JP5321790B2 - Liquid crystal aligning agent, method for forming liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal orientation agent capable of forming a liquid crystal orientation film achieving satisfactory liquid crystal orientation performance even by small amount of exposure by applying polarizing or non-polarizing radiation without requiring rubbing processing and preventing the occurrence of thermal decomposition when post-baking. <P>SOLUTION: This liquid crystal orientation agent contains (co)polymer of a specific compound represented by the compound expressed in formula (1-1-1), preferably, at least one kind of polymer or polysiloxane selected from a group of polyamic acid and polyimide furthermore. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a liquid crystal alignment agent, a method for forming a liquid crystal alignment film, and a liquid crystal display element.

Conventionally, a nematic liquid crystal having positive dielectric anisotropy is sandwiched with a substrate with a transparent electrode having a liquid crystal alignment film, and the major axis of the liquid crystal molecules is continuously twisted between 0 and 360 ° between the substrates as necessary. There are known liquid crystal display elements having liquid crystal cells such as TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and IPS (In Plane Switching) type (see Patent Documents 1 and 2). .
In such a liquid crystal cell, it is necessary to provide a liquid crystal alignment film on the substrate surface in order to align liquid crystal molecules in a predetermined direction with respect to the substrate surface. This liquid crystal alignment film is usually formed by a method (rubbing method) in which the organic film surface formed on the substrate surface is rubbed in one direction with a cloth material such as rayon. However, when the liquid crystal alignment film is formed by a rubbing process, dust and static electricity are likely to be generated in the process, so that there is a problem that dust adheres to the alignment film surface and causes display defects. In particular, in the case of a substrate having a TFT (Thin Film Transistor) element, there has been a problem that the circuit damage of the TFT element occurs due to the generated static electricity, resulting in a decrease in yield. Furthermore, in liquid crystal display elements that will be further refined in the future, unevenness is generated on the substrate surface as the density of pixels increases, and it is becoming difficult to perform rubbing treatment uniformly.
As another means of aligning the liquid crystal in the liquid crystal cell, light that imparts liquid crystal alignment ability by irradiating polarized or non-polarized radiation to a photosensitive thin film such as polyvinyl cinnamate, polyimide, or azobenzene derivative formed on the substrate surface. Orientation methods are known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (see Patent Documents 3 to 13).
By the way, in a liquid crystal cell of TN (Twisted Nematic) type, STN (Super Twisted Nematic) type or the like, the liquid crystal alignment film needs to have a pretilt angle characteristic that tilts liquid crystal molecules at a predetermined angle with respect to the substrate surface. There is. In the case of forming a liquid crystal alignment film by the photo-alignment method, the pretilt angle is usually given by tilting the incident direction of the irradiated radiation to the substrate surface from the substrate normal.

On the other hand, a vertical alignment mode VA (Vertical Alignment) type liquid crystal cell in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate is also known as an operation mode of a liquid crystal display element different from the above. It has been. In this operation mode, when a voltage is applied between the substrates and the liquid crystal molecules are tilted in the direction parallel to the substrate, the liquid crystal molecules must be tilted from the substrate normal direction to one direction in the substrate surface. There is. As a means for this, for example, a method of providing protrusions on the substrate surface, a method of providing stripes on the transparent electrode, or using a rubbing alignment film, liquid crystal molecules are slightly directed from the substrate normal direction to one direction in the substrate surface. A method of tilting (pretilting) has been proposed.
The photo-alignment method is known to be useful as a method for controlling the tilt direction of liquid crystal molecules in a vertical alignment mode liquid crystal cell. That is, it is known that the tilt direction of liquid crystal molecules at the time of voltage application can be uniformly controlled by using a vertical alignment film provided with alignment regulating ability and pretilt angle expression by a photo-alignment method (Patent Documents 11 to 12). And 14-16).
In addition, the liquid crystal alignment film produced by the photo-alignment method has a photosensitive site in the side chain of the polymer as the main component. In the conventionally known photo-alignment materials, the photosensitive site in the side chain is used. However, there is a concern that the possibility of thermal decomposition at the time of heating in the liquid crystal panel manufacturing process cannot be wiped out and a problem of contaminating the substrate or the panel manufacturing line is caused.
As described above, a liquid crystal alignment film having good liquid crystal alignment ability, excellent electrical properties, and high heat resistance can be formed by a photo-alignment method with a small radiation dose, causing a problem of thermal decomposition during post-baking. No liquid crystal aligning agent is known so far.
JP 56-91277 A JP-A-1-120528 JP-A-6-287453 JP-A-10-251646 Japanese Patent Laid-Open No. 11-2815 JP-A-11-152475 JP 2000-144136 A JP 2000-319510 A JP 2000-281724 A JP-A-9-297313 JP 2003-307736 A JP 2004-163646 A JP 2002-250924 A JP 2004-83810 A Japanese Patent Laid-Open No. 9-21468 JP 2003-114437 A JP-A 63-291922 Japanese translation of PCT publication No. 2003-520878 J. et al. of the SID 11/3, 2003, p579 T. T. et al. J. et al. Scheffer et. al. J. et al. Appl. Phys. vo. 19, p2013 (1980)

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal alignment film having a good liquid crystal alignment ability even with a small exposure amount by irradiation with polarized or non-polarized radiation without performing a rubbing treatment. A liquid crystal aligning agent that does not cause thermal decomposition problems during post-baking, a liquid crystal aligning method that uses the liquid crystal aligning agent, a method for forming a liquid crystal aligning film that is excellent in heat resistance, and various performances such as display characteristics and reliability Is to provide.

According to the present invention, the above objects and advantages of the present invention are as follows.
The following formula (1) or (2)

(In the formula (1), ^{R 1} represents a hydrogen atom, a monovalent organic group having 3 to 40 carbon atoms containing an alkyl or fluoroalkyl group or a alicyclic structure having a carbon number of 1 to 40, ^{R 2} is a single bond R ³ is a hydrogen atom, or R ² and R ³ are bonded to form a ring having 4 to 8 carbon atoms, and A ¹ is a single bond, an oxygen atom, a sulfur atom or ^* − COO—, * —OCO— (wherein the bond marked with “*” is bonded to R ¹ ), R ⁴ is a fluorine atom or a cyano group, and S ¹ is a methylene group or a carbon number of 2 to 10 P ¹ is a hydrogen atom or a methyl group, a is 0 or 1, b is an integer of 0 to 4,
In Formula (2), R ⁵ is a single bond and R ⁶ is a hydrogen atom, or R ⁵ and R ⁶ are bonded to form a ring having 4 to 8 carbon atoms, and R ⁷ is An alkyl group or fluoroalkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic structure, R ⁸ is a fluorine atom or a cyano group, A ² is a single bond, oxygen An atom, a sulfur atom, or —COO— ^* , —OCO— * (where a bond marked with “*” is bonded to R ⁵ ), and S ² is a methylene group or an alkylene group having 2 to 10 carbon atoms. There, ^{P 2} is a hydrogen atom or a methyl group, c is 0 or 1, d is an integer of 0-4. )
It achieves by the liquid crystal aligning agent containing the (co) polymer of the compound represented by these.
The above objects and advantages of the present invention are secondly,
The liquid crystal aligning agent is applied to form a coating film, and is achieved by a method of forming a liquid crystal alignment film in which the coating film is irradiated with radiation. Third,
This is achieved by a liquid crystal display element comprising a liquid crystal alignment film formed from the above liquid crystal aligning agent.
Further, the above object and advantage of the present invention are fourthly.
Achieved by a (co) polymer of a compound represented by the above formula (1) or (2),
This is achieved by the compound represented by the above formula (1) or (2).

