TWI504678B - Liquid crystal alignment agent, method for producing liquid alignment film and liquid crystal display element - Google Patents

Description

Liquid crystal alignment agent, method for producing liquid crystal alignment film, and liquid crystal display element

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

In the liquid crystal display device, in order to align liquid crystal molecules in a predetermined direction with respect to the substrate surface, a liquid crystal alignment film is provided on the surface of the substrate. The liquid crystal alignment film is usually formed by a method of rubbing in one direction (friction method) by using a cloth such as rayon on the surface of the organic film formed on the surface of the substrate. This is also the same in the liquid crystal display device of the horizontal electric field type. However, if the liquid crystal alignment film is formed by the rubbing treatment, there is a problem in that dust or static electricity is easily generated in the rubbing step, so that dust adheres to the surface of the alignment film, which causes the display to be poor, and in addition, In the case of a substrate having a TFT (Thin Film Transistor) element, there is a problem that the circuit of the TFT element is broken due to the generated static electricity, resulting in a decrease in product yield. Therefore, as another method of aligning liquid crystals in a liquid crystal cell, a photo-alignment method in which a polarized or non-polarized radiation is irradiated on a radiation-sensitive organic thin film formed on a surface of a substrate to impart a liquid crystal alignment ability has been proposed (see Patent Literature) 1~6). By the photo-alignment method, dust or static electricity can be generated in the step to form a uniform liquid crystal alignment.

Further, as the liquid crystal display element, a liquid crystal display using a level alignment mode of a nematic liquid crystal having positive dielectric anisotropy, such as a TN (twisted nematic) type or an STN (super twisted nematic) type, is known. An element, and a VA (Vertical Alignment) type liquid crystal display element using a homeotropic alignment mode of nematic liquid crystal having negative dielectric anisotropy. 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, the liquid crystal molecules must be inclined from the substrate normal direction in a certain direction. As such a method, for example, a method of providing a protrusion on a surface of a substrate; a method of providing a stripe stripe on a transparent electrode; and using a rubbing alignment film to tilt the liquid crystal molecules from the normal direction of the substrate toward one in the plane of the substrate Direction (pre-tilt) method, etc. The above photoalignment method can be used as a method of controlling the tilt direction of liquid crystal molecules in a liquid crystal display element of a vertical alignment mode. In other words, it is known that the liquid crystal alignment film can be uniformly controlled by applying a vertical alignment type liquid crystal alignment film capable of imparting alignment control ability and pretilt angle expression by a photo-alignment method (Patent Documents 1, 2, and 4~6).

Thus, the liquid crystal alignment film prepared by the photo-alignment method can be effectively applied to various liquid crystal display elements. However, in order to impart liquid crystal alignment ability to the organic thin film by the photo-alignment method, it is necessary to irradiate a strong radiation of 10,000 J/m ² or more, and the molecular structuring of the organic thin film causes a problem of deterioration in performance, and also causes radiation. The deterioration of the irradiation device with time (for example, deterioration of the light irradiation intensity of the ultraviolet lamp with time) has a problem from the viewpoint of reducing the manufacturing cost of the liquid crystal display element. Further, it is pointed out that the liquid crystal alignment film formed by the photo-alignment method sometimes changes with time even if it is initially formed with a pretilt angle, and improvement is required.

In this case, when a photo-alignment method is used, a new liquid crystal alignment film material exhibiting good liquid crystal alignment performance by a very small amount of radiation irradiation is reported, and poly-amic acid or poly group which introduces a specific photosensitive site in a molecule is reported. A material composed of quinone imine (Patent Documents 7 to 9). The liquid crystal alignment agent described in these documents can form a liquid crystal alignment film which exhibits good liquid crystal alignment properties by irradiation with radiation of about 500 to 3,000 J/m ² , and is an excellent material.

However, in recent years, there has been an increasing demand for high definition and high-speed response of liquid crystal display elements, and for this reason, it is necessary to continue to improve the hard surface of the substrate structure and the like. Therefore, a complicated height difference is inevitably generated on the substrate surface, and in order to ensure good visual confirmation of the height difference portion, the coating property or printability of the liquid crystal alignment agent is much higher than the current one. Further, in the liquid crystal display element having the liquid crystal alignment film according to the photoalignment method, there is a problem of image sticking and imprinting, and it is desired to improve it. In particular, due to the above-described pretilt angle, the brightness difference generated on the screen is considered by the observer to be an imprint, and it is urgent to improve it.

As described above, the liquid crystal alignment agent described below is not known, and it is highly desirable to provide the liquid crystal alignment agent; the liquid crystal alignment agent can advantageously exhibit the advantages of the photoalignment method according to a small amount of radiation irradiation, and can form an improved residue A liquid crystal alignment film having a shadow characteristic and an imprinting property.

Prior art literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2003-307736

Patent Document 2: Japanese Laid-Open Patent Publication No. 2004-163646

Patent Document 3: Japanese Laid-Open Patent Publication No. 2002-250924

Patent Document 4: Japanese Laid-Open Patent Publication No. 2004-83810

Patent Document 5: Japanese Laid-Open Patent Publication No. Hei 9-211468

Patent Document 6: Japanese Patent Laid-Open Publication No. 2003-114437

Patent Document 7: WO2009/25385A1

Patent Document 8: WO2009/25386A1

Patent Document 9: WO2009/25388A1

Patent Document 10: Japanese Laid-Open Patent Publication No. SHO 63-291922

Non-patent literature

Non-Patent Document 1: T. J. Scheffer et. al. J. Appl. Phys. vol. 19, p2013 (1980)

The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a liquid crystal alignment property which is excellent in coatability and printability on a panel having fine unevenness and a light alignment method by a small amount of radiation irradiation. (Pretilt angle embossing), and a liquid crystal alignment agent capable of imparting a liquid crystal alignment film excellent in branding characteristics.

Another object of the present invention is to provide a liquid crystal display element which is excellent in long-term reliability, and which has a liquid crystal alignment film which is excellent in branding characteristics by the liquid crystal alignment agent.

Another object and advantage of the present invention can be embodied by the following description.

The above objects and advantages of the present invention are achieved by a liquid crystal alignment agent comprising:

(A) a polyorganosiloxane having a structure represented by the following formula (A1),

In the formula (A1), R is a fluorine atom or a cyano group, a is an integer of 0 to 4, and "*" represents a linkage, and

(B) at least one polymer selected from the group consisting of polylysine and polyamidene obtained by dehydration ring closure of the polyamic acid, wherein the polyamic acid is a tetracarboxylic dianhydride and a diamine The diamine obtained by the reaction includes (b2) a diamine having a carboxyl group. The diamine preferably further comprises (b1) a diamine having an alkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, and a ring structure in which two or more 6 members are bonded. a group or a group having a steroid structure.

The above objects and advantages of the present invention are 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 is excellent in coating property or printability on a panel having fine unevenness, and at the same time, a good liquid crystal alignment property (pretilt angle embodying property) can be imparted by a light alignment method of a small amount of radiation irradiation, and further, A liquid crystal alignment film excellent in image retention and encapsulation properties can be imparted.

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 has improved imprinting characteristics and excellent long-term reliability, and the display performance is not deteriorated even when used for a long period of time. Therefore, the liquid crystal display element of the present invention can be effectively used in various devices, for example, preferably in a clock, a portable game machine, a word processor, a notebook computer, a navigation system, a video camera, a portable information terminal, a digital camera. It is used in display devices such as mobile phones, various monitors, and LCD TVs.

Hereinafter, the present invention will be described in detail.

As described above, the liquid crystal alignment agent of the present invention contains:

(A) a polyorganosiloxane having a structure represented by the above formula (A1), and

(B) Polyimine (hereinafter sometimes referred to as "poly-proline (B)") and polypyridyl acid obtained by dehydration ring closure (hereinafter, sometimes referred to as "poly" At least one polymer selected from the group consisting of ruthenium (B)"), wherein the polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine, the diamine comprising (b2) having a carboxyl group amine. The diamine preferably further comprises (b1) a diamine having an alkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, and a ring structure in which two or more 6 members are bonded. a group or a group having a steroid structure.

<polyorganooxane (A)>

The polyorganosiloxane (A) in the present invention is a polyorganosiloxane having a structure represented by the above formula (A1).

As a in the above formula (A1), it is preferably 0 or 1, more preferably 0.

As the structure represented by the above formula (A1), a structure formed by groups represented by the following formulas (A1-1) and (A1-2) is preferably exemplified:

In the formulae (A1-1) and (A1-2), R, a and "*" are respectively the same as defined in the above formula (A1); R ¹ in the formula (A1-1) is a hydrogen atom and contains an alicyclic ring. The group has a monovalent organic group having 3 to 40 carbon atoms or an alkyl group having 1 to 40 carbon atoms, wherein some or all of the hydrogen atoms of the above alkyl group may be substituted by a fluorine atom, and X ¹ is a single bond. , an oxygen atom, ⁺ -COO- or ⁺ -OCO- (above, a bond labeled "+" is bonded to R ¹ ), and R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused cyclic group, X ² is a single bond, an oxygen atom, ⁺ -COO- or ⁺ -OCO- (above, a bond of "+" and a R ² bond And b is an integer of 0 to 3; R ³ in the formula (A1-2) is a hydrogen atom, a monovalent organic group having 3 to 40 carbon atoms or an alicyclic group or a carbon atom An alkyl group of 1 to 40, wherein some or all of the hydrogen atoms of the above alkyl group may be substituted by a fluorine atom, X ³ is an oxygen atom or a divalent aromatic group, and R ⁴ is a divalent aromatic group. divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, X ⁴ is a single bond, an oxygen atom, -COO- or ^{+ +} -OCO- (more Mark "+" linkages and R ⁴ are bonded), c is an integer of 0 to 3.

