TWI448489B - Radiation-sensitive polyorganosiloxane, method for manufacturing radiation-sensitive polyorganosiloxane and liquid crystal aligning agent - Google Patents

Description

Method for producing radiation-sensitive polyorganosiloxane, radiation-sensitive polyorganosiloxane, and liquid crystal alignment agent

The present invention relates to a method for producing a radiation-sensitive polyorganosiloxane, a radiation-sensitive polyorganosiloxane, and a liquid crystal alignment agent. More specifically, it relates to a radiation-sensitive polyorganosiloxane which can be suitably used in a liquid crystal alignment agent used in a photo-alignment method and a method for its simple preparation.

Heretofore, it has been known that a nematic liquid crystal having positive dielectric anisotropy forms a sandwich structure in a substrate having a transparent electrode having a liquid crystal alignment film, and continuously twists a long axis of liquid crystal molecules between substrates as needed. A liquid crystal display element having a liquid crystal cell such as a TN (twisted nematic) type, an STN (super twisted nematic) type, or an IPS (in-plane switching) type produced by ~360° (refer to Patent Documents 1 and 2).

In such a liquid crystal cell, in order to align liquid crystal molecules in a certain direction with respect to the surface of the substrate, it is necessary to provide a liquid crystal alignment film on the surface of the substrate. Such a liquid crystal alignment film is usually formed by a method (grinding method) of rubbing the surface of the organic film formed on the surface of the substrate in a certain direction with a cloth such as rayon. However, when the formation of the liquid crystal alignment film is performed by the rubbing treatment, dust and static electricity are likely to be generated in the step, and dust adheres to the surface of the alignment film, which causes a display failure. In particular, in the case of a substrate having a TFT (Thin Film Transistor) device, there is a problem in that the generated static electricity causes damage to the TFT element circuit and causes a decrease in yield. Further, in the liquid crystal display element, which is increasingly highly refined in the future, the surface of the substrate is uneven due to the high density of the pixels, and it becomes difficult to perform the polishing process uniformly.

As another means for aligning the liquid crystal in the liquid crystal cell, it is known that a photosensitive film such as polyethylene cinnamate, polyimine or azobenzene derivative formed on the surface of the substrate is irradiated with polarized or non-polarized radiation. A photo-alignment method that produces a liquid crystal alignment capability. According to this method, static electricity and dust are not generated, and uniform liquid crystal alignment can be achieved (refer to Patent Documents 3 to 13).

Further, as an operation mode of the liquid crystal display element other than the above, a homeotrophic alignment mode in which liquid crystal molecules having negative dielectric anisotropy are vertically aligned on a substrate is also known. In this operation mode, when a voltage is applied between the substrates to tilt the liquid crystal molecules in a direction parallel to the substrate, it is necessary to tilt the liquid crystal molecules from the substrate normal direction in one direction in the substrate surface. As means for achieving such a purpose, for example, a method of providing a protrusion on a surface of a substrate, a method of providing a strip on a transparent electrode, and a direction in which a liquid crystal molecule is directed from a normal direction of a substrate to a surface of a substrate by using a polishing alignment film has been proposed. A method of slightly tilting (making it pre-tilted).

The above photoalignment method is also known to be useful as a method of controlling the tilt direction of liquid crystal molecules in a liquid crystal cell of a vertical alignment mode. In other words, it is known that the tilting direction of the liquid crystal molecules when the voltage is applied can be uniformly controlled by using the vertical alignment liquid crystal alignment film which imparts the alignment control force and the pretilt angle expression by the photo-alignment method (refer to Patent Documents 11 to 12). And 14~16).

Therefore, the liquid crystal alignment film produced by the photoalignment method can be effectively applied to various liquid crystal display elements. However, in the conventional photoalignment film, there is a problem that a large amount of radiation irradiation is required in order to obtain a large pretilt angle. For example, it has been reported that when a film having an azobenzene derivative is subjected to a liquid crystal alignment ability by a photo-alignment method, in order to obtain a sufficiently large pretilt angle, it is necessary to irradiate an optical axis of 10000 J/m ² or more from the substrate normal. Radiation (refer to Patent Documents 13 to 14 and Non-Patent Document 1). It has been pointed out that the liquid crystal alignment film formed by these techniques can exhibit a good pretilt angle at the initial stage of formation, but a phenomenon in which the pretilt angle expression is lost with time, and the stability of the pretilt angle with time is poor. .

In order to solve these problems, the present inventors have discovered and reported in recent years that a hydrocyclylation reaction is employed to introduce a group derived from a specific cinnamic acid derivative into hydrogen sesquioxane to prepare a radiation-sensitive polyorganism. The siloxane, the liquid crystal alignment agent containing the same, is capable of forming a liquid crystal alignment film which exhibits good liquid crystal alignment ability even by a light alignment method using a small amount of radiation irradiation, and exhibits a good pretilt angle. The stability of the expression and the pretilt angle with time (refer to Patent Documents 19 to 21). However, in this technique, since hydrogen sesquioxanes used as a raw material are unstable to moisture or the like, there is a problem that a special device or a need for care is required in terms of storage, handling, and the like.

current technology

Patent Document 1 Japanese Patent Laid-Open No. 56-91277

Patent Document 2 Japanese Patent Laid-Open No. Hei 1-120528

Patent Document 3 Japanese Patent Laid-Open No. Hei 6-287453

Patent Document 4 Japanese Patent Laid-Open No. Hei 10-251646

Patent Document 5 Japanese Patent Laid-Open No. 11-2815

Patent Document 6 Japanese Patent Laid-Open No. Hei 11-152475

Patent Document 7 Japanese Patent Laid-Open Publication No. 2000-144136

Patent Document 8 Japanese Patent Laid-Open Publication No. 2000-319510

Patent Document 9 Japanese Patent Laid-Open Publication No. 2000-281724

Patent Document 10 Japanese Patent Laid-Open No. Hei 9-297313

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

Patent Document 12, JP-A-2004-163646

Patent Document 13 Japanese Patent Laid-Open Publication No. 2002-250924

Patent Document 14 Japanese Patent Laid-Open Publication No. 2004-83810

Patent Document 15 Japanese Patent Laid-Open No. Hei 9-211468

Patent Document 16 Japanese Patent Laid-Open Publication No. 2003-114437

Patent Document 17 Japanese Laid-Open Patent Publication No. SHO63-291922

Patent Document 18 Japanese Patent Publication No. 2003-520878

Patent Document 19 Japanese Patent Application No. 2007-305525

Patent Document 20 PCT/JP2008/065228

Patent Document 21 PCT/JP2008/065231

Non-Patent Document 1 J. of the SID 11/3, 2003, p579

Non-Patent Document 2 Journal of American Chemical Society, Vol. 92, No. 19, p5586 (1970)

Non-Patent Document 3 T. J. Scheffer et al., J. Appl. Phys. Vol. 19, p2013 (1980)

Non-Patent Document 4 Chemical Reviews, Vol. 95, p1409 (1995)

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for easily preparing a radiation-sensitive polyorganosiloxane having a stable and easy-to-handle raw material, which is suitable for being capable of forming a liquid crystal. a liquid crystal alignment agent of an alignment film which exhibits good liquid crystal alignment ability even by a light alignment method using a small amount of radiation irradiation, and exhibits good pretilt performance and a change in pretilt angle with time. stability.

