formation.

The solvent [A] is preferably an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, or an alkoxyalkyl group having 2 to 10 carbon atoms in the ring part of γ-butyrolactone or δ-valerolactone. R ¹³ -OR ^14), alkoxyalkoxyalkyl group ^(-R ¹³ ^-OR 15 -OR ¹⁴ 2 to 10 carbon atoms), a compound having an alkoxyalkoxy group having 2 to 10 carbon atoms ^{^(-OR} 13 -OR ¹⁴⁾ ⁽ a-1) a compound (a-2) in which one ethylene group constituting the ring of substituted or unsubstituted γ-butyrolactone is replaced with a carbon-carbon double bond, and a nitrogen in the ring of ε-caprolactam It is a compound (a-3) in which "-COR ¹² " is bonded to an atom. Specifically, at least one selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3) preferable. R ¹³ represents an alkanediyl group, R ¹⁴ represents an alkyl group, and R ¹⁵ represents an alkanediyl group.

(In the formula (1), R ¹ represents an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxyalkyl group having 2 to 10 carbon atoms or It is a C2-C10 alkoxy alkoxy group, n is 1 or 2.)

(In formula (2), R ² is a divalent group represented by the following formula (4-1) or formula (4-2).)

(In Formula (4-1) and Formula (4-2), R ⁴ to R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. “* 1” represents an oxygen atom Indicates that it is a bond with

(In the formula (3), R ³ is an alkyl group having 1 to 3 carbon atoms.)

(Compound represented by formula (1))
In the above formula (1), R ¹ may be linear or branched. Specific examples of R ¹ include, as an alkyl group, for example, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group etc. as an alkoxy group; And each of the substituted alkyl groups is an oxygen atom or the like as an alkoxyalkyl group, for example, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, a propoxymethyl group, a propoxyethyl group, a butoxyethyl group etc .; As an alkoxy alkoxy alkyl group of -10, for example, methoxy methoxymethyl group, ethoxy methoxy group As an alkoxy alkoxy group, for example, a methoxy ethoxy group, an ethoxy ethoxy group, an ethoxy propoxy group, a propoxy propoxy group etc. can be mentioned as an alkoxy alkoxy group.

R ¹ is preferably linear, more preferably a linear alkyl group having 3 or more carbon atoms, still more preferably a linear alkyl group having 3 to 8 carbon atoms, and having 5 to 8 carbon atoms Particularly preferred is a linear alkyl group of R ¹ may be bonded to any position of the γ-butyrolactone ring or the δ-valerolactone ring, but is preferably bonded to the position α to the oxygen atom in the ring.

As specific examples of the compound represented by the above formula (1), examples of compounds in which n is 1 (γ-butyrolactones) include γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ -Nonanolactone, γ-decanolactone, γ-undecanolactone, γ-dodecanolactone, γ-tridecanolactone, γ-tetradecanolactone, α-propyl-γ-butyrolactone, α-butyl-γ-butyrolactone, α- Pentyl-γ-butyrolactone, α-hexyl-γ-butyrolactone, α-heptyl-γ-butyrolactone, α-octyl-γ-butyrolactone, α-decyl-γ-butyrolactone etc .;
Examples of compounds in which n is 2 (δ-caprolactones) include δ-heptanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, δ-tride Canolactone, δ-tetradecanolactone, δ-pentadecanolactone and the like can be mentioned, respectively. In addition, the compound represented by the said Formula (1) can be used individually by 1 type or in combination of 2 or more types.

(Compound represented by formula (2))
In the above formula (2), the alkyl group of R ⁴ to R ¹¹ in the above formulas (4-1) and (4-2) may be linear or branched and, for example, a methyl group, an ethyl group, n And -propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl and the like. In the above formula (4-1), it is preferable that at least one of R ⁴ to R ⁷ be an alkyl group in that the solubility of the polymer can be further increased, and the alkyl group is an oxygen atom in the ring More preferably, it is attached to the α position. In the above formula (4-2), at least one of R ⁸ to R ¹¹ is preferably an alkyl group, and the alkyl group is bonded to the alpha position to the oxygen atom in the ring More preferable. Among these, it is particularly preferable that R ⁴ and R ⁸ be a methyl group or an ethyl group, and R ⁵ to R ⁷ and R ⁹ to R ¹¹ be a hydrogen atom.
Specific examples of the compound represented by the above formula (2) include α-angelica lactone, β-angelica lactone and the like. In addition, the compound represented by the said Formula (2) can be used individually by 1 type or in combination of 2 or more types.

(Compound represented by formula (3))
In the above formula (3), R ³ may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. R ³ is preferably a methyl group or an ethyl group, more preferably a methyl group.
Specific examples of the compound represented by the above formula (3) include, for example, N-acetyl-ε-caprolactam, N-propionyl-ε-caprolactam and the like. Preferably, it is N-acetyl-ε-caprolactam. In addition, the compound represented by the said Formula (3) can be used individually by 1 type or in combination of 2 or more types.

Among the above, the solvent [A] preferably has a substituent at the ring portion of the cyclic ester in that the coating property on the substrate surface having a fine uneven electrode structure can be made better, More preferred is at least one selected from the group consisting of a compound represented by the formula (1) and a compound represented by the above formula (2). Particularly preferably, γ-heptanolactone, γ-octanolactone, γ-nonanolactone, γ-decanolactone, γ-undecanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ And at least one selected from the group consisting of dodecanolactone, δ-tridecanolactone, α-angelica lactone and β-angelica lactone.

<Solvent [B]>
The solvent component is at least one selected from the group consisting of alcohol solvents, chain ester solvents, ether solvents and ketone solvents together with the solvent [A] in that the wettability of the liquid crystal aligning agent can be further enhanced. It is preferable to further include a solvent which is different from the solvent [A] (hereinafter, also referred to as “solvent [B]”).

Specific examples of the solvent [B] include alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, and the like. -Methoxy-1-butanol, 3-methoxy-3-methylbutanol, benzyl alcohol and the like;
Examples of chain ester solvents include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, isoamyl propionate, Isoamyl isobutyrate etc;
As ether solvents, for example, 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, 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 Ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), tetrahydrofuran, a di-isopentyl ether and the like;
Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cycloheptanone, cyclopentanone, 3-methylcyclohexanone, 4-methylcyclohexanone, and diisobutyl ketone.