The monovalent organic group having 3 to 40 carbon atoms and having an alicyclic group as R ¹ in the above formula (A1-1) and R ³ in the above formula (A1-2) may, for example, be cholin Terpene, cholesteryl, adamantyl and the like. The alkyl group having 1 to 40 carbon atoms of R ¹ and R ³ is preferably an alkyl group having 1 to 20 carbon atoms, and some or all of the hydrogen atoms of the alkyl group may be 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-lauryl group, n-dodecyl group, n-tridecyl group, and positive Tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, 4,4,4-trifluorobutyl Base, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluoroalkyl, 3,3,4,4,5,5,5- Heptafluoroheptyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl) Ethyl, 2-(perfluorodecyl)ethyl and the like.

Examples of the divalent aromatic group of R ² in the above formula (A1-1) and R ⁴ in the above formula (A1-2) include, for example, 1,4-phenylene group, 2-fluoro-1,4. - phenyl, 3-fluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, etc.; as a divalent alicyclic group of R ² and R ⁴ The group may, for example, be a 1,4-cyclohexylene group, a 2-fluoro-1,4-cyclohexylene group, a 3-fluoro-1,4-cyclohexylene group, or a 2,3,5,6-tetrafluoro-1 group. 4- cyclohexylene and the like; R ² and R 2 as a divalent heterocyclic group ⁴ may include 1,4-pyridyl, 2,5-pyridyl, 1,4-furyl; R ² is Examples of the divalent condensed cyclic group of R ⁴ include a naphthyl group and the like.

The group represented by the above formula (A1-1) may, for example, be a group represented by the following formula:

In the above formula, R ¹ and "*" are the same as defined in the formula (A1-1), and d is an integer of 1 to 10.

The group represented by the above formula (A1-2) may, for example, be a group represented by the following formula.

In the above formula, R ³ and "*" are the same as defined in the formula (A1-2), respectively.

The polyorganosiloxane (A) of the present invention preferably has a structure represented by the above formula (A1) of from 0.2 to 6 mmol/g, more preferably from 0.3 to 5 mmol/g.

With respect to the polyorganosiloxane (A) of the present invention, the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is preferably from 1,000 to 500,000, more preferably from 2,000 to 200,000.

The polyorganosiloxane (A) as described above preferably has a structure represented by the above formula (A1) within the above range, and can be produced by any method, for example, containing an epoxy group and hydrolyzability. A mixture of a decane compound of a group of a decane compound (hereinafter referred to as "decane compound (1)") is preferably subjected to hydrolysis condensation in the presence of an organic solvent, water and a catalyst, and firstly, a polyorganofluorene having an epoxy group is synthesized. Oxysilane (hereinafter referred to as "precursor of polyorganosiloxane (A)"), and then reacting the polyorganosiloxane with a structure represented by the above formula (A1) and capable of reacting with an epoxy group The compound of the group (hereinafter referred to as "compound (A1)") is reacted to be synthesized. In this case, the compound (A1) may be used in combination with a compound (hereinafter referred to as "other reactive compound") having no structure represented by the above formula (A1) and having a group reactive with an epoxy group. group.

The above decane compound (1) may, for example, be 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane or 3-glycidoxypropylmethyldimethacrylate. Oxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 3-glycidoxypropyldimethylethoxy Decane, 2-glycidoxyethyltrimethoxydecane, 2-glycidoxyethyltriethoxydecane, 2-glycidoxyethylmethyldimethoxydecane, 2-glycidyloxy Ethylethyldiethoxy decane, 2-glycidoxyethyl dimethyl methoxy decane, 2-glycidoxyethyl dimethyl ethoxy decane, 4-glycidoxy butyl Trimethoxy decane, 4-glycidoxy butyl triethoxy decane, 4-glycidoxy butyl methyl dimethoxy decane, 4-glycidoxy butyl diethoxy decane, 4- Glycidoxybutyl dimethyl methoxy decane, 4-glycidoxy butyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethyl Baseline, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-ring As the cyclohexyl)propyltriethoxydecane or the like, one or more selected from them can be used.

The decane compound for synthesizing the polyorganosiloxane (A) precursor may be composed only of the above decane compound (1), or may contain other decane compounds in addition to the above decane compound (1) (hereinafter, It is "decane compound (2)").

As the decane compound (2) which can be used therein, for example, tetrachlorodecane, tetramethoxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane, tetra-n-butoxy Decane, tetra- or 2-butoxybutane, trichlorodecane, trimethoxydecane, triethoxydecane, tri-n-propoxydecane, triisopropoxydecane, tri-n-butoxydecane, tri- or di-butyl Oxydecane, trichlorodecane fluoride, trimethoxydecane fluoride, triethoxydecane fluoride, tri-n-propoxydecane fluoride, triisopropoxydecane fluoride, tri-n-butoxy fluoride Decane, fluorinated tri- or two-butoxybutane, methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane , methyl tri-n-butoxydecane, methyl tri- or 2-butoxybutane, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxydecane, 2 -(trifluoromethyl)ethyltriethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltriisopropoxydecane, 2 -(trifluoro Ethyl tri-n-butoxy decane, 2-(trifluoromethyl)ethyl tri-n-butoxy decane, (2-perfluoro-n-hexyl)ethyltrichloro decane, (2-perfluoro-n-hexyl) Ethyltrimethoxydecane, (2-perfluoro-n-hexyl)ethyltriethoxydecane, (2-perfluoro-n-hexyl)ethyltri-n-propoxydecane, (2-perfluoro-n-hexyl) Triisopropoxy decane, (2-perfluoro-n-hexyl)ethyltri-n-butoxy oxane, (2-perfluoro-n-hexyl)ethyltri-n-butoxy oxane, (2-perfluoro-n-octane Ethyl trichlorodecane, (2-perfluoro-n-octyl)ethyltrimethoxydecane, (2-perfluoro-n-octyl)ethyltriethoxydecane, (2-perfluoro-n-octyl) Ethyl tri-n-propoxy decane, (2-perfluoro-n-octyl)ethyl triisopropoxy decane, (2-perfluoro-n-octyl)ethyltri-n-butoxy decane, (2-perfluoro) N-octyl)ethyl tri- or 2-butoxybutane, hydroxymethyltrichlorodecane, hydroxymethyltrimethoxydecane, hydroxymethyltriethoxydecane, hydroxymethyltri-n-propoxydecane, hydroxymethyl Triisopropoxy decane, hydroxymethyl tri-n-butoxy decane, hydroxymethyl tri- or 2-butoxy decane, 3-(methyl) propyl Methoxypropyltrichloromethane, 3-(methyl)propenyloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, 3-(methyl) Propylene methoxypropyl tri-n-propoxy decane, 3-(methyl) propylene methoxypropyl triisopropoxy decane, 3-(methyl) propylene methoxy propyl tri-n-butoxy decane , 3-(methyl)propenyloxypropyl tri- or two-butoxybutane, 3-mercaptopropyltrichlorodecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane , 3-mercaptopropyltri-n-propoxy decane, 3-mercaptopropyltriisopropoxy decane, 3-mercaptopropyltri-n-butoxy decane, 3-mercaptopropyltri-n-butoxy decane, Mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, vinyltrichlorodecane, vinyltrimethoxydecane, vinyltriethoxydecane, vinyltri-n-propoxydecane, vinyl III Isopropoxy decane, vinyl tri-n-butoxy decane, vinyl tri- or 2-butoxy decane, allyl trichloro decane, allyl trimethoxy decane, allyl triethoxy decane, olefin Propyl tri-n-propyl Oxy decane, allyl triisopropoxy decane, allyl tri-n-butoxy decane, allyl tri-n-butoxy decane, phenyl trichloro decane, phenyl trimethoxy decane, phenyl Triethoxy decane, phenyl tri-n-propoxy decane, phenyl triisopropoxy decane, phenyl tri-n-butoxy decane, phenyl tri-n-butoxy decane, methyl dichloro decane, A Dimethoxy decane, methyl diethoxy decane, methyl di-n-propoxy decane, methyl diisopropoxy decane, methyl di-n-butoxy decane, methyl di-n-butoxy Decane, dimethyldichlorodecane, dimethyldimethoxydecane, dimethyldiethoxydecane, dimethyldi-n-propoxydecane, dimethyldiisopropoxydecane, dimethyl Di-n-butoxydecane, dimethyldi-2-butoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dichlorodecane, (methyl)[2-(perfluoro-positive Octyl)ethyl]dimethoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]diethoxydecane, (methyl)[2-(perfluoro-n-octyl) Di-n-propoxy decane, (methyl)[2-(perfluoro-n-octyl)ethyl]diisopropyloxide Baseline, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-butoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-butoxy Decane, (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-2-butoxy decane, (methyl) (vinyl) dichloro decane, (methyl) (vinyl) dimethoxy decane, (methyl)(vinyl)diethoxydecane, (methyl)(vinyl)di-n-propoxyoxydecane, (methyl)(vinyl)diisopropoxydecane, (methyl)(ethylene Di-n-butoxy decane, (methyl) (vinyl) di- or two-butoxy decane, divinyl chlorin, divinyl dimethoxy decane, divinyl diethoxy decane, Divinyl di-n-propoxy decane, divinyl diisopropoxy decane, divinyl di-n-butoxy decane, divinyl di-n-butoxy decane, diphenyl bis Decane, diphenyldimethoxydecane, diphenyldiethoxydecane, diphenyldi-n-propoxydecane, diphenyldiisopropoxydecane, diphenyldi-n-butoxydecane, Diphenyl di-2-butoxy decane, dimethyl decane chloride, methoxy dimethyl decane, ethoxy dimethyl decane, trimethyl decane chloride, trimethyl decane bromide, iodo Trimethyl decane, methoxy trimethyl decane, ethoxy trimethyl decane, n-propoxy trimethyl decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, secondary Butoxy trimethyl decane, tertiary butoxy trimethyl decane, (chlorinated) (vinyl) dimethyl decane, (methoxy) (vinyl) dimethyl decane, (ethoxy) (vinyl) dimethyl decane, (chlorinated) (methyl) diphenyl decane, (methoxy) (methyl) diphenyl decane, (ethoxy) (methyl) diphenyl decane, etc. A decane compound having one ruthenium atom, and further, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X may be mentioned by trade names. -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 is Shin-Etsu Chemical Industry Co., Ltd. ) Manufacturing); Glass Resin (manufactured by Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above manufactured by Toray Dow Coring Silicone) ; FZ3711, FZ3722 (above is manufactured by Japan UNICAR); 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 manufactured by Chisso); Methyl silicate MS51, Methyl silicate MS56 (above is manufactured by Mitsubishi Chemical Co., Ltd.); Ethyl silicate 28, Ethyl silicate 40, Ethyl silicate 48 (above manufactured by Colcoat); GR100, GR650, GR908, GR950 (above manufactured by Showa Denko) Partial condensate.