According to the present invention, the above objects and advantages of the present invention are attained by a radiation sensitive polyorganosiloxane having a structure represented by the following formula (3).

In the formula (3), R is a hydrogen atom or a methyl group, and n is an integer of 1 to 10. R ¹ is a group represented by the following formula (R ^1-1 ), R ² is a fluorine atom or a cyano group, and b is an integer of 0 to 4.

In the formula (R ¹ -1), R ¹ is an alkyl group having 1 to 40 carbon atoms, or a monovalent hydrocarbon group having 3 to 40 carbon atoms containing an alicyclic group or a fused ring group. Wherein a part or all of the hydrogen atom of the above alkyl group may be substituted by a fluorine atom, and R ^II is a single bond, an oxygen atom, *-COO- or *-OCO- (wherein the above linkage bond with "*" and R ^I connection), R ^III is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, R ^IV is a single bond, an oxygen atom, * -COO- or *-OCO- (where the above connection key with "*" is connected to R ^III ), a is an integer from 0 to 3.

Further, it is also achieved by a method for producing a radiation-sensitive polyorganosiloxane, which comprises a polyorganosiloxane having a structure represented by the following formula (1) and a compound represented by the following formula (2). Carrying out the reaction in the presence of a heavy metal compound or a heavy metal complex,

In the formula (1), R is a hydrogen atom or a methyl group, and n is an integer of 1 to 10.

In the formula (2), R ¹ is a group represented by the following formula (R ^1-1 ), R ² is a fluorine atom or a cyano group, b is an integer of 0 to 4, Z is a halogen atom, or has carbon An alkylsulfonate group of an alkyl group having 1 to 6 atoms, or an arylsulfonate group having an aryl group having 6 to 10 carbon atoms, wherein the alkylsulfonate group has The alkyl group may be substituted by a fluorine atom.

In the formula (R ¹ -1), R ^I is an alkyl group having 1 to 40 carbon atoms, or a monovalent hydrocarbon group having an alicyclic group or a fused ring group having 3 to 40 carbon atoms, wherein A part or all of the hydrogen atom of the above alkyl group may be substituted by a fluorine atom, and R ^II is a single bond, an oxygen atom, *-COO- or *-OCO- (wherein the above linkage bond with "*" is bonded to R ^I R ^III is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group, and R ^IV is a single bond, an oxygen atom, *- COO- or *-OCO- (where the above connection key with "*" is connected to R ^III ), a is an integer from 0 to 3.

According to the present invention, there is provided a process for the simple preparation of a radiation sensitive polyorganosiloxane using a stable and easily processable starting material. The radiation-sensitive polyorganosiloxane produced by the method of the present invention can be suitably used for a liquid crystal alignment agent used in a photo-alignment method, and a liquid crystal alignment agent containing the above-mentioned radiation-sensitive polyorganosiloxane, even by using a small amount of radiation irradiation. The photo-alignment method can also form a liquid crystal alignment film which exhibits good liquid crystal alignment ability and exhibits good pretilt performance and stability with respect to the pretilt angle with time.

detailed description

The process for producing a radiation-sensitive polyorganosiloxane according to the present invention is characterized in that a polyorganosiloxane having a structure represented by the above formula (1) (hereinafter referred to as "poly(organo)oxy group having a (meth) acryloxy group) The alkane ") is reacted with a compound represented by the above formula (2) (hereinafter referred to as "compound (2)") in the presence of a heavy metal compound or a heavy metal complex.

<Polyorganosiloxane having (meth)acryloxyloxy group>

Examples of the polyorganosiloxane having the structure represented by the above formula (1) include polyorganosiloxane having a repeating unit represented by the following formula (1'), hydrolyzate and hydrolyzate thereof. At least one of the group consisting of condensates,

In the formula (1'), R and n are each the same as defined in the above formula (1), and 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 An aryl group having 6 to 20 carbon atoms.

In the above formula (1), R is preferably a hydrogen atom. n in the formula (1) is preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3.

In the above formula (1'), the alkoxy group having 1 to 10 carbon atoms of Y ¹ 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-lauryl, n-dodecyl, positive Tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, etc.; as carbon Examples of the aryl group having 6 to 20 atoms include a phenyl group and the like.

The polyorganosiloxane having a (meth) propylene oxime group preferably has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) of from 500 to 100,000, more preferably from 1,000 to 10,000, further Good for 1000~5000.

Such a polyorganosiloxane having a (meth) acryloxy group may preferably be obtained by reacting a decane compound having a (meth) propylene fluorenyloxy group or a decane compound having a (meth) acryloxy group with The mixture of other decane compounds is preferably synthesized by hydrolysis, hydrolysis or condensation in the presence of a suitable organic solvent, water and a catalyst.

Examples of the decane compound having a (meth) propylene fluorenyloxy group include 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, and 3-propene oxime. Oxypropyl triethoxy decane, 3-methyl propylene methoxy propyl triethoxy decane, and the like.