  The liquid crystal aligning agent of the present invention is a liquid crystal aligning film having excellent liquid crystal aligning properties and electrical characteristics with a small radiation dose as compared with a liquid crystal aligning agent conventionally known as a liquid crystal aligning agent to which a photo-alignment method can be applied. In addition, there is no problem of thermal decomposition during post-baking. Therefore, when this liquid crystal alignment film is applied to a liquid crystal display element, the liquid crystal display element can be manufactured at a lower cost than before, and the various properties such as display characteristics and reliability are excellent. Therefore, these liquid crystal display elements can be effectively applied to various devices, and can be suitably used for devices such as desk calculators, watches, table clocks, counting display boards, word processors, personal computers, and liquid crystal televisions.

Hereinafter, the present invention will be described in detail.
The liquid crystal aligning agent of this invention contains the polymer obtained by superposing | polymerizing the compound represented by the said Formula (1) or (2).
<Compound represented by the above formula (1) or (2)>
The alkyl group or fluoroalkyl group having 1 to 40 carbon atoms of R ¹ in the above formula (1) is preferably an alkyl group or fluoroalkyl group having 1 to 20 carbon atoms. Specific examples thereof include, for example, methyl group, ethyl Group, n-propyl, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group N-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 4,4,4-trifluorobutyl Group, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl group, 3,3,4,4,5,5,5-hepta Fluoropentyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorooctyl) ethyl group, A 2- (perfluorodecyl) ethyl group can be exemplified. The monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group R ^1, may include, for example Koresuteniru group, cholestanyl group, an adamantyl group. S ¹ is preferably an alkylene group having 2 to 6 carbon atoms.
The ring having 4 to 8 carbon atoms formed by combining R ² and R ³ in the above formula (1) is a concept including an alicyclic ring and an aromatic ring, and may be a monocyclic ring, a polycyclic ring or a bridged ring. it can. Examples of the ring having 4 to 8 carbon atoms include a cyclohexane ring, a benzene ring, a cyclobutane ring, a cyclopentane ring, and a norbornene ring.
Examples of the compound represented by the above formula (1) include, for example, the following formulas (1-1) to (1-10):

(In the above formula, R ¹ and P ¹ have the same meanings as in the above formula (1), and e is an integer of 1 to 10.)
And the like, and the like. It is preferable that e is an integer of 2-6.
The ring having 4 to 8 carbon atoms formed by combining R ⁵ and R ⁶ in the above formula (2) is a concept including an alicyclic ring and an aromatic ring, and may be a monocyclic ring, a polycyclic ring or a bridged ring. it can. Examples of the ring having 4 to 8 carbon atoms include a cyclohexane ring, a benzene ring, a cyclobutane ring, a cyclopentane ring, and a norbornene ring. The alkyl group having 1 to 40 carbon atoms and the fluoroalkyl group of R ^{7 and} the monovalent organic group having 3 to 40 carbon atoms including the alicyclic structure are the same as those described for R ¹ in the above formula (1). is there. S ² is preferably an alkylene group having 2 to 6 carbon atoms.
Examples of the compound represented by the above formula (2) include, for example, the following formulas (2-1) to (2-3):

(In the above formula, R ⁷ and P ² are respectively synonymous with those in the above formula (2), and f is an integer of 1 to 10.)
And the like, and the like. f is preferably an integer of 2 to 6.
The compound represented by the formula (1) or (2) can be synthesized by appropriately combining organic chemistry methods.
For example, as a method for synthesizing the compound represented by the above formula (1-1), for example, the following two synthesis routes can be exemplified.
As a first synthetic route, a cinnamic acid derivative having an alkyl succinimide group is obtained as an intermediate by the reaction of alkyl succinic anhydride and 4-amino cinnamic acid, and this is converted into an acid chloride with thionyl chloride, and then hydroxyethyl. The method of making it react with an acrylate can be mentioned. The intermediate can be synthesized by, for example, a method of refluxing the raw material compound in acetic acid, a method of refluxing in toluene or xylene in the presence of a suitable base catalyst such as triethylamine, and the like. This reaction can be preferably performed in the presence of a suitable base such as triethylamine.
As a second synthesis route, the cinnamic acid derivative intermediate is reacted with bromoethanol in the presence of a suitable base such as potassium carbonate to form an ester, and then acrylic acid in the presence of a suitable base such as triethylamine. The method of making it react with a chloride can be mentioned.

Synthesis of the compound represented by the above formula (1-2) is performed by, for example, reacting malate ester with alkyl iodide or alkyl bromide in the presence of a suitable catalyst such as silver oxide to form an ether bond. And then hydrolyzing with alkaline water, dehydrating and ring-closing with acetic anhydride to obtain an acid anhydride having an alkyl ether, and then 4-amino in the same manner as the synthesis of the compound represented by the above formula (1-1). It is possible to use cinnamic acid by adding an acrylate via a cinnamic acid derivative intermediate.
The compound represented by the above formula (1-3) is represented by the above formula (1-1) after Michael addition of a thiol having an alkyl group to maleimide, hydrolysis and dehydration ring closure of the product. In the same manner as the synthesis of the compound, it can be synthesized by a method of adding acrylate through a cinnamic acid derivative intermediate using 4-aminocinnamic acid.
The compound represented by the above formula (1-4) is obtained by reacting, for example, hydrogenated trimellitic anhydride with thionyl chloride and then reacting this with alcohol in the presence of a suitable base such as triethylamine. In the same manner as the synthesis of the compound represented by the above formula (1-1), an acrylate is added to the product obtained by forming an ester bond by using 4-aminocinnamic acid via a cinnamic acid derivative intermediate. It can be synthesized by the method.
The compound represented by the above formula (1-5) is obtained by, for example, dehydrating hydroxyphthalic acid and cyclizing it, and then reacting 4-aminocinnamic acid in the same manner as in the above formula (1-1). The product can be synthesized by a method in which an alkyl iodide or alkyl bromide is subjected to a Williamson reaction and an acrylate is added via a cinnamic acid derivative intermediate.

The compound represented by the above formula (1-6) is obtained by, for example, combining a cinnamic acid derivative intermediate and vinyl bromide in the synthesis of the compound represented by the above formula (1-1) with the presence of a suitable base such as potassium carbonate. It can synthesize | combine by making it react under.
The compound represented by the above formula (1-7) is obtained by, for example, combining a cinnamic acid derivative intermediate and vinyl bromide in the synthesis of the compound represented by the above formula (1-2) with the presence of a suitable base such as potassium carbonate. It can synthesize | combine by making it react under.
The compound represented by the above formula (1-8) is obtained by, for example, combining a cinnamic acid derivative intermediate and vinyl bromide in the synthesis of the compound represented by the above formula (1-3) with the presence of a suitable base such as potassium carbonate. It can synthesize | combine by making it react under.
The compound represented by the above formula (1-9) is obtained by, for example, combining a cinnamic acid derivative intermediate and vinyl bromide in the synthesis of the compound represented by the above formula (1-4) with the presence of a suitable base such as potassium carbonate. It can synthesize | combine by making it react under.
The compound represented by the above formula (1-10) is obtained by, for example, combining a cinnamic acid derivative intermediate and vinyl bromide in the synthesis of the compound represented by the above formula (1-5) with the presence of a suitable base such as potassium carbonate. It can synthesize | combine by making it react under.
The liquid crystal alignment film preferably has no i-line absorption because the change in the liquid crystal alignment due to the manufacturing process of the liquid crystal panel and the irradiation of the backlight is small. From this viewpoint, among the above, the above formula (1-1) To (1-4), (1-6) to (1-9) and (2-1) are preferred, and the above formulas (1-1) to (1- Compounds represented by each of 4) and (2-1) are more preferred.