Among these decane compounds (2), preferred are tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, and 3-(methyl) propylene methoxy propylene. Trimethoxy decane, 3-(meth) propylene methoxy propyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, allyl trimethoxy decane, allyl Triethoxy decane, phenyltrimethoxydecane, phenyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, decylmethyltrimethoxydecane, Mercaptomethyltriethoxydecane, dimethyldimethoxydecane or dimethyldiethoxydecane.

The precursor of the polyorganosiloxane (A) preferably used in the present invention preferably has an epoxy equivalent of from 100 to 10,000 g/mol, more preferably from 150 to 1,000 g/mol, particularly preferably from 150 to 150. 300 g/mol. Therefore, in synthesizing the precursor of the polyorganosiloxane (A), it is preferred to set the use ratio of the decane compound (1) to the decane compound (2) such that the epoxy equivalent of the obtained polyorganosiloxane is in the above range Inside. In synthesizing the precursor of the polyorganosiloxane (A) used in the present invention, it is preferred to use only the decane compound (1), and no other decane compound is used.

Examples of the organic solvent which can be used in the synthesis of the precursor of the polyorganosiloxane (A) include a hydrocarbon, a ketone, an ester, an ether, an alcohol, and the like.

Examples of the hydrocarbon include toluene and xylene; and examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone; and the ester may be used. For example, ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, and the like are listed; as the ether, for example, ethylene Alcohol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, two 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 single N-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Among them, a solvent which is not water-soluble is preferred.

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

The amount of the organic solvent used 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 decane compound.

The amount of water used in the production of the polyorganosiloxane (A) precursor is preferably from 0.5 to 100 moles, more preferably from 1 to 30 moles per mole of the decane compound.

As the catalyst, 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.

Examples of the above organic base include, for example, ethylamine, diethylamine, piperidine, and piperidine. , organic primary and secondary amines of pyrrolidine and pyrrole; organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclononene An organic quaternary amine such as tetramethylammonium hydroxide. Among these organic bases, preferred are organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; organic tetra-orders such as tetramethylammonium hydroxide. amine.

As the catalyst in the production of the polyorganosiloxane (A) precursor, an alkali metal compound or an organic base is preferred. By using an alkali metal compound or an organic base as a catalyst, a side reaction such as ring opening of an epoxy group is not generated, and a target polyorganosiloxane can be obtained at a high hydrolysis and condensation rate, so that production stability is good, and it is preferable. for. In addition, the liquid crystal alignment agent of the present invention which is synthesized by using an alkali metal compound or an organic base as a catalyst and which is produced from a precursor, is preferably excellent in storage stability. The reason for this is presumably due to the fact that it is possible to promote the formation of a ternary structure and to form a polyorganosiloxane having a small content of a sterol group. In other words, it is presumed that the polyorganosiloxane (A) has a small content ratio of a sterol group, can suppress a condensation reaction between sterol groups, and further suppress a condensation reaction with the (B) polymer, and thus storage stability is obtained. Excellent.

As the catalyst, an organic base is particularly preferred. The amount of the organic base to be used varies depending on the type of the organic base, the reaction conditions, and the like, and needs to be appropriately set. For example, it is preferably 0.01 to 3 moles, more preferably 0.05 to 1 mole, based on the total of the decane compound. ear.

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

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

After completion of the reaction, the organic solvent layer separated from the reaction liquid is preferably washed with water. At the time of the washing, it is preferable to wash the water with a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2% by weight or the like, so that the washing operation is easy. After washing, the aqueous layer after washing is neutral, and then the organic solvent layer is dried with a desiccant, which is anhydrous calcium sulfate, molecular sieve, etc. as needed, and then the solvent is removed, thereby obtaining the desired polyorganosiloxane. Alkane (A) precursor.

For the precursor of polyorganosiloxane (A), the polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography is preferably from 1,000 to 1,000,000, more preferably from 1,500 to 300,000.

In the present invention, as a precursor of the polyorganosiloxane (A), a commercially available polyorganosiloxane having an epoxy group can be used. Examples of the commercially available product include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (the above are manufactured by Chisso Co., Ltd.).

The compound (A1) used in the present invention is a compound having a structure represented by the above formula (A1) and a group reactive with an epoxy group. The compound (A1) is a compound having a structure represented by the above formula (A1-1), and is preferably a compound represented by each of the following formulas (A1-1C) and (A1-2C).

R, R ¹ , R ² , X ¹ , X ² , a and b in the above formula (A1-1C) and R, R ³ , R ⁴ , X ³ and X ⁴ in the above formula (A1-2C), a and c are respectively the same as defined in the above formula (A1-1) or (A1-2); X ⁵ in the above formula (A1-1C) is a single bond, an oxygen atom, a sulfur atom, a methylene group, a carbon atom a 2 to 10 alkylene group, an alkenylene group having 2 to 10 carbon atoms or a divalent aromatic group. When X ⁵ is a single bond, e is 1 and R ⁵ is a hydrogen atom. ^{When 5} is a methylene group, an alkylene group, an alkenylene group or a divalent aromatic group, e is 0 or 1, and R ⁵ is a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R above) Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, -CH=CH ₂ or -SO ₂ Cl; R ⁶ in the above formula (A1-2C) is a divalent aromatic group, and is divalent. a heterocyclic group or a divalent fused ring group, and X ⁶ is an oxygen atom, -COO- ⁺ or -OCO- ⁺ (wherein the above-mentioned "+" linkage is bonded to R ⁶ ), f is an integer of 0 to 3, and R ⁷ 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 or -SO ₂ Cl, X ⁷ is a single bond, -OCO-(CH ₂ ) _i - ⁺ or -O-(CH ₂ ) _j - ⁺ (where The above i and j are each an integer of 0 to 10, and a "+" linkage is given to the R ⁷ bond) as a compound represented by the above formula (A1-1C), preferably in the above formula (A1-1C), X. ⁵ is a single bond, R ⁵ is a carboxyl group, or X ⁵ is a methylene group, an alkylene group or a divalent aromatic group, R ⁵ is carboxy; as the compound of formula (A1-2C) represented by Preferably, in the above formula (A1-2C), R ⁷ is a compound of a carboxyl group. Hereinafter, the compound (A1) having a carboxyl group is referred to as "carboxylic acid (A1)".

The carboxylic acid (A1) is more preferably a compound represented by the above formula (A1-1C), and each of the compounds represented by the following formula;

In the above formula, R ¹ is the same as defined in the formula (A1-1), and d is an integer of 1 to 10; and as the compound represented by the above formula (A1-2), the compounds represented by the following formulas and the like can be respectively listed;

In the above formula, R ³ is the same as defined in the formula (A1-2).

The other reactive compound is preferably a compound having a carboxyl group as a group capable of reacting with an epoxy group, and examples thereof include a carboxylic acid having a pretilt angle-conforming structure (hereinafter referred to as "other carboxylic acid (1)"). a carboxylic acid having at least one of a structure in which a radical is generated by light irradiation and a structure having a photo-sensitizing function (hereinafter referred to as "other carboxylic acid (2)"), and other carboxylic acids other than the above ( Hereinafter, it may be referred to as "other carboxylic acid (3)") or the like, and at least one of them may be used.

The so-called pretilt embodying structure in the above other carboxylic acid (1) may, for example, be an alkyl group or alkoxy group having 8 to 20 carbon atoms, a fluorinated alkyl group having 1 to 21 carbon atoms or fluorinated. An alkoxy group or a structure comprising an alicyclic group having a monovalent organic group having 3 to 40 carbon atoms.

Examples of the other carboxylic acid (1) having such a structure include compounds represented by the following formulas (C-1) to (C-4), respectively.