The other decane compound may, for example, be tetrachlorodecane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane or tetra-second butyl. Oxy decane, trichloro decane, trimethoxy decane, triethoxy decane, tri-n-propoxy decane, triisopropoxy decane, tri-n-butoxy decane, tri-butoxy decane, fluoro Trichlorodecane, fluorotrimethoxydecane, fluorotriethoxydecane, fluorotri-n-propoxy decane, fluorotriisopropoxy decane, fluorotri-n-butoxy decane, fluorotriene Dibutoxydecane, methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane, methyltri-n-butyl Oxydecane, methyl tri-tert-butoxydecane, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxydecane, 2-(trifluoromethyl) Ethyltriethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltriisopropoxydecane, 2-(trifluoromethyl) Ethyl n-Butoxydecane, 2-(trifluoromethyl)ethyltri-t-butoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxy Baseline, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 2-(perfluoro-n-hexane 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 Tris-butoxy decane, 2-(perfluoro-n-octyl)ethyltrichlorodecane, 2-(perfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro-n-octyl)ethyl Triethoxy decane, 2-(perfluoro-n-octyl)ethyltri-n-propoxy decane, 2-(perfluoro-n-octyl)ethyltriisopropoxydecane, 2-(perfluoro-n-octyl) Ethyl tri-n-butoxy decane, 2-(perfluoro-n-octyl)ethyltri-n-butoxy decane, hydroxymethyltrichloro decane, hydroxymethyltrimethoxy decane, hydroxyethyltrimethoxy Base decane, methylol tri-n-propoxy decane, hydroxymethyl triisopropoxy decane, hydroxymethyl tri-n-butoxy decane, hydroxymethyl three-butoxy decane, vinyl trichloro decane, Vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane, vinyl tri-n-butoxy decane, vinyl tri-n-butoxy Decane, allyltrichloromethane, allyltrimethoxydecane, allyltriethoxydecane,allyltri-n-propoxydecane,allyltriisopropoxydecane,allyl-3 N-butoxy decane, allyl tri-tert-butoxy decane, phenyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl tri-n-propoxy decane, phenyl tri Isopropoxydecane, phenyltri-n-butoxydecane, phenyltri-n-butoxydecane, methyldichlorodecane, methyldimethoxydecane, methyldiethoxydecane, methyldi N-propoxy decane, methyl diisopropoxy decane, methyl di-n-butoxy decane, methyl di-butoxy decane, dimethyl dichloro guanidine , dimethyl dimethoxy decane, dimethyl diethoxy decane, dimethyl di-n-propoxy decane, dimethyl diisopropoxy decane, dimethyl di-n-butoxy decane, two Methyl di-butoxy decane, (methyl) [2-(perfluoro-n-octyl)ethyl]dichlorodecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dimethyl Oxydecane, (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)diethoxydecane, (methyl)(vinyl)di Chlorodecane, (meth) (vinyl) dimethoxy decane, (methyl) (vinyl) diethoxy decane, (methyl) (vinyl) di-n-propoxy decane, (methyl) (vinyl) diisopropoxy decane, (methyl) (vinyl) di-n-butoxy decane, (methyl) (vinyl) di-butoxy decane, divinyl dichloro decane, two Vinyl dimethoxy decane, two Alkenyl diethoxy decane, divinyl di-n-propoxy decane, divinyl diisopropoxy decane, divinyl di-n-butoxy decane, divinyl di-n-butoxy decane, two Phenyldichlorodecane, diphenyldimethoxydecane, diphenyldiethoxydecane, diphenyldi-n-propoxydecane, diphenyldiisopropoxydecane, diphenyldi-n-butyl Oxy decane, diphenyl bis second butoxy decane, chlorodimethyl decane, methoxy dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl Decane, iodotrimethyldecane, methoxytrimethyldecane, ethoxytrimethylnonane, n-propoxytrimethyldecane, isopropoxytrimethyldecane, n-butoxytrimethyl Decane, second butoxytrimethylnonane, third butoxytrimethyldecane, (chloro)(vinyl)dimethylsilane, (methoxy)(vinyl)dimethylsilane, ( Ethoxy)(vinyl)dimethyl decane, (chloro)(methyl)diphenylnonane, (methoxy)(methyl)diphenylnonane, (ethoxy)(methyl)di Phenyl decane has one ruthenium atom The decane compound may be exemplified by, 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 by Shin-Etsu Chemical Co., Ltd.); Glass Resin (made by Showa Denko); SH804, SH805, SH806A, SH840 , SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above by Toray Dow Corning Co., Ltd.); FZ3711, FZ3722 (above by Unicar Co., Ltd.); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DM S-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above by CHISSO); Methyl Silicate MS51, Methyl Silicate MS56 (above by Mitsubishi Chemical Co., Ltd.); Ethyl Silicate 28, Ethyl Silicate 40, Ethyl Silicate 48 (above by COLCOAT); GR100, GR650, GR908, GR950 (above by Showa Denko A partial condensate such as (stock).

Among these other decane compounds, preferred are tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane. , allyl trimethoxy decane, allyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, dimethyl dimethoxy decane, 3-epoxy propoxy propyl Triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane or dimethyl Diethoxy decane.

The content ratio of the (meth)acryloxy group in the polyorganosiloxane having a (meth) acryloxy group used in the present invention is preferably 0.1 to 10 mmol/g, more preferably 1 to 7.5 mmol/ g. Therefore, in the synthesis of a polyorganosiloxane having a (meth) acryloxy group, the use ratio of the decane compound having a (meth) propylene oxime group to other decane compounds is preferably such that the obtained polyorgano oxime The content ratio of the (meth)acrylomethoxy group in the alkane is adjusted to the above range and is set.

Examples of the organic solvent which can be used in the synthesis of the polyorganosiloxane having a (meth) acryloxy group include hydrocarbons, ketones, esters, ethers, alcohols and the like.

Examples of the hydrocarbons include toluene and xylene; and examples of the ketones include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, and cyclohexanone. And the above-mentioned esters may, for example, be ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate or the like; Examples of the ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, and An alkane or the like; examples of the above alcohols include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and 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, a water-insoluble solvent is preferred.

These organic solvents may be used singly or in combination of two or more.

The amount of the organic solvent is preferably from 10 to 10,000 parts by weight, more preferably from 50 to 1,000 parts by weight, per 100 parts by weight of the total of the decane compound.

The amount of water used in the preparation of the polyorganosiloxane having a (meth) acryloxy group is preferably from 0.5 to 100 moles, more preferably from 1 to 30 moles per mole of the decane compound.

As the catalyst, for example, an acid, an alkali metal compound, an organic ruthenium, 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.

The organic hydrazine may, for example, be an organic primary or secondary amine such as ethylamine, diethylamine, oxazine, acridine, pyrrolidine or pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine or 4- An organic tertiary amine such as dimethylaminopyridine or diazabicycloundecene; or an organic quaternary ammonium salt such as tetramethylammonium hydroxide. Among these organic oximes, organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine; and organic quaternary ammonium salts such as tetramethylammonium hydroxide are preferred.