<(Co) polymer of compound represented by formula (1) or (2)>
The liquid crystal aligning agent of this invention contains the (co) polymer of the compound represented by the said Formula (1) or (2) as mentioned above. This (co) polymer has the following formula (3) or (4)

(In the formulas (3) and (4), R ^{1 to} R ⁸ , A ¹ , A ² , S ¹ , S ² , P ¹ , P ² , a, b, c and d are each represented by the above formula (1). Or the same meaning as in (2).)
It has the repeating unit represented by these. These repeating units are derived from the compound represented by the above formula (1) or (2), respectively.
The (co) polymer may be a polymer of the compound represented by the above formula (1) or (2), or the compound represented by the above formula (1) or (2) and other polymerizations. It may be a copolymer with an unsaturated compound.
Other polymerizable unsaturated compounds used herein include polymerizable unsaturated compounds having an epoxy group, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, aryl acrylate Esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides and other unsaturated compounds Mention may be made of saturated compounds.

Specific examples thereof include polymerizable unsaturated compounds having an epoxy group such as glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylic acid. Glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6 7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like;
Examples of the methacrylic acid alkyl ester include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethylglycoside, 4 -Hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate and the like;
Examples of alkyl acrylate esters include methyl acrylate and isopropyl acrylate;
Examples of cyclic alkyl esters of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6 ]. Decan-8-yloxyethyl methacrylate, isobornyl methacrylate, cholestanyl methacrylate, etc .;
Examples of acrylic acid cyclic alkyl esters include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ]. Decan-8-yloxyethyl acrylate, isobornyl acrylate, cholestanyl acrylate, etc .;
Examples of methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate;

Examples of acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
As unsaturated dicarboxylic acid diesters, for example, diethyl maleate, diethyl fumarate, diethyl itaconate, etc .;
Bicyclo unsaturated compounds include, for example, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1]. Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 .1] Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2- Ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di ( 2'-hydroxyethyl) bicyclo [2.2.1] hept-2-e 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5- Methylbicyclo [2.2.1] hept-2-ene and the like;
Examples of maleimide compounds include phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Maleimidopropionate, N- (9-acridinyl) maleimide and the like;

Examples of unsaturated aromatic compounds include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like;

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like;
As unsaturated monocarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid and the like;
Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
As unsaturated dicarboxylic acid anhydrides, the anhydrides of the above unsaturated dicarboxylic acids;
Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, and the like.
The other polymerizable unsaturated compound preferably includes a polymerizable unsaturated compound having an epoxy group.

The copolymerization ratio of the compound represented by the formula (1) or (2) in the polymer is preferably 30% by weight or more, more preferably 50% by weight or more based on the total unsaturated compounds. . The polymer preferably has a repeating unit derived from a polymerizable unsaturated compound having an epoxy group in addition to a repeating unit derived from the compound represented by the formula (1) or (2). . In this case, the copolymerization ratio of the polymerizable unsaturated compound having an epoxy group in the polymer is preferably 0 to 70% by weight, more preferably 20 to 60% by weight.
The polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography for the polymer is preferably 2,000 to 200,000, more preferably 3,000 to 50,000, and further 4, It is preferable that it is 000-10,000.
The (co) polymer of the compound represented by the above formula (1) or (2) is a polymerizable unsaturated compound containing the compound represented by the above formula (1) or (2), preferably a suitable organic compound. It can be synthesized by radical polymerization in a solvent. This radical polymerization can be performed according to a known method.

<Other ingredients>
The liquid crystal aligning agent of this invention contains the (co) polymer of the compound represented by the said Formula (1) or (2) as mentioned above.
The liquid crystal aligning agent of the present invention contains other components in addition to the (co) polymer of the compound represented by the above formula (1) or (2) as described above, as long as the effects of the present invention are not impaired. You may do it. Examples of such other components include polymers other than (co) polymers of the compounds represented by the above formula (1) or (2) (hereinafter referred to as “other polymers”) in the molecule. A compound having at least one epoxy group (hereinafter referred to as “epoxy compound”), a functional silane compound, a surfactant, and the like can be given.
Said other polymer can be used in order to improve the solution characteristic of the liquid crystal aligning agent of this invention, and the electrical property of the liquid crystal aligning film obtained. Examples of such other polymers include at least one polymer selected from the group consisting of polyamic acid and polyimide, polysiloxane, polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene- Phenylmaleimide) derivatives, poly (meth) acrylates and the like.
The polyamic acid can be obtained by reacting tetracarboxylic dianhydride with a diamine compound.
Examples of tetracarboxylic dianhydrides that can be used for the synthesis of polyamic acid include 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5, 6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2, 5-Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydride) -2,5-dioxo-3-furanyl) -8-methyl-naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl- 3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, the following formula (T-1) ~ (T-4)

An aliphatic or alicyclic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by each of
Pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-Tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide Dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′ , 4 4′-perfluoroisopropylidenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis ( Triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid)- 4,4′-diphenylmethane dianhydride, the following formulas (T-5) to (T-8)

An aromatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by each of the above. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.
The tetracarboxylic dianhydride used to synthesize polyamic acid is 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl among the above. ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -8 -Methyl-naphtho [1,2-c] -furan-1,3-dione, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetra Carboxylic acid Water, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid At least one selected from the group consisting of a dianhydride and a tetracarboxylic dianhydride represented by each of the above formulas (T-1), (T-2) and (T-5) to (T-8) It is preferable that it contains a seed, and it is more preferable that at least one of these is included in an amount of 20 mol% or more, more preferably 50 mol% or more, based on the total tetracarboxylic dianhydride, In particular, it is preferable to contain 80 mol% or more.

  Examples of diamines that can be used for the synthesis of polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3, 3-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1 , 3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 2,2-bis (4-a Nophenoxy) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4 -Aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) Benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) Fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobipheny 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4 ′-(p-phenyleneisopropylidene) Bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-2 , 2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl,

6- (4-Calconyloxy) hexyloxy (2,4-diaminobenzene), 6- (4′-fluoro-4-chalconyloxy) hexyloxy (2,4-diaminobenzene), 8- (4- Calconyloxy) octyloxy (2,4-diaminobenzene), 8- (4′-fluoro-4-calconyloxy) octyloxy (2,4-diaminobenzene), 1-dodecyloxy-2,4-diamino Benzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4- Diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, 1-cholestanyloxy-2,4-diaminobenzene, Decyloxy (3,5-diaminobenzoyl), tetradecyloxy (3,5-diaminobenzoyl), pentadecyloxy (3,5-diaminobenzoyl), hexadecyloxy (3,5-diaminobenzoyl), octadecyloxy (3 , 5-diaminobenzoyl), cholesteryloxy (3,5-diaminobenzoyl), cholestanyloxy (3,5-diaminobenzoyl), (2,4-diaminophenoxy) palmitate, (2,4-diaminophenoxy) stearylate , (2,4-diaminophenoxy) -4-trifluoromethylbenzoate, the following formulas (D-1) to (D-7)

(Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5.)
An aromatic diamine such as a diamine compound represented by each of
Aromatic diamines having hetero atoms such as diaminotetraphenylthiophene; metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoin danylenediethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyl diamine, aliphatic or cycloaliphatic diamines such as 4,4'-methylenebis (cyclohexylamine);
Examples include diaminoorganosiloxanes such as diaminohexamethyldisiloxane.
In the aromatic diamine, the benzene ring may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group).
These diamines can be used alone or in combination of two or more.

  Among the above, the diamine used for synthesizing the polyamic acid is p-phenylenediamine, 4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4′-diamino. Diphenyl ether, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4 '-Bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluoro Phenyl, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, 1-cholestanyloxy-2,4-diamino Benzene, hexadecyloxy (3,5-diaminobenzoyl), octadecyloxy (3,5-diaminobenzoyl), cholesteryloxy (3,5-diaminobenzoyl), cholestanyloxy (3,5-diaminobenzoyl) and the above formula It is preferable that it contains at least one selected from the group consisting of the compounds represented by each of (D-1) to (D-7), and at least one of these is based on the total diamine. More preferably, the content is more than 20 mol%, and more than 50 mol%. But more preferably, it is preferable that in particular include over 80 mol%.