C _h F _2h+1 ─C _i H _2i ─COOH (C-1)

In the formula (C-1), h is an integer of 1 to 3, i is an integer of 3 to 18; j in the formula (C-2) is an integer of 5 to 20; k in the formula (C-3) is An integer of 1 to 3, m is an integer of 0 to 18; and n in the formula (C-4) is an integer of 1 to 18.

Among them, a compound represented by each of the above formulas (C-2), (C-3) and (C-4) is preferred, and a compound represented by the above formula (C-2) is more preferred, and 4-( N-pentyl)benzoic acid, 4-(n-hexyl)benzoic acid, 4-(n-heptyl)benzoic acid, 4-(n-octyl)benzoic acid, 4-(n-decyl)benzoic acid, 4-(positive Benzyl)benzoic acid, 4-(n-dodecyl)benzoic acid, 4-(n-octadecyl)benzoic acid, etc.; as a compound represented by the above formula (C-3), for example, the following formula ( Compounds represented by C-3-1)~(C-3-3), etc.;

The compound represented by the above formula (C-4) may, for example, be 4-(n-butoxy)benzoic acid, 4-(n-pentyloxy)benzoic acid, 4-(n-hexyloxy)benzoic acid, 4-( N-heptyloxy)benzoic acid, 4-(n-octyloxy)benzoic acid, 4-(n-decyloxy)benzoic acid, 4-(n-decyloxy)benzoic acid, 4-(n-dodecyloxy) Benzenecarboxylic acid, 4-(n-octadecyloxy)benzoic acid, etc., may be selected from one or more selected from them.

The sensitization function of the carboxylic acid in the above other carboxylic acid (2) means that after a heavy excitation state is formed by light irradiation, the inter-term intersection is quickly caused, and the triple-term excitation state is transferred. In the triple-excited state, By colliding with other molecules, the opponent is changed to the excited state, and the function of returning to the base state is restored. The light sensitizing function can also coexist with the function of generating radicals by light irradiation.

As a structure of at least one of a structure which generates a radical by light irradiation and a structure which has a photo-sensitization function, a benzophenone structure, a 9,10-dioxanhydroindoline structure, and a 1,3-dinitrate can be cited. a benzene structure and a 1,4-dihydroxanthene-2,5-diene structure, that is, a structure represented by the following formulas (1) to (4),

It may be at least one structure selected from. Examples of the other carboxylic acid (2) having such a structure include 3-benzoin benzoic acid, 4-benzoin benzoic acid, and 3-(4-diethylamino-2-hydroxybenzoin) benzene. Formic acid, 4-(2-hydroxybenzoin) benzoic acid, 3-(2-hydroxybenzoin) benzoic acid, 2-(2-hydroxybenzoin) benzoic acid, 4-(4-methylphenylene) Benzoic acid, 4-(3,4-dimethylbenzoin)benzoic acid, 3-(4-benzoin-phenoxy)propionic acid, 9,10-di- oxadihydroindan-2 -carboxylic acid (indole-2-carboxylic acid), 3-(9,10-di-oxo-oxo-9,10-dihydroindol-2-yl)propionic acid, [3-(4,5-dimethoxy) 3-,6-di-oxocyclohexyl-1,4-dienyl)propoxy]acetic acid, 3,5-dinitrobenzoic acid, 4-methyl-3,5-dinitro Benzoic acid, 3-(3,5-dinitrophenoxy)propionic acid, 2-methyl-3,5-dinitrobenzoic acid, and the like.

Examples of the other carboxylic acid (3) include formic acid, acetic acid, propionic acid, and benzoic acid.

The use ratio of the carboxylic acid (A1) used in the production of the polyorganosiloxane (A) of the present invention is preferably 0.001 to 1 mol based on the epoxy group of the precursor of 1 mol of the polyorganosiloxane (A). It is preferably 0.1 to 1 mol, still more preferably 0.2 to 0.9 mol.

The ratio of use of the other carboxylic acid (1) used in the production of the polyorganosiloxane (A) of the present invention is preferably 0.5 mol or less with respect to the epoxy group of the precursor of 1 mol of the polyorganosiloxane (A). More preferably, it is 0.01 to 0.3 mol.

The ratio of use of the other carboxylic acid (2) used in the production of the polyorganosiloxane (A) of the present invention is preferably 0.3 mol or less based on the epoxy group of the precursor of 1 mol of the polyorganosiloxane (A). More preferably, it is 0.0001 to 0.1 mol.

The ratio of use of the other carboxylic acid (3) used in the production of the polyorganosiloxane (A) of the present invention is preferably 0.3 mol or less based on the epoxy group of the precursor of 1 mol of the polyorganosiloxane (A). More preferably, it is 0.0001 to 0.2 mol.

In the production of the polyorganosiloxane (A) of the present invention, in addition to the carboxylic acid (A1), in the case of using other carboxylic acids in combination, it is preferred to use 10 mol of the carboxylic acid (A1) based on the total amount of the total carboxylic acid. %the above. Further, in the case of using the other carboxylic acid (2), in order to ensure better image sticking properties, the use ratio is preferably 30 mol% or less, more preferably 15 mol% or less, based on the total amount of all the carboxylic acids.

In the production of the polyorganosiloxane (A) of the present invention, the use ratio of the total of the carboxylic acid is preferably 0.01 to 1 mol, more preferably 0.01 to 1 mol, based on the epoxy group of the precursor of 1 mol of the polyorganosiloxane (A). Good is 0.1~0.75mol.

The reaction of the precursor of the polyorganosiloxane (A) with the carboxylic acid as described above in the presence of a suitable catalyst is preferably carried out in a suitable organic solvent.

As the catalyst to be used, an organic base can be used, and in addition to this, a known compound which is a so-called curing accelerator which can promote the reaction between the epoxy compound and the carboxylic acid can be used.

Examples of the above organic base include, for example, ethylamine, diethylamine, piperidine, and piperidine. , organic primary and secondary amines of pyrrolidine and pyrrole; organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclononene An organic quaternary amine such as tetramethylammonium hydroxide. Among these organic bases, preferred are organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; and organic four such as tetramethylammonium hydroxide. As the amine, one or more selected from them can be used.

The curing accelerator may, for example, be a tertiary amine such as benzyldimethylamine, 2,4,6-glycol (dimethylaminomethyl)phenol, cyclohexyldimethylamine or triethanolamine; 2-methylimidazole, 2-n-butylimidazole, 2-n-dodecyl imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-ethylimidazole, 1- (2-cyanoethyl)-2-n-dodecyl imidazole, 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-cyanoethyl) -2-phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-dodecyl imidazolium benzene Triester, 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolinium Trimellitic acid ester, 2,4-diamino-6-[2'-methylimidazolium-(1')]ethyl-s-triazole, 2,4-diamino-6-(2' -n-dodecyl imidazole)ethyl-s-triazole, 2,4- Amino-6-[2'-ethyl-4'-methylimidazolium-(1')]ethyl-s-triazole, isocyanurate adduct of 2-methylimidazole, 2-benzene Isocyanurate adduct of imidazole, isocyanurate addition of 2,4-diamino-6-[2'-methylimidazolium-(1')]ethyl-s-triazole Imidazole compound; organic phosphorus compound such as diphenylphosphine, triphenylphosphine, triphenyl phosphite; such as benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenyl bromide Antimony, ethyl triphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylacetate, tetra-n-butyl鏻, o, o-diethyl dithiophosphate, tetra-n-butyl benzotriazole salt, tetra-n-butyl fluorene tetrafluoroborate, tetra-n-butyl fluorene tetraphenyl borate, four a quaternary phosphonium salt of a phosphonium salt of phenylphosphonium tetraphenylborate; such as 1,8-diazabicyclo[5.4.0]undec-7, an organic acid salt of a diazabicycloalkane; An organometallic compound of zinc octoate, tin octoate, and acetonitrile aluminum complex; such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-negative a quaternary ammonium salt of ammonium chloride; a boron compound such as boron trifluoride or triphenyl borate; a metal halide such as zinc chloride or stannous chloride; such as dicyanodiamine or an amine and a ring a high-melting-point-dispersion latent curing accelerator such as an amine addition accelerator such as an adduct of an oxygen resin; a microcapsule-type potential in which a surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is covered with a polymer A curing accelerator; an amine salt type latent curing accelerator; a latent curing accelerator such as a high temperature decomposing thermal cationic polymerization type latent curing accelerator such as a Lewis acid salt or a Bronsted acid salt.

Among them, preferred are tetra-ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

The catalyst is preferably 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, based on 100 parts by weight of the precursor of the polyorganosiloxane (A). use.

Examples of the organic solvent used in the reaction of the precursor of the polyorganosiloxane (A) with a carboxylic acid include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, a guanamine compound, and an alcohol compound. Among them, an ether compound, an ester compound, and a ketone compound are preferred from the viewpoints of the solubility of the raw material and the product and the ease of purification of the product. The solid content concentration of the solvent (the ratio of the total amount of the components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, and more preferably 5 to 50% by weight.

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.

The polyorganosiloxane (A) which is preferred in the present invention is a raw material obtained by the above formula (A1) by using a polyorganosiloxane having an epoxy group as a raw material by ring-opening addition of an epoxy group. structure. This manufacturing method is simple. Further, in particular, it is a very good method from the viewpoint of improving the introduction rate of the structure represented by the above formula (A1).