As a catalyst for preparing a polyorganosiloxane having a (meth) propylene fluorenyloxy group, an alkali metal compound or an organic hydrazine is preferred.

A liquid crystal alignment agent containing a radiation-sensitive polyorganosiloxane which is prepared from a polyorganosiloxane having a (meth) propylene oxime group synthesized using an alkali metal compound or an organic ruthenium as a catalyst, and has excellent storage stability. It is very convenient. The reason is as indicated in Non-Patent Document 4 (Chemical Reviews, Vol. 95, p. 409 (1995)), and it is presumed that it may be due to the use of an alkali metal compound or organic ruthenium as a catalyst in the hydrolysis or condensation reaction. A random structure, a trapezoidal structure or a cage structure is formed to obtain a polyorganosiloxane having a small content ratio of sterol groups. It is presumed that since the content ratio of the sterol group is small, the condensation reaction between the sterol groups can be suppressed, and when the above liquid crystal alignment agent further contains other polymers, the condensation reaction of the sterol group with other polymers can be suppressed. Thus, excellent results in storage stability are obtained.

As a catalyst, it is particularly preferred to be an organic hydrazine. The use ratio of the organic hydrazine varies depending on the type of the organic hydrazine, the reaction conditions, and the like, and should be appropriately set. For example, it is preferably 0.01 to 3 moles, more preferably 0.05 to 1 mole, based on the total decane compound. .

Hydrolysis or hydrolysis condensation reaction for preparing a polyorganosiloxane having a (meth) propylene oxime group, preferably by dissolving a decane compound having a (meth) propylene oxime group and other decane compounds as needed In the organic solvent, the solution is mixed with organic hydrazine and water, and further heated by, for example, an oil bath.

In the hydrolysis condensation reaction, the heating temperature is preferably 130 ° C or lower, more preferably 40 to 100 ° C, more preferably 0.5 to 12 hours, more preferably 1 to 8 hours. The mixture may be stirred during heating or placed under reflux.

After completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction liquid with water. At the time of this washing, it is preferable to wash with a water containing a small amount of salt, for example, an aqueous solution containing about 0.2% by weight of ammonium nitrate, from the viewpoint of facilitating the washing operation. The washing is carried out until the aqueous layer after washing is neutral, and then the organic solvent layer is dried with an appropriate desiccant such as anhydrous calcium sulfate or molecular sieve as needed, and then the solvent is removed to obtain (meth) propylene oxide. A polyorganosiloxane target for the base.

In the present invention, a commercially available product can also be used as the polyorganosiloxane having a (meth)acryloxy group. Examples of such a commercially available product include AC-SQ and MC-SQ (all of which are manufactured by East Asia Synthetic Co., Ltd.).

<compound (2)>

The compound (2) used in the process for producing a radiation sensitive polyorganosiloxane of the present invention is a compound represented by the above formula (2).

R ¹ in the above formula (2) is a group represented by the above formula (R ^1-1 ).

The alkyl group having 1 to 40 carbon atoms of R ¹ in the above formula (R ¹ -1) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 4 to 20 carbon atoms. The alkyl group is preferably a linear alkyl group, and a part or all of the hydrogen atoms of the alkyl group may be substituted by a fluorine atom. As examples of such a group, for example, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecane may be mentioned. 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-(perfluorooctyl Ethyl, 2-(perfluorodecyl)ethyl and the like.

The monovalent organic group having 3 to 40 carbon atoms of the alicyclic group or the fused ring group of R ¹ may, for example, be a cholesteryl group, a cholesteryl group or an adamantyl group.

Examples of the divalent aromatic group of R ^III include a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, and 2,3. 5,6-tetrafluoro-1,4-phenylene; etc.; as the divalent alicyclic group of R ^III , for example, 1,4-cyclohexylene, etc.; as a divalent heterocyclic group of R ^III For example, a 1,4-pyridylpyridyl group, a 2,5-extended pyridyl group, a 1,4-extended furyl group, etc., and a divalent condensed cyclic group of R ^III may, for example, be an extended naphthyl group.

a is preferably 0 or 1.

b is preferably 0 or 1, more preferably 0.

Examples of the halogen atom of Z include a chlorine atom, a bromine atom, an iodine atom, and the like; and an alkylsulfonate group having an alkyl group having 1 to 6 carbon atoms (in which an alkylsulfonate group has an alkane) The group may be substituted by a fluorine atom, and examples thereof include a methylsulfonate group, an ethylsulfonate group, a trifluoromethylsulfonate group, and the like; and an aryl group having an aryl group having 6 to 10 carbon atoms; Examples of the sulfonate group include a phenylsulfonate group and a p-tolylsulfonate group. The Z in the above formula (2) is preferably a bromine atom, an iodine atom, a methylbenzenesulfonyl group, a trifluoromethylbenzenesulfonyl group or a p-tolylsulfonyl group.

Preferred examples of the compound (2) include compounds represented by the following formulas (2-1) to (2-9), and the like.

In the formulae (2-1) to (2-9), R ^I is the same as defined in the above formula (R ¹ -1), and Z is the same as defined in the above formula (2).

The use ratio of the compound (2) in the method of the present invention is preferably 0.001 to 1.5 moles per 1 mole of (meth)acryloxyloxy group in the polyorganosiloxane having a (meth)acryloxy group. The ear is more preferably 0.01 to 1 mol, further preferably 0.05 to 0.9 mol.

<Heavy metal compound or heavy metal complex>

The heavy metal element contained in the heavy metal compound or the heavy metal complex used in the process for producing the radiation sensitive polyorganosiloxane of the present invention is preferably palladium.

In the present invention, as the heavy metal compound or heavy metal complex, a divalent palladium compound or a zero-valent palladium complex is preferably used, and a divalent palladium compound is more preferably used, and palladium acetate is particularly preferably used.

In the present invention, as the heavy metal compound or the heavy metal complex, when a divalent palladium compound is used, it may be coexisted with at least one selected from the group consisting of a compound having a phosphorus atom and ruthenium. Examples of the compound having a phosphorus atom include triphenylphosphine and tris(phosphinotolyl)phosphine; and examples of the hydrazine include triethylamine and potassium carbonate. As the heavy metal compound or the heavy metal complex, when a divalent palladium compound is used, it is more preferable to coexist with both the compound having a phosphorus atom and the ruthenium.