Among the above, the solvent [B] is preferably at least one selected from the group consisting of alcohol solvents, chain ester solvents and ether solvents, from the viewpoint of a higher effect of improving the coating properties, and ethylene, 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 one selected from the group consisting of 3-methoxy-1-butanol It is more preferable that In addition, as a solvent [B], 1 type can be used individually or in combination of 2 or more types.

<Solvent [C]>
The solvent component secures the solubility of the polymer in the solvent component, and for the purpose of suppressing the reduction in product yield caused by the precipitation of the polymer in the coating step, together with the solvent [A], the boiling point at 1 atmospheric pressure is 200 ° C. or higher It is preferable to further include a solvent different from the solvent [A] (hereinafter, also referred to as “solvent [C]”).

The solvent [C] is preferably at least one selected from the group consisting of aprotic polar solvents and phenols, and is more preferably aprotic polar solvents. Specifically, from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, gamma butyrolactone, propylene carbonate and a compound represented by the following formula (5) Particularly preferred is at least one selected from the group consisting of

(In the formula ^{(5), R 21} and ^{R 22} are each independently a hydrogen atom, or a monovalent hydrocarbon group which has carbon atoms 1 be ~ 6 have an ether ^{bond, R 21} and R ²² may combine with each other to form a ring, and R ²³ is an alkyl group having 1 to 4 carbon atoms.

(Compound represented by formula (5))
In the above formula (5), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms as R ²¹ and R ²² include, for example, a chain hydrocarbon group having 1 to 6 carbon atoms, and an alicyclic having 3 to 6 carbon atoms. A hydrocarbon group, an aromatic hydrocarbon group having 5 or 6 carbon atoms and the like can be mentioned. The monovalent group having an ether bond includes, for example, an alkoxyalkyl group having 2 to 6 carbon atoms. The ring R ^21, R ²² is bonded to R ²¹ and R ²² are formed together with the nitrogen atom bonded with each other, such as pyrrolidine ring, and a nitrogen-containing heterocyclic ring such as a piperidine ring. A monovalent chain hydrocarbon group such as a methyl group may be bonded to these nitrogen-containing heterocycles.
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, still more 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 (5) include, for example, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N- Dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide and the like. In addition, the compound represented by the said Formula (5) can be used individually by 1 type or in combination of 2 or more types.

It is preferable that the content rate of solvent [A] is 10 mass% or more with respect to the whole quantity of the solvent component contained in a liquid crystal aligning agent among solvent components. When the content is less than 10% by mass, the effect of improving the coating properties of the liquid crystal aligning agent tends to be hardly obtained. The content ratio of the solvent [A] is more preferably 10 to 85% by mass, and still more preferably 15 to 15%, since the balance between the solubility of the polymer component and the wettability of the liquid crystal aligning agent can be improved. It is 75% by mass, particularly preferably 15 to 60% by mass.
The content ratio of the solvent [B] is preferably 10 to 80% by mass with respect to the total amount of the solvent component contained in the liquid crystal aligning agent, in that the wettability of the liquid crystal aligning agent can be further enhanced. It is more preferable to set it to 70% by mass, and it is further preferable to set it to 20 to 50% by mass.
The content ratio of the solvent [C] is preferably 70% by mass or less in order to lower the heating temperature at the time of film formation. From the viewpoint of securing the solubility of the polymer component in the solvent, the content ratio of the solvent [C] is more preferably 1 to 70% by mass with respect to the total amount of the solvent component contained in the liquid crystal aligning agent It is more preferably 5 to 65% by mass, and particularly preferably 10 to 60% by mass.

The liquid crystal aligning agent may contain only the solvent [A] as a solvent component, but the solvent component consists of the solvent [A] and the solvent [B], or the solvent [A] and the solvent [B] and the solvent It is particularly preferable to consist of [C]. However, in the present specification, “consists of the solvent [A] and the solvent [B]” and “the solvent component is composed of the solvent [A], the solvent [B] and the solvent [C]” It is acceptable to contain solvents [B] and other solvents other than the solvent [C] to such an extent that they do not interfere with the effects of the present invention.
Examples of other solvents include halogenated hydrocarbon solvents, hydrocarbon solvents and the like. Specific examples of these include halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene and the like; hydrocarbon solvents such as hexane, heptane and octane , Benzene, toluene, xylene and the like can be mentioned respectively. The content ratio of the other solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and more preferably 0.2% by mass or less based on the total amount of the solvent component in the liquid crystal aligning agent. It is further preferred that

«Other ingredients»
The liquid crystal aligning agent contains a polymer component and a solvent component, but may contain other components as needed. Examples of such other components include epoxy group-containing compounds (for example, N, N, N ', N'- tetraglycidyl-m-xylene diamine, N, N, N', N'- tetraglycidyl-4, 4 Functional amino compounds (eg, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, etc.), antioxidants, metal chelate compounds, curing A catalyst, a hardening accelerator, surfactant, a filler, a dispersing agent, a photosensitizer, etc. are mentioned. The blend ratio of the other components can be appropriately selected according to each compound as long as the effects of the present disclosure are not impaired.

The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc. 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 too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coatability decreases. 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 using the liquid crystal alignment agent described above. Liquid crystal elements can be effectively applied to various applications. For example, clocks, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions It can be used as various display devices such as information display, light control film, retardation film and the like. When used as a liquid crystal display device, the operation mode of the liquid crystal is not particularly limited. For example, TN type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB The present invention 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. Step 1 differs in the substrate used according to the desired operation mode. Steps 2 and 3 are common to each operation mode.

(Step 1: formation of coating film)
First, a liquid crystal aligning agent is applied on a substrate, and preferably a coated surface is formed to form a coating film on the substrate. As the substrate, for example, glass such as float glass and soda glass; transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and poly (alicyclic olefin) can be used. As a transparent conductive film provided on one side of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Etc. can be used. In the case of manufacturing a TN type, STN type or VA type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, in the case of manufacturing a liquid crystal element of IPS type or FFS type, a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and a counter substrate not provided with an electrode Use For example, a film made of a metal such as chromium can be used as the metal film. The application of the liquid crystal aligning agent to the substrate is preferably performed by an offset printing method, a spin coating method, a roll coater method, a flexographic printing method, or an ink jet printing method on the electrode formation surface.