<Polyamic acid (B)>

The polyamic acid (B) in the liquid crystal alignment agent of the present invention can be obtained by using a tetracarboxylic dianhydride and a diamine including (b2) a diamine having a carboxyl group (hereinafter referred to as "diamine (b2)"). The reaction is obtained. The diamine preferably further includes a (b1) diamine having an alkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, and a group linking two or more 6-membered ring structures. a group or a group having a steroid structure.

Examples of the tetracarboxylic dianhydride used therein include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the aliphatic tetracarboxylic dianhydride include, for example, butyric acid dianhydride; and examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutane IV. Carboxylic dianhydride, 2,3,5-tricarboxycyclopentylcarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxo- 3-furyl)-naphthalene[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-)2 , 5-dioxa-3-furanyl)-naphthalene [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-di-oxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1 ,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethyl group Alkyl-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:3,5:6-dianhydride, 4,9-two side Oxytricyclo [5.3.1.0 ^2,6 ]undec-3,5,8,10-tetraketone, etc., and examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride.

The tetracarboxylic dianhydride described in Japanese Patent Application No. 2009-157556 can be used.

As the tetracarboxylic dianhydride for synthesizing the polyamic acid (B), it is preferred to contain an alicyclic tetracarboxylic dianhydride, and more preferably a 2,3,5-tricarboxycyclopenteneacetic acid. The dianhydride or the 1,2,3,4-cyclobutanetetracarboxylic dianhydride, particularly preferably contains 2,3,5-tricarboxycyclopentene acetic acid dianhydride.

As the tetracarboxylic dianhydride for synthesizing the polyamic acid (B), it is preferred to contain 10 mol% or more of 2,3,5-tricarboxycyclopentene acetic acid dianhydride or all of the tetracarboxylic dianhydride. 1,2,3,4-cyclobutanetetracarboxylic dianhydride, more preferably 20 mol% or more, most preferably only 2,3,5-tricarboxycyclopentene acetate dianhydride or 1,2 , 3,4-cyclobutane tetracarboxylic dianhydride. The diamine (b1) is an alkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having two or more 6 membered ring structures, or a group having a steroid structure. Diamine. The diamine (b1) wherein the diamine having a group linking two or more 6-membered ring structures or a group having a steroid structure may further have an alkyl group having 4 to 20 carbon atoms and having a carbon number of 4 to 20 of alkoxy groups having a fluorinated alkyl group having 4 to 20 carbon atoms. Among them, examples of the group having a steroid structure include, for example, cholest-3-yl, cholestane-5-en-3-yl, cholestane-24-en-3-yl, and cholestane-5. , 24-dien-3-yl, lanostan-3-yl and the like. The diamine (b1) in the present invention may, for example, be 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-di ( 4-((Aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptane Cyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, represented by the following formula (b1-1) Compound.

In the formula (b1-1), X is a single bond, a methylene group, an alkylene group having 2 or 3 carbon atoms, *-O-, *-COO-, *-OCO-, *-X'- R"-, *-R"-X'- or *-X'-R"-X'-, where X' represents ⁺ -O-, ⁺ -COO- or ⁺ -OCO-, respectively, where "+ "The bond to which it is attached is directed to the left direction of the formula (3-1-1), and R" is an alkylene group having 2 or 3 carbon atoms, respectively, and a linkage bond and a diaminophenyl bond imparting "*". N1 is an integer of 0 to 2, and n2 is 0 or 1. When n1+n2 is 2 or more, R' is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 1 to 20. The fluorinated alkyl group, when n1+n2 is 0 or 1, R' is a group having a steroid structure, an alkyl group having 4 to 20 carbon atoms or a fluorinated alkyl group having 4 to 20 carbon atoms. The alkyl group and the fluorinated alkyl group in the above formula (b1-1) are each preferably a straight chain.

The diamine (b1) in the present invention is preferably a compound represented by the above formula (b1-1), and specific examples thereof include n-dodecyloxy-2,4-diaminobenzene. Tetradecyloxy-2,4-diaminobenzene, n-pentadecanyloxy-2,4-diaminobenzene, n-hexadecyloxy-2,4-diaminobenzene, positive eighteen Alkoxy-2,4-diaminobenzene, n-dodecyloxy-2,5-diaminobenzene, n-tetradecyloxy-2,5-diaminobenzene, n-pentadecane Base-2,5-diaminobenzene, n-hexadecyloxy-2,5-diaminobenzene, n-octadecyloxy-2,5-diaminobenzene, cholestyloxy-3 , 5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteneoxy-2,4-diamine Terphenyl, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid cholesteryl ester, 3, Wool alkyl 5-diaminobenzoic acid, 3,6-bis(4-aminobenzoinoxy)cholestane, 3,6-bis(4-aminobenzoinoxy) cholesta Terpene, a group represented by the following formulas (b1-1-1) to (b1-1-7), and the like.

Particularly preferred is a liquid crystal alignment agent containing a polyamido acid (B) synthesized by using a diamine containing a diamine (b1) as described above, and a polyimine (B) obtained by dehydration of the polyglycine. A liquid crystal alignment film of a VA type liquid crystal display element.

The above diamine (b2) is a diamine having a carboxyl group. The diamine (b2) is preferably a compound represented by the following formula (b2-1).

In the formula (b2-1), y is an integer of 0 to 2; x is an integer of 0 to 4, respectively, wherein, when there are a plurality of x, each x may be the same or different; R ^I is a single bond a methylene group, an alkylene group having 2 to 6 carbon atoms or a cyclohexylene group, wherein the above alkylene group may also be interrupted by an ether bond or an ester bond in the chain; X ^I is a single bond, a methylene group, Fluorinated methylene group, alkylene group having 2 to 4 carbon atoms, fluorinated alkyl group having 2 to 4 carbon atoms, oxygen atom, carbonyl group, *-COO-, *-OCO-, *-NH -, *-CONH-, *-NHCO- ("*" indicates the direction to which the linking chain to which it is imparted (b2-1)) or a group represented by the following formula (X ^I -1),

In the formula (X ^I -1), R ^II is a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms or a cycloalkyl group, wherein the above alkyl group may also be ether in the chain. The bond or the ester bond is interrupted; R ^III is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a group -R ^IV COOH (wherein R ^IV is a single bond, a methylene group, and a carbon number of 2 to 6) The alkyl group or the cyclohexyl group may be interrupted by an ether bond or an ester bond in the chain, and the total number of carboxyl groups in the formula (b2-1) is an integer of from 1 to 4. R ^I in the above formula (b2-1) is preferably a methylene group or an alkylene group having 2 to 5 carbon atoms. The compound represented by the above formula (b2-1) is preferably a compound in which at least one of x in the above formula (b2-1) is 1, and the group X ^I is not a compound represented by the above formula (X ^I -1), Or x in the above formula (b2-1) is all 0, and the group X ^I is a compound represented by the above formula (X ^I -1). The compound represented by the above formula (b2-1) is more preferably a compound represented by each of the following formulas (b2-1-1) to (b2-1-5).

In the above formula, X ^I is the same as X ^I in the above formula (b2-1); R ^III is an alkyl group having 1 to 6 carbon atoms; x is an integer of 1 to 4; z is 1 respectively. An integer of ~5, d is an integer from 1 to 4. x and d in the above formulae (b2-1-1), (b2-1-2), and (b2-1-5) are each preferably 1.

The compound represented by the above formula (b2-1) is preferably a compound represented by (b2-1-1), (b2-1-2) or (b2-1-5), as a preferred specific example thereof. A compound represented by 3,5-diaminobenzoic acid, each of the following formulas (b2-1-2-1) and (b2-1-5-1) can be cited.

The diamine in the present invention may be one composed only of the above-described diamine (b1) and diamine (b2), or may be contained in addition to the diamine (b1) and the diamine (b2). A diamine other than (hereinafter, referred to as a diamine (b3)).

The diamine (b3) which can be used therein may be, for example, an aliphatic diamine other than the diamine (b1) and the diamine (b2), an alicyclic diamine, an aromatic diamine, or a diamine organic decane. Wait. Specific examples thereof include, as the aliphatic diamine, m-xylylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, and 1,6-hexanediamine. And as the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, and 1,5-diamino group. Naphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7- Diamino hydrazine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-amino group Phenyl) fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-2(4-aminophenyl)hexafluoropropane, 4,4' -(p-phenylenediisopropyl)bis(aniline), 4,4'-(m-phenyleneisopropylidene)bis(aniline), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-di Amino acridine, 3,6-diaminocarbazole, 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-bis-(4-aminophenyl)-peripipeline , 4-(4'-trifluoromethoxybenzhydrazide)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzhydrazide)cyclohexyl-3, 5-diamino benzoic acid ester or the like; examples of the diamine organic oxirane include, for example, 1,3-bis(3-aminopropyl)-tetramethyldioxane, and the like. Further, among the diamines described in Japanese Patent Application No. 2009-157556, those which do not conform to the diamine (b1) and the diamine (b2) can be used.

The diamine for synthesizing the polyamic acid (B) preferably contains 10% or more of the above diamine (b1), more preferably 30 to 70% by mole, even more preferably all of the diamine. 35 to 60 mol%; preferably 10% or more of the above diamine (b2), more preferably 30 to 70 mol%, still more preferably 40 to 65 mol%, based on the entire diamine. The diamine for synthesizing the polyamic acid (B) may contain, as the above-mentioned diamine (b3), preferably in the range of 5 to 40 mol%, in the range of 80 mol% or less based on the entire diamine.