The use ratio of the heavy metal compound or the heavy metal complex in the method of the present invention is preferably 0.0005 to 1 mol, more preferably 0.005 to 0.1 mol, based on 1 mol of the compound (2). When a compound having a phosphorus atom is used in combination, the use ratio thereof is preferably 0.001 to 1 mol, more preferably 0.01 to 0.5 mol, based on 1 mol of the compound (2). When hydrazine is used, its use ratio is preferably from 1 mole to 100 moles, more preferably from 2 to 10 moles, per mole of the compound (2).

<Preparation of Radiation-Linear Polyorganosiloxanes>

The method for producing a radiation-sensitive polyorganosiloxane according to the present invention is characterized in that the polyorganosiloxane having a (meth)acryloxy group as described above and the compound (2) are as described above for a heavy metal compound or In the presence of a heavy metal complex, it is preferred to carry out the reaction in a suitable organic solvent. This reaction is usually applied to a reaction called "Heck reaction".

Examples of the organic solvent which can be used in the method of the present invention include toluene, xylene, diethyl ether, tetrahydrofuran, anisole, methyl ethyl ketone, methyl isobutyl ketone, and N,N-dimethylformamide. N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl acetate, and the like. The use ratio of the solvent is preferably 5,000 parts by weight or less, more preferably 200 to 2,000 parts by weight, per 100 parts by weight of the compound (2).

The reaction temperature is preferably from 20 to 200 ° C, more preferably from 50 to 150 ° C. The reaction time is preferably from 0.1 to 48 hours, more preferably from 0.5 to 12 hours.

<Inductive radioactive polyorganosiloxane>

The radiation-sensitive linear polyorganosiloxane prepared by the method of the present invention has a structure represented by the following formula (3).

In the formula (3), R and n are the same as defined in the above formula (1), and R ¹ , R ² and b are respectively the same as defined in the above formula (2). Since this structure is easily isomerized according to the direction of radiation polarization by irradiation of radiation, the radiation-sensitive polyorganosiloxane can be suitably used as a component of a liquid crystal alignment agent used in a photo-alignment method.

Hereinafter, a preferred embodiment of the liquid crystal alignment agent prepared by using the radiation sensitive polyorganosiloxane prepared by the method of the present invention will be described, but the present invention is not limited thereto.

<Liquid alignment agent>

A liquid crystal alignment agent containing a radiation-sensitive polyorganosiloxane prepared by the method of the present invention contains the radiation-sensitive polyorganosiloxane as a main component, and may further contain other components as needed.

Examples of such other components include polymers other than the radiation-sensitive polyorganosiloxane prepared by the method of the present invention (hereinafter referred to as "other polymers") and compounds having at least one epoxy group in the molecule (hereinafter referred to as It is an "epoxy compound", a functional decane compound, a hardener, a hardening catalyst, a hardening accelerator, a surfactant, etc.

[Other polymers]

The other polymer may, for example, be at least one polymer selected from the group consisting of polylysine and polyimine, a polyoxyalkylene selected from the following formula (4), and a hydrolyzate thereof. At least one of the group consisting of condensates of hydrolyzates (hereinafter referred to as "other polyoxyalkylenes"), polyphthalates, polyesters, polyamines, cellulose derivatives, polyacetals, poly a styrene derivative, a poly(styrene-phenylmaleimide) derivative, a poly(meth)acrylate, or the like,

In the formula (4), X ² is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, and Y ² It is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

As the other polymer, at least one polymer selected from the group consisting of polylysine and polyimine, or other polyoxyalkylene is preferable.

- Polyproline -

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

Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples thereof include butane tetracarboxylic acid. Acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c]-furan- 1,3-diketone, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-8-methyl-naphthalene [1 ,2-c]-furan-1,3-dione, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane IV A carboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, pyromellitic dianhydride, etc.

Examples of the diamine include an aromatic diamine, an aliphatic diamine, and an alicyclic diamine. Specific examples thereof include p-phenylenediamine and 4,4'-diaminodiphenylmethane. 1,5-Diaminonaphthalene, 2,7-diaminoguanidine, 4,4'-diaminodiphenyl ether, 4,4'-(p-phenylisopropylene)diphenylamine, 2 ,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-di[4-( 4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4' - bis[(4-amino-2-trifluoromethyl)phenoxy]octafluorobiphenyl, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy- 2,4-Diaminobenzene, 1-cholinyloxy-2,4-diaminobenzene, 1-cholestyloxy-2,4-diaminobenzene, hexadecyloxy (3 ,5-diaminobenzimidamide), octadecyloxy (3,5-diaminobenzimidamide), cholesteryloxy (3,5-diaminobenzimidamide), cholestane Oxy (3,5-diaminobenzimid) and the like.

The synthesis reaction of polylysine (reaction of tetracarboxylic dianhydride with diamine as described above) is preferably in a suitable organic solvent, preferably at -20 to 150 ° C, more preferably 0 to 100. Under the temperature condition of °C, it is preferably carried out for 0.5 to 24 hours, more preferably for 2 to 10 hours.

[polyimine]

The above polyiminoimine can be produced by subjecting the proline structure of the polyamic acid obtained as described above to dehydration ring-opening oxime imidization.

a dehydration ring closure of polylysine, which may be (i) by heating a polyphthalic acid or (ii) by dissolving polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution according to It needs to be carried out by heating.

The method of the above (i) can be carried out by heating at, for example, a temperature of 50 to 200 ° C for, for example, 0.5 to 48 hours.

Examples of the dehydrating agent in the above method (ii) include an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride. Examples of the dehydration ring-closure catalyst include pyridine, trimethylpyridine, dimethylpyridine, and triethyl hydride. A tertiary amine such as an amine. The dehydration ring closure reaction is preferably carried out, for example, at a temperature of, for example, 0 to 180 ° C for 0.5 to 20 hours.

[other polyoxyalkylene]

The above-mentioned other polyoxyalkylene may be preferably at least one decane compound (hereinafter also referred to as "raw decane compound") selected from the group consisting of, for example, an alkoxydecane compound and a halogenated decane compound. The organic solvent is prepared by performing hydrolysis or hydrolytic condensation in the presence of water and a catalyst.

Examples of the starting decane compound which can be used herein include tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, and phenyl triethyl hydride. Oxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, trimethylmethoxydecane, trimethylethoxydecane, and the like.

Examples of the catalyst which can be used in the synthesis of the other polyoxyalkylene oxide include a metal chelating agent compound, an organic acid, and an inorganic acid.

