TWI512014B - Liquid crystal alignment agent and liquid crystal display device - Google Patents

Description

Liquid crystal alignment agent and liquid crystal display element

The present invention relates to a liquid crystal alignment agent and a liquid crystal display element.

At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (Twisted Nematic) liquid crystal cell is known, and a liquid crystal composed of an organic resin or the like is formed on a surface of a substrate on which a transparent conductive film is provided. The alignment film is used as a substrate for a liquid crystal display element, and the two layers are arranged to face each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a cell of a sandwich structure, and the long axis of the liquid crystal molecule is One substrate is continuously twisted by 90° toward the other substrate. In addition, an STN (Super Twisted Nematic) liquid crystal display element having a higher contrast ratio than a TN liquid crystal display element or an IPS (In-Plane Switching) type liquid crystal having a small viewing angle dependency has been developed. A display element, a VA (Vertical Alignment) type liquid crystal display element using nematic liquid crystal having negative dielectric anisotropy, and the like (Patent Documents 1 to 5).

The operating principles of these various liquid crystal display elements are roughly classified into a transmissive type and a reflective type. The transmissive liquid crystal display element is displayed by a change in the transmitted light intensity of the backlight source from the back surface of the element during operation of the element. The reflective liquid crystal display element does not use a light source for backlighting, and displays a change in intensity of reflected light from external light such as sunlight when the element is driven, and is considered to be particularly advantageous in outdoor use because of a small power consumption compared with a transmissive type. use.

For a transmissive liquid crystal display element, a liquid crystal alignment film having therein is exposed to light from a backlight source for a long time. In particular, in addition to commercial use, in recent years, as a liquid crystal projector having an increased demand for a home theater, a light source having a very high irradiation intensity such as a metal halide lamp is used. Further, it is considered that the temperature of the entire liquid crystal display element rises during operation with light having a strong irradiation intensity.

The reflective liquid crystal display element is highly likely to be used outdoors, in which case sunlight containing strong ultraviolet light is used as a light source. In addition, the reflective liquid crystal display element has a longer distance in the element than the transmissive type.

Further, for example, there is a tendency to spread a transmissive liquid crystal display element or a reflective liquid crystal display element in a home automobile, and as a method of using a liquid crystal display element, a practical problem is use and setting at a high temperature as compared with the currently studied method. surroundings.

However, in the manufacturing step of the liquid crystal display element, the method of starting the use from the viewpoint of shortening the process and improving the efficiency is a liquid crystal dropping method, that is, an ODF (One Drop Fill) method. The ODF method differs from the conventional method in which a thermosetting sealant is used in advance to inject liquid crystal into the assembled empty liquid crystal cell, and is necessary after applying an ultraviolet curable sealant at a necessary position of a substrate on which one side of the liquid crystal alignment film is applied. The liquid crystal is dropped at a position, and after bonding another substrate, the entire surface is irradiated with ultraviolet light to harden the sealing agent to produce a liquid crystal cell. The ultraviolet light that is irradiated at this time is usually strong to several joules per square centimeter. That is, in the liquid crystal display element manufacturing step, the liquid crystal alignment film and the liquid crystal are exposed together under the strong ultraviolet light.

As described above, in the liquid crystal display device, it is required to be exposed to high-intensity light irradiation, high-temperature environments, long-time operation, and the like, which have not been considered for a long time, as it is multi-functionalized, versatile, and improved in manufacturing processes. In this environment, the electrical properties or display properties such as liquid crystal alignment and voltage retention are superior to those of the prior art, and the liquid crystal display device is required to have a longer life.

As a material of the liquid crystal alignment film constituting the liquid crystal display element, organic resins such as polyimine, polylysine, polyamine, and polyester have been known so far. In particular, polyimine is excellent in physical properties such as heat resistance, liquid crystal affinity, and mechanical strength, and is used in many liquid crystal display devices (Patent Documents 6 to 8).

However, in recent liquid crystal display elements, new demands have been made due to the excessively harsh manufacturing environment and use environment described above, and the heat resistance and light resistance of the currently allowable organic resins are insufficient.

Therefore, research has been conducted on a liquid crystal alignment film which is excellent in heat resistance and light resistance. For example, Patent Document 9 discloses a vertical alignment type liquid crystal alignment film formed of a polyorganosiloxane solution obtained from a ruthenium compound having four alkoxy groups and a ruthenium compound having three alkoxy groups, and is described as a liquid crystal. The alignment film is excellent in vertical alignment property, heat resistance and uniformity, and is also excellent in stability as a coating liquid. However, the liquid crystal alignment film formed by this technique cannot satisfy the performance required in the current manufacturing environment and the use environment, and the storage stability of the coating liquid is also insufficient, so the convenience in industrial use is also improved. something wrong.

Further, as a liquid crystal display element, there is no problem of image sticking, that is, development requirements of a liquid crystal alignment agent excellent in electrical properties are still strong.

On the other hand, if the liquid crystal alignment film is formed by the rubbing treatment, dust or static electricity is likely to be generated in the step, so that dust is attached to the surface of the alignment film, which causes a problem of poor display, and thus it is known that there is a problem. A photosensitive film such as a polyvinyl cinnamate, a polyimide, or an azobenzene derivative formed on the surface of the substrate is irradiated with polarized or non-polarized radiation to impart a liquid alignment function to the liquid crystal alignment method (Patent Documents 10 to 12). According to these methods, uniform liquid crystal alignment can be achieved without generating static electricity or dust. However, it is also pointed out that the liquid crystal alignment film formed by these techniques exhibits a phenomenon in which the pretilt angle appears to be missing with time even if a good pretilt angle is exhibited at the initial stage, and the pretilt angle lacks stability with time. .

As described above, it is not known that a liquid crystal alignment film having sufficient heat resistance and light resistance can be imparted in an extremely harsh current manufacturing environment and use environment, and the storage stability is excellent, and when a liquid crystal display element is formed, the display is performed. A liquid crystal alignment agent excellent in electrical properties. Further, when formed by the photo-alignment method, a liquid crystal alignment agent which exhibits a sufficient pretilt angle stability over time is not known.

In order to solve these problems, the inventors of the present invention have introduced a structure having a liquid crystal alignment ability by using a polyorganosiloxane having an epoxy group in recent years, and obtained a liquid crystal-containing polyorganosiloxane. The liquid crystal alignment agent is reported (Patent Documents 13 to 16).

However, it has been found that the above-mentioned use environment is becoming more and more severe, and it is required to further improve the heat resistance of the liquid crystal alignment film in particular.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 4-156622

[Patent Document 2] Japanese Patent Laid-Open Publication No. SHO 60-107020

[Patent Document 3] Japanese Patent Laid-Open No. 56-91277

[Patent Document 4] US Patent No. 5,928,733

[Patent Document 5] Japanese Patent Laid-Open No. Hei 11-258605

[Patent Document 6] Japanese Patent Laid-Open No. Hei 9-197411

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2003-149648

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2003-107486

[Patent Document 9] Japanese Patent Laid-Open No. Hei 9-281502

[Patent Document 10] Japanese Patent Laid-Open No. Hei 6-287453

[Patent Document 11] Japanese Patent Laid-Open Publication No. 2003-307736

[Patent Document 12] Japanese Patent Laid-Open Publication No. 2004-163646

[Patent Document 13] Japanese Patent Application No. 2008-19346

[Patent Document 14] WO No. 2009/25385

[Patent Document 15] WO No. 2009/25386

[Patent Document 16] WO No. 2009/25388

[Patent Document 17] JP-A-63-291922

[Patent Document 18] Japanese Patent Laid-Open No. Hei 6-222366

[Patent Document 19] Japanese Patent Laid-Open No. Hei 6-281937

[Patent Document 20] Japanese Patent Laid-Open No. Hei 5-170044

[Non-patent literature]

[Non-Patent Document 1] "Science of Sol-Gel Method", Agne Chengfeng (share), 1988, pp. 155-161

[Non-Patent Document 2] T. J. Scheffer et. al., J. Appl. Phys. vol. 48, p. 1783 (1977)

[Non-Patent Document 3] F. Nakano, et. al., JPN. J. Appl. Phys. vol. 19, p. 2013 (1980)

The present invention has been made in view of the above problems, and an object thereof is to provide a liquid crystal alignment agent which can form an excellent liquid crystal alignment property and has high light resistance, in particular, even a high intensity light irradiation, a decrease in voltage holding ratio A liquid crystal alignment film having few electrical properties and excellent storage stability.

Another object of the present invention is to provide a liquid crystal display element which is excellent in light resistance and electrical properties. When a liquid crystal alignment film is formed by a photoalignment method, display performance does not deteriorate even if it is continuously operated for a long period of time. The stability of the inclination angle with time is excellent.

Other objects and advantages of the invention are indicated by the following description.

According to the present invention, the above objects and advantages of the present invention, first achieved by a liquid crystal alignment agent, comprising a polyorganosiloxane having an acetal structure of a carboxylic acid At least one structure selected from the group consisting of a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a tertiary alkyl ester structure of a carboxylic acid.

The above objects and advantages of the present invention are at least achieved by a liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent.

The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film which is excellent in liquid crystal alignment property and has high light resistance, and particularly has a small decrease in voltage holding ratio even in high-intensity light irradiation, and is excellent in electrical properties, and the liquid crystal alignment agent is preserved. Good stability.

The liquid crystal display element of the present invention having the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is excellent in light resistance and electrical properties, and the pretilt angle is stable with time even in the case where the liquid crystal alignment film is formed by photoalignment. Excellent also.

[Formation for implementing the invention]

The liquid crystal alignment agent of the present invention contains at least a polyorganosiloxane as described above.

(A) polyorganosiloxane compound

The polyorganosiloxane compound of the present invention has an acetal structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a tertiary alkyl ester structure of a carboxylic acid. At least one structure selected from the group consisting of.

The polyorganosiloxane can be obtained by (a) a polyorganosiloxane having an epoxy group (hereinafter referred to as "polyorganosiloxane having an epoxy group") and the following compound (hereinafter referred to as "Compound b") is preferably obtained by reacting in the presence of a catalyst in the presence of an organic solvent, which has a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or At least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, -CH=CH ₂ and -SO ₂ Cl, and a acetal ester structure of a carboxylic acid, a ketal ester of a carboxylic acid At least one structure selected from the group consisting of a structure, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a tertiary alkyl ester structure of a carboxylic acid.

The above (A) polyorganosiloxane is preferably an epoxy structure. The epoxy equivalent of the above (A) polyorganosiloxane is preferably from 100 to 10,000 g/mol, more preferably from 150 to 1,000 g/mol.

<(a) Polyorganosiloxane having an epoxy group>

(a) The polyorganosiloxane having an epoxy group is a acetal structure in which a carboxylic acid is introduced, a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a tertiary alkyl salt of a carboxylic acid. The compound before the ester structure is not particularly limited as long as it introduces an epoxy group as a side chain on the polyorganosiloxane. The polyorganosiloxane having the epoxy group is preferably a group of a polyorganosiloxane having a structural unit represented by the following formula (1), a hydrolyzate thereof, and a condensate of the hydrolyzate thereof. At least one of the selected ones.

(In the formula (1), X ¹ is a monovalent organic group having an epoxy group. Y ¹ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms or carbon An aryl group with an atomic number of 6 to 20.)

Further, the hydrolysis condensate of the polyorganosiloxane having the structural unit represented by the above formula (1) is not only a hydrolysis condensate between the polyorganosiloxanes, but also included in the above formula (1). Hydrolysis condensation of the case where the polyorganooxane obtained by branching or crosslinking of the main chain has a structural unit represented by the above formula (1) in the process of producing a polyorganosiloxane by the hydrolysis condensate of the structural unit The concept of things.

X ¹ in the above formula (1) is not particularly limited as long as it is a monovalent organic group having an epoxy group, and examples thereof include a glycidyl group, a glycidoxy group, and an epoxycyclohexyl group. . X ^{1 is} preferably represented by the following formula (X ¹ -1) or (X ¹ -2).

(In the formula (X ¹ -1), A is an oxygen atom or a single bond. h is an integer of 1 to 3. i is an integer of 0 to 6. Here, when i is 0, A is a single bond.

In the formula (X ¹ -2), j is an integer of 1 to 6.

In the formulas (X ¹ -1) and (X ¹ -2), "*" indicates a connection key. )

Further, among the epoxy groups represented by the above formula (X ¹ -1) or (X ¹ -2), it is preferably a formula (X ¹ -1-1) or a formula (X ¹ -2-1) The group shown.

In the formula (X ¹ -1-1) or the formula (X ¹ -2-1), "*" indicates a connection key. )

In the Y ¹ in the above formula (1), the alkoxy group having 1 to 10 carbon atoms may, for example, be a methoxy group or an ethoxy group; and the alkyl group having 1 to 20 carbon atoms may be used. For example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-dodecyl, n-tridecane Base, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, etc.; as the number of carbon atoms Examples of the aryl group of 6 to 20 include a phenyl group and the like.

The polyorganosiloxane having an epoxy group has a polystyrene-equivalent weight average molecular weight (Mw) as measured by gel permeation chromatography (GPC) of preferably 500 to 100,000, more preferably 1,000 to 10,000, particularly preferably 1,000 to 5,000.

Further, Mw in the present specification is a value in terms of polystyrene measured by GPC in the following manner.

Column: manufactured by Tosoh Corporation, TSKgelGRCXLII

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 6.8MPa

The polyorganosiloxane having an epoxy group is preferably a mixture of a decane compound having an epoxy group or a decane compound having an epoxy group and another decane compound, preferably in a suitable organic solvent, water and In the presence of a catalyst, it is synthesized by hydrolysis or hydrolysis or condensation.

Examples of the above decane compound having an epoxy group include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycidoxypropyl group. Dimethoxy decane, 3-glycidoxy propyl methyl diethoxy decane, 3-glycidoxy propyl dimethyl methoxy decane, 3-glycidoxy propyl dimethyl Ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, and the like.