The proportion of tetracarboxylic dianhydride and diamine used in the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 1 equivalent to 1 equivalent of an amino group contained in the diamine. A ratio of 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
The polyamic acid synthesis reaction is preferably performed in an organic solvent, preferably at a temperature of −20 to 150 ° C., more preferably at a temperature of 0 to 100 ° C., preferably 0.5 to 24 hours, more preferably 2 to 10 Done for hours. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, Aprotic polar solvents such as N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide; phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol Can do. The amount (a) of the organic solvent used is such that the total amount (b) of tetracarboxylic dianhydride and diamine compound is preferably 0.1 to 50% by weight, more preferably 5 to 5%, based on the total amount (a + b) of the reaction solution. The amount is 30% by weight.
As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. Polyamic acid can be isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator. it can. Further, the polyamic acid can be purified by a method of dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent, or a method of performing the step of distilling under reduced pressure with an evaporator once or several times.

The polyimide can be produced by dehydrating and ring-closing the amic acid structure of the polyamic acid obtained as described above. At this time, all of the amic acid structure may be dehydrated and closed to completely imidize, or only a part of the amic acid structure may be dehydrated and closed to form a partially imidized product in which the amic acid structure and the imide structure coexist. Also good.
The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. By the method.
The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained may decrease. The reaction time in the method of heating the polyamic acid is preferably 0.5 to 48 hours, more preferably 2 to 20 hours.
On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the polyamic acid structural unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C., more preferably 10 to 150 ° C., and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.
The polyimide obtained in the above method (i) may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after purifying the obtained polyimide. On the other hand, in the above method (ii), a reaction solution containing polyimide is obtained. This reaction solution may be used as it is for the preparation of a liquid crystal aligning agent, or may be used for the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution. It may be used for the preparation of a liquid crystal aligning agent or may be used for the preparation of a liquid crystal aligning agent after purifying the isolated polyimide. In order to remove the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. The isolation and purification of the polyimide can be performed by performing the same operation as described above as the isolation and purification method of the polyamic acid.

  The polysiloxane is, for example, the following formula (α)

(In the formula (α), X is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, and Y is a hydroxyl group or 1 carbon atom. ˜6 alkoxyl groups.)
It is at least 1 sort (s) selected from the group which consists of polysiloxane which has a repeating unit represented by these, its hydrolyzate, and a hydrolysis condensate.
The polysiloxane is, for example, at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter also referred to as “raw silane compound”), preferably in a suitable organic solvent. It can be synthesized by hydrolysis or hydrolysis / condensation in the presence of water and a catalyst.
Examples of the raw material silane compound that can be used here include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-. Butoxysilane, tetrachlorosilane; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane , Methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxy Lan, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane; dimethyldimethoxysilane, dimethyldiethoxysilane, Examples include dimethyldichlorosilane; trimethylmethoxysilane, trimethylethoxysilane, and trimethylchlorosilane. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane or trimethylethoxysilane are preferred.
The polysiloxane has a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography, preferably 500 to 100,000, more preferably 1,000 to 20,000.

Examples of the organic solvent that can be optionally used when synthesizing the polysiloxane include alcohol compounds, ketone compounds, amide compounds, ester compounds, and other aprotic compounds. These can be used alone or in combination of two or more.
Examples of the alcohol compound include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol , Sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol , Phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, monoalcohol compounds such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2- Polyhydric alcohol compounds such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, the partial ethers of polyhydric alcohol compound and dipropylene glycol monopropyl ether, can be mentioned, respectively. These alcohol compounds may be used alone or in combination of two or more.

Examples of the ketone compound include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, and methyl-n-. Monoketone compounds such as hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fencheon;
Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5 -Methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione, etc. The β-diketone compound and the like can be mentioned respectively. These ketone compounds may be used alone or in combination of two or more.
Examples of the amide compound include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-ethyl. Acetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. Can be mentioned. These amide compounds may be used alone or in combination of two or more.

  Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, acetic acid. i-butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, acetic acid n-nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene acetate monoethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, vinegar Acid diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Examples include amyl, diethyl malonate, dimethyl phthalate, and diethyl phthalate. These ester compounds may be used alone or in combination of two or more.

Examples of the other aprotic compounds include acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N— Ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N -Methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone and the like can be mentioned.
Of these solvents, polyhydric alcohol compounds, partial ethers or ester compounds of polyhydric alcohol compounds are particularly preferred.
The amount of water used in the synthesis of the polysiloxane is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, relative to 1 mol of the total amount of alkoxyl groups and halogen atoms of the starting silane compound. Furthermore, it is preferable that it is 1-1.5 mol.

Examples of the catalyst that can be used in the synthesis of the polysiloxane include metal chelate compounds, organic acids, inorganic acids, organic bases, ammonia, alkali metal compounds, and the like.
Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di- n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetate) Natto) titanium, di-t-butoxy Su (acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n -Butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri -S c-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, Di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis ( Ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy・ Tris (ethyl aceto Acetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl aceto) Titanium chelate compounds such as acetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium;

Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) ziru Ni, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetyl) Acetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetyl) Acetonato) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetate) Acetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis ( Ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di- sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n- Propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) Zirconium, mono-t-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium;
Examples thereof include aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum.

Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, and gallic acid. Acid, butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Examples include acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.
Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclo. Nonane, diazabicycloundecene, tetramethylammonium hydroxide and the like can be mentioned.
Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.
These catalysts may be used alone or in combination of two or more.
Of these catalysts, metal chelate compounds, organic acids or inorganic acids are preferred, and titanium chelate compounds or organic acids are more preferred.
The amount of the catalyst used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the raw material silane compound.
Water added during the synthesis of polysiloxane can be added intermittently or continuously in the raw material silane compound or in a solution in which the silane compound is dissolved in an organic solvent.
The catalyst may be added in advance to a raw material silane compound or a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in the added water.
The reaction temperature during the synthesis is preferably 0 to 100 ° C, more preferably 15 to 80 ° C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

  The use ratio of the other polymer as described above in the liquid crystal aligning agent of the present invention is preferably 10,000 with respect to 100 parts by weight of the (co) polymer of the compound represented by the formula (1) or (2). Or less, more preferably 10 to 10,000 parts by weight, still more preferably 100 to 5,000 parts by weight, and particularly preferably 500 to 2,000 parts by weight.

The said epoxy compound can be used from a viewpoint which improves the adhesiveness with respect to the substrate surface of the liquid crystal aligning film formed. Examples of such epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, 1,3,5,6-tetraglycidyl Oxy-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) Preferred examples include cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane and the like. it can. When the liquid crystal aligning agent of the present invention contains an epoxy compound, the epoxy compound may be used in combination with an appropriate base catalyst such as 1-benzyl-2-methylimidazole for the purpose of efficiently causing an epoxy group crosslinking reaction.
The use ratio of the epoxy compound in the liquid crystal aligning agent of the present invention refers to the total of the polymers (the total of the (co) polymer of the compound represented by the above formula (1) or (2) and other polymers). The same)) 100 parts by weight or less, preferably 100 parts by weight or less, more preferably 50 parts by weight or less.

The said functional silane compound can be used in order to improve the adhesiveness with the board | substrate of the liquid crystal aligning film formed. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3. -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltri Methoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7 Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl- 3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene ) -3-Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And the patent text 17 is described in (JP 63-291922 JP) include a reaction product of a silane compound having a tetracarboxylic dianhydride and an amino group.
When the liquid crystal aligning agent of the present invention contains a functional silane compound, the content ratio is preferably 50 parts by weight or less, more preferably 20 parts by weight or less, with respect to 100 parts by weight of the total polymer. is there.

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. it can.
When the liquid crystal aligning agent of this invention contains surfactant, as the content rate, Preferably it is 10 weight part or less with respect to 100 weight part of the whole liquid crystal aligning agent, More preferably, it is 1 weight part or less. is there.