The preparation of other polyoxyalkylene can be carried out, for example, at a temperature of from 0 to 100 ° C for, for example, from 0.5 to 24 hours.

[epoxy compound]

As the above epoxy group compound, for example, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamino group) is preferable. Methyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N - diglycidyl-aminomethylcyclohexane or the like.

[Liquid alignment agent]

A liquid crystal alignment agent containing a radiation sensitive polyorganosiloxane prepared by the method of the present invention, containing a radiation sensitive polyorganosiloxane and other components used as needed, preferably a solution prepared by dissolving each component in an organic solvent Composition. The solid content concentration of the liquid crystal alignment agent, that is, the ratio of the weight of all components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent, is appropriately selected depending on the coating method to be considered in view of viscosity, volatility, and the like. It is in the range of 1 to 10% by weight.

<Method of Forming Liquid Crystal Alignment Film>

Next, a method of forming a liquid crystal alignment film using the above liquid crystal alignment agent will be described.

As a method of forming a liquid crystal alignment film, a method of forming a coating film by applying the liquid crystal alignment agent to a transparent substrate provided with a patterned transparent conductive film, for example, and then producing a liquid crystal alignment ability by the photoalignment method is included.

The coating is carried out by a suitable coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. After coating, the coated surface is preheated (prebaked) and then fired (post-baked) to form a coating film. The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C, and the post-baking conditions are, for example, 5 to 200 minutes at 120 to 300 ° C. The thickness of the coating film after post-baking is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

Then, the coating film is irradiated with linearly polarized or partially polarized radiation or non-polarized radiation to impart liquid crystal alignment ability. Here, as the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used, and ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferably used.

The irradiation amount of radiation, preferably 1J / m ² or more and not to 10000J / m ^2, more preferably 10 ~ 3000J / m ^2. Further, the liquid crystal alignment agent comprising a sense prepared by the process according to the invention radiation-sensitive polyorganosiloxane silicon siloxane irradiated amount of radiation when even if the optical alignment method 3000J / m ² or less, even 1000J / m ² or less, also yield good The liquid crystal alignment ability has an advantage of contributing to lowering the manufacturing cost of the liquid crystal display element.

The liquid crystal alignment film formed as described above can be suitably applied to various liquid crystal display elements. The production of the liquid crystal display element can be carried out by a known method using a substrate having a liquid crystal alignment film formed as described above.

[Examples]

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

The weight average molecular weight in the following examples is a polystyrene-converted value measured by gel permeation chromatography under the following conditions.

Pipe column: manufactured by TOSO (stock), TSK gel GRCXL II

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kg f/cm ²

Further, in the following examples, the amount required in the subsequent examples was ensured by repeating the raw material compound and the polymer as follows according to the following synthetic route.

<Synthesis Example of Compound (2)>

Synthesis Example 1 (Synthesis of Compound (2-4-1))

Compound (2-4-1) was synthesized according to the following Scheme 1.

Synthetic route 1

To a 1 L eggplant-shaped 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 of 4, 4 was added. 4-Trifluoro-1-iodobutane was stirred at 100 ° C for 5 hours. After the reaction was completed, reprecipitation was carried out with water. To the resulting precipitate, 48 g of sodium hydroxide and 400 ml of water were added, and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, neutralization was carried out by adding hydrochloric acid to the reaction mixture, and the resulting precipitate was recrystallized from ethanol to obtain 102 g of a white crystal of compound (2-4-1A).

23 g of the compound (2-4-1A) was placed in a reaction vessel, and 200 ml of sulfinium chloride and 144 μL of N,N-dimethylformamide were added thereto, and the mixture was stirred at 80 ° C for 1 hour. Then, the sulfinium chloride was distilled off under reduced pressure, dichloromethane was added, and the obtained organic layer was washed with aqueous sodium hydrogencarbonate, and then dried over magnesium sulfate, and the solvent was distilled off, and then tetrahydrofuran was added to prepare a solution.

Then, 19 g of 4-bromophenol, 11 g of triethylamine, and 100 ml of tetrahydrofuran were placed in a 500 mL three-necked flask other than the above. The solution was ice-cooled, and the above tetrahydrofuran solution was slowly added dropwise, and further reacted at room temperature for 2 hours with stirring. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed three times with water. Then, the organic layer was dried over magnesium sulfate, concentrated, and then evaporated, and then recrystallized from ethanol to give 28 g of compound (2-4-1).

<Preparation of Radiation-Linear Polyorganosiloxanes> Example S-1

To a 500 ml three-necked flask equipped with a nitrogen gas introduction tube, a thermometer, and a reflux tube, 16.5 g of an AC-SQ (manufactured by Toagos Corporation) and 15.5 g of a compound represented by the following formula (2-9-1) were added. (Compound 2-9-1),

0.11 g of palladium acetate, 0.61 g of tris(o-tolyl)phosphine, 27.8 ml of triethylamine and 100 ml of N,N-dimethylacetamide were reacted at 115 ° C for 3 hours. After completion of the reaction, the reaction mixture was filtered to remove insoluble components, and ethyl acetate was added to the filtrate. The obtained organic layer was applied twice with dilute hydrochloric acid, and then washed three times with water, and then concentrated under reduced pressure. The obtained concentrate was reprecipitated with methanol to obtain 15 g of a radiation-sensitive linear polyorganosiloxane (S-1).

¹ H-NMR analysis of the radiation-sensitive polyorganosiloxane (S-1) was carried out, and it was confirmed that 38 mol% of the acryloxy group contained in the AC-SQ as a raw material was reacted and replaced with a group of the compound (2-9-1).

The radiation-sensitive linear polyorganosiloxane (S-1) had a weight average molecular weight Mw of 6,200.

Example S-2

In Example S-1, the same operation as in Example S-1 was carried out except that 16.5 g of the compound (2-4-1) obtained in the above Synthesis Example 1 was used instead of the compound (2-9-1). This gave 16 g of a radiation-sensitive polyorganosiloxane (S-2).

Performed the radiation sensitive polyorganosiloxane silicon siloxane ^{(S-2) 1 H-} NMR analysis, it was confirmed AC-SQ as a starting material has a group of 33 mole% Bing Xixi were reacted replaced from compound a group of (2-4-1).

The radiation-sensitive linear polyorganosiloxane (S-2) had a weight average molecular weight Mw of 6,600.