After the application of the liquid crystal alignment agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal alignment agent. The prebake temperature is preferably 30 to 200 ° C., and the prebake time is preferably 0.25 to 10 minutes. Thereafter, a baking (post-baking) step is carried out to completely remove the solvent and, if necessary, thermally imidize the amic acid structure present in the polymer. The baking temperature (post-baking temperature) at this time 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. After the liquid crystal aligning agent is applied onto the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film to be the liquid crystal alignment film.

(Step 2: orientation treatment)
In the case of producing a TN type, STN type, IPS type or FFS type liquid crystal display element, a treatment (alignment treatment) for imparting liquid crystal alignment ability to the coating film formed in the above step 1 is carried out. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. For example, rubbing treatment is performed by rubbing the coating film in a fixed direction with a roll wound with a cloth made of fibers such as nylon, rayon and cotton, or light irradiation to the coating film formed on the substrate using a liquid crystal alignment agent. The optical alignment processing etc. which carry out and provide liquid crystal aligning ability to a coating film are mentioned. On the other hand, in the case of producing a vertical alignment type 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 alignment treatment. The liquid crystal aligning agent suitable for a liquid crystal display element of a vertical alignment type can also be used suitably also for a liquid crystal display element of a PSA (Polymer sustained alignment) type.

(Step 3: Construction of Liquid Crystal Cell)
Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal is disposed between two substrates disposed opposite to each other to manufacture a liquid crystal cell. In order to produce a liquid crystal cell, for example, (1) two substrates are disposed opposite to each other with a spacer between them so that the liquid crystal alignment film faces each other, and peripheral portions of the two substrates are sealed using a sealing agent. Liquid crystal is injected and filled into a cell gap separated by a substrate surface and a sealing agent, and then the injection hole is sealed, (2) a seal is made at a predetermined place on one substrate on which a liquid crystal alignment film is formed. Liquid crystal is applied onto the surface of the liquid crystal alignment film, and then 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.). The liquid crystal cell produced is preferably further heated to a temperature at which the liquid crystal used has an isotropic phase, and then gradually cooled to room temperature to remove the flow alignment at the time of liquid crystal filling.

As the sealing agent, for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used. A photo spacer, a bead spacer, etc. can be used as a spacer. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred. In addition, cholesteric liquid crystals, chiral agents, ferroelectric liquid crystals, etc. may be added to nematic liquid crystals or smectic liquid crystals, for example.

Subsequently, a polarizing plate is attached to the outer surface of the liquid crystal cell as required. Examples of the polarizing plate include a polarizing plate called a “H film” obtained by absorbing iodine while stretching and orienting polyvinyl alcohol, sandwiched by a cellulose acetate protective film, or a polarizing plate consisting of the H film itself. Thus, a liquid crystal display element is obtained.

Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited by these examples.

In the following examples, the weight average molecular weight Mw of the polymer, the imidation 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 necessary amounts of the raw material compounds and the polymers used in the following examples were secured by repeating the synthesis on the synthesis 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 conversion value measured by GPC under the following conditions.
Column: Tosoh Corp. TSKgel GRC XLII
Solvent: Tetrahydrofuran Temperature: 40 ° C.
Pressure: 68 kgf / cm ²
[Imidation rate of polyimide]
The solution of the polyimide was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. The imidation ratio [%] was determined from the obtained ¹ H-NMR spectrum by the following formula (1).
Imidation ratio [%] = (1− (A ¹ / (A ² × α))) × 100 (1)
(In the formula (1), A ¹ is a proton-derived peak area of an NH group appearing in the vicinity of a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a precursor of a polymer (polyamic acid It is the number ratio of other protons to one proton of NH group in).
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]
The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

Abbreviations of the compounds are as follows. In the following, the compound represented by the formula (DA-X) (wherein X is an integer of 1 to 6) may be simply referred to as the “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 acid dianhydride, 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) are dissolved in 166 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C. for 6 hours to obtain a polyamic acid A solution containing 20% by mass of A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 90 mPa · s.
Then, NMP was added to the obtained polyamic acid solution to make 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 dehydration ring closure reaction was performed at 110 ° C. for 4 hours . After dehydration ring closure reaction, the solvent in the system is solvent-substituted with fresh NMP (pyridine and acetic anhydride used for dehydration ring closure reaction are removed out of the system by this operation. The same applies hereinafter), and the imidization rate is about 68. A solution containing 26% by weight 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)
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 as tetracarboxylic acid dianhydride 160 g (0.50 mol) of [1,2-c] furan-1,3-dione, 91 g (0.85 mol) of PDA as a diamine, 25 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane 0.10 mol) and 25 g (0.040 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane and 1.4 g (0.015 mol) of aniline as a monoamine are dissolved in 960 g of NMP at 60 ° C. The reaction was carried out for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution of 10 mass% of polyamic acid concentration was 60 mPa · s.
Then, 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 dehydration ring closure reaction was carried out at 110 ° C. for 4 hours. After dehydration and ring closure reaction, about 2,500 g of a solution containing 15% by mass of polyimide (PI-2) having an imidization ratio of about 95% is obtained by replacing the solvent in the system with new γ-butyrolactone (GBL). 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)
The above-mentioned Synthesis Example 1 and Example 2 were changed except that the diamine used was changed to 0.08 moles of 3,5-diaminobenzoic acid (3,5DAB) and 0.02 moles of cholestanyloxy-2,4-diaminobenzene (HCODA). A polyamic acid solution was obtained by the same method. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution of 10 mass% of polyamic acid concentration was 80 mPa · s.
Then, imidization was performed by the same method as in Synthesis Example 1 to obtain a solution containing 26 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)
The above-mentioned Synthesis Example 1 was repeated 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). A polyamic acid solution was obtained by the same method. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution of 10 mass% of polyamic acid concentration was 60 mPa · s.
Then, imidization was performed 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)
While changing the tetracarboxylic acid dianhydride used to 0.08 moles of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride and 0.02 moles of pyromellitic dianhydride, the diamine used is Other than 0.098 mol of 4-aminophenyl 4-aminobenzoate (compound represented by the above formula (DA-6)) and 0.002 mol of 3,6-bis (4-aminobenzoyloxy) cholestane A polyamic acid solution was obtained in the same manner as in Synthesis Example 1 above. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution of 10 mass% of polyamic acid concentration was 80 mPa · s.
Then, imidization was performed by the same method as in Synthesis Example 1 to obtain a solution containing 26% by mass of polyimide (PI-5) having an imidization rate of about 75%. 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 41 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 at 40 ° C. under reduced pressure for 15 hours to obtain polyimide (PI-5).