<Liquid crystal aligning agent>
As described above, the liquid crystal aligning agent of the present invention contains a (co) polymer of the compound represented by the above formula (1) or (2) as an essential component, and additionally contains other components as necessary. However, it is preferably prepared as a solution composition in which each component is dissolved in an organic solvent.
Examples of the organic solvent that can be used for preparing the liquid crystal aligning agent of the present invention include (co) polymers of the compounds represented by the above formula (1) or (2) and other optionally used compounds. Those that dissolve the components and do not react with them are preferred.
The organic solvent that can be preferably used in the liquid crystal aligning agent of the present invention varies depending on the type of other polymer that is optionally added.
The liquid crystal aligning agent of the present invention contains a (co) polymer of the compound represented by the above formula (1) or (2) and at least one polymer selected from the group consisting of polyamic acid and polyimide. Preferred organic solvents in some cases include the organic solvents exemplified above as those used for the synthesis of polyamic acid. At this time, you may use together the poor solvent illustrated as what is used for the synthesis | combination of the polyamic acid of this invention. These organic solvents can be used alone or in combination of two or more.
On the other hand, as a preferable organic solvent when the liquid crystal aligning agent of the present invention contains a (co) polymer of the compound represented by the above formula (1) or (2) and polysiloxane, for example, 1-ethoxy -2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether Lucerosolve), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, N-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, Examples include 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, and isoamyl acetate. Of these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate and the like can be mentioned.

The preferable solvent used for the preparation of the liquid crystal aligning agent of the present invention is obtained by combining one or more of the above organic solvents, and is contained in the liquid crystal aligning agent at the following preferable solid content concentration. Each component does not precipitate, and the surface tension of the liquid crystal aligning agent is in the range of 25 to 40 mN / m.
The solid content concentration of the liquid crystal aligning agent of the present invention, that is, the ratio of the weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, Preferably it is the range of 1-10 weight%. The liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal aligning film. When the solid content concentration is less than 1% by weight, the film thickness of this coating film becomes too small. In some cases, it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film due to excessive film thickness, and the viscosity of the liquid crystal aligning agent increases, resulting in insufficient coating characteristics. There is a case. The particularly preferable range of the solid content concentration varies depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the range of 1.5 to 4.5% by weight is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.
The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 0 ° C to 200 ° C, more preferably 20 ° C to 60 ° C.

<Method for forming liquid crystal alignment film>
The liquid crystal aligning agent of this invention can be used conveniently in order to form a liquid crystal aligning film by the photo-alignment method.
As a method for forming the liquid crystal alignment film, for example, a method of forming a coating film of the liquid crystal alignment film of the present invention on a substrate and then imparting liquid crystal alignment ability to the coating film by a photo-alignment method can be mentioned.
First, the liquid crystal aligning agent of the present invention is applied to the transparent conductive film side of the substrate provided with the patterned transparent conductive film by an appropriate application method such as a roll coater method, a spinner method, a printing method, an ink jet method or the like. For example, the coating film is formed by heating at a temperature of 40 to 250 ° C. for 0.1 to 120 minutes. The thickness of the coating film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm, as the thickness after removal of the solvent.
As the substrate, for example, a glass such as float glass or soda glass, a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used.
As the transparent conductive film, a NESA film made of SnO ₂ , an ITO film made of In ₂ O ₃ —SnO _2, or the like can be used. For patterning these transparent conductive films, a photo-etching method or a method using a mask when forming the transparent conductive film is used.
When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate or the transparent conductive film and the coating film, a functional silane compound, titanate or the like is previously applied on the substrate and the transparent conductive film. Also good.

Next, the coating film is irradiated with linearly polarized light, partially polarized radiation or non-polarized radiation, and optionally subjected to a heat treatment at a temperature of 150 to 250 ° C., preferably for 1 to 120 minutes, thereby improving the liquid crystal alignment ability. Give. Here, as the radiation, for example, ultraviolet rays including light having a wavelength of 150 nm to 800 nm and visible light can be used, but ultraviolet rays including light having a wavelength of 300 nm to 400 nm are preferable. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination thereof. May be. When irradiating non-polarized radiation, the direction of irradiation needs to be an oblique direction.
As a light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The ultraviolet rays in the preferable wavelength region can be obtained by means of using the light source in combination with, for example, a filter, a diffraction grating, or the like.
The irradiation dose of radiation, preferably less than 1 J / ^{m 2} or more 10,000 J / ^{m 2,} more preferably from 10~3,000J / ^{m 2.} In addition, when providing the liquid crystal aligning ability by the photo-alignment method to the coating film formed from the conventionally known liquid crystal aligning agent, the irradiation dose of 10,000 J / m < ² > or more was required. However, when the liquid crystal aligning agent of the present invention is used, good liquid crystal alignment is imparted even when the radiation irradiation amount in the photo-alignment method is 3,000 J / m ² or less, and further 1,000 J / m ² or less. This contributes to the reduction of the manufacturing cost of the liquid crystal display element.
The “pretilt angle” in the present invention represents an angle of inclination of liquid crystal molecules from a direction parallel to the substrate surface.

<Method for manufacturing liquid crystal display element>
The liquid crystal display element formed using the liquid crystal aligning agent of this invention can be manufactured as follows, for example.
Prepare a pair (two sheets) of substrates on which the liquid crystal alignment film is formed as described above, and make these liquid crystal alignment films face each other so that the polarization direction of the irradiated linearly polarized radiation becomes a predetermined angle. A peripheral portion between the substrates is sealed with a sealing agent, liquid crystal is injected and filled, and a liquid crystal injection port is sealed to constitute a liquid crystal cell. Next, it is desirable that the liquid crystal cell is heated to a temperature at which the liquid crystal used takes an isotropic phase, and then cooled to room temperature to remove the flow alignment during injection.
Then, a polarizing plate is bonded to both surfaces so that the polarization direction forms a predetermined angle with the alignment easy axis of the liquid crystal alignment film of the substrate, thereby obtaining a liquid crystal display element. When the liquid crystal alignment film is horizontally aligned, by adjusting the angle formed by the polarization direction of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate in the two substrates on which the liquid crystal alignment film is formed A liquid crystal display element having a TN type or STN type liquid crystal cell can be obtained. On the other hand, in the case where the liquid crystal alignment film is vertically aligned, the cell is configured so that the directions of easy alignment axes of the two substrates on which the liquid crystal alignment film is formed are parallel, By bonding the polarization directions so as to form an angle of 45 ° with the orientation easy axis, a liquid crystal display element having a VA type liquid crystal cell can be obtained.
As the sealing agent, for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. In the case of a TN liquid crystal cell or STN liquid crystal cell, a nematic liquid crystal having positive dielectric anisotropy is preferable. For example, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl A cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal, or the like is used. Further, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, cholesteryl carbonate; chiral agents such as those sold under the trade names C-15 and CB-15 (Merck); p-decyloxybenzylidene Ferroelectric liquid crystals such as -p-amino-2-methylbutylcinnamate can be further added and used.
On the other hand, in the case of a vertical alignment type liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy is preferable. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl type. A liquid crystal, a phenylcyclohexane type liquid crystal, or the like is used.
A polarizing plate used outside the liquid crystal cell is composed of a polarizing film called a “H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine while sandwiching it with a cellulose acetate protective film, or the H film itself. A polarizing plate etc. can be mentioned.
The liquid crystal display element of the present invention thus produced is excellent in various properties such as display characteristics and reliability.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
In the following examples, the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions.

Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²

The epoxy equivalent was measured according to the “hydrochloric acid-methyl ethyl ketone method” of JIS C2105.
The solution viscosity is a value measured at 25 ° C. using an E-type viscometer for the polymer solution indicated in each synthesis example.
<Synthesis of the compound represented by the above formula (1) or (2)>
Synthesis Example 1 (Synthesis of Compound (1-1-1))
Scheme 1 below

The compound (1-1-1) was synthesized according to
(Synthesis of Compound (1-1-1a))
A 1 L eggplant flask equipped with a reflux tube, a nitrogen introduction tube and a Dean-Stark tube was charged with 72 g of decylsuccinic anhydride, 49 g of 4-aminocinnamic acid, 70 mL of triethylamine, 500 mL of toluene and 200 mL of tetrahydrofuran, and reacted under reflux for 36 hours. Went. After completion of the reaction, the reaction mixture was washed successively with dilute hydrochloric acid and water, dried over magnesium sulfate, concentrated, and recrystallized with a mixed solvent of ethanol and tetrahydrofuran to give compound (1-1 72 g of white crystals of -1a) were obtained.
(Synthesis of Compound (1-1-1))
A 300 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube was charged with 39 g of compound (1-1-1a), 200 mL of thionyl chloride and 0.2 mL of N, N-dimethylformamide, and reacted at 80 ° C. for 1 hour. . After completion of the reaction, thionyl chloride was removed under reduced pressure, and 300 mL of methylene chloride was added to the residue. The resulting organic layer was washed with water three times and then dried over magnesium sulfate, and then methylene chloride was distilled off under reduced pressure. Further, 200 mL of tetrahydrofuran was added (this is referred to as reaction solution 1A).
On the other hand, 13 g of hydroxyethyl methacrylate, 10.1 g of triethylamine and 50 mL of tetrahydrofuran were charged into a 500 mL three-necked flask equipped with a dropping funnel, a thermometer and a nitrogen introduction tube, and cooled with ice. The above reaction solution 1A was added dropwise with a dropping funnel over 30 minutes, and returned to room temperature for further 2 hours of reaction. After completion of the reaction, 500 mL of ethyl acetate was added to the reaction mixture, washed with water three times, dried over magnesium sulfate, concentrated, and the solvent was removed to obtain 47 g of compound (1-1-1).
Synthesis Example 2 (Synthesis of Compound (1-4-1))
Scheme 2 below

The compound (1-4-1) was synthesized according to
(Synthesis of Compound (1-4-1a))
A 2 L eggplant flask equipped with a reflux tube was charged with 198 g of 1,2,4-cyclohexanetricarboxylic acid anhydride, 500 mL of thionyl chloride and 2 mL of N, N-dimethylformamide, and reacted at 80 ° C. for 1 hour under reflux. . After completion of the reaction, thionyl chloride was removed under reduced pressure, methylene chloride was added to the residue, and the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, then dried over magnesium sulfate, concentrated and dried. Thereafter, 500 mL of tetrahydrofuran was added.
On the other hand, 178 g of 4,4-5,5,5-pentafluoropentanol, 160 mL of pyridine and 1.5 L of tetrahydrofuran were charged into a 3 L three-necked flask equipped with a dropping funnel, a thermometer and a nitrogen introduction tube, and cooled in an ice bath. . A tetrahydrofuran solution containing a reaction product of 1,2,4-cyclohexanetricarboxylic acid anhydride and thionyl chloride was slowly added dropwise as described above, and the reaction was further stirred for 4 hours at room temperature. After completion of the reaction, extraction was performed with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, and purified with a silica column to obtain 268 g of compound (1-4-1a).

(Synthesis of Compound (1-4-1b))
A 200 mL eggplant flask equipped with a Dean-Stark tube was charged with 241 g of compound (4-5-1a), 109 g of 4-aminocinnamic acid, 190 mL of triethylamine, 16 g of 4-dimethylaminopyridine, 1 L of toluene and 2 L of tetrahydrofuran, and refluxed for 24 hours. The reaction was performed. After completion of the reaction, the reaction mixture was washed with dilute hydrochloric acid water and water. The organic layer was dried over magnesium sulfate and then recrystallized from methanol to obtain 78 g of compound (1-4-1b).
(Synthesis of Compound (1-4-1))
A 300 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube was charged with 50 g of compound (1-4-1b), 300 mL of thionyl chloride and 0.2 mL of N, N-dimethylformamide, and reacted at 80 ° C. for 1 hour. After completion of the reaction, thionyl chloride was removed under reduced pressure, 400 mL of methylene chloride was added to the residue, the organic layer obtained was washed three times with water and dried over magnesium sulfate, and then the methylene chloride was distilled off under reduced pressure. , Tetrahydrofuran (300 mL) was added (this is referred to as reaction solution 2A).
On the other hand, 13 g of hydroxyethyl methacrylate, 10.1 g of triethylamine and 50 mL of tetrahydrofuran were charged into a 500 mL three-necked flask equipped with a dropping funnel, a thermometer and a nitrogen introduction tube, and cooled with ice. The above reaction solution 2A was added dropwise over 30 minutes using a dropping funnel, and the reaction was continued for 2 hours after returning to room temperature. After completion of the reaction, 700 mL of ethyl acetate was added and the organic layer obtained was washed with water three times, dried over magnesium sulfate, concentrated, and the solvent was removed to obtain 60 g of compound (1-4-1). Obtained.
Synthesis Example 3 (Synthesis of Compound (1-5-1))
Scheme 3 below

The compound (1-5-1) was synthesized according to
(Synthesis of Compound (1-5-1a) 90 g of 5-hydroxyphthalic acid and 500 mL of diethylbenzene were charged into a 2 L three-necked flask equipped with a reflux tube, a Dean-Stark tube and a nitrogen introduction tube, and refluxed for 1 hour. Then, 80 g of 4-aminocinnamic acid and 500 mL of tetrahydrofuran were added thereto, and the reaction was carried out under reflux for 12 hours After completion of the reaction, the reaction mixture was washed successively with dilute hydrochloric acid and water, further dried over magnesium sulfate and concentrated. Then, 95g of compounds (1-5-1a) were obtained by recrystallizing with the mixed solvent of ethyl acetate and tetrahydrofuran.
(Synthesis of Compound (1-5-1b))
A 500 mL eggplant-shaped flask was charged with 75 g of compound (1-5-1a), 70 g of potassium carbonate, and 150 mL of N-methyl-2-pyrrolidone and stirred at room temperature for 1 hour, and then 4,4,4-1 -Iodobutane 59g was added and it stirred at room temperature for 24 hours. After completion of the reaction, 1 L of water was added to collect the precipitate. About this precipitation, after refine | purifying with a silica column using the mixed solvent which consists of ethyl acetate and hexane as an elution medium, 50g of compounds (1-5-1b) were obtained by removing a solvent.
(Synthesis of Compound (1-5-1))
A 300 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube was charged with 42 g of compound (1-5-1b), 200 mL of thionyl chloride and 0.2 mL of N, N-dimethylformamide, and reacted at 80 ° C. for 1 hour. . After completion of the reaction, thionyl chloride was removed under reduced pressure, and 300 mL of methylene chloride was added to the residue. The resulting organic layer was washed three times with water and dried over magnesium sulfate, and then methylene chloride was distilled off under reduced pressure. Then, 200 mL of tetrahydrofuran was added (this is referred to as reaction solution 3A).
On the other hand, 13 g of hydroxyethyl methacrylate, 10.1 g of triethylamine and 50 mL of tetrahydrofuran were charged into a 500 mL three-necked flask equipped with a dropping funnel, a thermometer and a nitrogen introduction tube, and cooled with ice. The above-mentioned reaction solution 3A was added dropwise over 30 minutes using a dropping funnel, and the reaction was continued for 2 hours after returning to room temperature. After completion of the reaction, 500 mL of ethyl acetate was added to the reaction mixture, washed with water three times, dried over magnesium sulfate, concentrated, and the solvent was removed to obtain 50 g of compound (1-5-1).
Synthesis Example 4 (Synthesis of Compound (2-1-1))
Scheme 4 below