Example S-3

In Example S-1, the same operation as in Example S-1 was carried out except that 33 g of the compound (2-4-1) obtained in the above Synthesis Example 1 was used instead of the compound (2-9-1). 18 g of a radiation sensitive polyorganosiloxane (S-3) was obtained.

¹ H-NMR analysis of the radiation-sensitive polyorganosiloxane (S-3) was carried out, and it was confirmed that 48 mol% of the acryloxy group contained in the AC-SQ as a raw material was reacted and replaced with a compound derived from the compound. a group of (2-4-1).

The radiation-sensitive linear polyorganosiloxane (S-3) had a weight average molecular weight Mw of 7,500.

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

109 g (0.50 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 98 g (0.50 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as 4 of diamine. 200 g (1.0 mol) of 4-diaminodiphenyl ether was dissolved in 2290 g of N-methyl-2-pyrrolidone, and after reacting at 40 ° C for 3 hours, 1350 g of N-methyl-2-pyrrolidone was added. A solution containing 10% by weight of poly-proline (PA-1) was obtained in an amount of about 4000 g. The solution viscosity of the polyaminic acid solution was 210 mPa·s.

Synthesis Example PA-2

22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 14.23 g (0.1 mol) of cyclohexane bis(methylamine) as a diamine It was allowed to react at 60 ° C for 6 hours in 329.3 g of N-methyl-2-pyrrolidone. Next, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C for 15 hours to obtain 32 g of polyamine (PA-2).

Synthesis Example PA-3

196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, 2,2'-dimethyl-4,4'-di as diamine Aminobiphenyl 212 g (1.0 mol) was dissolved in 4050 g of N-methyl-2-pyrrolidone, and reacted at 40 ° C for 3 hours to obtain about 3700 g of 10% by weight polyglycine (PA-3). Solution. The solution viscosity of the polyaminic acid solution was 170 mPa ‧ s.

[Synthesis of Polyimine] Synthesis example PI-1

2,3,5-tricarboxycyclopentyl acetic acid dianhydride 112 g (0.50 mol) and 1,3,3a,4,5,9b-hexahydro-8-methyl-5 as tetracarboxylic dianhydride -(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione 157 g (0.50 mol), and benzene as a diamine Diamine 95g (0.88 moles), 2,2-bis(trifluoromethyl)-4,4-diaminobiphenyl 32g (0.10 moles), 3,6-bis(4-aminobenzamide) Oxy)cholinane 6.4 g (0.010 mol) and octadecyloxy-2,5-diaminobenzene 4.0 g (0.015 mol) are dissolved in 960 g of N-methyl-2-pyrrolidone at 60 The reaction was carried out for 9 hours at °C. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 58 mPa·s.

2740 g of N-methyl-2-pyrrolidone, 396 g of pyridine and 409 g of acetic anhydride were added to the obtained polyamic acid solution, 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 is subjected to solvent replacement with a new N-methyl-2-pyrrolidone (by the solvent replacement operation, the pyridine and acetic anhydride used in the dehydration ring closure reaction are removed to the outside of the system) About 2500 g of a solution containing 15% by weight of polyamidimide (PI-1) having a ruthenium iodide ratio of about 95% was obtained.

A small amount of the polyimine solution was taken, and the solvent was removed under reduced pressure, and then dissolved in γ-butyrolactone to prepare a solution having a polymer concentration of 8.0% by weight, and the measured solution viscosity was 33 mPa·s.

Synthesis Example PI-2

20.9 g (0.093 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 9.2 g (0.085 mol) of p-phenylenediamine as diamine and the following formula ( D-6)

The compound represented by 4.9 g (0.009 mol) was dissolved in 140 g of N-methyl-2-pyrrolidone, and allowed to react at 60 ° C for 4 hours to obtain a solution containing polylysine. A small amount of the obtained polyaminic acid solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was measured to be 126 mPa·s.

Then, 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 further 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 to obtain about 220 g of a polyimine (PI) containing 16.1% by weight of a ruthenium iodide ratio of about 54%. -2) solution.

A small amount of the polyimine solution was taken, and N-methyl-2-pyrrolidone was added to prepare a solution having a polymer concentration of 10% by weight, and the solution viscosity was determined to be 75 mPa·s.

[Synthesis of other polyoxyalkylenes] Synthesis example PS-1

20.8 g of tetraethoxysilane and 28.2 g of 1-ethoxy-2-propanol were placed in a 200 ml three-necked flask equipped with a condenser, and the mixture was stirred under heating at 60 °C. 0.26 g of maleic anhydride prepared in another flask having a capacity of 20 ml was dissolved in 10.8 g of aqueous maleic anhydride solution, and the mixture was further heated and stirred at 60 ° C for 4 hours to carry out a reaction. The solvent was distilled off from the obtained reaction mixture, and then 1-ethoxy-2-propanol was added, followed by concentration to obtain a polymer solution containing 10% by weight of polyorganosiloxane (PS-1). The weight average molecular weight Mw of PS-1 was 5,100.

Example A-1 <Modulation of liquid crystal alignment agent>

A polyglycine (PA-1)-containing solution prepared in the above Synthesis Example PA-1 in an amount equivalent to 1000 parts by weight of polylysine (PA-1) contained therein is used as another polymer. 100 parts by weight of the radiation-sensitive polyorganosiloxane (S-1) obtained in the above Example S-1, and then N-methyl-2-pyrrolidone and butyl cellosolve were added thereto to form a solvent group. A solution of N-methyl-2-pyrrolidone: butyl cellosolve = 50:50 (weight ratio) and a solid content concentration of 3.0% by weight. This solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent (A-1).

This liquid crystal alignment agent (A-1) was stored at -15 ° C for 6 months. The viscosity was measured at 25 ° C with an E-type viscometer before and after storage. When the rate of change before and after storage of the solution was less than 10%, the storage stability was evaluated as "good", and when it was 10% or more, the storage stability was evaluated as "poor", and the liquid crystal alignment agent (A-1) was stably stored. Sex is "good."

<Formation of Liquid Crystal Alignment Film and Manufacture of Liquid Crystal Display Element>

The liquid crystal alignment agent (A-1) prepared above was applied onto the transparent electrode surface of a glass substrate made of a transparent electrode made of an ITO film by a spin coating method, and prebaked on a hot plate at 80 ° C for 1 minute. The inside was heated in a nitrogen-exchanged oven at 200 ° C for 1 hour (post-baking) to form a coating film having a film thickness of 0.1 μm. Then, a polarized ultraviolet ray having a bright line of 313 nm of 200 J/m ^{2 was} irradiated to the surface of the film by a Hg-Xe lamp and a Glan-Taylor prism in a direction inclined by 40° from the normal line of the substrate to prepare a liquid crystal alignment film. The same operation was repeated to obtain a pair of (two pieces) substrates having a liquid crystal alignment film.