Synthesis Example 6: Synthesis of Polyamic Acid (PA-1)
200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (CB) as tetracarboxylic acid dianhydride, 210 g of 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine (1.0 mol) was dissolved in a mixed solvent of NMP 370 g and GBL 3, 300 g and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a solid concentration of 10 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 at 40 ° C. under reduced pressure for 15 hours to obtain polyamic acid (PA-1).

Synthesis Example 7: Synthesis of Polyamic Acid (PA-2)
7.0 g (0.031 mol) of TCA as tetracarboxylic acid dianhydride, 13 g of a compound (DA-5) (corresponding to 1 mol per 1 mol of TCA) as a diamine are dissolved in 80 g of NMP and 4 at 60 ° C. By performing the reaction for time, a solution containing 20% by mass of polyamic acid (PA-3) was obtained. The solution viscosity of this polyamic acid solution was 2,000 mPa · s. Compound (DA-5) was synthesized according to the description in JP-A-2011-100099. 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 at 40 ° C. under reduced pressure for 15 hours to obtain polyamic acid (PA-2).

Synthesis Example 8 Synthesis of Polyamic Acid (PA-3)
Polyamic acid solution in the same manner as in Synthesis Example 6 except that the diamine used was changed to 0.7 mol of 1,3-bis (4-aminophenethyl) urea and 0.3 mol of compound (DA-2) I got A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by mass was 70 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 at 40 ° C. under reduced pressure for 15 hours to obtain polyamic acid (PA-3).

Synthesis Example 9 Synthesis of Polyamic Acid (PA-4)
The diamine used is p-phenylenediamine while the tetracarboxylic acid dianhydride used is changed to 1.0 mol of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride. .3 A polyamic acid solution by the same method as in Synthesis Example 6 except that 3 moles, 0.2 mole of compound (DA-3) and 0.5 moles of 1,2-bis (4-aminophenoxy) ethane were changed I got A small amount of the obtained polyamic acid solution was fractionated, 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 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 A polyamic acid solution was obtained in the same manner as in Synthesis Example 6 above. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution of 10 mass% of polyamic acid concentration 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 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 is added to 20 ml of thionyl chloride, a catalytic amount of N, N-dimethylformamide is added, and then the mixture is heated to 80 ° C. The mixture was stirred for 1 hour. Thereafter, the reaction solution was concentrated, and the residue was dissolved in 113 g of γ-butyrolactone (GBL) (this solution was called 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-4), 6.9 g of pyridine, 44.5 g of NMP, and GBL 33 Add in .5g to dissolve and cool it to 0 ° C. Then, the reaction solution A was slowly added dropwise to this solution over 1 hour, and after completion of the dropwise addition, the solution was stirred at room temperature for 4 hours. The resulting solution of polyamic acid ester was added dropwise to 800 ml of pure water with stirring, and the deposited precipitate was filtered. Subsequently, it was washed 5 times with 400 ml of isopropyl alcohol (IPA) and dried to obtain 15.5 g of a 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, thermometer, dropping funnel and reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine Charge and mix at room temperature. Next, 100 g of deionized water was added dropwise over 30 minutes from the dropping funnel, and then reaction was performed at 80 ° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer is taken out and washed with a 0.2 mass% aqueous ammonium nitrate solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to obtain a reactive polyorganosiloxane. (EPS-1) was obtained as a viscous transparent liquid. ¹ H-NMR analysis of this reactive polyorganosiloxane (EPS-1) showed that a peak based on the epoxy group was obtained around the chemical shift (δ) = 3.2 ppm according to theoretical strength, and during the reaction It was confirmed that no epoxy side reaction had occurred. The weight average molecular weight Mw of the obtained reactive polyorganosiloxane was 3,500, and the epoxy equivalent was 180 g / mol.
Then, in a 200-mL three-necked flask, 10.0 g of a 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 0.10 g of 18X (trade name, manufactured by San-Apro Co., Ltd.) was charged, and the reaction was carried out under stirring at 100 ° C. for 48 hours. After completion of the reaction, ethyl acetate is added to the reaction mixture, the solution obtained is washed three times with water, and the organic layer is dried using magnesium sulfate, and then the solvent is distilled off to obtain a liquid crystal alignment polyorganosiloxane (APS- Obtained 9.0g of 1). The weight average molecular weight Mw of the obtained polymer was 9,900.

Example 1
1. Preparation of Liquid Crystal Alignment Agent In 100 parts by mass of the polyimide (PI-1) obtained in the above Synthesis Example 1, γ-heptanolactone (γHL), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added as a solvent In addition, a solution with a solid content concentration of 6.5% by mass and a solvent mixing ratio of γHL: NMP: BC = 40: 30: 30 (mass ratio) was obtained. The solution was sufficiently stirred and then filtered through a filter with a pore size of 1 μm to prepare a liquid crystal aligning agent (S-1). The liquid crystal aligning agent (S-1) is mainly for the production of a vertical alignment type liquid crystal display element.

2. Evaluation of surface asperity (printability) The liquid crystal aligning agent (S-1) prepared in the above was applied onto a glass substrate using a spinner, prebaked on a hot plate at 80.degree. C. for 1 minute, and then 1 inside a 200.degree. A coating film with an average film thickness of 0.1 μm was formed by time heating (post-baking). The surface of the obtained coating film was observed with an atomic force microscope (AFM) to measure the center average roughness (Ra). The case where Ra was 5 nm or less was evaluated as printability "good (○)", the case where Ra was more than 5 nm and less than 10 nm was "good (Δ)", and the case where 10 nm or more was "defect (x)". As a result, in this example, the printability was evaluated as "good".