The compound (2-1-1) was synthesized according to
(Synthesis of Compound (2-1-1a))
In a 300 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 9.7 g of 4-nitrocinnamic acid, 12 g of 4,4,4-trifluoro-1-iodobutane, 14 g of potassium carbonate and 150 mL of 1-methyl-2-pyrrolidone And stirred for 1 hour at 50 ° C. to carry out the reaction. After completion of the reaction, the reaction mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, concentrated, and the solvent was removed to obtain 14 g of compound (2-1-1a).
(Synthesis of Compound (2-1-1b))
A 300 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube was charged with 14 g of compound (2-1-1a), 53 g of tin chloride dihydrate, and 150 mL of ethanol, and the reaction was performed by stirring at 70 ° C. for 1 hour. . After completion of the reaction, the reaction mixture was poured into ice water, neutralized with 2M aqueous sodium hydroxide solution, and ethyl acetate was added to remove the precipitate. Ethyl acetate was added to the filtrate for extraction to obtain an organic layer. This organic layer was washed with water, dried over magnesium sulfate, concentrated, and the solvent was removed to obtain 12 g of compound (2-1-1b).
(Synthesis of Compound (2-1-1c))
A 200 mL eggplant flask equipped with a reflux tube and a nitrogen introduction tube was charged with 12 g of compound (2-1-1b), 8.7 g of 1,2,4-cyclohexanetricarboxylic acid anhydride and 100 mL of acetic acid, and refluxed for 1 hour. Reaction was performed. After completion of the reaction, the reaction mixture was extracted with ethyl acetate to obtain an organic layer. The organic layer was washed with water, dried over magnesium sulfate, concentrated to remove the solvent, and recrystallized with a mixed solvent consisting of ethyl acetate and hexane to give white crystals of compound (2-1-1c). 11 g was obtained.
(Synthesis of Compound (2-1-1))
A 100 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube was charged with 9 g of compound (2-1-1c), 50 mL of thionyl chloride and 0.05 mL of N, N-dimethylformamide, and reacted at 80 ° C. for 1 hour. . After completion of the reaction, thionyl chloride was removed under reduced pressure, and 100 mL of methylene chloride was added to the residue. The resulting organic layer was washed three times with water and dried over magnesium sulfate, and then the methylene chloride was distilled off under reduced pressure. Then, 50 mL of tetrahydrofuran was added (this is referred to as reaction solution 4A).
Meanwhile, 2.6 g of hydroxyethyl methacrylate, 2.0 g of triethylamine and 20 mL of tetrahydrofuran were added to a 200 mL three-necked flask equipped with a dropping funnel, a thermometer and a nitrogen introduction tube, and the mixture was ice-cooled. 4 A of said reaction liquid was dripped here over 30 minutes or more with the dropping funnel, and it returned to room temperature, and also reacted for 2 hours. After completion of the reaction, 100 mL of ethyl acetate was added to the reaction mixture, and the organic layer obtained was washed three times with water, dried over magnesium sulfate, concentrated, and the solvent was removed to remove the compound (2-1-1). ) Was obtained.

<Synthesis of Copolymer of Compound Represented by Formula (1) or (2)>
Example 1
In a 100 mL three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 14 g of compound (1-1-1), 6 g of glycidyl methacrylate, 1.2 g of azobisisobutyronitrile, 1.2 g of styrene dimer and propylene glycol After charging 40 g of monomethyl ether acetate and sufficiently substituting the inside of the system with nitrogen, the reaction was carried out at 95 ° C. for 4 hours to obtain a solution containing 34% by weight of the copolymer (CPA-1). The weight average molecular weight Mw of the copolymer (CPA-1) was 5,000, and the epoxy equivalent was 170.
Examples 2-5
Except having used the unsaturated compound of the kind and quantity shown in Table 1, it implemented similarly to Example 1 and obtained the solution which respectively contains copolymer CPA-2-CPA-5. The weight average molecular weight Mw of these copolymers is shown in Table 1.
In addition, the abbreviation “GMA” of other unsaturated compounds in Table 1 means glycidyl methacrylate.

<Synthesis of other polymers>
[Synthesis of polyamic acid]
Synthesis example 5
196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212 g (1, .2) of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine. 0 mol) was dissolved in 3,670 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours to obtain about 4,000 g of a solution containing polyamic acid (PAA-1). The solution viscosity of this solution was 160 mPa · s.
[Synthesis of polyimide]
Synthesis Example 6
20.9 g (0.093 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 9.2 g (0.085 mol) of p-phenylenediamine as diamine and the above formula (D -6) The compound represented by 4.9 g (0.009 mol) was dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 4 hours to obtain a solution containing polyamic acid. . A small amount of the obtained polyamic acid solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 126 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 7.4 g of pyridine and 9.5 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone (pyridine substitution and acetic anhydride used for the dehydration cyclization reaction were removed from the system by this solvent substitution, the same applies hereinafter). As a result, about 200 g of a solution containing 16.1% by weight of an imidized polymer (PI-1) having an imidization ratio of about 54% was obtained.
A small amount of this solution was collected, N-methyl-2-pyrrolidone was added to make a solution with an imidized polymer concentration of 10% by weight, and the solution viscosity was 75 mPa · s.

Synthesis example 7
2,3,5-tricarboxycyclopentylacetic acid dianhydride 17.3 g (0.077 mol) as tetracarboxylic dianhydride and 5.9 g (0.054 mol) of p-phenylenediamine as diamine, the above formula (D −6) 4.1 g (0.008 mol) of the compound represented by formula (D-7) and 7.7 g (0.016 mol) of the compound represented by the above formula (D-7) are dissolved in 140 g of N-methyl-2-pyrrolidone. And the solution containing polyamic acid was obtained by reacting at 60 degreeC for 4 hours. A small amount of the obtained polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 117 mPa · s.
Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 6.1 g of pyridine and 7.9 g of acetic anhydride were added, and dehydration ring closure was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system is replaced with new N-methyl-2-pyrrolidone to contain 15.4% by weight of an imidized polymer (PI-2) having an imidization ratio of about 55%. About 210 g of solution was obtained. A small amount of this solution was collected, N-methyl-2-pyrrolidone was added to make a solution with an imidized polymer concentration of 10% by weight, and the solution viscosity was 109 mPa · s.

[Synthesis of polysiloxane]
Synthesis Example 8
A 200 mL three-necked flask equipped with a condenser was charged with 20.8 g of tetraethoxysilane and 28.2 g of 1-ethoxy-2-propanol, heated to 60 ° C. and stirred. A maleic anhydride aqueous solution prepared by dissolving 0.26 g of maleic anhydride in 10.8 g of water prepared in another flask having a capacity of 20 mL was added thereto, and the reaction was performed by heating and stirring at 60 ° C. for further 4 hours. The solvent was distilled off from the resulting reaction mixture, 1-ethoxy-2-propanol was added, and the mixture was concentrated again to obtain a polymer solution containing 10% by weight of polysiloxane PS-1. The weight average molecular weight Mw of PS-1 was 5,100.

<Preparation of liquid crystal aligning agent>
Example 6
A polymer containing the solution containing the copolymer (CPA-1) obtained in Example 1 and the solution containing the polyamic acid (PAA-1) obtained in Synthesis Example 5 in these solutions. So that the ratio of (CPA-1) :( PAA-1) = 100: 1,000 (weight ratio) is added, 1-methyl-2-pyrrolidone and butyl cellosolve are added thereto, and the solvent composition is 1- Methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (weight ratio) and a solid content concentration of 3.0% by weight was used.
Liquid crystal aligning agent A-1 was prepared by filtering this solution with a filter having a pore diameter of 1 μm.
Examples 7-14
Liquid crystal aligning agents A-2 to A-9 were respectively prepared in the same manner as in Example 6 except that the types and amounts of the polymers contained in the used solution were as shown in Table 2.
Example 15
A polymer containing the solution containing the copolymer (CPA-2) obtained in Example 2 and the solution containing the polysiloxane (PS-1) obtained in Synthesis Example 8 in these solutions. Is mixed so that the ratio of (CPA-2) :( PS-1) = 100: 1,000 (weight ratio), 1-ethoxy-2-propanol is added thereto, and the solid content concentration is 3.0. A weight percent solution was obtained.
Liquid crystal aligning agent A-10 was prepared by filtering this solution with a filter having a pore diameter of 1 μm.