The diamine for synthesizing the polyamic acid (B), by containing the diamine (b1) in the above range, can maintain good coatability and printability in the obtained liquid crystal alignment, and can be obtained with the same imprint resistance. A liquid crystal alignment film which is excellent in properties and good pretilt angle is preferable. Further, by containing the diamine (b2) in the above range, the good printability of the obtained liquid crystal alignment agent is excellent in balance with the electrical characteristics (especially, voltage holding ratio) of the formed liquid crystal alignment film, which is preferable.

Polylysine (B) can be synthesized by reacting a tetracarboxylic dianhydride as described above with a diamine.

The ratio of the tetracarboxylic dianhydride to the diamine used for the synthesis reaction of the polyaminic acid (B) is preferably an amine group of 1 equivalent of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents. More preferably, it is a ratio of 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 0 to 100 ° C, preferably for 0.1 to 24 hours, more preferably for 0.5 to 0.5 °. 12 hours.

Among them, examples of the organic solvent include an aprotic polar solvent, phenol and a derivative thereof, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. Specific examples of the organic solvent include, as the aprotic polar solvent, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamidine. An amine, dimethyl hydrazine, γ-butyrolactone, tetramethyl urea, hexamethylphosphonium triamide or the like; examples of the phenol derivative include m-cresol, xylenol, halogenated phenol, etc.; Examples of the ketone include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, and ethylene glycol monomethyl ether. Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, and methyl methoxypropionic acid. Ester, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, etc.; as the ether, for example, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether , ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol II Ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc.; Examples of the halogenated hydrocarbon include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, and the like. Alkane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, diisoheptyl ether, and the like. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and phenol and a derivative thereof (first organic solvent), or one or more selected from the above-mentioned first organic solvent and selected from the above are preferably used. A mixture of more than one of an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon (a second organic solvent). In the latter case, the ratio of use of the second organic solvent to the total amount of the first organic solvent and the second organic solvent is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight. %the following.

The amount (a) of the organic solvent used is preferably from 0.1 to 50% by weight based on the total amount (b) of the tetracarboxylic dianhydride and the diamine relative to the total amount (a+b) of the reaction solution. As described above, a reaction solution in which polyamic acid (B) is dissolved can be obtained. The reaction solution can be directly used for preparation of a liquid crystal alignment agent, and is used for preparing a liquid crystal alignment agent after separating the polyamic acid (B) contained in the reaction solution, or after separating the separated polyamic acid (B). For the preparation of liquid crystal alignment agents. In the case where the poly (proline) acid (B) is dehydrated and closed to form a polyimine (B), the above reaction solution can be directly supplied to the dehydration ring closure reaction, and the polylysine contained in the reaction solution can be contained. (B) After separation, it is supplied to the dehydration ring closure reaction, or may be supplied to the dehydration ring closure reaction after the separated polyamic acid (B) is purified. The separation and purification of polyamic acid (B) can be carried out according to a known method.

<polyimine (B)>

The polyimide (B) of the present invention can be obtained by subjecting the polyamic acid (B) synthesized as described above to dehydration ring closure and imidization of hydrazine. The polyimine (B) in the present invention may be a fully ruthenium imide which dehydrates and closes all of the guanamine structure of the polyglycolic acid (B) as a precursor thereof, or may be only a proline A part of the structure is dehydrated and closed, and the guanidinium structure of the proline structure and the quinone ring structure coexist. The polyimine (B) in the present invention preferably has a quinone imidization ratio of preferably 10 to 90%, more preferably 20 to 80%. The ruthenium imidization ratio is expressed as a percentage of the amount of the guanidine structure relative to the polyimine and the sum of the number of quinone ring structures, and the proportion of the quinone ring structure. Wherein a part of the quinone ring may be an isoindole ring. The dehydration ring closure of poly-proline (B) is preferably a method of heating poly-proline (B) or dissolving poly-proline (B) in an organic solvent, adding a dehydrating agent and a dehydration ring in the solution. The catalyst is carried out according to a method of heating as needed. Among them, the latter method is preferred.

In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of the polyamic acid (B), an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on the structure of the proline of 1 mol of polyamic acid. As the dehydration ring-closure structure, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. The amount of the dehydration ring-closure catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. The organic solvent used for the dehydration ring-closure reaction is exemplified as the organic solvent exemplified as the solvent used for the synthesis of the 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 1.0 to 120 hours, more preferably from 2.0 to 30 hours. Thus, a reaction solution containing polyimine (B) was obtained. The reaction solution can be directly used for the preparation of the liquid crystal alignment agent, or the liquid crystal alignment agent can be prepared on the basis of removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or can be used for liquid crystal alignment after separating the polyimine (B). The preparation of the agent, or the purification of the isolated polyimine (B), is used for the preparation of a liquid crystal alignment agent. These purification operations can be carried out according to a known method.

<Other ingredients>

The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of polyorganooxane (A) and polyammonic acid (B) and polyimine (B) as described above, as long as it is not Any other component may be contained in the case of impairing the effects of the present invention. Examples of other components which can be used therein include polymers other than the above polyorganosiloxane (A), polyglycine (B), and polyimine (B) (hereinafter referred to as "other polymers"). A curing agent, a curing catalyst, a curing accelerator, a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), a functional decane compound, a surfactant, a photosensitizer, and the like.

[Other polymers]

The above other polymers can be used to further improve the solution characteristics of the liquid crystal alignment agent of the present invention and the electrical characteristics of the resulting liquid crystal alignment film. Examples of the other polymer include polyorganosiloxane (hereinafter referred to as "other organic oxirane") other than polyorganosiloxane (A), and polyamine other than polyamine (B). Acid (hereinafter referred to as "other poly-proline"), polyimine (other than "polyimine"), polyphthalamide, polyester Polyamide, cellulose derivatives, polyacetal, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like. Among them, other organic decane, other poly-proline, and other polyimine may be used, and one or more selected from the group consisting of them may be used.

The above other polyorganosiloxane may be obtained by subjecting at least one selected from the decane compounds (1) and (2) to hydrolysis condensation. The precursor of the polyorganosiloxane (A) can also be used as the other polyorganosiloxane described therein. In the polyorganosiloxane of the present invention, the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is preferably from 500 to 100,000, more preferably from 500 to 10,000.

The synthesis reaction and separation and purification of other polyorganosiloxanes can be carried out according to the examples of polyorganosiloxane (A), as will be apparent to those skilled in the art.

The other polyamine may be obtained by reacting a tetracarboxylic dianhydride with at least one diamine selected from the above diamines (b1) and (b3), or a tetracarboxylic acid and an anhydride selected from the above diamines ( B2) is obtained by reacting at least one diamine of (b3). Other polyimines can be obtained by hydrazine imidation by dehydration of other polylysines as described above. The ruthenium imidation ratio of the other polyimine is preferably 30% or more, more preferably 40 to 80%.

The synthesis, separation and purification of other polyaminic acids and other polyimines can be carried out according to the examples of polyglycolic acid (B) or polyimine (B).

[Curing agent and curing agent catalyst and curing accelerator]

In order to more firmly carry out the crosslinking reaction of the polyorganosiloxane (A), the liquid crystal alignment agent of the present invention may contain the above-mentioned curing agent and curing catalyst, and in order to promote the curing reaction of the curing agent, the liquid crystal alignment in the present invention The above curing accelerator may be contained in the agent.

As the curing agent, a curing agent which is usually used as a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used, and examples thereof include polyamines, polycarboxylic anhydrides, and polycarboxylic acids. Acid, etc.

Examples of the polyvalent carboxylic acid anhydride include an acid anhydride of cyclohexanetricarboxylic acid and another polyvalent carboxylic acid anhydride.

The acid anhydride of the above cyclohexanetricarboxylic acid may, for example, be cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride or cyclohexane-1,2,3-tricarboxylic acid-2,3. An acid anhydride or the like, and examples of the other polybasic acid anhydride include 4-methyltetrahydrophthalic anhydride and methyl group lowering. Alkenoic anhydride, dodecene succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, a compound represented by the following formula, and

In the above formula, m is an integer from 1 to 20.

The tetracarboxylic dianhydride which is usually used for the synthesis of poly-proline, and an alicyclic compound having a conjugated double bond such as α-terpinene or Alloocimene and a horse may be mentioned. Diels-Alder reaction products of anhydrides, hydrogenated products thereof and the like.

As the curing catalyst, for example, a ruthenium hexafluoride compound, a phosphorus hexafluoride compound, aluminum triacetate acetate or the like can be used. These catalysts can catalyze the cationic polymerization of epoxy groups by heating.

Examples of the curing accelerator include an imidazole compound; a quaternary phosphonium compound; a quaternary ammonium compound; and a diaza complex such as 1,8-diazabicyclo[5.4.0]undecene-7 and an organic acid salt thereof. a bicyclic olefin; an organometallic compound such as zinc octoate, tin octoate, and an aluminum acetate acetate complex; a boron compound such as boron trifluoride or triphenyl borate; a metal halide such as zinc chloride or stannous chloride; High-melting-point-distribution latent curing accelerators such as dicyanodiammonium, amine-forming accelerators of amines and epoxy resins; microcapsule-type potentials in which the surface of the quaternary phosphonium salt is covered with a polymer A curing accelerator; an amine salt type latent curing accelerator; a latent curing accelerator such as a Lewis acid salt, a Bronsted acid salt, a thermal decomposition polymerization type latent curing accelerator, and the like.