3. Evaluation of Continuous Printability With respect to the liquid crystal aligning agent (S-1) prepared above, the printability (continuous printability) when printing on a substrate was continuously performed was evaluated. Evaluation was performed as follows. First, using the liquid crystal alignment film printing machine (Nippon Photo Printing Machine Co., Ltd., Ongstromer type "S40L-532"), the amount of drop of the liquid crystal alignment agent (S-1) on the anilox roll is reciprocated 20 drops It printed on the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film | membrane on conditions of (about 0.2 g). The printing on the substrate was performed 20 times using fresh substrate at 1 minute intervals.
Subsequently, the liquid crystal aligning agent (S-1) is dispensed (one-way) on the anilox roll at one-minute intervals, and each time, the operation (hereinafter referred to as idle operation) of bringing the anilox roll and printing plate into contact It did (it does not print on a glass substrate during this time). This idle operation is an operation carried out to intentionally carry out the printing of the liquid crystal alignment agent under severe conditions.
After 10 blanking operations, main printing was subsequently performed using a glass substrate. In this printing, after idle operation, five substrates are loaded at intervals of 30 seconds, 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 ( The film was post-baked to form a coating having a thickness of about 0.08 μm. The printability (continuous printability) was evaluated by observing the coating film with a microscope with a magnification of 20 times. In the evaluation, continuous printability “good (○)” is observed when precipitation of the polymer is not observed from the first printing after idling, while precipitation of the polymer is observed at the first printing after idling. Continuous printability is "Available (析出)" when precipitation of the polymer is not observed during 5 times of actual printing, and continuous precipitation is observed when precipitation of the polymer is observed even after repeating 5 times of actual printing. Printability was "bad (x)". As a result, in this example, continuous printability was "good (o)". In the liquid crystal aligning agent having good printability, it has been known by experiments that the precipitation of the polymer is improved (disappeared) while the substrate is continuously introduced. Furthermore, when the number of idle operations was changed to 15, 20 and 25 times and the printability of the liquid crystal aligning agent was evaluated in the same manner as described above, in this example, the idle operation was 15 times and 20 In the case of the round, it was "good (○)", and in the case of 25 times it was "good (可)".

4. Evaluation of Applicability to the Surface of Fine Asperity Surface Using the ITO electrode substrate 10 for evaluation shown in FIG. 1, the applicability of the liquid crystal aligning agent to the surface of the fine asperity surface was evaluated. As the ITO electrode substrate 10 for evaluation, what carried out multiple arrangement | positioning of the stripe-shaped ITO electrode 12 at predetermined intervals on one surface of the glass substrate 11 was used (refer FIG. 1). The electrode width A was 50 μm, the inter-electrode distance B was 2 μm, and the electrode height C was 0.2 μm. Using the wettability evaluation device LSE-A100T (manufactured by Nick) on the electrode formation surface of this ITO electrode substrate 10 for evaluation, the above 1. The liquid crystal aligning agent (S-1) prepared in the above was dropped to evaluate the easiness of the substrate to the uneven surface. At this time, the coating property of the liquid crystal aligning agent on the fine uneven surface is better, the larger the wetting and spreading of the droplets (specifically, the larger the wetting spread area S (mm ² / μL) of the droplets with respect to the liquid amount). You can say that.
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 If it is greater than 10 mm ² / [mu] L than ² / [mu] L "permitted (△)", the area S is defined as a "bad (×)" in the case is less than 5 mm ² / [mu] L. As a result, in the present example, the area S was 10 mm ² / μL, and the coating property on the surface of fine asperity was judged as “good”.

5. Production of Vertical Alignment Liquid Crystal Cell Above 1. The liquid crystal aligning agent (S-1) prepared in the above was treated with a liquid crystal alignment film printing machine (Nippon Photo Printing Co., Ltd.), a glass substrate with a transparent electrode having a fine slit ITO electrode structure, and a patterned ITO electrode structure. It apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which has, respectively. Next, after heating (pre-baking) on an 80 ° C. hot plate for 1 minute to remove the solvent, heating (post-baking) on a 180 ° C. hot plate for 10 minutes to form a coating having an average film thickness of 0.8 μm It formed. Each coated substrate was subjected to ultrasonic cleaning for 1 minute in ultrapure water and then dried in a clean oven at 100 ° C. for 10 minutes. Thus, a pair of substrates (two sheets) having a liquid crystal alignment film was obtained.
Next, an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film, and then a pair of substrates are superposed and pressure bonded so that the liquid crystal alignment film faces each other. The agent was allowed to cure. Then, nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Ltd.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to manufacture a liquid crystal cell.
Further, a liquid crystal cell was manufactured by the same method as described above except that the post-baking temperature was changed from 180 ° C. to 120 ° C. or 230 ° C., respectively. The obtained liquid crystal cell is as described in 6. below. Used in the evaluation of

6. Evaluation of variation characteristics (post-bake margin) of pretilt angle with respect to temperature unevenness of post-baking Pre-tilt angles of liquid crystal cells obtained by producing liquid crystal alignment films at different post-baking temperatures (120 ° C., 180 ° C. and 230 ° C.) It was measured. The measured value of the pretilt angle of the liquid crystal cell with a postbake temperature of 230 ° C. is used as the reference pretilt angle θp, and the measured value of the pretilt angle θa of the liquid crystal cell with a postbake temperature of 120 ° C. or 180 ° C. From the difference Δθ (= θp−θa), the variation characteristics of the pretilt angle with respect to the temperature unevenness of the post bake was evaluated. It can be said that the smaller the Δθ, the smaller the variation in the pretilt angle with respect to the temperature unevenness of the post bake, and the better. The measurement of the pretilt angle is based on the method described in Non-patent document (T. J. Scheffer et. Al. J. Appl. Phys. Vo. 19, p. 2013 (1980)), He-Ne laser light The value of the inclination angle of the liquid crystal molecules from the substrate surface measured by the crystal rotation method using the above was taken as the pretilt angle [°]. The evaluation is “good (○)” when Δθ is 0.2 ° or less, “good (Δ)” when it is greater than 0.2 ° and less than 0.5 °, 0.5 ° The case where it is above was made into "defect (x)." As a result, in this example, when the post-baking temperature was 180 ° C., the post-baking margin was evaluated as “good” and when it was 120 ° C., it was evaluated as “good”.