Example 16
<Formation of liquid crystal alignment film and production of VA type liquid crystal display element>
On the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film, the liquid crystal aligning agent A-1 prepared in Example 6 was applied using a spinner, prebaked for 1 minute on a hot plate at 80 ° C., and then stored. The coating was heated at 200 ° C. for 1 hour in an oven purged with nitrogen to form a coating film having a thickness of 0.1 μm. Next, the surface of the coating film was irradiated with polarized ultraviolet rays of 1,000 J / m ² containing a 313 nm emission line from a direction inclined by 40 ° from the normal to the liquid crystal alignment film using a Hg-Xe lamp and a Grand Taylor prism. did. The same operation was repeated to manufacture a pair (two) of substrates having a liquid crystal alignment film.
An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface of the substrate having the liquid crystal alignment film by screen printing, and the liquid crystal alignment film surfaces of the pair of substrates are made to face each other. The adhesive was pressure-bonded so that the projection direction of the optical axis of the ultraviolet ray of each substrate onto the substrate surface was antiparallel, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, a 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 150 ° C. and then gradually cooled to room temperature. Next, the polarizing plates are bonded to both the outer surfaces of the substrate so that the polarization directions thereof are orthogonal to each other and form an angle of 45 ° with the projection direction of the optical axis of the liquid crystal alignment film onto the substrate surface. A VA liquid crystal display element was manufactured.
This liquid crystal display element was evaluated by the following method. The evaluation results are shown in Table 3.

<Evaluation method of VA type liquid crystal display element>
(1) Evaluation of liquid crystal orientation For the liquid crystal display device manufactured above, the presence or absence of abnormal domains in the change in brightness when a voltage of 5 V is turned ON / OFF (applied / released) is observed with a polarizing microscope. The case where there was no “good”
(2) Evaluation of pretilt angle The liquid crystal display device manufactured above is subjected to the method described in Non-Patent Document 2 (T. J. Scheffer et. Al. J. Appl. Phys. Vo. 19, p2013 (1980)). In conformity, the pretilt angle was measured by a crystal rotation method using He—Ne laser light.
(3) Evaluation of voltage holding ratio After the voltage of 5 V was applied to the liquid crystal display element manufactured above with a 60 microsecond application time and a 167 millisecond span, the voltage holding ratio after 167 milliseconds from the application release was obtained. It was measured. The measuring apparatus used was VHR-1 manufactured by Toyo Corporation.
(4) Evaluation of burn-in The liquid crystal display element manufactured above was applied with a 30 Hz, 3 V rectangular wave on which 5 V DC was superimposed at an ambient temperature of 60 ° C. for 2 hours, and remained in the liquid crystal cell immediately after the DC voltage was turned off. The residual DC voltage was determined by the flicker-erasing method.
(5) Evaluation of heat resistance A liquid crystal alignment film was formed on the substrate in the same manner as in Example 16 except that the heating temperature in the oven at the time of forming the coating film was changed to 240 ° C to produce a liquid crystal display element.
About the obtained liquid crystal display element, liquid crystal orientation was investigated. That is, the liquid crystal orientation was “good” when the black display was uniform, and the liquid crystal orientation was “bad” when light leakage was observed.

Examples 17-23
A liquid crystal alignment film was formed in the same manner as in Example 16 except that the type of the liquid crystal alignment agent used was as described in Table 3, and a liquid crystal display element was produced and evaluated. The results are shown in Table 3.
Example 24
<Formation of liquid crystal alignment film and manufacture of TN alignment type liquid crystal display element>
The liquid crystal aligning agent A-7 prepared in Example 12 was applied onto the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a spinner, prebaked for 1 minute on a hot plate at 80 ° C., and then 180 A coating film having a thickness of 0.1 μm was formed by heating at 0 ° C. for 1 hour. By using a Hg-Xe lamp and a Grand Taylor prism, the surface of this coating film was irradiated with polarized ultraviolet rays of 1,000 J / m ² containing a 313 nm emission line from a direction inclined by 40 ° from the substrate normal, thereby aligning the liquid crystal. A liquid crystal alignment film was formed by imparting performance.
The same operation as above was repeated to produce a pair (two) of glass substrates having a liquid crystal alignment film on the transparent conductive film surface.
An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied by screen printing to the periphery of each surface of the pair of substrates on which the liquid crystal alignment film is formed, and then the irradiation direction of polarized ultraviolet rays becomes orthogonal. The substrates were stacked and pressure-bonded as described above, and heated at 150 ° C. for 1 hour to thermally cure the adhesive. Next, a positive nematic liquid crystal (Merck, MLC-6221, containing a chiral agent) was injected and filled into the gap between the substrates through 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 150 ° C. for 10 minutes and then gradually cooled to room temperature. Next, a TN alignment type liquid crystal display element was manufactured by bonding the polarizing plates on both outer surfaces of the substrate so that the polarization directions thereof were orthogonal to each other and parallel to the polarization direction of the liquid crystal alignment film.
The liquid crystal orientation, voltage holding ratio, and image sticking of this liquid crystal display element were evaluated in the same manner as in Example 16. However, for the liquid crystal alignment in (5) heat resistance evaluation, the liquid crystal alignment “good” was defined as the case where the white display was uniformly performed. The evaluation results are shown in Table 3.
Example 25
A liquid crystal alignment film was formed in the same manner as in Example 24 except that the type of liquid crystal alignment agent used was as described in Table 3, and a liquid crystal display element was produced and evaluated. The results are shown in Table 3.

Claims (7)

The following formula (1) or (2)

(In the formula (1), ^{R 1} represents a hydrogen atom, a monovalent organic group having 3 to 40 carbon atoms containing an alkyl or fluoroalkyl group or a alicyclic structure having a carbon number of 1 to 40, ^{R 2} is a single bond R ³ is a hydrogen atom, or R ² and R ³ are bonded to form a ring having 4 to 8 carbon atoms, and A ¹ is a single bond, an oxygen atom, a sulfur atom or ^* − COO—, * —OCO— (wherein the bond marked with “*” is bonded to R ¹ ), R ⁴ is a fluorine atom or a cyano group, and S ¹ is a methylene group or a carbon number of 2 to 10 P ¹ is a hydrogen atom or a methyl group, a is 0 or 1, b is an integer of 0 to 4,
In Formula (2), R ⁵ is a single bond and R ⁶ is a hydrogen atom, or R ⁵ and R ⁶ are bonded to form a ring having 4 to 8 carbon atoms, and R ⁷ is An alkyl group or fluoroalkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic structure, R ⁸ is a fluorine atom or a cyano group, A ² is a single bond, oxygen An atom, a sulfur atom, or —COO— ^* , —OCO— * (where a bond marked with “*” is bonded to R ⁵ ), and S ² is a methylene group or an alkylene group having 2 to 10 carbon atoms. There, ^{P 2} is a hydrogen atom or a methyl group, c is 0 or 1, d is an integer of 0-4. )
The liquid crystal aligning agent characterized by including the (co) polymer of the compound represented by these.   The liquid crystal aligning agent according to claim 1, further comprising at least one polymer selected from the group consisting of polyamic acid and polyimide.   Furthermore, the liquid crystal aligning agent of Claim 1 containing polysiloxane.   A method for forming a liquid crystal alignment film, comprising: applying a liquid crystal aligning agent according to any one of claims 1 to 3 on a substrate to form a coating film; and irradiating the coating film with radiation. .   A liquid crystal display element comprising a liquid crystal alignment film formed from the liquid crystal aligning agent according to claim 1.   (Co) polymer of the compound represented by the above formula (1) or (2).   A compound represented by the above formula (1) or (2).