Examples of the other decane compound include tetrachlorodecane, tetramethoxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane, tetra-n-butoxydecane, and tetrad. Dibutoxy decane, trichlorodecane, trimethoxy decane, triethoxy decane, tri-n-propoxy decane, triisopropoxy decane, tri-n-butoxy decane, tri-second butoxy decane, Fluorine trichlorodecane, fluorotrimethoxydecane, fluorotriethoxydecane, fluorotri-n-propoxy decane, fluorotriisopropoxy decane, fluorotri-n-butoxy decane, fluorine Generation 3 second butoxy decane, methyl trichloro decane, methyl trimethoxy decane, methyl triethoxy decane, methyl tri-n-propoxy decane, methyl triisopropoxy decane, Tri-n-butoxy decane, methyl tri-tert-butoxy decane, 2-(trifluoromethyl)ethyl trichlorodecane, 2-(trifluoromethyl)ethyltrimethoxy decane, 2-(Trifluoromethyl)ethyltriethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltriisopropoxide base Alkane, 2-(trifluoromethyl)ethyltri-n-butoxydecane, 2-(trifluoromethyl)ethyltri-n-butoxydecane, 2-(perfluoro-n-hexyl)ethyl Trichlorodecane, 2-(perfluoro-n-hexyl)ethyltrimethoxydecane, 2-(perfluoro-n-hexyl)ethyltriethoxydecane, 2-(perfluoro-n-hexyl)ethyltri N-propoxy decane, 2-(perfluoro-n-hexyl)ethyltriisopropoxy decane, 2-(perfluoro-n-hexyl)ethyltri-n-butoxy decane, 2-(perfluoro-n-hexyl) Ethyl tri-tert-butoxydecane, 2-(perfluoro-n-octyl)ethyltrichlorodecane, 2-(perfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro Alkyn-octyl)ethyltriethoxydecane, 2-(perfluoro-n-octyl)ethyltri-n-propoxydecane, 2-(perfluoro-n-octyl)ethyltriisopropoxydecane , 2-(perfluoro-n-octyl)ethyltri-n-butoxydecane, 2-(perfluoro-n-octyl)ethyltri-t-butoxydecane, hydroxymethyltrichlorodecane, hydroxymethyl Trimethoxy decane, hydroxyethyl trimethoxy decane, hydroxymethyl tri-n-propoxy decane, hydroxymethyl triisopropoxy decane, hydroxymethyl n-Butoxydecane, hydroxymethyl tri-tert-butoxydecane, 3-(meth)acryloxypropyltrichlorodecane, 3-(methyl)propenyloxypropyltrimethoxydecane , 3-(methyl)propenyloxypropyltriethoxydecane, 3-(methyl)propenyloxypropyltri-n-propoxyoxydecane, 3-(methyl)propenyloxypropyl Triisopropoxy decane, 3-(methyl) propylene methoxypropyl tri-n-butoxy decane, 3-(methyl) propylene oxypropyl tri-tert-butoxy decane, 3-mercaptopropyl propyl Trichlorodecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxyoxydecane, 3-mercaptopropyltriisopropoxydecane , 3-mercaptopropyltri-n-butoxydecane, 3-mercaptopropyltri-tert-butoxybutane, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, vinyltrichlorodecane, Vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane, vinyl tri-n-butoxy decane, vinyl tri-n-butoxy Decane, allyl trichloro Decane, allyltrimethoxydecane, allyltriethoxydecane, allyltri-n-propoxydecane, allyltriisopropoxydecane, allyltri-n-butoxydecane, alkene Propyl tri-tert-butoxydecane, phenyltrichlorodecane, phenyltrimethoxydecane, phenyltriethoxydecane, phenyltri-n-propoxydecane, phenyltriisopropoxydecane, Phenyl tri-n-butoxy decane, phenyl tri-tert-butoxy decane, methyl dichloro decane, methyl dimethoxy decane, methyl diethoxy decane, methyl di-n-propoxy decane , methyl diisopropoxy decane, methyl di-n-butoxy decane, methyl di-butoxy decane, dimethyl dichloro decane, dimethyl dimethoxy decane, dimethyl di Ethoxy decane, dimethyl di-n-propoxy decane, dimethyl diisopropoxy decane, dimethyl di-n-butoxy decane, dimethyl di-butoxy decane, (methyl) [2-(Perfluoro-n-octyl)ethyl]dichlorodecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dimethoxydecane, (methyl)[2- (perfluoro-n-octyl)ethyl]diethoxydecane (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-propoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]diisopropoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-butoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-butoxybutane , (methyl)(3-mercaptopropyl)dichlorodecane, (methyl)(3-mercaptopropyl)dimethoxydecane, (methyl)(3-mercaptopropyl)diethoxydecane , (methyl) (3-mercaptopropyl) di-n-propoxy decane, (methyl) (3-mercaptopropyl) diisopropoxy decane, (methyl) (3-mercaptopropyl) di-positive Butoxy decane, (methyl) (3-mercaptopropyl) di-butoxy decane, (methyl) (vinyl) dichloro decane, (methyl) (vinyl) dimethoxy decane , (methyl) (vinyl) diethoxy decane, (methyl) (vinyl) di-n-propoxy decane, (methyl) (vinyl) diisopropoxy decane, (methyl) ( Vinyl)di-n-butoxydecane, (methyl)(vinyl)di-butoxybutane,divinyldichlorodecane,divinyldimethoxydecane,divinyldiethoxy Decane, divinyldi-n-propoxy fluorene , divinyl diisopropoxy decane, divinyl di-n-butoxy decane, divinyl bis second butoxy decane, diphenyl dichloro decane, diphenyl dimethoxy decane, two Phenyldiethoxydecane, diphenyldi-n-propoxydecane, diphenyldiisopropoxydecane, diphenyldi-n-butoxydecane, diphenyldi-butoxybutane, chlorine Dimethyl decane, methoxy dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, trimethyl decane iodide, methoxy trimethyl decane , ethoxy trimethyl decane, n-propoxy trimethyl decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, second butoxy trimethyl decane, third butoxide Trimethyl decane, (chloro) (vinyl) dimethyl decane, (methoxy) (vinyl) dimethyl decane, (ethoxy) (vinyl) dimethyl decane, (chlorinated) a decane compound having one ruthenium atom such as (methyl)diphenyl decane, (methoxy) (methyl) diphenyl decane or (ethoxy) (methyl) diphenyl decane.

Expressed by the trade name, for example,

KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22-176B, X- 22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40- 9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, Shin-Etsu Chemical Co., Ltd.); Glass Resin (Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Toray ‧Dow Corning); FZ3711, FZ3722 (above, UNICAR, Japan); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS -S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332 PDS-1615, PDS-9931, XMS-5025 (above, chisso); Methyl silicate MS51, Methyl silicate MS56 (above, Mitsubishi Chemical Corporation); Ethyl silicate 28, Ethyl silicate 40, Ethyl silicate 48 (above, COLCOAT); GR100, Partial condensate such as GR650, GR908, GR950 (above, Showa Denko).

Among these other decane compounds, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, and methyl triethoxy oxy group are preferable from the viewpoint of the alignment property and storage stability of the obtained liquid crystal alignment film. Baseline, 3-(meth)acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxy Base decane, allyl trimethoxy decane, allyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, 3-mercaptopropyl trimethoxy decane, 3-mercaptopropyl Triethoxydecane, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, dimethyldimethoxydecane or dimethyldiethoxydecane.

The polyorganosiloxane having an epoxy group used in the present invention is produced by introducing a sufficient amount of the compound (b) and a photo-alignment side chain which is required as needed, and in order to suppress an excessive introduction amount of the epoxy group. The undesired side reaction or the like is preferably from 100 g/mol to 10,000 g/mol, more preferably from 150 g/mol to 1,000 g/mol, as the epoxy equivalent. Therefore, when synthesizing a polyorganosiloxane having an epoxy group, it is preferred to set a use ratio of a decane compound having an epoxy group and other decane compounds to prepare an epoxy equivalent of the obtained polyorganosiloxane. The way the scope is.

Specifically, the total amount of such other decane compound is preferably from 0% by mass to 50% by mass, more preferably from 5% by mass to 30% by mass, based on the total amount of the decane compound having an epoxy group and the other decane compound.

Examples of the organic solvent which can be used in the synthesis of the polyorganosiloxane having an epoxy group include a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, and an alcohol compound.

Examples of the hydrocarbon compound include toluene and xylene; and examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, and cyclohexane. A ketone or the like; examples of the ester include ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate. And the like; examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, and An alkane or the like; as the above-mentioned alcohol, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether Ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Among them, those which are not water-soluble are preferred. These solvents may be used alone or in combination of two or more.

The organic solvent is preferably used in an amount of from 10 parts by mass to 10,000 parts by mass, more preferably from 50 parts by mass to 1,000 parts by mass, per 100 parts by mass of the total of the decane compound. Further, the amount of water used as the polyorganosiloxane having an epoxy group is preferably from 0.5 to 100 moles, more preferably from 1 to 20 moles per mole of the total decane compound. .

As the above catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound or the like can be used.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.

As the above organic base, for example, for example,

Ethylamine, diethylamine, piperazine , piperidine, pyrrolidine, pyrrole and other organic primary and secondary amines; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo-11 An organic tertiary amine such as an ene; an organic quaternary ammonium salt such as tetramethylammonium hydroxide or the like. Among these organic bases, organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and the like are preferable in view of stable reaction. An organic quaternary ammonium salt such as tetramethylammonium.

As a catalyst for producing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferred. By using an alkali metal or an organic base as a catalyst, a side reaction such as ring opening of an epoxy group is not generated, and a desired polyorganosiloxane is obtained at a high hydrolysis and condensation rate. Therefore, it is excellent in production stability and is preferably used. Further, the organic semiconductor alignment composition of the present invention containing a reactant of an epoxy group-containing polyorganosiloxane and a specific cinnamic acid derivative synthesized using an alkali metal compound or an organic base as a catalyst is excellent in storage stability. So suitable.

The reason is as pointed out in Chemical Reviews, Vol. 95, p. 409 (1995). It is presumed that if an alkali metal compound or an organic base is used as a catalyst in the hydrolysis or condensation reaction, a random structure, a ladder structure or In the cage structure, a polyorganosiloxane having a small content of a stanol group cannot be obtained. In the case where the content of the stanol group is small, the condensation reaction between the stanol groups is suppressed, and when the organic semiconductor alignment composition of the present invention contains other polymers described later, the stanol group and other polymers are inhibited. The condensation reaction results in excellent storage stability.

Particularly preferred as the catalyst is an organic base. The amount of the organic base to be used varies depending on the type of the organic base, the reaction conditions such as the temperature, and the like, and can be appropriately set. The specific amount of the organic base to be used is, for example, preferably 0.01 to 3 moles, more preferably 0.05 to 2 moles per mole of the total decane compound.

The hydrolysis or hydrolysis, condensation reaction in the production of the polyorganosiloxane having an epoxy group is preferably carried out by dissolving a decane compound having an epoxy group and other decane compounds used as needed in an organic solvent. The organic base is mixed with water and heated by, for example, an oil bath.

In the hydrolysis and condensation reaction, the heating temperature of the oil bath is desirably 130 ° C or lower, more preferably 40 ° C to 100 ° C, preferably 0.5 hour to 12 hours, more preferably 1 hour to 8 hours. When heating, the mixture may be stirred or may be refluxed.

After completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction liquid with water. In the washing, it is preferred to wash by a water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2% by mass, for the purpose of easy washing operation. The washing is carried out until the aqueous layer after washing is neutral. Thereafter, the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve, and then the solvent is removed, whereby the desired polyorganosiloxane having an epoxy group can be obtained.

In the present invention, commercially available ones can be used as the polyorganosiloxane having an epoxy group. Examples of such a product include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (above, chisso).

The organooxane (a) having an epoxy group may contain a portion derived from a hydrolyzate formed by hydrolysis of a polyorganosiloxane having an epoxy group, and a hydrolysis condensation between a polyorganosiloxane having an epoxy group. A portion forming a hydrolysis condensate. These hydrolyzate and hydrolysis condensate which are the constituent materials of the above-mentioned part can also be prepared similarly to the hydrolysis or condensation conditions of the polyorganosiloxane which has an epoxy group.

<compound b>

The compound b is composed of a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH=CH ₂ and -SO ₂ Cl. At least one group selected from the group and a acetal ester structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a tertiary alkyl ester structure of a carboxylic acid A compound of at least one structure selected from the group consisting of.

Examples of the group forming the acetal structure of the carboxylic acid include groups represented by the following formula (B-1) and formula (B-2).

(In the formula (B-1), R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or An aralkyl group having 7 to 10 carbon atoms, and n1 is an integer of 2 to 10 in the formula (B-2).

Here, it is an alkyl group as R ¹ in the above formula (B-1), preferably a methyl group; a cyclohexyl group as an alicyclic group; a phenyl group as an aryl group; and an aralkyl group; The group is preferably a benzyl group; the alkyl group as R ² is preferably an alkyl group having 1 to 6 carbon atoms; and the alicyclic group is preferably an alicyclic group having 6 to 10 carbon atoms. As the aryl group, a phenyl group is preferred; as the aralkyl group, a benzyl group or a 2-phenylethyl group is preferred; and as the formula (B-2), n1 is preferably 3 or 4.

The group represented by the above formula (B-1) includes, for example, 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, and 1 -isopropoxyethoxycarbonyl, 1-n-butoxyethoxycarbonyl, 1-isobutoxyethoxycarbonyl, 1-secondbutoxyethoxycarbonyl, 1-tert-butoxy Ethyloxycarbonyl, 1-cyclopentyloxyethoxycarbonyl, 1-cyclohexyloxyethoxycarbonyl, 1-descyloxyethoxycarbonyl, 1-cyloxy B Oxycarbonyl, 1-phenoxyethoxycarbonyl, 1-(1-naphthalenyloxy)ethoxycarbonyl, 1-benzyloxyethoxycarbonyl, 1-phenylethyloxyethoxycarbonyl (cyclohexyl)(methoxy)methoxycarbonyl, (cyclohexyl)(ethoxy)methoxycarbonyl, (cyclohexyl)(n-propoxy)methoxycarbonyl, (cyclohexyl)(iso) Propyl)methoxycarbonyl, (cyclohexyl)(cyclohexyloxy)methoxycarbonyl, (cyclohexyl)(phenoxy)methoxycarbonyl, (cyclohexyl)(benzyloxy)methoxy Carbocarbonyl, (phenyl)(methoxy)methoxycarbonyl, (phenyl)(ethoxy)methoxycarbonyl, (phenyl)(n-propoxy)methoxycarbonyl, (benzene (isopropoxy)methoxycarbonyl, (phenyl)(cyclohexyloxy)methoxycarbonyl, (phenyl)(phenoxy)methoxycarbonyl, (phenyl)(benzyloxy) Methoxycarbonyl, (benzyl)(methoxy)methoxycarbonyl, (benzyl)(ethoxy)methoxycarbonyl, (benzyl)(n-propoxy)methoxycarbonyl, (benzyl)(isopropoxy)methoxycarbonyl, (benzyl)(cyclohexyloxy)methoxycarbonyl, (benzyl)(phenoxy)methoxycarbonyl, (benzyl)(benzyl) The group represented by the above formula (B-2) may, for example, be a 2-tetrahydrofuranyloxycarbonyl group or a 2-tetrahydropyranyloxycarbonyl group. Among them, preferred is 1-ethoxyethoxycarbonyl, 1-n-propoxyethoxycarbonyl, 1-cyclohexyloxyethoxycarbonyl, 2-tetrahydropyranyloxycarbonyl, 2 - tetrahydropyranyloxycarbonyl and the like.