7. Evaluation of AC Persistence Characteristic The above-described 5., except that the electrode structure is changed to two systems of ITO electrodes (electrode 1 and electrode 2) which can switch application / non-application of voltage separately. A liquid crystal cell for evaluation was produced in the same manner as in the above. The liquid crystal cell for evaluation was placed at 60 ° C., and an AC voltage of 10 V was applied to the electrode 1 for 300 hours without applying a voltage to the electrode 2. Immediately after a lapse of 300 hours, a voltage of 3 V AC was applied to both the electrode 1 and the electrode 2 to measure the difference ΔT [%] of the light transmittance between both electrodes. At this time, when the ΔT is less than 2%, the AC residual image characteristic is “good (○)”, and when it is 2% or more and less than 3%, “good (Δ)”, 3% or more It evaluated as "defect (x)." As a result, it was an evaluation of "good" in this example.

8. Evaluation of DC afterimage characteristics The liquid crystal cell for evaluation is placed at 60 ° C., a voltage of 0.5 V DC is applied to the electrode 1 for 24 hours, and the voltage (residual DC voltage) remaining on the electrode 1 immediately after the DC voltage is cut It calculated | required by the flicker elimination method. At this time, when the residual DC voltage is less than 100 mV, the DC residual image characteristic "good (○)", when it is 100 mV or more and less than 300 mV is "OK (△)", when it is 300 mV or more ×) ”. As a result, it was an evaluation of "good" in this example.

[Examples 2 to 10 and Comparative Examples 1 to 8]
Liquid crystal aligning agents (S-2 to S-10, SR-1 to SR-8) in the same manner as in Example 1 except that the type and blending amount of the polymer, and the solvent composition were as described in Table 1 below, respectively. Were prepared. Further, various evaluations were performed in the same manner as in Example 1 using the prepared liquid crystal aligning agent. The evaluation results are shown in Tables 2 and 3 below.

[Example 11]
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 described in Table 1 below. The liquid crystal aligning agent (S-11) is mainly for the production of a horizontal alignment type liquid crystal display element.
2. Evaluation of Liquid Crystal Alignment Agent The surface asperity, the continuous printability, and the coating property on the fine asperity 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. Production of Rubbed FFS-Type Liquid Crystal Cell On each surface of a glass substrate on which a flat plate electrode, an insulating layer and a comb-like electrode are laminated in this order on one side and an opposing glass substrate not provided with an electrode, The liquid crystal aligning agent (S-11) prepared in 5. above was applied using a spinner, and was heated (prebaked) for 1 minute on an 80 ° C. hot plate. Then, drying (post-baking) was performed for 30 minutes in the oven of 230 degreeC which substituted the inside of a chamber | room for 30 minutes, and the coating film of average film thickness 0.1 micrometer was formed. The coating film surface was rubbed at a roll rotational speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair-foot push-in length of 0.1 mm by a rubbing machine having a roll wound with rayon cloth. Then, ultrasonic cleaning was performed 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, a pair of substrates having a liquid crystal alignment film is screen-printed with an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 μm, leaving a liquid crystal injection port on the edge of the surface on which the liquid crystal alignment film is formed. The layers were superposed and pressed, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, nematic liquid crystal (manufactured by Merck, MLC-7028) was filled from a liquid crystal injection port between a pair of substrates, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 120 ° C. and then gradually cooled to room temperature to manufacture a liquid crystal cell.
4. Evaluation of Liquid Crystal Cell Above 3. The postbake margin, the AC afterimage characteristics and the DC afterimage characteristics were evaluated in the same manner as in Example 1 except that the rubbing FFS type liquid crystal cell obtained in the above was used. The results are shown in Table 2 below.

[Examples 12 and 13]
Liquid crystal aligning agents (S-12) and (S-13) were respectively prepared in the same manner as in Example 1 except that the polymer component and the solvent composition were changed as described in Table 1 below. Moreover, while evaluating the surface asperity, continuous printability, and coating property on fine asperity surface in the same manner as in Example 1 except that the liquid crystal aligning agents (S-12) and (S-13) were used, respectively, In the same manner as in Example 11, a rubbing FFS type liquid crystal cell was manufactured and various evaluations were performed. The results are shown in Table 2 below.

Example 14
1. Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-14) was prepared in the same manner as in Example 1 except that the polymer components and the solvent composition were changed as described in Table 1 below. The liquid crystal aligning agent (S-14) is mainly for the production of a PSA type liquid crystal display element.
2. Evaluation of Liquid Crystal Alignment Agent The surface asperity, the continuous printability, and the coating property on the fine asperity 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. Preparation of Liquid Crystal Composition The liquid crystal compound represented by the following formula (L1-1) was represented by 5% by mass with respect to 10 g of nematic liquid crystal (MLC-6608 manufactured by Merck Ltd.), and by the following formula (L2-1) The liquid crystal composition LC1 was obtained by adding 0.3 mass% of the photopolymerizable compounds and mixing them.