[epoxy compound]

The above epoxy compound is a compound having at least one epoxy group in the molecule, but does not include the above-mentioned polyorganosiloxane (A) or other polyorganosiloxane.

The liquid crystal alignment agent of the present invention may contain the epoxy compound 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 glycol. Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl- 2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane Alkane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl Amino-aminomethylcyclohexane or the like is preferred.

In the case where the liquid crystal alignment agent of the present invention contains an epoxy compound, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination in order to effectively carry out the crosslinking reaction.

[functional decane compound]

In order to improve the adhesion of the obtained liquid crystal alignment film to the substrate, the above functional decane compound can be used. The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyltri Ethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Decane, 3-guanidinopropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl- 3-Aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxycarbamido- 1,4,7-triazadecane, 10-triethoxycarbamimidyl-1,4,7-triazadecane, 9-trimethoxyformamido-3,6-diaza Mercaptoacetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl- 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxygen) Vinyl)-3-amine Propyltrimethoxydecane, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane, 3-glycidylpropyltrimethoxydecane, 2-(3,4-epoxy Further, the reaction of a tetracarboxylic dianhydride and a decane compound having an amine group described in Patent Document 10 (JP-A-63-291922) is also mentioned. Things and so on.

[Surfactant]

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a polyoxyalkylene surfactant, a polyalkylene oxide surfactant, and a fluorine-containing surfactant. Surfactant and the like.

[Photosensitizer]

Examples of the photosensitizer include tetramethylbenzene, benzonitrile, butyl benzene, acetophenone, acetophenone, anthrone, 4-methoxyacetophenone, and 3-methoxyacetophenone. Anthrone, benzaldehyde, 4,4'-dimethoxybenzophenone, benzophenone, anthracene, terphenyl, biphenyl, 9-oxo , 蒽醌, 4,4'-bis(diethylamino)benzophenone, phenanthrene, naphthalene, 4-phenylacetophenone, 4-phenylbenzophenone, 2-iodophthalene, anthracene (acenaphthene) 2-naphthonitrile, 1-iodonaphthalene, 1-naphthonitrile, Pyridinium, pyrene, benzyl, fluoranthene, anthracene, 1,2-benzopyrene, acridine, anthracene, tetracene, 2-methoxynaphthalene, 1,4-dicyanophthalene, 9-cyano Ruthenium, 9,10-dicyanoguanidine, 2,6,9,10-tetracyanoguanidine, and the like.

<Use ratio of each component>

The proportion of use of each component in the liquid crystal alignment agent of the present invention is as follows.

In the case where the liquid crystal alignment agent of the present invention contains at least one polymer selected from other polyglycines and other polyimines, the ratio of use of these other polymers is preferably relative to polyglycolic acid and polyfluorene. The sum of imines (ie, refers to the sum of poly-proline (B) and polyimine (B) and other poly-proline and any other polyamidiamine used arbitrarily. The following is the same), 90% by weight Hereinafter, it is more preferably 70% by weight or less.

The liquid crystal alignment agent of the present invention comprises a polyorganosiloxane (A) and at least one polymer selected from the group consisting of polyamic acid (B) and polyimine (B) as a polymer, and a ratio of use thereof The polyorganosiloxane (A) is preferably used in an amount of from 0.1 to 100 parts by weight, more preferably from 1 to 5 parts by weight, based on the total of 100 parts by weight of the polyamic acid and the polyamidene. Good for 5 to 15 parts by weight. By using the ratio of use in this range, it is preferable to maintain good coatability and printability of the obtained liquid crystal alignment agent, and to realize an appropriate pretilt angle embodyability.

In the case where the liquid crystal alignment agent of the present invention contains another polyorganosiloxane, the use ratio thereof is preferably 100 parts by weight or less, more preferably 50% by weight based on 100 parts by weight of the total of polyamic acid and polyimine. It is more preferably 20 parts by weight or less in parts by weight or less.

In the case where the liquid crystal alignment agent of the present invention contains a curing agent, the use ratio thereof is preferably 100 parts by weight or less based on 100 parts by weight of the polyorganosiloxane (A).

In the case where the liquid crystal alignment agent of the present invention contains a curing catalyst, the use ratio thereof is preferably 2 parts by weight or less based on 100 parts by weight of the polyorganosiloxane (A).

In the case where the liquid crystal alignment agent of the present invention contains a curing accelerator, the use ratio thereof is preferably 10 parts by weight or less based on 100 parts by weight of the polyorganosiloxane (A).

In the case where the liquid crystal alignment agent of the present invention contains an epoxy compound, the use ratio thereof is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight based on 100 parts by weight of the total of the polyaminic acid and the polyimide. Share. Further, in the case where the base catalyst is used together with the epoxide, the use ratio thereof is preferably 10 parts by weight or less, more preferably 0 to 2 parts by weight, per 100 parts by weight of the epoxy compound.

In the case where the liquid crystal alignment agent of the present invention contains a functional decane compound, the use ratio thereof is preferably 50 parts by weight or less, more preferably 20 parts by weight based on 100 parts by weight of the total of polyglycine and polyimine. The following.

In the case where the liquid crystal alignment agent of the present invention contains a surfactant, the use ratio thereof is preferably 10 parts by weight or less, more preferably 1 part by weight or less based on 100 parts by weight of all the liquid crystal alignment agents of the present invention.

When the liquid crystal aligning agent of the present invention contains a photosensitizer, the use ratio thereof is preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of the polyorganosiloxane (A).

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention contains the polymer as described above and any other components, and is preferably prepared in the form of a solution composition which is dissolved in a suitable organic solvent.

As an organic solvent which can be used for the preparation of the liquid crystal alignment agent of the present invention, it is preferably selected from the group consisting of polyorganooxane (A) and polyphosphoric acid (B) and polyimine (B). At least one polymer and any other component used arbitrarily, which does not react with it. The organic solvent which can be preferably used in the liquid crystal alignment agent of the present invention is exemplified as used in the synthesis of polyorganosiloxane (A), polyphosphonic acid (B) and polyimine (B). The organic solvent to be exemplified above may be one or more selected from the group consisting of the organic solvents exemplified above.

In the preparation of the liquid crystal alignment agent of the present invention, it is preferred that the solvent contains one of the above organic solvents, or two or more of the above organic solvents are combined, and in the preferred solid concentration of the liquid crystal alignment agent, The components contained therein are not precipitated, and the surface tension of the liquid crystal alignment agent is in the range of 25 to 45 mN/m.

The solid content concentration of the liquid crystal alignment agent of the present invention, 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 can be selected in consideration of viscosity, volatility, etc., preferably from 1 to 10% by weight. In the range. When the liquid crystal alignment agent of the present invention is applied onto a substrate to form a coating film as a liquid crystal alignment film, when the solid content concentration is less than 1% by weight, the film thickness of the coating film may be too small, and it may be difficult to obtain a good liquid crystal alignment. membrane. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too large, and it is difficult to obtain a favorable liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases, and the coating property may be insufficient. The range of the particularly preferable solid content concentration differs depending on the method employed when the liquid crystal alignment agent is coated on the substrate. For example, in the case of being carried out by a spin coating method, it is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, whereby the solution viscosity is in the range of 12 to 50 mPa·s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, 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.

<Method of Forming Liquid Crystal Alignment Film>

The liquid crystal alignment agent of the present invention is preferably used for forming a liquid crystal alignment film by a photoalignment method.

As a method of forming a liquid crystal alignment film, for example, a liquid crystal alignment film of the present invention is applied onto a substrate to form a coating film, and then the coating film is irradiated with polarized or non-polarized radiation to impart a liquid crystal alignment ability.

First, the liquid crystal alignment agent of the present invention is applied to the transparent conductive film side of the substrate on which the pattern-shaped transparent conductive film is provided by an appropriate coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method, and then The coated surface is preheated (prebaked) and then calcined (post baked) to form a coating film. The prebaking conditions are, for example, 40 to 120 ° C for 0.1 to 5 minutes, and the post-baking conditions are preferably 120 to 300 ° C, more preferably 150 to 250 ° C, and preferably 5 to 200. In a minute, it is more preferably carried out for 10 to 100 minutes, and the film thickness after post-baking is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

As the substrate, for example, glass of float glass or soda glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and cyclic olefin resin can be used. A transparent substrate or the like.

As the transparent conductive film, for example, a NESA (registered trademark) film made of SnO ₂ or an ITO film made of In ₂ O ₃ -SnO ₂ can be used. In order to pattern these transparent conductive films, a known method can be used.

When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate or the transparent conductive film and the coating film, a functional decane compound, a titanate compound or the like may be applied to the substrate or the transparent conductive film in advance.

Then, the liquid crystal alignment ability is imparted by irradiating linearly or partially polarized radiation or non-polarized radiation to the coating film. Among them, 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 preferable. When the radiation to be used is linearly polarized or partially polarized, the irradiation may be performed in a direction perpendicular to the substrate surface, or may be performed from the oblique direction in order to impart the pretilt angle, or may be combined. In the case of irradiating non-polarizing radiation, the direction of irradiation must be a direction of inclination.

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, in the conventional coating film formed of the liquid crystal alignment agent, when the liquid crystal alignment ability is imparted by the photo-alignment method, a radiation irradiation amount of 10,000 J/m ² or more is required. However, the liquid crystal alignment agent of the present invention can impart a good liquid crystal alignment ability and can reduce liquid crystal display elements even when the amount of radiation irradiation in the photo-alignment method is 3,000 J/m ² or less and further 1,000 J/m ² or less. Manufacturing costs.