Examples of the group forming the ketal ester structure of the carboxylic acid include groups represented by the following formulas (B-3) to (B-5), respectively.

(In the formula (B-3), R ³ is an alkyl group having 1 to 12 carbon atoms, and R ⁴ and R ⁵ are each an alkyl group having 1 to 12 carbon atoms and a fat having 3 to 20 carbon atoms. a cyclic group, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and in the formula (B-4), R ⁶ is an alkyl group having 1 to 12 carbon atoms. N2 is an integer of 2 to 8, and in the formula (B-5), R ⁷ is an alkyl group having 1 to 12 carbon atoms, and n3 is an integer of 2 to 8).

Here, each is an alkyl group as R ³ in the above formula (B-3), preferably a methyl group; an alkyl group as R ⁴ is preferably a methyl group; and an alicyclic group is preferably a cyclohexyl group; The aryl group is preferably a phenyl group; the aralkyl group is preferably a benzyl group; the alkyl group as R ⁵ is preferably an alkyl group having 1 to 6 carbon atoms; and the alicyclic group is preferred. An alicyclic group having 6 to 10 carbon atoms; preferably an aryl group; and an aralkyl group, preferably a benzyl group or a 2-phenylethyl group; as the above formula (B-4) The alkyl group of R ⁶ in the ) is preferably a methyl group; and as n 2 is preferably 3 or 4.

The alkyl group of R ⁷ in the above formula (B-5) is preferably a methyl group; and n3 is preferably 3 or 4.

The group represented by the above formula (B-3) includes, for example, 1-methyl-1-methoxyethoxycarbonyl group, 1-methyl-1-ethoxyethoxycarbonyl group, and 1- Methyl-1-n-propoxyethoxycarbonyl, 1-methyl-1-isopropoxyethoxycarbonyl, 1-methyl-1-n-butoxyethoxycarbonyl, 1-methyl 1-isobutoxyethoxycarbonyl, 1-methyl-1-butoxyethoxycarbonyl, 1-methyl-1-butoxyethoxycarbonyl, 1-methyl -1-cyclopentyloxyethoxycarbonyl, 1-methyl-1-cyclohexyloxyethoxycarbonyl, 1-methyl-1-norzyloxyethoxycarbonyl, 1-methyl Keto-1-alkyloxyethoxycarbonyl, 1-methyl-1-phenoxyethoxycarbonyl, 1-methyl-1-(1-naphthalenyloxy)ethoxycarbonyl, 1- Methyl-1-benzyloxyethoxycarbonyl, 1-methyl-1-phenylethyloxyethoxycarbonyl, 1-cyclohexyl-1-methoxyethoxycarbonyl, 1-cyclohexyl 1-ethoxyethoxycarbonyl, 1-cyclohexyl-1-n-propoxyethoxycarbonyl, 1-cyclohexyl-1-isopropoxyethoxycarbonyl, 1-cyclohexyl-1- Cyclohexyloxyethoxycarbonyl, 1-cyclohexyl-1-phenoxyethoxycarbonyl, 1-cyclohexyl 1-benzyloxyethoxycarbonyl, 1-phenyl-1-methoxyethoxycarbonyl, 1-phenyl-1-ethoxyethoxycarbonyl, 1-phenyl-1-positive Propoxyethoxycarbonyl, 1-phenyl-1-isopropoxyethoxycarbonyl, 1-phenyl-1-cyclohexyloxyethoxycarbonyl, 1-phenyl-1-phenoxy Ethoxycarbonyl, 1-phenyl-1-benzyloxyethoxycarbonyl, 1-benzyl-1-methoxyethoxycarbonyl, 1-benzyl-1-ethoxyethoxycarbonyl , 1-benzyl-1-n-propoxyethoxycarbonyl, 1-benzyl-1-isopropoxyethoxycarbonyl, 1-benzyl-1-cyclohexyloxyethoxycarbonyl, 1 -benzyl-1-phenoxyethoxycarbonyl, 1-benzyl-1-benzyloxyethoxycarbonyl, etc.; as a group represented by the above formula (B-4), for example, 2 - (2-methyltetrahydrofuranyl)oxycarbonyl, 2-(2-methyltetrahydropyranyl)oxycarbonyl, etc.; as a group represented by the above formula (B-5), for example, 1 a methoxycyclopentyloxycarbonyl group, a 1-methoxycyclohexyloxycarbonyl group or the like. Among them, 1-methyl-1-methoxyethoxycarbonyl group, 1-methyl-1-cyclohexyloxyethoxycarbonyl group and the like are preferable.

The group which forms the structure of the 1-alkylcycloalkyl ester of the above-mentioned carboxylic acid is, for example, a group represented by the following formula (B-6).

In the formula (B-6), R ⁸ is an alkyl group having 1 to 12 carbon atoms, and n 4 is an integer of 1 to 8. )

Here, the alkyl group as R ⁸ in the above formula (B-6) is preferably an alkyl group having 1 to 10 carbon atoms.

The group represented by the above formula (B-6) includes, for example, 1-methylcyclopropoxycarbonyl group, 1-methylcyclobutoxycarbonyl group, 1-methylcyclopentyloxycarbonyl group, and 1- Methylcyclohexyloxycarbonyl, 1-methylcycloheptyloxycarbonyl, 1-methylcyclooctyloxycarbonyl, 1-methylcyclononyloxycarbonyl, 1-methylcyclononyloxycarbonyl, 1- Ethylcyclopropoxycarbonyl, 1-ethylcyclobutoxycarbonyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclohexyloxycarbonyl, 1-ethylcycloheptyloxycarbonyl, 1- Ethylcyclooctyloxycarbonyl, 1-ethylcyclodecyloxycarbonyl, 1-ethylcyclodecyloxycarbonyl, 1-(iso)propylcyclopropoxycarbonyl, 1-(iso)propylcyclobutane Oxycarbonyl, 1-(iso)propylcyclopentyloxycarbonyl, 1-(iso)propylcyclohexyloxycarbonyl, 1-(iso)propylcycloheptyloxycarbonyl, 1-(iso)propyl Cyclooctyloxycarbonyl, 1-(iso)propylcyclodecyloxycarbonyl, 1-(iso)propylcyclodecyloxycarbonyl, 1-(iso)butylcyclopropoxycarbonyl, 1-(iso) Butylcyclobutoxycarbonyl, 1-(iso)butylcyclopentyloxycarbonyl, 1-(iso)butylcyclohexyloxycarbonyl, 1-(iso)butylcycloheptyloxycarbonyl, 1-( Isobutyl octyloxycarbonyl, 1 -(iso)butylcyclomethoxycarbonyl, 1-(iso)butylcyclomethoxycarbonyl, 1-(iso)pentylcyclopropoxycarbonyl, 1-(iso)pentylcyclobutoxycarbonyl , 1-(iso)pentylcyclopentyloxycarbonyl, 1-(iso)pentylcyclohexyloxycarbonyl, 1-(iso)pentylcycloheptyloxycarbonyl, 1-(iso)pentylcyclooctyloxy Carbocarbonyl, 1-(iso)pentylcyclodecyloxycarbonyl, 1-(iso)pentylcyclodecyloxycarbonyl, 1-(iso)hexylcyclopropoxycarbonyl, 1-(iso)hexylcyclobutoxy Carbocarbonyl, 1-(iso)hexylcyclopentyloxycarbonyl, 1-(iso)hexylcyclohexyloxycarbonyl, 1-(iso)hexylcycloheptyloxycarbonyl, 1-(iso)hexylcyclooctyloxycarbonyl , 1-(iso)hexylcyclodecyloxycarbonyl, 1-(iso)hexylcyclodecyloxycarbonyl, 1-(iso)heptylcyclopropoxycarbonyl, 1-(iso)heptylcyclobutoxycarbonyl , 1-(iso)heptylcyclopentyloxycarbonyl, 1-(iso)heptylcyclohexyloxycarbonyl, 1-(iso)heptylcycloheptyloxycarbonyl, 1-(iso)heptylcyclooctyloxy Carbocarbonyl, 1-(iso)heptylcyclodecyloxycarbonyl, 1-(iso)heptylcyclodecyloxycarbonyl, 1-(iso)octylcyclopropoxycarbonyl, 1-(iso)octyl ring Butoxycarbonyl, 1-(iso)octylcyclopentyloxycarbonyl, 1-(iso)octyl Hexyloxycarbonyl, 1-(iso)octylcycloheptyloxycarbonyl, 1-(iso)octylcyclooctyloxycarbonyl, 1-(iso)octylcyclodecyloxycarbonyl, 1-(iso)octyl A base ring methoxycarbonyl group or the like.

The group having the tertiary alkyl ester structure of the carboxylic acid may, for example, be a tertiary alkoxycarbonyl group. Examples of the tertiary alkoxycarbonyl group include a third butoxycarbonyl group, a third pentyloxycarbonyl group, a 2-methyl-2-pentyloxycarbonyl group, a 3-methyl-3-pentyloxycarbonyl group, and an anthracene. Oxycarbonyl group. Among them, a third butoxycarbonyl group and a third pentoxycarbonyl group are preferred, and a third butoxycarbonyl group is particularly preferred.

The compound b in the present invention is the following formula (B),

B _n RC (B)

(In the formula (B), B is preferably a group represented by any one of the above formulas (B-1) to (B-6) or a tertiary alkoxycarbonyl group, and n is an integer of 1 to 10, and R is A group obtained by removing (n+1) hydrogen from a heterocyclic compound having 3 to 10 carbon atoms, or a (n+1)-valent hydrocarbon group having 1 to 18 carbon atoms.

C is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH=CH ₂ and -SO ₂ Cl, and preferably a carboxyl group. )

n in the above formula (B) is preferably 1 or 2.

Specific examples of R in the above formula (B) include a single bond, a methyl group, an alkyl group having 2 to 12 carbon atoms, a 1,2-phenyl group, and 1 when n is 1. , 3-phenylene, 1,4-phenylene, 2,6-anthranyl, 5-sodium sulfo-1,3-phenylene, 5-tetrabutylsulfonyl-1,3- Examples of the case where n is 2 include a group represented by the following formula, a 1,3,5-methylphenyl group, and the like.

The above alkylene group is preferably linear.

The compound b represented by the above formula (B) can be synthesized by a conventional method of organic chemistry or by a conventional method in which organic chemistry is appropriately combined.

For example, a compound in which the group B in the above formula (B) is a group represented by the above formula (B-1) (excluding the case where R ¹ is a phenyl group) is preferably in the presence of a phosphoric acid catalyst, The compound CR-(COOH) _n (wherein C, R and n are respectively the same as defined in the above formula (B)), and the compound R ² -O-CH=R ^{1 '} (wherein R ² and the above formula (B) The definition of -1) is the same, and R ^{1 '} is a group obtained by removing a hydrogen atom from the one-carbon of the group R ¹ in the above formula (B-1).

In the polyorganosiloxane of the present invention, a side chain having photo-alignment properties can be introduced as needed. By introducing a photo-alignment group, alignment can be performed by light irradiation without rubbing.

As the photo-alignment group, a group derived from various compounds exhibiting photo-alignment properties can be used, and examples thereof include an azobenzene group containing azobenzene or a derivative thereof as a basic skeleton, and cinnamic acid or a derivative thereof. a benzophenone-containing group having a cinnamic acid structure as a basic skeleton, a chalcone group containing a chalcone or a derivative thereof as a basic skeleton, and a benzophenone containing a benzophenone or a derivative thereof as a basic skeleton A group containing a coumarin group containing coumarin or a derivative thereof as a basic skeleton, a polyimide-containing structure containing a polyimine or a derivative thereof as a basic skeleton, and the like. Among these photo-alignment groups, a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton is preferable in view of high alignment ability and ease of introduction.

The structure of the group having a cinnamic acid structure is not particularly limited as long as it contains cinnamic acid or a derivative thereof, and is preferably a group derived from the specific cinnamic acid derivative described below.

The compound represented by the following formula (2) or the compound represented by the following formula (3) can be mentioned.

(In the formula (2), R ⁹ is a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms or an alkyl group having 1 to 40 carbon atoms, and an alkyl group having an alicyclic group; A part or all of the hydrogen atom may be substituted by a fluorine atom, R ¹⁰ is a single bond, an oxygen atom, -COO- or -OCO-, R ¹¹ is a divalent aryl group, a divalent alicyclic group, and a divalent group. a heterocyclic group or a divalent fused ring group, R ¹² is a single bond, an oxygen atom, -COO- or -OCO-, and R ¹³ is a single bond, a methyl group, and a 2 to 10 carbon atom. a divalent aryl group, when R ¹³ is a single bond, t is 0 and R ¹⁴ is a hydroxyl group or -SH, and R ¹³ is a methyl group, an alkyl group or a divalent aryl group, and t is 0 or 1 And R ¹⁴ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR, -CH=CH ₂ or -SO ₂ Cl, wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹⁵ is fluorine. Atom or cyano, a is an integer from 0 to 3, and b is an integer from 0 to 4.