On the outer periphery of one surface of the substrate having the liquid crystal alignment film, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied by screen printing, and the liquid crystal alignment film of the pair of substrates is opposed to each other. The projection directions of the ultraviolet light axes of the respective substrates on the substrate surface were pressed against each other in parallel, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, a negative liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled 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. Further, in order to eliminate the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C and then slowly cooled to room temperature. Then, the polarizing plates were bonded to both surfaces of the substrate so that the polarization directions thereof were perpendicular to each other, and the liquid crystal display element was obtained at an angle of 45° with respect to the projection direction of the ultraviolet light axis of the liquid crystal alignment film on the substrate surface.

The liquid crystal display element was evaluated by the following method. The evaluation results are shown in Table 2.

<Evaluation method of liquid crystal display element> (1) Evaluation of liquid crystal alignment

The liquid crystal display element manufactured above was observed by an optical microscope to be turned on. When the 5 V DC voltage was cut (applied and released), there was an abnormal region in the change in brightness and darkness, and when there was no abnormal region, it was evaluated as "good".

(2) Evaluation of pretilt angle

The pretilt angle of the liquid crystal display element produced above was measured by a crystal rotation method using He-Ne laser according to the method described in T. J. Scheffer et al., J. Appl. Phys., Vol. 19, p. 2013 (1980).

(3) Evaluation of voltage retention rate

A voltage of 5 V was applied to the liquid crystal display element manufactured above with an application time of 60 microseconds and a time span of 167 milliseconds, and then the voltage holding ratio from the voltage release to 167 milliseconds was measured. The measuring device was a VHR-1 manufactured by Dongyang Technology Co., Ltd.

(4) Evaluation of pretilt stability

After the liquid crystal display element manufactured above was stored at 23 ° C for 30 days, the pretilt angle was measured again. When the amount of change from the initial stage was less than 1°, the pretilt stability was evaluated as "good".

Example A-2

100 parts by weight of the radioactive polyorganosiloxane (S-1) obtained in the above Example S-1 and 1000 parts by weight of the polyamic acid prepared in the above Synthesis Example PA-2 as another polymer (PA-2) is mixed, and N-methyl-2-pyrrolidone and butyl cellosolve are added thereto to prepare a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50:50 (weight ratio), A solution having a solid content concentration of 3.0% by weight. This solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent (A-2).

The liquid crystal alignment agent was subjected to various evaluations in the same manner as in Example A-1. The evaluation results are shown in Tables 1 and 2.

Examples A-3~A-6, A-8~A-10, A-12 and A-14~A-16

In Example A-1, as a solution containing other polymers, a solution containing a polymer of the kind and amount shown in Table 1 was used as a radiation-sensitive polyorganosiloxane, each using 100 parts by weight in Table 1. A liquid crystal alignment agent was prepared in the same manner as in the above Example A-1 except that the radiation-sensitive polyorganosiloxane of the type shown was used, and various evaluations were carried out. The evaluation results are shown in Tables 1 and 2.

Examples A-7 and A-13

In Example A-2, a liquid crystal alignment agent was prepared in the same manner as in the above Example A-2, except that 100 parts by weight of the type shown in Table 1 was used for the radiation-sensitive polyorganosiloxane. Each of these liquid crystal alignment agents was used, and various evaluations were carried out in the same manner as in the above Example A-1. The evaluation results are shown in Tables 1 and 2.

Example A-11

A solution containing other polyaluminoxane (PS-1) prepared in the above Synthesis Example PS-1 in an amount equivalent to 2000 parts by weight of polyfluorene oxide (PS-1) contained therein is used as another polymerization. And adding 100 parts by weight of the radiation-sensitive polyorganosiloxane (S-1) obtained in the above Example S-1, and then adding 1-ethoxy-2-propanol to form a solid content concentration It is a 4.0% by weight solution. This solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent (A-7).

The liquid crystal alignment agent was subjected to various evaluations in the same manner as in Example A-1. The evaluation results are shown in Tables 1 and 2.

Claims (5)

A radiation-sensitive polyorganosiloxane having a structure represented by the following formula (3), In the formula (3), R is a hydrogen atom or a methyl group, n is an integer of 1 to 10, R ¹ is a group represented by the following formula (R ^1-1 ), and R ² is a fluorine atom or a cyano group, b Is an integer from 0 to 4, In the formula (R ¹ -1), R ^I is an alkyl group having 1 to 40 carbon atoms, or a monovalent hydrocarbon group having 3 to 40 carbon atoms containing an alicyclic group or a fused ring group. Wherein a part or all of the hydrogen atom of the above alkyl group may be substituted by a fluorine atom, and R ^II is a single bond, an oxygen atom, *-COO- or *-OCO- (wherein the above linkage bond with "*" and R ^I connection), R ^III is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, R ^IV is a single bond, an oxygen atom, * -COO- or *-OCO- (where the above connection key with "*" is connected to R ^III ), a is an integer from 0 to 3. A method for producing a radiation-sensitive polyorganosiloxane, characterized in that a polyorganosiloxane having a structure represented by the following formula (1) and a compound represented by the following formula (2) are palladium compound or palladium The reaction is carried out in the presence of a compound, In the formula (1), R and n are the same as defined in the above formula (3), In the formula (2), R ¹ , R ² and b are each the same as defined in the above formula (3), and Z is a halogen atom or an alkylsulfonate group having an alkyl group having 1 to 6 carbon atoms. Or an arylsulfonate group having an aryl group having 6 to 10 carbon atoms, wherein the alkyl group of the above alkylsulfonate group may be substituted with a fluorine atom. The method for producing a radiation-sensitive polyorganosiloxane according to the second aspect of the invention, wherein the radiation-sensitive polyorganosiloxane is a radiation-sensitive polyorganosiloxane having a structure represented by the above formula (3). The method for producing a radiation-sensitive polyorganosiloxane according to the second or third aspect of the patent application, wherein the radiation-sensitive polyorganosiloxane is used for a liquid crystal alignment agent. A liquid crystal alignment agent characterized by containing a radiation-sensitive polyorganosiloxane having a structure represented by the above formula (3), and at least one selected from the group consisting of polyproline and polyimine polymer.