4. Production of PSA-Type Liquid Crystal Cell A liquid crystal alignment film printing machine (Nippon Photography printing (A) was carried out on each electrode surface of two glass substrates each having a conductive film consisting of an ITO electrode and the liquid crystal alignment agent (S-14) prepared above. (Pre-baking) on a hot plate at 80 ° C. for 2 minutes to remove the solvent, and then heating (post-baking) on a hot plate at 150 ° C. for 10 minutes to obtain an average film. A coating of 0.06 μm in thickness was formed. The coated films were subjected to ultrasonic cleaning in ultrapure water for 1 minute and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a pair (two sheets) of substrates having a liquid crystal alignment film. The pattern of the used electrode is the same pattern as the electrode pattern in the PSA mode.
Subsequently, an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 μm is applied to the outer edge of the surface of the one of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces one another. It was pressure-bonded together and the adhesive was cured. Next, the liquid crystal composition LC1 prepared above was filled between a pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to manufacture a liquid crystal cell. Thereafter, an AC 10V frequency 60Hz was applied between the conductive film of the liquid crystal cell, in a state where the liquid crystal is driven, using an ultraviolet irradiation apparatus using a metal halide lamp as a light source, the irradiation amount of 100,000J / m ² It irradiated ultraviolet rays at. In addition, this irradiation amount is the value measured using the actinometer measured by wavelength 365 nm reference | standard.
5. Evaluation of Liquid Crystal Cell Above 4. The postbake margin, the AC afterimage characteristics and the DC afterimage characteristics were evaluated in the same manner as in Example 1 except that the PSA type liquid crystal cell obtained in 1. above was used. The results are shown in Table 2 below.

[Examples 15 to 17, 27, 28]
Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the polymer component and the solvent composition were changed as described in Table 1 below. Moreover, while evaluating surface asperity, continuous printability, and coating property on fine asperity surface in the same manner as in Example 1 except that each liquid crystal aligning agent was used, in the same manner as in Example 14, a PSA type liquid crystal cell was obtained. It manufactured and performed various evaluations. The results are shown in Tables 2 and 3 below.

[Example 18]
1. Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-18) was prepared in the same manner as in Example 1 except that the polymer components and the solvent composition were changed as described in Table 1 below. The liquid crystal aligning agent (S-18) is mainly for the production of a liquid crystal display element of the light vertical alignment type.
2. Evaluation of Liquid Crystal Alignment Agent The surface asperity, the continuous printability, and the coating property on the fine asperity 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. Production of Light Vertically Aligned Liquid Crystal Cell The liquid crystal aligning agent (S-18) prepared above is applied on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner, and a hot plate at 80 ° C. Pre-baked for 1 minute. Thereafter, the inside of the chamber was heated at 230 ° C. for 1 hour in an oven purged with nitrogen to form a coating having a thickness of 0.1 μm. Then, using a Hg-Xe lamp and a Glan-Taylor prism, this coated film surface is irradiated with polarized ultraviolet light of 1,000 J / m ² containing an emission line of 313 nm from a direction inclined 40 ° from the substrate normal to obtain liquid crystal alignment ability. Granted. The same operation was repeated to form a pair (two sheets) of substrates having a liquid crystal alignment film.
An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 μm is applied by screen printing to the outer periphery of the surface having a liquid crystal alignment film of one of the above substrates, and then the liquid crystal alignment film surfaces of a pair of substrates are made to face each other. Pressure bonding was performed so that the projection direction of the optical axis of each substrate to the substrate surface was antiparallel, and the adhesive was thermally cured at 150 ° C. for one hour. Next, negative liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 130 ° C. and then gradually cooled to room temperature.
4. Evaluation of Liquid Crystal Cell Above 3. The postbake margin, the AC afterimage characteristics and the DC afterimage characteristics were evaluated in the same manner as in Example 1 except that the light vertical alignment type liquid crystal cell obtained in 1. above was used. The results are shown in Table 2 below.

[Examples 19 and 20]
Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the polymer component and the solvent composition were changed as described in Table 1 below. Moreover, while evaluating surface asperity, continuous printability, and coating property on fine asperity surface in the same manner as in Example 1 except that each liquid crystal aligning agent was used, optical vertical alignment liquid crystal as in Example 18 The cell was manufactured and various evaluations were performed. The results are shown in Table 2 below.

[Example 21]
1. Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-21) was prepared in the same manner as in Example 1 except that the polymer components and the solvent composition were changed as described in Table 1 below. The liquid crystal aligning agent (S-21) is mainly for producing a light horizontal alignment type liquid crystal display element.
2. Evaluation of Liquid Crystal Alignment Agent The surface asperity, the continuous printability, and the coating property on the fine asperity surface were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-21) was used. The results are shown in Table 2 below.

3. Production of Lightly Horizontally Aligned Liquid Crystal Cell Above each of the glass substrate on which the flat plate electrode, the insulating layer and the comb electrode are laminated in this order on one side, and the opposite glass substrate on which the electrode is not provided The prepared liquid crystal aligning agent (S-21) was applied using a spinner, and was heated (prebaked) for 1 minute on an 80 ° C. hot plate. Then, drying (post-baking) was performed for 30 minutes in the oven of 230 degreeC which substituted the inside of a chamber | room for 30 minutes, and the coating film of average film thickness 0.1 micrometer was formed. The coating film surface is irradiated with ultraviolet light of 1,000 J / m ² including a linearly polarized light emission line of 254 nm from the normal direction of the substrate using an Hg-Xe lamp to perform photoalignment treatment, and liquid crystal alignment on the substrate A film was formed.
Next, a pair of substrates having a liquid crystal alignment film is screen-printed with an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 μm, leaving a liquid crystal injection port at the edge of the surface on which the liquid crystal alignment film is formed. The substrates were superposed and pressure-bonded so that the projection directions of the polarization axes on the substrate surface at this time were antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, nematic liquid crystal (manufactured by Merck, MLC-7028) was filled from a liquid crystal injection port between a pair of substrates, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 120 ° C. and then gradually cooled to room temperature to manufacture a liquid crystal cell.
4. Evaluation of Liquid Crystal Cell Above 3. The postbake margin, the AC afterimage characteristics and the DC afterimage characteristics were evaluated in the same manner as in Example 1 except that the light horizontal alignment type liquid crystal cell obtained in 1. above was used. The results are shown in Table 2 below.

[Examples 22 to 26]
Liquid crystal aligning agents were prepared in the same manner as in Example 1 except that the polymer component and the solvent composition were changed as described in Table 1 below. Moreover, while evaluating surface asperity, continuous printability, and coating property on fine asperity surface in the same manner as in Example 1 except that each liquid crystal aligning agent was used, in the same manner as in Example 21, a light horizontal alignment type liquid crystal The cell was manufactured and various evaluations were performed. The results are shown in Table 2 below.