(In the formula (3), R ¹⁶ is a monovalent organic group having 3 to 40 carbon atoms or an alkyl group having 1 to 40 carbon atoms containing an alicyclic group, wherein the hydrogen atom of the aforementioned alkyl group Some or all of them may be substituted by a fluorine atom, R ¹⁷ is an oxygen atom, a divalent aryl group or a single bond, R ¹⁸ is an oxygen atom, -COO- or -OCO-, R ¹⁹ is a divalent aryl group, a divalent impurity a cyclic group or a divalent fused ring group, R ²⁰ is a single bond, -OCO-(CH ₂ ) _e -* or -O-(CH ₂ ) _g -*, wherein the aforementioned e and g are each an integer of 1 to 10 "*" denotes a linking bond with R and R ²¹ respectively, and R ²¹ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR, -CH=CH ₂ or -SO ₂ Cl, wherein the aforementioned R is a hydrogen atom Or an alkyl group having 1 to 6 carbon atoms, R ²² is a fluorine atom or a cyano group, c is an integer of 0 to 3, and d is an integer of 0 to 4).

The monovalent organic group having 3 to 40 carbon atoms of the alicyclic group-containing group of R ⁹ in the above formula (2) may, for example, be a cholesteryl group, a cholesteryl group or an adamantyl group. . The alkyl group having 1 to 40 carbon atoms of R ⁹ is, for example, preferably an alkyl group having 1 to 20 carbon atoms, and a part or the whole of the hydrogen atom of the alkyl group is substituted by a fluorine atom. Examples of the alkyl group include n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecane. Base, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, 4,4,4- Trifluorobutyl, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl, 3,3,4,4,5,5 ,5-heptafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluoro Octyl)ethyl, 2-(perfluorodecyl)ethyl and the like.

Examples of the divalent aryl group of R ¹² and R ¹³ include, for example, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene; etc.; as the divalent heterocyclic group of R ¹² , for example, 1,4-pyridylpyridyl, 2,5-extended pyridyl group , 1,4-furyl group; R ¹² as a divalent condensed cyclic group, for example, may include a naphthyl group and the like.

Examples of the divalent alicyclic group of R ¹² include a 1,4-cyclohexylene group and the like.

The compound represented by the above formula (2) is preferably a compound of the above formula (2), wherein R ¹³ is a single bond and t is 0, and R ¹⁴ is a hydroxyl group, or R ¹³ is a methyl group or an alkyl group. Or a divalent aryl group and t is 0 or 1, and R ¹⁵ is a compound of a carboxyl group.

Preferable examples of the compound represented by the above formula (2) include a compound represented by the following formulas (2-1) to (2-34), and the like.

(wherein R ¹ is the same as the definition of R ⁹ in the above formula (2), and f is an integer of 1 to 10, respectively.)

The monovalent organic group having 3 to 40 carbon atoms of the R ¹⁶ -containing alicyclic group in the above formula (3) may, for example, be a cholesteryl group, a cholesteryl group or an adamantyl group. Wait. The alkyl group having 1 to 40 carbon atoms of R ¹⁶ is, for example, preferably an alkyl group having 1 to 20 carbon atoms, and a part or the whole of the hydrogen atom of the alkyl group is substituted by a fluorine atom. An example of the alkyl group is, for example, an alkyl group exemplified as the alkyl group of R ⁹ in the above formula (2). The divalent aryl group, heterocyclic group or fused ring group of R ¹⁷ and R ¹⁹ may, for example, be a divalent aryl group, a heterocyclic group or a fused ring group as R ¹² and R ¹³ in the above formula (2). Those illustrated separately.

R ^{13 is} preferably a carboxyl group.

Preferable examples of the compound represented by the above formula (3) include compounds represented by the following formulas (3-1) to (3-11), for example.

(wherein R ⁸ is the same as the definition of R ¹⁶ in the above formula (3), and u is an integer of 1 to 10, respectively.)

Such a compound can be synthesized by appropriately combining organically synthesized information. The synthetic route and reaction conditions can be easily set according to the general knowledge of those skilled in the art and a small amount of preparation test.

In the present invention, the polyorganosiloxane (a) having an epoxy group can be further reacted with a compound represented by the following formula (4) within a range not impairing the effects of the present invention. In this case, the synthesis of the polyorganosiloxane (A) can be carried out by using a polyorganosiloxane (a) having an epoxy group and a compound b and a cinnamic acid derivative as needed, and the following formula ( 4) A mixture of the compounds shown is reacted.

A ¹ -L ⁰ -L ¹ -Z (4)

In the above formula (4),

A ¹ is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkyl group or an alkoxy group having 1 to 20 carbon atoms. Or a hydrocarbon group having a steroidal skeleton having 17 to 51 carbon atoms. Here, a part or all of the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a substituent such as a cyano group, a fluorine atom or a trifluoromethyl group.

L ⁰ is a single bond, *-O-, *-COO- or *-OCO-. The connection key with "*" is connected to A ¹ .

L ¹ is a single bond, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a phenyl group, a cyclohexylene group, a dicyclohexylene group or a formula (L ¹ -1) or (L ¹ -2) ) the group shown.

Z is a monovalent organic group capable of reacting with an epoxy group in the [A] polyorganosiloxane compound to form a linking group.

Wherein, when L ¹ is a single bond, L ⁰ is a single bond.

In the above formula (L ¹ -1) or (L ¹ -2), the connection keys with "*" are respectively connected to Z.

Z is preferably a carboxyl group.

In the above formula (4), the linear or branched alkyl group having 1 to 30 carbon atoms represented by A ¹ may, for example, be a methyl group, an ethyl group, a n-propyl group or an isopropyl group. n-Butyl, t-butyl, tert-butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylpropyl, hexyl Base, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, N-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 4,4-dimethylpentyl, 3,4-dimethyl Pentyl, 2,4-dimethylpentyl, 1,4-dimethylpentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 1,3-dimethyl Pentyl, 2,2-dimethylpentyl, 1,2-dimethylpentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl, 1,3, 3-trimethylbutyl, 1,2,3-trimethylbutyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl 2-methylheptyl 1-methylheptyl, 2-ethylhexyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-heptadecyl , n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and the like.

The cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkyl group or an alkoxy group having 1 to 20 carbon atoms may, for example, be a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. Cyclodecyl, cyclodecyl, cyclododeyl and the like.

The hydrocarbon group having a carbon atom number of 17 to 51 having a steroid skeleton is, for example, a group represented by the following formulas (A-1) to (A-3).

As A ¹ in the above formula (4), an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and the above formula (A-1) or (A-) are preferable. 3) The group.

The compound represented by the above formula (4) is preferably a compound represented by any one of the following formulas (4-1) to (4-6).

In the above formulae (4-1) to (4-6), u is an integer of 1 to 5. v is an integer from 1 to 18. w is an integer from 1 to 20. k is an integer from 1 to 5. p is 0 or 1. q is an integer from 0 to 18. r is an integer from 0 to 18. s and t are each independently an integer of 0-2.

Among these compounds, the compounds represented by the following formulas (5-1) to (5-7) are more preferred.

The compound represented by the above formula (4) is a compound obtained by reacting a specific carboxylic acid and a polyorganosiloxane having an epoxy group, and forming a site for imparting a pretilt angle in the obtained liquid crystal alignment film. In the present specification, the compound represented by the above formula (4) is sometimes referred to as "another pretilt angle developing compound".

The ratio of the use of the compound b in the synthesis of the polyorganosiloxane (A) in the present invention is preferably 0.01 to 0.5 mol, more preferably 0.01 to 0.5 mol, per 1 mol of the epoxy group of the polyorganosiloxane having an epoxy structure. Preferably, it is 0.03 to 0.4 mol, and further preferably 0.05 to 0.30 mol.

When a compound having a photo-alignment group is used, the ratio thereof is preferably 0.1 to 0.5 mol, more preferably 0.15 to 0.4 mol, per mol of the epoxy group of the polyorganosiloxane having an epoxy structure. Further, it is more preferably 0.2 to 0.3 mol.

Further, when other pretilt angle developing compounds are used, the ratio of use is preferably from 0.01 to 0.4 mol, more preferably from 0.03 to 0.3 mol, per 100 mol of the epoxy group of the polyorganosiloxane having an epoxy structure. Further, it is more preferably 0.05 to 0.2 mol.

As the catalyst, a compound known as a so-called hardening accelerator for promoting the reaction of an organic base or an epoxy compound and an acid anhydride can be used.

Examples of the above organic base include, for example, ethylamine, diethylamine, and piperazine. An organic primary or secondary amine such as piperidine, pyrrolidine or pyrrole; like triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo An organic tertiary amine such as undecene; an organic quaternary amine such as tetramethylammonium hydroxide. Among these organic bases, organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine are preferred; tetramethylammonium hydroxide is preferred. Organic quaternary amine.

The hardening accelerator may, for example, be a tertiary amine such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine or triethanolamine. Like 2-methylimidazole, 2-n-heptyl imidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyanoethyl)-2-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2- Ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2-cyano) Ethyl)-2-phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium Benzoate, 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole Anthracene trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-three 2,4-Diamino-6-(2'-n-undecylimidazolyl)ethyl-s-three 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-three , isocyanuric acid addition product of 2-methylimidazole, isocyanuric acid addition product of 2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1') ]ethyl-s-three Imidazole compound such as isocyanuric acid adduct; organic phosphorus compound such as diphenylphosphine, triphenylphosphine, triphenyl phosphite; like benzyltriphenylphosphonium chloride, tetra-n-butyl bromide Base, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyl three Phenyl hydrazine acetate, tetra-n-butyl fluorene, O, O-diethylphosphorus dithiosulfate, tetra-n-butyl benzotriazole salt, tetra-n-butyl fluorene tetrafluoroborate, tetra-n-butyl a quaternary phosphonium salt such as butyl phosphonium tetraphenyl borate or tetraphenylphosphonium tetraphenyl borate; like 1,8-diazabicyclo[5.4.0]undecene-7 and its organic acid salt Such diazabicycloalkenes; organometallic compounds such as zinc octoate, tin octoate, acetonitrile aluminum complex; like tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethyl chloride a quaternary ammonium salt such as ammonium or tetra-n-butylammonium chloride; a boron compound such as boron trifluoride or triphenyl borate; a metal halide such as zinc chloride or tin chloride; and a dicyano group Indoleamine or amine and ring a high-melting-point-dispersion latent curing accelerator such as an amine addition accelerator such as an adduct of a resin; a microcapsule-type potential formed by covering a surface of a hardening accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt with a polymer A hardening accelerator; an amine salt type latent curing accelerator; a latent curing accelerator such as a pyrolysis type thermal cation polymerization type latent curing accelerator such as a Lewis acid salt or a Bronsted acid salt.

Among these, a quaternary ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride or tetra-n-butylammonium chloride is preferred.

The catalyst is preferably used in an amount of 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the polyorganosiloxane having an epoxy group.

The reaction temperature is preferably from 0 to 200 ° C, more preferably from 50 to 150 ° C.

The reaction time is preferably from 0.1 to 50 hours, more preferably from 0.5 to 20 hours.

Examples of the organic solvent which can be used in the synthesis of the polyorganosiloxane are a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, a guanamine compound, an alcohol compound, and the like. Among these, an ether compound, an ester compound, and a ketone compound are preferable from the viewpoints of the solubility of the raw material and the product and the ease of purification of the product. The solvent is preferably used in an amount of 0.1% by weight or more, and more preferably 5 to 50% by weight, based on the solid content concentration (the ratio of the total weight of the components other than the solvent in the reaction solution).

<Other ingredients>

The liquid crystal alignment agent of the present invention comprises a polyorganosiloxane such as described above.

The liquid crystal alignment agent of the present invention may further contain other components in addition to the above polyorganosiloxane, as long as the effects of the present invention are not impaired. Examples of such other components include a polymer other than a radiation-sensitive polyorganosiloxane (hereinafter referred to as "another polymer"), a curing agent, a curing catalyst, a curing accelerator, and at least one molecule. An epoxy group compound (hereinafter referred to as "epoxy compound"), a functional decane compound, a surfactant, a photosensitizer, and the like.

[Other polymers (C)]

The above other polymers can be used to further improve the solution properties of the liquid crystal alignment agent of the present invention and the electrical properties of the resulting liquid crystal alignment film. Examples of the other polymer include at least one polymer (C1) selected from the group consisting of polyproline and polyimine, a acetal structure without a carboxylic acid, and a ketal of a carboxylic acid. Polyorganosiloxane (hereinafter, referred to as "other polyorganosiloxane (C2)")), an ester structure, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a tertiary alkyl ester structure of a carboxylic acid Glutamine, polyester, polyamine, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate Wait.

{polyglycine}

The above polylysine can be obtained by reacting tetracarboxylic dianhydride with a diamine.

Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid in the present invention include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of such an aliphatic tetracarboxylic dianhydride include, for example, butyric acid dianhydride; and examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-ring. Butyric acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3- Furyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione- 6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene- 1,2-Dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorzol-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[ 3.3.0] Octane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undec-3,5,8,10-tetraketone, etc. The aromatic tetracarboxylic dianhydride may, for example, be pyromellitic dianhydride or the like; in addition to the above, the tetracarboxylic dianhydride described in JP-A-2010-97188 may be used.

As the tetraacid dianhydride for synthesizing the aforementioned polyaminic acid, tetracarboxylic dianhydride containing an alicyclic tetracarboxylic dianhydride is preferable, and more preferably contains 2,3,5-tricarboxyl group. At least one tetracarboxylic dianhydride selected from the group consisting of cyclopentyl acetic acid dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride, particularly preferably comprising a 2,3,5-tricarboxyl ring Tetraic acid dianhydride of pentyl acetic acid dianhydride.

The tetracarboxylic dianhydride for synthesizing the polyamic acid preferably contains 10 mol% or more, more preferably 20 mol% or more of 2,3,5-tricarboxycyclopentyl group, based on the total tetracarboxylic dianhydride. At least one tetrakisic dianhydride selected from the group consisting of acetic acid dianhydride and 1,2,3,4-cyclotetracarboxylic dianhydride; most preferably only from 2,3,5-tricarboxycyclopentane At least one selected from the group consisting of acetal dianhydride and 1,2,3,4-cyclotetracarboxylic dianhydride.

Examples of the diamine used for the synthesis of the polyamic acid include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, and a diamine organic decane. Specific examples of such an aliphatic diamine include, for example, metaxylylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, and 1 , 6-hexanediamine, etc.; as the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methyl-bis(cyclohexylamine), 1,3-double (Aminomethyl)cyclohexane; etc.; as the aromatic diamine, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Thioether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoro Methyl)biphenyl, 2,7-diaminostilbene, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminobenzene) Hexafluoropropane, 4,4'-(p-phenylenedi-isopropyl)bis(aniline), 4,4'-(m-phenylenedi-isopropyl)bis(aniline), 1,4-double ( 4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4- Diaminopyrimidine, 3,6-diaminoacridine, 3,6-diamino Carbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-di-(4 -aminophenyl)-piper , 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4 -diaminobenzene,hexadecanyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene , tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy Base-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2,4 -diaminobenzene, cholesteneoxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate , 3,5-diaminobenzoic acid lanthanum alkyl ester, 3,6-bis(4-aminobenzylideneoxy)cholestane, 3,6-bis(4-aminophenoxy) Cholestane, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzonitrileoxy) Cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1- Bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-( (aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4-g Cyclohexyl)cyclohexane, N-(2,4-diaminophenyl)perazine And a compound represented by the following formula (D-1);

(In the formula (D-1), X ^I is an alkyl group having 1 to 3 carbon atoms, *-O-, *-COO- or *-OCO- (wherein a linkage bond with a "*" and a diamine) Phenylphenyl linkage.), x is 0 or 1, y is an integer of 0 to 2, and z is an integer of 1 to 20); as the diamine organooxane, for example, 1,3-bis (3) In addition to the above, a diamine described in JP-A-2010-97188 can also be used.

As the (D-1) in the above formula ^I X is preferably an alkyl group having a carbon number of 1 to 3, * - O- or -COO- * (wherein, linkages with "*" and benzene diamine Base connection). Specific examples of the group C _z H _2z+1 include, for example, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, an n-octyl group, and a n-decyl group. N-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecane Base, n-icosyl group, etc. The two amine groups of the diaminophenyl group are preferably the 2,4-position or the 3,5-position relative to the other groups.

Specific examples of the compound represented by the above formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-4), and the like.

In the above formula (D-1), x and y are preferably not 0 at the same time.

These diamines can be used individually or in combination of 2 or more types.

The ratio of use of the tetraacid dianhydride and the diamine used in the synthesis reaction of polyproline is preferably 0.2 to 2 equivalents based on the amine group contained in one equivalent of the diamine compound. The ratio is preferably from 0.3 to 1.2 equivalents.

The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at -20 ° C to 150 ° C, more preferably at a temperature of 0 ° C to 100 ° C, preferably 0.5 to 24 hours, more preferably Good for 2 to 10 hours. In addition, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyaminic acid, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N. Aprotic polar solvents such as N-dimethylformamide, N,N-dimethylimidazolidinone, dimethyl hydrazine, γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The amount of the organic solvent (a) is the total amount of the tetraacid dianhydride and the diamine compound (b) is preferably 0.1 to 50% by weight, more preferably 5 to 30% by weight based on the total amount of the reaction solution (a+b). The amount of %.

As described above, a reaction solution in which polylysine is dissolved can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after separating the polyamic acid contained in the reaction solution, or purifying the separated polyamic acid to prepare a liquid crystal alignment. Agent.

When the poly (proline) is dehydrated and closed to form a polyimine, the above reaction solution can be directly used for the dehydration ring closure reaction; or the polylysine contained in the reaction solution can be separated and used for the dehydration ring closure reaction; or the separation can be carried out. After the polyamic acid is refined, it is used for the dehydration ring closure reaction.

The method for separating polylysine by injecting the above reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure; or distilling the organic solvent in the reaction solution by an evaporator under reduced pressure Wait. Alternatively, the polylysine may be redissolved in an organic solvent and then precipitated in a poor solvent; or the solution may be washed again by repeating one or more times, and then reduced by an evaporator. The poly-proline is purified by a method such as a step of distilling off the organic solvent in the solution.

[polyimine]

The above polyimine can be produced by dehydrating and ring-closing the structure of the proline which the polyamic acid obtained above has. In this case, the proline structure can be completely dehydrated and closed, and completely ytterbium imidized; or a part of the proline structure can be dehydrated and closed, and a part of the proline structure and the quinone ring structure can be formed. Amine.

The dehydration ring of polylysine is preferably (i) a method of heating poly-proline, or (ii) dissolving poly-proline in an organic solvent, and adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. It is carried out according to the method of heating required.

The reaction temperature in the method of heating poly-proline in the above (i) is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring closure reaction cannot be sufficiently carried out; if the reaction temperature exceeds 200 ° C, the molecular weight of the obtained polyfluorene imidized polymer may be lowered. The reaction time in the method of heating the polyamic acid is preferably from 0.5 to 48 hours, more preferably from 2 to 20 hours.

On the other hand, in the method of adding the dehydrating agent and the dehydration ring-closure catalyst to the polyaminic acid solution of the above (ii), as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent is preferably 0.01 to 20 mol based on the structural unit of 1 mol of polyamic acid. The dehydration ring-closing catalyst may, for example, be a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine. However, it is not limited to this. The amount of the dehydration ring-closure catalyst is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. The organic solvent used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably from 0.5 to 20 hours, more preferably from 1 to 8 hours.

The polyimine obtained in the above method (i) can be directly used for preparing a liquid crystal alignment agent, or after the obtained polyimine is refined, and used for preparing a liquid crystal alignment agent. On the other hand, in the above method (ii), a reaction solution containing polyienimine can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after removing a dehydrating agent and a dehydration ring-closing catalyst from the reaction solution; and can also be used for preparing a liquid crystal alignment agent after separating the polyimine. Or after the isolated polyimine is refined, it is used to prepare a liquid crystal alignment agent. In order to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method such as solvent replacement is suitably employed. Separation and purification of the polyimine can be carried out by the same operation as described above for the separation and purification of polylysine.

[Other polyorganooxane (C2)]

The above polyorganosiloxane (C2) may be at least one decane compound (hereinafter, also referred to as "raw material decane compound") selected from the group consisting of an alkoxy decane compound and a halogenated decane compound, for example. It is preferably synthesized by hydrolysis, hydrolysis or condensation in the presence of water and a catalyst in a suitable organic solvent.

As the raw material decane compound which can be used herein, for example, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, and fourth second are mentioned. Butoxy decane, tetra-tert-butoxy decane, tetrachloro decane; methyl trimethoxy decane, methyl triethoxy decane, methyl tri-n-propoxy decane, methyl triisopropoxy decane, Methyl tri-n-butoxy decane, methyl tri-tert-butoxy decane, methyl tri-tert-butoxy decane, methyl triphenyloxy decane, methyl trichloro decane, ethyl trimethoxy decane, Ethyl triethoxy decane, ethyl tri-n-propoxy decane, ethyl triisopropoxy decane, ethyl tri-n-butoxy decane, ethyl tri-n-butoxy decane, ethyl tri-third Butoxy decane, ethyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl trichloro decane; dimethyl dimethoxy decane, dimethyl diethoxy decane, Dimethyldichlorodecane; trimethyl methoxy decane, trimethyl ethoxy decane, trimethyl chloro decane, and the like. Among these, preferred are tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, Dimethyldimethoxydecane, dimethyldiethoxydecane, trimethylmethoxydecane or trimethylethoxydecane.

In the case of synthesizing another polyorganosiloxane, the organic solvent which can be used arbitrarily may, for example, be an alcohol compound, a ketone compound, a guanamine compound, an ester compound or other aprotic compound. They may be used alone or in combination of two or more.

Examples of the above alcohol compound include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol, and 2-methyl. Butanol, second pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, second heptanol, 3 -heptanol, n-octanol, 2-ethylhexanol, second octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-nonanol, eicosyl alcohol, trimethyl Base alcohol, tetradecanol, heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc. Monohydric alcohol compound; ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol , 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and other polyol compounds; ethylene glycol monomethyl ether, ethylene Alcohol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl 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 a partial ether of a polyol compound such as propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or dipropylene glycol monopropyl ether. 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 isobutyl ketone, and methyl n-amyl ketone. ,ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl fluorenone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetone a monoketone compound such as acetone or acetophenone; etidylacetone, 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 a β-diketone compound such as heptanedione or 1,1,1,5,5,5-hexafluoro-2,4-heptanedione or the like. These alcohol compounds may be used alone or in combination of two or more.

Examples of the above guanamine compound include formamide, N-methylformamide, N,N-dimethylformamide, N-ethylformamide, and N,N-diethylformamidine. Amine, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-methylpropionamidine Amine, N-methylpyrrolidone, N-methyl fluorenyl Porphyrin, N-methylpyridyl piperidine, N-methylpyridyl pyrrolidine, N-ethyl fluorenyl Porphyrin, N-ethinylpiperidine, N-ethinylpyrrolidine, and the like. These guanamine 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, and acetic acid. N-propyl ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate Base ester, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, methyl ethyl acetate, B Ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, two Glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol single Methyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxy triethylene glycol acetate, ethyl propionate, n-propionic acid , isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate Ester, diethyl phthalate, etc. These ester compounds may be used alone or in combination of two or more.

Examples of the other aprotic compound include acetonitrile, dimethyl hydrazine, N, N, N', N'-tetraethyl thio amide, trimethylamine hexamethyl phosphate, and N-methyl group. Linoleone, N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrrolidine, N-methylpiperidine, N-ethylpiperidine, N,N-dimethylper , 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.

Among these solvents, a polyol compound or a partial ether or ester compound of a polyol compound is particularly preferred.

The ratio of the water used in the synthesis of the other polyorganosiloxane is preferably from 0.5 to 100 mol, more preferably from 1 to 30 mol, based on the total amount of the alkoxy group and the halogen atom of the starting decane compound. More preferably, it is a ratio of 1 to 1.5 mol.

Examples of the catalyst which can be used in the synthesis of other polyorganosiloxanes include metal chelate compounds, organic acids, inorganic acids, organic bases, amines, alkali metal compounds and the like.

The metal chelate compound may, for example, be triethoxy-mono(ethylmercaptoacetoate) titanium, tri-n-propoxy-mono(ethylmercaptoacetoate) titanium, or triisopropoxy- Mono (acetylpyruvate) titanium, tri-n-butoxy-mono(ethylmercaptoacetoate) titanium, three second butoxy-mono(ethylmercaptoacetoate) titanium, three third Oxy-mono(ethylmercaptoacetoate) titanium, diethoxy-bis(acetamidopyruvate) titanium, di-n-propoxy-bis(ethylmercaptoacetoate) titanium, diisopropyl Oxy-bis(acetylthiopyruvate) titanium, di-n-butoxy-bis(ethyl phthalate) titanium, two second butoxy-bis(ethyl phthalate) titanium, two Third butoxy-bis(ethylmercaptoacetoate) titanium, monoethoxy-tris(ethylpyruvate) titanium, mono-n-propoxy-tris(ethylpyruvate) titanium, Monoisopropoxy-tris(acetamidopyruvate) titanium, mono-n-butoxy-tris(acetamidopyruvate) titanium, mono-second butoxy-tris(ethylpyruvylate) Titanium, mono-tert-butoxy-tris(acetate-pyruvate) titanium, tetrakis(acetate-pyruvate) titanium, triethoxy-mono(acetonitrile) , tri-n-propoxy-mono (acetic acid ethyl acetate) titanium, triisopropoxy-mono (acetic acid ethyl acetate) titanium, tri-n-butoxy-mono (acetic acid ethyl acetate) titanium, three Second butoxy-mono(acetonitrile ethyl acetate) titanium, tri-tert-butoxy-mono(acetonitrile ethyl acetate) titanium, diethoxy-bis(acetic acid ethyl acetate) titanium, two positive Propyloxy-bis(acetonitrile ethyl acetate) titanium, diisopropoxy-bis(acetic acid ethyl acetate) titanium, di-n-butoxy-bis(acetic acid ethyl acetate) titanium, two second Oxy-bis(acetic acid ethyl acetate) titanium, di-t-butoxy-bis(acetic acid ethyl acetate) titanium, monoethoxy-tris(ethyl acetate) titanium, mono-n-propoxy - tris(acetonitrile ethyl acetate) titanium, monoisopropoxy-tris(ethyl acetate) titanium, mono-n-butoxy-tris(ethyl acetate) titanium, single second butoxy- Tris(acetate ethyl acetate) titanium, mono-tert-butoxy-tris(acetate ethyl acetate) titanium, tetrakis(acetate ethyl acetate) titanium, mono(ethylmercaptopyruvate) tris(acetonitrile) a titanium chelate compound such as titanium, bis(ethyl decyl pyruvate) bis(acetic acid ethyl acetate) titanium, tris(ethyl decyl pyruvate) mono(acetonitrile ethyl acetate) titanium; Oxy-mono(ethylmercaptopyruvate) zirconium, tri-n-propoxy-mono(ethylmercaptopyruvate) zirconium, triisopropoxy-mono(ethylmercaptopyruvate) zirconium, three-positive Butoxy-mono(ethylmercaptopyruvate)zirconium, three second butoxy-mono(ethylmercaptopyruvate)zirconium, tri-tert-butoxy-mono(ethylmercaptopyruvate)zirconium , diethoxy bis(ethyl decyl pyruvate) zirconium, di-n-propoxy bis(ethyl decyl pyruvate) zirconium, diisopropoxy bis(ethyl decyl pyruvate) zirconium, two positive Butyloxybis(ethylmercaptopyruvate)zirconium, di-n-butoxybis(ethylmercaptoacetoate)zirconium, di-t-butoxybis(ethylmercaptoacetoate)zirconium, single B Oxygen tris(acetate-pyruvate) zirconium, mono-n-propoxy tris(ethinyl pyruvate) zirconium, monoisopropoxy tris(ethionyl pyruvate) zirconium, mono-n-butoxy Tris(acetylthiopyruvate) zirconium, single second butoxy tris(ethinyl pyruvate) zirconium, mono-tert-butoxy tris(ethionylpyruvate) zirconium, tetrakis(ethylene) Pyruvate) zirconium, triethoxy-mono(acetonitrile ethyl acetate) zirconium, tri-n-propoxy-mono(ethyl acetate) zirconium, triisopropoxy-single (B) Ethyl acetate) zirconium, tri-n-butoxy-mono(ethyl acetate) zirconium, tri-tert-butoxy-mono(acetonitrile)zirconium, tri-tert-butoxy-mono(acetonitrile) Ethyl acetate, zirconium, zirconium diethoxy bis(acetonitrile), zirconium di-n-propoxy bis(acetic acid ethyl acetate), zirconium diisopropoxy bis(acetonitrile), zirconium, Di-n-butoxy bis(acetic acid ethyl acetate) zirconium, two second butoxy bis(acetic acid ethyl acetate) zirconium, di-t-butoxy bis(acetic acid ethyl acetate) zirconium, monoethoxy Zirconium (ethyl acetate) zirconium, mono-n-propoxy tris(ethyl acetate) zirconium, monoisopropoxy tris(ethyl acetate) zirconium, mono-n-butoxy three (acetamidine) Ethyl acetate) zirconium, zirconium monobutoxysuccinate (ethyl acetate) zirconium, zirconium monobutoxysuccinate (ethyl acetate) zirconium, tetrakis(acetate ethyl acetate) zirconium, single ( Ethyl pyruvate) tris(acetonitrile ethyl acetate) zirconium, bis(ethyl phthalate) bis(acetate ethyl acetate) zirconium, tris(ethyl acetonate) monoacetate Ethyl ester; zirconium chelate compound such as zirconium; aluminum chelate compound such as aluminum tris(ethylpyruvylate), aluminum tris(acetate), or the like.