[Example 29]
1. Preparation of Liquid Crystal Alignment Agent A liquid crystal alignment agent (S-29) was prepared in the same manner as in Example 1 except that the polymer components and the solvent composition were changed as described in Table 1 below. The liquid crystal aligning agent (S-29) is mainly for the production of a TN mode liquid crystal display element.
2. Evaluation of Liquid Crystal Alignment Agent The surface asperity, the continuous printability, and the coating property on the fine asperity surface were evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent (S-29) was used. The results are shown in Table 3 below.

3. Production of TN Liquid Crystal Cell On the transparent electrode surface of a glass substrate with a transparent electrode formed of an ITO film, the above 1. The liquid crystal aligning agent (S-29) prepared in the above was applied using a spinner, and prebaked for 1 minute on a hot plate at 80.degree. Thereafter, the inside of the chamber was heated at 230 ° C. for 1 hour in an oven purged with nitrogen to form a coating having a thickness of 0.1 μm. The coating film was rubbed at a roll rotational speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair-foot push-in length of 0.1 mm by a rubbing machine having a roll wound with rayon cloth. Then, ultrasonic cleaning was performed 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. By repeating this series of operations, a pair (two sheets) of substrates having a liquid crystal alignment film was formed.
An epoxy resin adhesive containing aluminum oxide spheres with a diameter of 3.5 μm is applied by screen printing to the outer periphery of the surface of one of the above substrates having a liquid crystal alignment film, and then the liquid crystal alignment film surfaces are superimposed to face each other. It was pressure-bonded together and the adhesive was cured. Next, nematic liquid crystal (manufactured by Merck, MLC-6221) was filled between a pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive.
4. Evaluation of Liquid Crystal Cell Above 3. The postbake margin, the AC afterimage characteristics and the DC afterimage characteristics were evaluated in the same manner as in Example 1 except that the TN type liquid crystal cell obtained in 1. above was used. The results are shown in Table 3 below.

In Table 1, the numerical value of a polymer component shows the compounding ratio (mass part) of each polymer with respect to a total of 100 mass parts of the polymer component used for preparation of a liquid crystal aligning agent. The numerical value of the solvent composition indicates the blending ratio (parts by mass) of each solvent to 100 parts by mass in total of the solvent components used for the preparation of the liquid crystal aligning agent. Abbreviations of the compounds are as follows.
<Solvent>
a: γ-heptanolactone b: γ-octanolactone c: γ-nonanolactone d: γ-undecanolactone e: δ-octanolactone f: δ-decanolactone g: δ-dodecanolactone h: δ- toride Canolactone i: α-angelica lactone j: β-angelica lactone k: N-acetyl-ε-caprolactam L: γ-butyrolactone m: γ-valerolactone n: γ, γ-dimethyl-γ-butyrolactone o: δ-valero Lactone p: N-methylcaprolactam q: 1,3-dimethyl-2-imidazolidinone r: N-methyl-2-pyrrolidone s: butyl cellosolve t: diacetone alcohol u: diethylene glycol diethyl ether v: N-ethyl-2- Pyrrolidone

As is clear from Tables 2 and 3, in Examples 1 to 29 including the solvent [A], any of the surface asperity, continuous printability, and the coatability on the fine asperity surface is "excellent", "good" or It was an evaluation of "OK". Further, the post-baking margin was also small, and the AC residual image characteristics and the DC residual image characteristics of the obtained liquid crystal display element were evaluated as "good" or "good". On the other hand, in Comparative Examples 1 to 8 which did not contain the solvent [A], the coating property on the surface of fine irregularities was inferior to that of the example. Further, in Comparative Examples 1 to 3, the polymer was easily precipitated, and the continuous printability was also inferior.

10 ... ITO electrode substrate for evaluation, 11 ... glass substrate, 12 ... ITO electrode

Claims

Containing a polymer component and a solvent component,
The solvent component is at least one member selected from the group consisting of 5-membered ring lactones, 6-membered ring lactones and 7-membered ring lactams, and is an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 2 to 10 carbon atoms, An alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, a group “—COR 12 ” (wherein R 12 is an alkyl having 1 to 3 carbon atoms) A liquid crystal alignment agent containing a solvent [A] having at least one partial structure selected from the group consisting of a group) and a carbon-carbon double bond forming part of a ring.
The solvent [A] is at least one selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3) The liquid crystal aligning agent of Claim 1.

(In the formula (1), R 1 represents an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxyalkyl group having 2 to 10 carbon atoms or It is a C2-C10 alkoxy alkoxy group, n is 1 or 2.)

(In formula (2), R 2 is a divalent group represented by the following formula (4-1) or formula (4-2).)

(In Formula (4-1) and Formula (4-2), R 4 to R 11 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. “* 1” represents an oxygen atom Indicates that it is a bond with

(In the formula (3), R 3 is an alkyl group having 1 to 3 carbon atoms.)
The liquid crystal aligning agent of Claim 1 or 2 whose content rate of the said solvent [A] is 10 mass% or more with respect to the whole quantity of the said solvent component.
The said solvent component further contains solvent [B] which is at least 1 type chosen from the group which consists of alcohol solvent, chain-like ester solvent, ether solvent, and ketone solvent, any one of Claims 1-3. The liquid crystal aligning agent as described in.
The liquid crystal aligning agent according to claim 4, wherein a content ratio of the solvent [B] is 20 to 90% by mass with respect to a total amount of the solvent component.
The liquid crystal aligning agent according to claim 4, wherein the solvent component further contains a solvent [C] having a boiling point of 200 ° C. or higher at 1 atmospheric pressure.
The content ratio of the solvent [B] is 20 to 80% by mass with respect to the total amount of the solvent component,
The liquid crystal aligning agent according to claim 6, wherein a content ratio of the solvent [C] is 10 to 70% by mass with respect to a total amount of the solvent component.
The liquid crystal aligning agent according to any one of claims 1 to 7, wherein the polymer component contains at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide.
A method for producing a liquid crystal element, comprising forming a liquid crystal alignment film using the liquid crystal alignment agent according to any one of claims 1 to 8.
A liquid crystal alignment film formed using the liquid crystal alignment agent according to any one of claims 1 to 8.
The liquid crystal element which comprises the liquid crystal aligning film of Claim 10.