Examples of the organic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, and adipic acid. Azelaic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid , p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic 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 above organic base include pyridine, pyrrole, and piperidine. , pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyldiethanolamine, triethanolamine, dioxodicyclooctane, diterpenes Bicyclodecane, dioxodicycloundecene, tetramethylammonium hydroxide, and the like.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

These catalysts may be used alone or in combination of two or more.

Among these catalysts, a metal chelate compound, an organic acid or an inorganic acid is preferred, and a titanium chelate compound or an organic acid is more preferred.

The amount of the catalyst to be used is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 1 part by weight, per 100 parts by weight of the starting decane compound.

The water added when synthesizing other polyorganosiloxane (C2) may be added intermittently or continuously to a solution formed in a decane compound as a raw material or a decane compound dissolved in an organic solvent.

The catalyst may be previously added to the decane compound as a raw material or a solution in which the decane compound is dissolved in an organic solvent, or may be dissolved or dispersed in the added water.

The reaction temperature at the time of synthesizing another polyorganosiloxane (C2) is preferably 0 to 100 ° C, more preferably 15 to 80 ° C. The reaction time is preferably from 0.5 to 24 hours, more preferably from 1 to 8 hours.

[Use ratio of other polymers (C)]

When the liquid crystal alignment agent of the present invention further contains the other polymer (C) while containing the polyorganosiloxane (A), the content ratio of the other polymer is relatively 100 parts by weight of the polyorganosiloxane (A). Preferably it is 10,000 parts by weight or less. The more desirable content of the other polymer (C) varies depending on the kind of other polymers.

The liquid crystal alignment agent of the present invention is more preferably used when at least one polymer (C1) selected from the group consisting of polyorganooxane (A) and polyamid acid and polyimine. The ratio is 200 to 5,000 parts by weight, particularly preferably 500 to 2,500 parts by weight, based on 100 parts by weight of the polyorganosiloxane (A), and the total amount of the polyamic acid and the polyimine.

On the other hand, when the liquid crystal alignment agent of the present invention contains polyorganosiloxane (A) and other polyorganosiloxane (C2), the preferred ratio of use is relative to 100 parts by weight of polyorganosiloxane. (A), the amount of the other polyorganosiloxane (C2) is 100 to 2,000 parts by weight.

When the liquid crystal alignment agent of the present invention contains the polyorganosiloxane (A) and further contains the other polymer (C), the type of the other polymer (C) is preferably polyglycolic acid and polyimine. At least one polymer (C1) selected from the group consisting of, or other polyorganosiloxane (C2). As the other polymer (C), at least one polymer (C1) selected from the group consisting of polyproline and polyimine is particularly preferred.

[epoxy compound]

The epoxy compound can be contained in the liquid crystal alignment agent of the present invention from the viewpoint of further improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate. Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetrahydration Glyceryl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl) Cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N- As the preferred material, diglycidyl-aminomethylcyclohexane or the like is preferred.

The mixing ratio of these epoxy compounds is preferably 40 parts by weight or less with respect to 100 parts by weight of the total of the polymer (refer to the total amount of the polyorganosiloxane (A) and the other polymer (C)). It is preferably 0.1 to 30 parts by weight. When the liquid crystal alignment agent of the present invention contains an epoxy compound, it can be used together with a base catalyst such as 1-benzyl-2-methylimidazole for the purpose of efficiently producing a crosslinking reaction of an epoxy group.

[functional decane compound]

The functional decane compound can be used for the purpose of improving the adhesion between the obtained liquid crystal alignment film and the substrate. The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyl. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Baseline, 3-guanidinopropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl 3-aminopropyltriethoxydecane, N-triethoxycarbenylpropyltriethylamine, N-trimethoxymethylidenepropyltriethylamine, 10- Trimethoxymethyl decyl-1,4,7-triazadecane, 10-triethoxymethyl decyl-1,4,7-triazadecane, 9-trimethoxyformamidinyl- 3,6-diazaindolyl acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxy Decane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxy Decane, N-bis(oxyl) Ethyl)-3-aminopropyltrimethoxydecane, N-bis(oxyethylidene)-3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, In the case of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, the tetracarboxylic dianhydride and the amine group described in Patent Document 17 (JP-A-63-291922) The reactant of the decane compound, and the like.

When the liquid crystal alignment agent of the present invention contains a functional decane compound, the content thereof is preferably 50 parts by weight or less, and more preferably 20 parts by weight or less based on 100 parts by weight of the total of the polymer.

[hardener, hardening catalyst]

The above-mentioned curing agent and curing catalyst can be contained in the liquid crystal alignment agent of the present invention for the purpose of further enhancing the crosslinking of the polyorganosiloxane (A) and further improving the strength of the liquid crystal alignment film. When the liquid crystal alignment agent of the present invention contains a hardener, it can be further used together with a hardening accelerator.

As the curing agent, a curing agent which is usually used in the curing of an epoxy group can be used. Examples of such a curing agent include polyamines, polycarboxylic acids, and polycarboxylic anhydrides. Specific examples thereof include benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-triacid, cyclohexane-1,2,4-tricarboxylic acid, and cyclohexane-1,3. 5-tricarboxylic acid, cyclohexane-1,2,3-tricarboxylic acid, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-triacid- 3,5-anhydride, cyclohexane-1,2,3-triacid-2,3-anhydride, 4-methyltetrahydrophthalic anhydride, nadic acid anhydride, twelve Alkenyl succinic anhydride and Diels-Alder reaction products of conjugated double bonds and arsenic compounds such as α-pinene and allo-ocimene, and their hydrides, succinic anhydride, maleic anhydride, orthophthalic acid Toluene anhydride, trimellitic anhydride, and the compounds exemplified above as the tetraacid dianhydride used in the synthesis of polyproline.

Examples of the curing accelerator include an imidazole compound, a quaternary phosphorus compound, a quaternary amine compound, and a dinitrogen such as 1,8-difluorenebicyclo[5.4.0]undecene-7 and an organic acid salt thereof. a heterobicyclic olefin; an organometallic compound such as zinc octoate, tin octoate or acetonitrile aluminum complex; a boron compound such as boron trifluoride or triphenyl borate; such as zinc chloride or tin chloride; a high-melting-point-dispersion latent hardening accelerator such as an amine-forming accelerator such as a metal halide; an anacyanoguanamine; an addition product of an amine and an epoxy resin; and a surface of a hardening accelerator such as the above-mentioned quaternary phosphonium salt Microcapsule-type latent hardening accelerator formed by polymer coating; amine salt type latent hardening accelerator; latent acid salt, Bronsted acid salt and other pyrolysis type thermal cationic polymerization type latent hardening accelerator Sex hardening accelerator.

As the hardening catalyst, for example, a ruthenium hexafluoride compound, a phosphorus hexafluoride compound, and aluminum triethyl phosphonium acetonide can be used.

[Surfactant]

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, an organic cerium surfactant, a polyalkylene oxide surfactant, and a fluorine-containing surfactant. Surfactants, etc.

When the liquid crystal alignment agent of the present invention contains a surfactant, the content thereof is preferably 10 parts by weight or less, more preferably 1 part by weight or less based on 100 parts by weight of the entire liquid crystal alignment agent.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention contains the polyorganosiloxane compound (A) as an essential component as described above, and may contain other components as needed, and it is preferred to dissolve the components in an organic solvent to prepare a solution. Composition.

As the organic solvent which can be used for formulating the liquid crystal alignment agent of the present invention, a solvent which dissolves the polyorganosiloxane (A) and any other components used arbitrarily without reacting with them is preferable.

The organic solvent which can be preferably used in the liquid crystal alignment agent of the present invention varies depending on the type of the other polymer (C) to be added.

The liquid crystal alignment agent of the present invention is a preferred organic solvent when it contains at least one polymer (C1) selected from the group consisting of polyorganooxane (A) and polyglycine and polyimine. The organic solvent exemplified above as the organic solvent used in the synthesis of the polyamic acid may be mentioned. These organic solvents may be used alone or in combination of two or more.

On the other hand, when the liquid crystal alignment agent of the present invention contains only polyorganosiloxane (A) as a polymer or polyorganosiloxane (A) and other polyorganosiloxane (C2), Preferred examples of the organic solvent include 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, and 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 (butyl cellosolve), ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate Ester, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, isopropyl acetate, n-butyl acetate, Isobutyl acetate, dibutyl acetate, n-pentyl acetate, second amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethyl acetate Butyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate and the like. Among these, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, dibutyl acetate, n-pentyl acetate, and second amyl acetate are preferable.

A preferred solvent for preparing the liquid crystal alignment agent of the present invention is a solvent obtained by combining one or two or more kinds of the above organic solvents depending on whether or not another polymer and its kind are used, at a preferred solid concentration of the following, The components contained in the liquid crystal alignment agent are not precipitated, and the surface tension of the liquid crystal alignment agent is in the range of 25 to 40 mN/m.

The solid content concentration of the liquid crystal alignment agent of the present invention, that is, the weight of all the components other than the solvent in the liquid crystal alignment agent, accounts for the total weight of the liquid crystal alignment agent, and is preferably 1 to 10 in consideration of viscosity, volatility, and the like. The range of % by weight. The liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film formed of a liquid crystal alignment film. However, when the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small, and it may be difficult to obtain a favorable liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too large, and a favorable liquid crystal alignment film may not be obtained, or the viscosity of the liquid crystal alignment agent may increase, and coating properties may be insufficient. The range of the particularly preferable solid content concentration varies depending on the method employed when the liquid crystal alignment agent is applied onto the substrate. For example, when it is carried out by a spin coating method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. When the printing method is used, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, whereby the solution viscosity is preferably in the range of 12 to 50 mPa·s. When the inkjet method is used, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, whereby the solution viscosity is in the range of 3 to 15 mPa·s.

The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 0 ° C to 200 ° C, more preferably from 10 ° C to 60 ° C.

<Liquid crystal display element>

The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention as described above.

Method for Forming Liquid Crystal Alignment Film Using Liquid Crystal Aligning Agent of the Present Invention When the polyorganosiloxane (A) of the present invention has no photo-alignment group, the liquid crystal alignment agent of the present invention can be applied onto a substrate to form a coating film. A rubbing treatment is performed as needed to form a liquid crystal alignment film.

On the other hand, when the polyorganosiloxane (A) has a photo-alignment group, the liquid crystal alignment agent of the present invention can be applied onto a substrate to form a coating film, and then the coating film is irradiated with radiation to form a liquid crystal alignment film. .

[Polyorganosiloxane (A) has no photo-alignment group]

First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then a coating film is formed on the substrate by heating the coated surface. The two substrates on which the patterned transparent conductive film is provided are formed in a pair, and are preferably coated on each of the transparent conductive film forming faces by a roll coating method, a spin coating method, a printing method, or an inkjet method. The liquid crystal alignment agent of the present invention. After coating, the coated surface is formed by preheating (prebaking) and then firing (post-baking). The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C, and the post-baking conditions are preferably 120 to 300 ° C, more preferably 150 to 250 ° C, preferably 5 to 200 minutes, more preferably Good for 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

As the substrate, for example, glass such as float glass or soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, or alicyclic ring can be used. A transparent substrate formed of a plastic such as polyolefin.

As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, USA) formed of tin oxide (SnO ₂ ) may be used, and indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) may be used. ITO film, etc. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photolithography after forming a non-graphic transparent conductive film, or a method of forming a transparent conductive film using a mask having a desired pattern can be obtained. When the liquid crystal alignment agent is applied, in order to make the surface of the substrate and the transparent conductive film and the coating film more adhesive, a functional decane compound, a functional titanium compound, or the like may be previously coated on the surface of the substrate on which the coating film should be formed. Pre-treatment.

When the liquid crystal alignment film for a vertical alignment type liquid crystal display device is formed by using the liquid crystal alignment agent of the present invention, the coating film formed as described above can be used as a liquid crystal alignment film for a vertical alignment type liquid crystal display element, or the coating film surface can be arbitrarily Friction treatment. On the other hand, when a horizontal alignment type liquid crystal display element is formed using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film can be formed by subjecting the coating film formed as above to a rubbing treatment.

The rubbing treatment is performed by rubbing a roll of a cloth formed of, for example, a fiber such as nylon, rayon, or cotton, in a certain direction. In this case, the formed liquid crystal alignment film is processed, and by changing the liquid crystal alignment ability of each region of the liquid crystal alignment film, the viewing angle property of the obtained horizontal liquid crystal display element can be improved, wherein the liquid crystal film is subjected to For example, a part of the liquid crystal alignment film is irradiated with ultraviolet rays to change the liquid crystal pretilt angle, as shown in the patent document 18 (JP-A-H06-222366) or the patent document 19 (JP-A No. 6-281937). And a process of forming a resist film on a part of the surface of the formed liquid crystal alignment film, and performing rubbing treatment in a direction different from the previous rubbing treatment, as shown in the patent document 20 (JP-A-5-107544) Thereafter, the treatment of the resist film is removed.

Two substrates on which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal cells were produced by disposing liquid crystal between the two substrates. When manufacturing a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a currently known method. First, in order to arrange the liquid crystal alignment films in the opposite direction, the two substrates are arranged to face each other by a gap (cell gap), and the peripheral portions of the two substrates are bonded together using a sealant, and are separated by the surface of the substrate and the sealant. After filling the liquid crystal into the cell gap and sealing the injection hole, a liquid crystal cell can be manufactured.

The second method is a method called ODF (One Drop Fill). Applying, for example, a UV curable sealing material to a predetermined position on one of the two substrates forming the liquid crystal alignment film, and then dropping the liquid crystal on the liquid crystal alignment film surface, bonding the other substrate and aligning the liquid crystal The film is opposed, and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, and a liquid crystal cell can be produced.

In the case of any of the methods, it is desirable to subsequently heat the liquid crystal cell to a temperature at which the liquid crystal used is isotropic, and then slowly cool to room temperature to remove the flow alignment at the time of liquid crystal injection.

Then, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell.

As the sealant, for example, an epoxy resin containing an alumina ball as a separator and a curing agent can be used.

As the liquid crystal, for example, a nematic liquid crystal, a dish liquid crystal, or the like can be used. When a liquid crystal display element having a TN type liquid crystal cell or an STN type liquid crystal cell is produced, a liquid crystal (positive liquid crystal) having positive dielectric anisotropy in a nematic liquid crystal is preferable, and for example, a biphenyl liquid crystal, Phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, two An alkane liquid crystal, a bicyclooctane liquid crystal, a cubic liquid crystal, or the like. In these liquid crystals, for example, a cholesteric liquid crystal such as cholestyl chloride, cholesterol phthalate or cholesterol carbonate can be further added; and the product sold under the trade names C-15 and CB-15 (manufactured by Merck) can be used. A reagent; a strong dielectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutyl cinnamate or the like.

On the other hand, in the case of a vertical alignment type liquid crystal cell, a liquid crystal (negative liquid crystal) having a negative dielectric anisotropy in a nematic liquid crystal is preferable, and for example, a dicyanobenzene liquid crystal or a ruthenium can be used. Liquid crystal, Schiff base liquid crystal, oxidized azo liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, and the like.

The polarizing plate used for the outer side of the liquid crystal cell may be a polarizing film formed by stretching a polyvinyl alcohol by a polarizing film which absorbs iodine called "H film" while extending the polyvinyl alcohol, or by the H film itself. A polarizing plate is formed.

[Polyorganosiloxane (A) has a photo-alignment group]

In this case, in the method for producing a liquid crystal alignment film in the case where the polyorganosiloxane (A) has no photo-alignment group, a radiation irradiation treatment can be performed instead of the rubbing treatment, whereby a liquid crystal display element can be manufactured.

As the radiation used in the radiation irradiation treatment, linearly polarized or partially polarized radiation or non-polarized radiation may be used, and for example, ultraviolet light or visible light including light having a wavelength of 150 to 800 nm may be used, and preferably 300 to 400 nm wavelength is included. The ultraviolet light of the light. When the radiation to be used is linearly polarized or partially polarized, the irradiation may be performed from the direction of the vertical substrate surface, or may be performed from the oblique direction in order to impart the pretilt angle, or may be combined. When irradiating radiation of unpolarized light, the irradiation direction must be an oblique direction.

As the 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 light preferably having a wavelength region as described above can be obtained by a mechanism for using the light source together with, for example, a filter, a diffraction grating, or the like.

The irradiation amount of the radiation is preferably 1 J/m ² or more, less than 10,000 J/m ² , and more preferably 10 to 3,000 J/m ² . In addition, when the liquid crystal alignment ability is imparted to a coating film formed of a liquid crystal alignment agent known in the art by a photo-alignment method, a radiation irradiation amount of 10,000 J/m ² or more is required. However, when the liquid crystal alignment agent of the present invention is used, the amount of radiation irradiation in the photo-alignment method is preferably 3,000 J/m ² or less, more preferably 1,000 J/m ² or less, and particularly preferably 500 J/m ² or less. The liquid crystal alignment property helps to reduce the manufacturing cost of the liquid crystal display element.

The liquid crystal display element of the present invention is preferably a vertical alignment type liquid crystal display element.

The liquid crystal display element of the present invention produced in this manner is excellent in heat resistance, light resistance, and electrical properties, and even when a liquid crystal alignment film is formed by radiation irradiation treatment, the stability of the pretilt angle with time is excellent.

[Examples]

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

In the following examples, the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography under the following conditions.

Pipe column: manufactured by Tosoh (stock), TSKgelGRCXLII

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf/cm ²

The epoxy equivalent is measured in accordance with the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

The following synthesis examples were repeated as needed by the following synthesis route to ensure the necessary amounts of products used in the following synthesis examples and examples.

<Synthesis of epoxy group-containing polyorganosiloxane (a)> Synthesis Example 1

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine was mixed at room temperature. Next, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was mixed under reflux, and reacted at 80 ° C for 6 hours. After the completion of the reaction, the organic layer was taken out, washed with a 0.2% by weight aqueous solution of ammonium nitrate until the washed water was neutral, and then the solvent and water were distilled off under reduced pressure to give a polyorganooxane EPS-1 as a viscous. Transparent liquid.

¹ H-NMR analysis of the polyorganooxynonane EPS-1 gave a theoretical strength based on an oxirane group near a chemical shift (δ) = 3.2 ppm, confirming that no epoxy group was produced in the reaction. side effects.

The polyorganoboxane EPS-1 had an Mw of 2,200 and an epoxy equivalent of 186.

<Synthesis of Compound b>

Compound b (B-1-1) was synthesized according to the following route.

Synthesis Example 2

1.80 g of monomethyl terephthalate, 3.27 g of di-tert-butyl dicarbonate, and 25 ml of THF were mixed, and stirred at room temperature for 10 minutes. After adding 0.37 g of 4-dimethylaminopyridine, the reaction was stirred at 25 ° C for 6 hours. After mixing with ethyl acetate, it was washed with a saturated aqueous solution of sodium hydrogencarbonate and distilled water. Concentration and drying gave 1.54 g of the desired intermediate. 1.16 g of the above intermediate, 0.42 g of lithium hydroxide monohydrate, 6 ml of methanol and 2 ml of distilled water were mixed, and the reaction was stirred at 25 ° C for 1 hour. After mixing with 50 ml of ethyl acetate, it was washed with diluted hydrochloric acid and distilled water and concentrated. The obtained powder was mixed with chloroform, and the insoluble matter was removed by filtration. The filtrate was concentrated and dried to give 0.80 g of Compound b (B-1-1) as white powder.

Synthesis Example 3

According to the following route, 45 g of the compound represented by the compound b (B-1-2) was obtained.

5.0 g of (1,1-dimethylethyl)methyl 1,3-benzoate and 16.35 g of di-tert-butyl dicarbonate and 50 ml of THF were mixed and stirred at room temperature for 10 minutes. After adding 1.85 g of 4-dimethylaminopyridine, the reaction was stirred at 25 ° C for 6 hours. After mixing with ethyl acetate, it was washed with a saturated aqueous solution of sodium hydrogencarbonate and distilled water. Concentration and drying gave 7.70 g of the desired intermediate. 5.80 g of the above intermediate, 2.10 g of lithium hydroxide monohydrate, 20 ml of methanol and 4 ml of distilled water were mixed, and the reaction was stirred at 25 ° C for 1 hour.

After mixing with 50 ml of ethyl acetate, it was washed with diluted hydrochloric acid and distilled water and concentrated. The obtained powder was mixed with chloroform, and the insoluble matter was removed by filtration. The filtrate was concentrated and dried to give 3.0 g of Compound b (B-1-2) as white powder.

Synthesis Example 4

According to the following route, 7.2 g of the compound represented by the compound b (B-1-3) was obtained.

0.15 mol (15.0 g) of succinic anhydride, 0.045 mol (5.0 g) of N-hydroxysuccinimide, 0.015 mol (1.75 g) of 4-dimethylaminopyridine, and 75 ml of toluene were mixed and stirred. The reaction was carried out by mixing with 17.5 ml of tributanol and 6.25 ml of triethylamine, and heating under reflux for 24 hours. After mixing with 75 ml of ethyl acetate, it was washed with a 10% aqueous citric acid solution and saturated brine, and dried over sodium sulfate. Concentrated by a rotary evaporator to obtain a viscous liquid. Recrystallization from acetone gave 0.04 mol (7.2 g) of compound b (B-1-3).

<Synthesis of specific cinnamic acid derivatives>

The synthesis reaction of the specific cinnamic acid derivative is carried out entirely in an inert gas atmosphere.

Synthesis Example 5

The cinnamic acid derivative (A-1) was synthesized according to the following route.

31 g of the compound (A-1-1), 0.23 g of palladium acetate, 1.2 g of tris(o-tolyl)phosphine, and 56 mL of triethylamine were placed in a 500 mL three-necked flask equipped with a reflux condenser, a thermometer, and a nitrogen introduction tube. 8.2 mL of acrylic acid and 200 mL of N,N-dimethylacetamide were stirred at 120 ° C for 3 hours to carry out a reaction. After completion of the reaction, the reaction mixture was filtered, and 1 L of ethyl acetate was added to the obtained filtrate, and the obtained organic layer was washed twice with diluted hydrochloric acid and three times with water, dried over magnesium sulfate, and then evaporated. The solid was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain crystals of 15 g of the cinnamic acid derivative (A-1).

Synthesis Example 6

The cinnamic acid derivative (A-2) was synthesized according to the following route.

In a 1 L eggplant type flask, 91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate and 320 mL of N-methyl-2-pyrrolidone were added, and after stirring at room temperature for 1 hour, 99.7 g was added. The 1-bromopentane was stirred at 100 ° C for 5 hours to carry out a reaction. After the reaction was completed, it was precipitated again with water. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the precipitate formed by neutralization with hydrochloric acid was recrystallized from ethanol to obtain white crystals of 104 g of Compound (A-2A).

104 g of this intermediate (A-2A) was placed in a reaction vessel, and 1 L of sulfinium chloride and 770 μL of N,N-dimethylformamide were added thereto, and the mixture was stirred at 80 ° C for 1 hour. Next, under reduced pressure, sulfinium chloride was distilled off, dichloromethane was added, and the mixture was washed with a sodium hydrogencarbonate aqueous solution, dried over magnesium sulfate, concentrated, and then evaporated to afford a solution.

Next, 74 g of 4-hydroxycinnamic acid, 138 g of potassium carbonate, 4.8 g of tetrabutylammonium, 500 mL of tetrahydrofuran, and 1 L of water were placed in a 5-L three-necked flask different from the above. While cooling the aqueous solution with ice, a tetrahydrofuran solution containing the reactant of the above intermediate (A-2A) and sulfinium chloride was slowly added dropwise, followed by stirring for 2 hours to carry out a reaction. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and extracted with ethyl acetate. The extract was dried over magnesium sulfate, and then concentrated, and then recrystallized from ethanol to give white crystals of 90 g of cinnamic acid derivative (A-2).

Synthesis Example 7

The cinnamic acid derivative (A-3) was synthesized according to the following route.

In a 1 L eggplant type flask, 82 g of methyl 4-hydroxybenzoate, 166 g of potassium carbonate, and 400 mL of N,N-dimethylacetamide were added, and after stirring at room temperature for 1 hour, 95 g of 4 was added. 4,4-Trifluoro-1-pyrobutane was stirred at room temperature for 5 hours to carry out a reaction. After the reaction was completed, it was precipitated again with water. Next, 32 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 4 hours to carry out a hydrolysis reaction. After completion of the reaction, the precipitate formed by neutralization with hydrochloric acid was recrystallized from ethanol to obtain white crystals of 80 g of intermediate (A-3A).

46.4 g of this intermediate (A-3A) was charged into a reaction vessel, and 200 mL of sulfoxide and 0.2 mL of N,N-dimethylformamide were added thereto, and the mixture was stirred at 80 ° C for 1 hour. Next, under reduced pressure, sulfinium chloride was distilled off, dichloromethane was added, and the mixture was washed with a sodium hydrogencarbonate aqueous solution, dried over magnesium sulfate, and concentrated, and then a solution was added to tetrahydrofuran.

Next, 36 g of 4-hydroxycinnamic acid, 55 g of potassium carbonate, 2.4 g of tetrabutylammonium, 200 mL of tetrahydrofuran, and 400 mL of water were placed in a 2-L three-necked flask different from the above. While cooling the aqueous solution with ice, a tetrahydrofuran solution containing the reactant of the above intermediate (A-3A) and sulfinium chloride was slowly added dropwise, followed by stirring for 2 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and extracted with ethyl acetate. The extract was dried over magnesium sulfate, concentrated, and then recrystallized from ethanol to give white crystals of 39 g of cinnamic acid derivative (A-3).

Synthesis Example 8

The cinnamic acid derivative (A-4) was synthesized according to the following route.

That is, except that in the above Synthesis Example 6, 14 g of 4-pentyl-transdicyclohexylcarboxylic acid was used in place of the intermediate (A-2A), and the cinnamic acid derivative (A-2) of Synthesis Example 6 was used. The synthesis was carried out in the same manner to obtain white crystals of 15 g of the cinnamic acid derivative (A-4).

Synthesis Example 9

The cinnamic acid derivative (A-5) was synthesized according to the following route.

In a 1 L eggplant type flask, 82 g of p-hydroxycinnamic acid, 304 g of potassium carbonate, and 400 mL of N-methyl-2-pyrrolidone were added, and after stirring at room temperature for 1 hour, 166 g of 1-bromopentane was added. The alkane was stirred at 100 ° C for 5 hours. Thereafter, the solvent was decanted under reduced pressure. 48 g of sodium hydroxide and 400 mL of water were added thereto, and refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the reaction system was neutralized with hydrochloric acid, and the resulting precipitate was collected and recrystallized from ethanol to obtain white crystals of 80 g of the cinnamic acid derivative (A-5).

<Synthesis of other pretilt-developing compounds> Synthesis Example 10

The compound (T-1) was synthesized according to the following route.

Synthetic route 8

In a 500 mL three-necked flask equipped with a reflux condenser and a nitrogen introduction tube, 39 g of β-cholesterol, 20 g of succinic anhydride, 1.5 g of N,N-dimethylaminopyridine, 200 mL of ethyl acetate, and 17 mL of triethyl were added. The amine was refluxed for 8 hours to carry out the reaction. After the completion of the reaction, 200 mL of tetrahydrofuran was added to the reaction mixture, and the obtained organic layer was washed twice with 1N aqueous hydrochloric acid and then washed three times with water, and dried over magnesium sulfate. The ethyl ester was recrystallized to obtain 38 g of a white crystal of Compound (T-1).

<Synthesis of polyorganosiloxane (A)> Synthesis Example 11

In a 200 mL three-necked flask, 10.0 g of the epoxy group-containing polyorganooxane EPS-1 synthesized in the above Synthesis Example 1, 30.28 g of methyl isobutyl ketone, and 1.16 g of the compound b obtained in the above Synthesis Example 2 ( B-1-1) (corresponding to 10 mol% of the epoxy group of the polyorganooxyalkylene ESP-1), 1.59 g of the specific cinnamic acid derivative (A-1) obtained in the above Synthesis Example 5 (relative The polyoxyalkylene oxide ESP-1 has an epoxy group corresponding to 10 mol%) and 2.06 g of the specific cinnamic acid derivative (A-6) shown below (relative to the polyorganooxyalkylene ESP-1). The epoxy group (corresponding to 10 mol%) and 0.10 g of UCAT 18X (trade name, a hardening accelerator of an epoxy compound manufactured by San-apro Co., Ltd.) were stirred at 100 ° C for 48 hours to carry out a reaction. After the completion of the reaction, methanol was added to the reaction mixture to form a precipitate. The precipitate was dissolved in ethyl acetate, and the obtained solution was washed with water three times. The organic layer was dried over magnesium sulfate, and then the solvent was evaporated to give 8.1 g. A white powder of alkane POS-1. The weight average molecular weight of POS-1 is 10,700.

Synthesis Examples 12 to 34, Comparative Synthesis Examples 1 to 6

The polyorganooxane (A) POS was obtained in the same manner as in Synthesis Example 11 except that the compound shown in Table 1 was used instead of the compound b (B-1-1) and the specific cinnamic acid derivative (A-1). -2~23 and white powder of POSA-1~6.

Among them, the specific cinnamic acid derivative (A-7) has the following structure.

The use ratio of the compound b, the specific cinnamic acid derivative, and other pretilt angle developing compounds in Table 1 is the mol% of the epoxy group which is possessed with respect to the polyorganosiloxane 0.8-1.

In the table, T-2 is stearic acid.

<Synthesis of other polymers> [Synthesis of polyglycine] Synthesis Example PA-1

196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 212 g (1.0 mol) of 2,2'-dimethyl-4,4' as a diamine -diaminobiphenyl dissolved in 4,050 g of N-methyl-2-pyrrolidone and reacted at 40 ° C for 3 hours to obtain 4,400 g of a solution containing 10% by weight of polyglycine (PA-1) . The solution viscosity of the polyaminic acid solution was 170 mPa ‧ s.

Synthesis Example PA-2

41 g of 1,2,3,4-cyclotetracarboxylic dianhydride as tetracarboxylic dianhydride and 46 g of pyromellitic dianhydride and 114 g of BAPC as a diamine were dissolved in 800 g of N-methyl-2- In the pyrrolidone, after reacting at 40 ° C for 3 hours, 1,000 g of N-methyl-2-pyrrolidone was added to obtain about 1,900 g of a solution containing 10% by weight of poly-proline (PA-2). The solution viscosity of the polyaminic acid solution was 115 mPa ‧ s.

Synthesis Example PA-3

82 g of 2,3,5-tricarboxydicyclopentyl acetic acid dihydrate as tetracarboxylic dianhydride and 20 g of p-phenylenediamine as a diamine and 97 g of 3ξ-cholest-3-yl-3 The 5-diaminobenzoic acid ester was dissolved in 800 g of N-methyl-2-pyrrolidone, and after reacting at 60 ° C for 5 hours, 3 g of maleic anhydride as a polymerization terminator was added to obtain about 1,000 g. A solution containing 20% by weight of polylysine (PA-3). The solution viscosity of the polylysine was 110 mPa ‧ s.

Synthesis Example PA-4

38 g of 2,3,5-tricarboxydicyclopentyl acetic acid dihydrate as tetracarboxylic dianhydride and 17 g of 4,4'-diaminodiphenyl ether as diamine and 44 g of 3 ξ-cholesterium The alk-3-yl-3,5-diaminobenzoate was dissolved in 400 g of N-methyl-2-pyrrolidone, and after reacting at 60 ° C for 5 hours, 2 g of a horse as a polymerization terminator was added. To the anhydride, about 500 g of a solution containing 20% by weight of polyglycine (PA-4) was obtained. The solution viscosity of the polylysine was 80 mPa ‧ s.

Synthesis Example PA-5

512 g of 2,3,5-tricarboxydicyclopentyl acetic acid dihydrate as tetracarboxylic dianhydride and 324 g of 4,4'-diaminodiphenyl ether as diamine and 363 g of 3ξ-cholesterium The alk-3-yl-3,5-diamino benzoate was dissolved in 4800 g of N-methyl-2-pyrrolidone, and after reacting at 60 ° C for 5 hours, 22 g of a horse as a polymerization terminator was added. To the anhydride, about 6000 g of a solution containing 20% by weight of polyglycine (PA-5) was obtained. The solution viscosity of the polylysine was 80 mPa ‧ s.

[Synthesis of Polyimine] Synthesis example PI-1

20.9 g (0.093 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 9.2 g (0.085 mol) of p-phenylenediamine as diamine and 4.9 g (0.009 mol) The compound of the formula (D-2) was dissolved in 140 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 4 hours to obtain a solution containing polylysine.

A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 126 mPa·s.

Next, 325 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 7.4 g of pyridine and 9.5 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain about 210 g of a polyamidene (PI-1) containing 16.1% by weight of a ruthenium iodide ratio of about 54%. )The solution.

The polyimine solution was dispensed in small portions, and N-methyl-2-pyrrolidone was added to form a solution having a polymer concentration of 10% by weight, and the measured solution viscosity was 75 mPa·s.

[Synthesis of hardener] Synthesis Example S-1

The compound (S-1) was synthesized according to the following route.

21 g of trimesic acid, 60 g of n-butyl vinyl ether, and 0.09 g of phosphoric acid were placed in a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, and the mixture was stirred at 50 ° C for 30 hours to carry out a reaction. After completion of the reaction, 500 mL of hexane was added to the reaction mixture, and the obtained organic layer was washed twice with a 1 M aqueous sodium hydroxide solution and then with water. Then, the solvent was distilled off from the organic layer to obtain 50 g of the compound (S-1) as a colorless transparent liquid.

<Evaluation of preparation and storage stability of liquid crystal alignment agent> Example 1

A solution containing poly-proline PA-1 synthesized by the above-mentioned synthesis example PA-1 as another polymer was selected, and the amount of PA-1 was equivalent to 2,000 parts by weight, and 100 parts by weight was added thereto as polyorganosiloxane. The polyorganooxane POS-1 synthesized in the above synthesis example is then added with N-methyl-2-pyrrolidone and butyl cellosolve to form a solvent to form N-methyl-2-pyrrolidone: butyl cellosolve = 50:50 (weight ratio), a solution having a solid concentration of 3.6% by weight. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent C-1. The liquid crystal alignment agent C-1 was evaluated for storage stability by the following method and judgment criteria, and the storage stability of the liquid crystal alignment agent C-1 was "good".

[Evaluation of preservation stability]

The liquid crystal alignment agent was stored at -15 ° C for 6 months. The viscosity was measured by an E-type viscometer at 25 ° C before and after storage. When the rate of change before and after storage of the solution viscosity was less than 10%, the storage stability was evaluated as "good", and when it was 10% or more, the storage stability was "not good".

Examples 2 to 23 and Comparative Examples 1 to 11

The liquid crystal alignment agents C-2 to 23 and CA-1 to 11 were prepared in the same manner as in the above Example 1, except that the types and amounts of the polyorganosiloxane were as shown in Table 2, and the storage stability was evaluated. The evaluation results are shown in Table 2.

In the table, S-2 is 1,2,4-benzenetricarboxylic acid.

Example 24 <Manufacture and evaluation of liquid crystal display elements> [Manufacture of liquid crystal display elements]

The liquid crystal alignment agent C-1 prepared in the above Example 1 was applied onto the transparent electrode surface of the glass substrate having the transparent electrode formed of the ITO film, and prebaked on a hot plate at 80 ° C for 1 minute. The film was heated at 200 ° C for 1 hour in a nitrogen purge oven in a box to form a coating film having a film thickness of 0.1 μm. Next, on the surface of the coating film, a polarized ultraviolet ray of 200 J/m ² containing a ray of 313 nm was irradiated from a direction in which the substrate normal was inclined by 40° using an Hg-Xe lamp and a Glan-Taylor prism to form a liquid crystal alignment film. The same operation was repeated to manufacture a pair of (two pieces) substrates having a liquid crystal alignment film.

On the outer periphery of the surface of the substrate having a liquid crystal alignment film, an epoxy resin adhesive having a diameter of 5.5 μm is applied by screen printing, and the liquid crystal alignment film of the pair of substrates is faced. The bonding was performed so that the ultraviolet light axis of each substrate was reversely parallel to the projection direction of the substrate surface, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, a negative liquid crystal (manufactured by Merck, MLC-6608) was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, it was heated to 150 ° C, and then slowly cooled to room temperature. Next, the polarizing plates were bonded to the outer surfaces of the substrate so that the polarization directions thereof were orthogonal to each other, and the ultraviolet light axis of the liquid crystal alignment film was formed at an angle of 45° toward the projection direction of the substrate surface to fabricate a liquid crystal display element.

[Evaluation of liquid crystal display elements]

In addition to (1) evaluation of liquid crystal alignment property and (2) measurement of voltage holding ratio of the liquid crystal display element manufactured as described above, (3) evaluation of light resistance and (4) evaluation of pretilt stability were performed. The evaluation results are shown in Table 3.

(1) Evaluation of liquid crystal alignment

When the 5 V voltage was turned ON and OFF (applied ‧ released) by the visual observation of the liquid crystal display element manufactured as described above, there was an abnormal region where there was no change in brightness.

When the voltage is OFF, no light is observed to pass through the cell, and when the voltage is applied, the cell drive region is displayed in white, and the region other than the light is not transmitted as the liquid crystal alignment property. When the voltage is turned off, the light is observed. When the light is transmitted through the cell or when the voltage is turned on, it is evaluated that the light is transmitted from the region other than the driving region, and the liquid crystal alignment property is "not good", and the liquid crystal alignment property of the liquid crystal display device is "good".

(2) Evaluation of voltage retention rate

For each of the liquid crystal display elements manufactured above, a voltage of 5 V was applied at 60 ° C for an application time of 60 μsec and an interval of 167 msec, and then the voltage holding ratio after the application was released for 167 msec was measured. VHR-1 was used as a measuring device for the voltage holding ratio.

(3) Light resistance evaluation

The initial voltage holding ratio was measured under the same conditions as the voltage holding ratio evaluation of the liquid crystal display element manufactured as described above. Thereafter, the distance was 5 cm under a 100 watt white fluorescent lamp, and after 500 hours of light irradiation, the voltage holding ratio was measured again under the same conditions as above. When the voltage reduction rate is 1% or less, the light resistance is "A", and when it is more than 1%, it is "B" when it is less than 2%, and when it is more than 2%, the light resistance is "C". "."

(4) Evaluation of the stability of the pretilt angle

Each of the liquid crystal display elements manufactured as described above is based on Non-Patent Document 2 (TJ Scheffer et. al., J. Appl. Phys. vol. 48, p. 1783 (1977)) and Non-Patent Document 3 (F. Nakano, et. Al., JPN. J. Appl. Phys. vol. 19, p. 2013 (1980)), the pretilt angle (initial pretilt angle) is measured by a crystal rotation method using a He-Ne laser.

Next, the liquid crystal display element after measuring the initial pretilt angle was allowed to stand at 23 ° C for 30 days, and then the pretilt angle (pretilt angle after storage) was measured again by the same method as described above.

At this time, the amount of change in the pretilt angle after storage from the initial pretilt angle was examined. When the value is less than 0.1°, the stability of the pretilt angle with time is “good”, and when it is 0.1° or more and less than 0.3°, it is “yes”, and when it is 0.3° or more, it is “not acceptable”.

Examples 25 to 39, 42 to 45, and Comparative Examples 12 to 17

A liquid crystal display element was produced and evaluated in the same manner as in Example 24 except that the type of the liquid crystal alignment agent used was as described in Table 3. The results are shown in Table 3.

Example 40, 41, Comparative Example 18-21

In addition to irradiating polarized ultraviolet rays from the normal direction of the substrate, a polarizing plate was bonded using nematic liquid crystal (manufactured by Merck, ZLI-1565) so that the polarization directions thereof were orthogonal to each other, and the optical axis of the liquid crystal alignment film and the polarized ultraviolet light were directed to the substrate surface. The liquid crystal display elements were produced and evaluated in the same manner as in the above-described Example 24 except that the projection directions were orthogonal. The results are shown in Table 3.

Example 46, Comparative Example 22

The liquid crystal display element was produced and evaluated in the same manner as in Example 24 except that the type of the liquid crystal alignment agent used was as described in Table 3, except that the step of irradiating the polarized ultraviolet light was not performed. The results are shown in Table 3.

Claims (7)

A liquid crystal alignment agent comprising a polyorganosiloxane having a acetal structure of a carboxylic acid, a ketal structure of a carboxylic acid, a 1-alkylcycloalkyl group of a carboxylic acid At least one structure selected from the group consisting of an ester structure and a tertiary alkyl ester structure of a carboxylic acid. The liquid crystal alignment agent of claim 1, wherein the polyorganosiloxane has an epoxy structure. The liquid crystal alignment agent according to claim 1, wherein the polyorganosiloxane is a polyorganosiloxane obtained by reacting a polyorganosiloxane having an epoxy group with a compound having the following compound, the compound having At least one group selected from the group consisting of a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR, -CH=CH ₂ and -SO ₂ Cl, and a acetal ester structure of a carboxylic acid, a condensation of a carboxylic acid At least one structure selected from the group consisting of a ketoester structure, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a tertiary butyl ester structure of a carboxylic acid, wherein R is a hydrogen atom or has 1 carbon atom ~6 alkyl. The liquid crystal alignment agent of claim 1, wherein the polyorganosiloxane has a photo-alignment group. The liquid crystal alignment agent according to any one of claims 1 to 4, further comprising at least one polymer selected from the group consisting of polyproline and polyimine. The liquid crystal alignment agent according to any one of claims 1 to 4, further comprising an acetal structure free of a carboxylic acid, a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkane of a carboxylic acid A polyorganosiloxane having a lactone structure and a tertiary alkyl ester structure of a carboxylic acid. A liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal alignment agent according to any one of claims 1 to 6.