<Method of Manufacturing 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. The liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is particularly preferable when it is used for a vertical alignment type liquid crystal display element to maximize its advantageous effects.

The liquid crystal display element of the present invention can be produced, for example, as follows.

Two substrates on which a liquid crystal alignment film was formed as described above were prepared, and liquid crystal was provided between the two substrates to produce a liquid crystal cell. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

In order to produce a liquid crystal cell using this liquid crystal, the following two methods are mentioned, for example.

In the first method, the two substrates are opposed by a gap (cell gap), and the liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together by using a sealant, and are divided by the substrate surface and the sealant. After filling the liquid crystal into the cell gap, a method of sealing the injection hole is sealed, whereby the liquid crystal cell can be manufactured.

The second method is a method called the ODF (One Drop Fill) method. In a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed, for example, by applying an ultraviolet curable sealing agent, liquid crystal is dropped onto the liquid crystal alignment film, and then the other substrate is bonded to the liquid crystal. The alignment film is opposed to each other, and then ultraviolet light is irradiated on the entire surface of the substrate to cure the sealant, thereby producing a liquid crystal cell.

In either case, it is preferred to heat the liquid crystal cell to a temperature at which the liquid crystal is formed, and then slowly cool to room temperature, thereby removing the flow alignment at the time of liquid crystal filling.

Further, the liquid crystal display element of the present invention can be obtained by laminating a sheet of light on the outer surface of the liquid crystal cell. In the case where the liquid crystal alignment film has a vertical alignment property, the alignment means makes the alignment between the two substrates forming the liquid crystal alignment film parallel to the axis direction, and the polarizing plate is bonded thereto to make the polarization direction and the alignment easy. The shaft forms an angle of 45° to form a liquid crystal display element having a vertical liquid crystal alignment type liquid crystal cell.

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

As the liquid crystal, a nematic liquid crystal, a smectic liquid crystal or the like can be preferably used.

In the case of a vertical alignment type unit, a nematic liquid crystal having dielectric anisotropy is preferably used, and for example, a dicyanobenzene liquid crystal or a ruthenium can be used. A liquid crystal, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenyl cyclohexene liquid crystal, or the like.

The polarizing plate used for the outer side of the liquid crystal cell may be a polarizing plate called a "H film", which is obtained by pulverizing a polyvinyl alcohol with a cellulose acetate protective film and absorbing iodine or by an H film. A polarizing plate made of itself or the like.

The liquid crystal display device of the present invention thus prepared is excellent in various properties such as display characteristics and long-term reliability.

Example

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

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

Column: manufactured by Tosoh, 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 solution viscosity of the polymer is a polymer solution (solvent: N-methyl-2-pyrrolidone) having a polymer concentration of 20% by weight as indicated in each synthesis example, using an E-type viscometer at 25 ° C Measured value.

The ruthenium iodide ratio of the polyimine is obtained by adding a polyimine solution obtained in each synthesis example to pure water, and the resulting precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in dihydro dimethyl hydrazine. The ¹ H-NMR spectrum measured at room temperature with tetramethylnonane as a reference material was calculated by the following mathematical formula (1).

Yttrium imidation rate (%) = (1-A ¹ /A ² ×α)×100 (1)

In the formula (1), A ¹ represents a peak area from a proton of an NH group which appears near a chemical shift of 10 ppm, A ² is a peak area from other protons, and α is a polymer precursor (polyamide) The ratio of the number of other protons of the NH proton in the acid).

Further, in the following, the synthesis of the raw material compound and the polymer is repeated as needed according to the following synthesis scale, thereby ensuring the necessary amount used in the following synthesis.

<Synthesis of a polyorganosiloxane having an epoxy group (precursor of polyorganosiloxane)

Synthesis Example E-1

100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 500 g of methyl isobutyl ketone and 10.0 were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. g Triethylamine, mixed at room temperature. Then, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, followed by mixing under reflux, and reacted at 80 ° C for 6 hours. After completion of the reaction, the organic layer was taken out and 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 obtain a viscous transparent liquid form. Polyorganosiloxane (EPS-1) having an epoxy group.

The polyorganosiloxane (EPS-1) was subjected to ¹ H-NMR analysis, and an epoxy group-based peak having a theoretical strength as obtained was obtained in the vicinity of a chemical shift (δ) = 3.2 ppm, and it was confirmed that it did not cause a reaction in the reaction. A side reaction of an epoxy group.

The polyorganosiloxane (EPS-1) had a weight average molecular weight Mw of 2,200 and an epoxy equivalent of 186 g/mol.

<Synthesis of Carboxylic Acid (A1)>

In the following synthesis examples, the following formulas (A-1) to (A-8) are synthesized.

Compounds indicated separately. Hereinafter, the compounds represented by the above formulas (A-1) to (A-8) are referred to as "compounds (A-1) to (A-8)" and the like.

Synthesis Example A-1

In a 200 mL eggplant type flask having a reflux tube, 12 g of n-decyl succinic anhydride, 8.2 g of 4-aminocinnamic acid and 100 mL of acetic acid were added, and the mixture was reacted under reflux for 2 hours. After completion of the reaction, the reaction mixture was extracted with EtOAc. EtOAc (EtOAc) 2 (volume ratio)) was purified, and recrystallized from a mixed solvent of ethanol and tetrahydrofuran to obtain 10 g of a white crystal (purity: 98.0%) of the compound (A-1).

Synthesis Example A-2

In a 1 L eggplant type flask, 82 g of p-hydroxycinnamic acid, 304 g of calcium carbonate and 400 mL of N-methyl-2-pyrrolidone were added, and stirred at room temperature for 1 hour, and then 212 g of 1-brominated octane was added. Stir at 100 ° C for 5 hours. Then, the solvent was removed by distillation 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 the reaction, the reaction system was neutralized with hydrochloric acid, and the resulting precipitate was recovered and recrystallized from ethanol to obtain white crystals of 80 g of Compound (A-2).

Synthesis Example A-3

107 g of 4-brominated cinnamic acid was refluxed in 83 g of sulfinium chloride for 4 hours to obtain a red transparent solution. Then, unreacted sulfinium chloride was distilled off, and the residue was recrystallized from toluene, and the obtained crystal was washed with n-hexane to obtain white crystals of 85 g of 4-bromo cinnabarium chloride.

Then, 25.0 g (0.147 mol) of 4-aminocyclohexanol was dissolved in 25 mL of pyridine. The temperature of the solution was maintained at about 3 ° C, and 43.3 g (0.176 mol) of 4-brominated cinnabarin chloride was suspended in 350 mL of pyridine, and reacted for further 3 hours. The obtained reaction mixture (suspension) was added to 1.3 kg of hydrochloric acid acidic ice water, and the resulting precipitate was recovered, washed with water, and dried to obtain 50 g of crude 4-n-pentylcyclohexyl 4-bromocinnamate (cream powder). ).

In a mixture of 50 g of the above-mentioned crude 4-bromo-cinnamic acid 4-n-pentylcyclohexyl ester, 0.28 g of palladium acetate and 1.52 g of cis (o-tolyl) phosphine, under a nitrogen atmosphere, 125 mL of dryness was added. Triethylamine is reacted. After the crude 4-n-pentylcyclohexyl cinnamate was completely dissolved, 10.8 g of acrylic acid was injected through a syringe, and the reaction was continued at 95 ° C for 2 hours. The resulting dark green reaction mixture was added to 1.3 kg of hydrochloric acid acidic ice water, and the resulting precipitate was recovered. A solution obtained by dissolving the obtained solid in 500 mL of ethyl acetate was washed successively with 1N hydrochloric acid and a 5% by weight sodium hydrogen carbonate solution, and then dried over magnesium sulfate, and the solvent was evaporated to give 56 g of the above formula (A-3). Crude compound (yellow solid). The crude product was recrystallized from ethanol to give 30 g (yield: 55%) of a yellow powder of Compound (A-3).

Synthesis Example A-4

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 the mixture was stirred at room temperature for 1 hour, and then 157.1 g was added. The 1-iodo-4,4,4-trifluorobutane was stirred at 100 ° C for 5 hours. After the reaction was completed, the reaction mixture was added to water to carry out reprecipitation. Then, 48 g of sodium hydroxide and 400 mL of water were added to the resulting precipitate, and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and the resulting precipitate was recovered and recrystallized from ethanol to obtain white crystals of 110 g of 4-(4,4,4-trifluorobutoxy)benzoic acid.

12.41 g of the 4-(4,4,4-trifluorobutoxy)benzoic acid was taken out from the reaction vessel, and 100 mL of sulfinium chloride and 77 μL of N,N-dimethylformamide were added thereto. Stir at 80 ° C for 1 hour. Then, sulfinium chloride was distilled off under reduced pressure, dichloromethane was added, and the organic layer was washed with aqueous sodium hydrogencarbonate, dried over magnesium sulfate, and then evaporated. The resulting solid was dissolved in tetrahydrofuran to form a solution.

Next, in a separate 500 mL three-necked flask different from the above, 7.39 g of 4-hydroxycinnamic acid, 13.82 g of potassium carbonate, 0.48 g of tetrabutylammonium bromide, 50 mL of tetrahydrofuran, and 100 mL of water were added. The solution was ice-cooled, and the above tetrahydrofuran was slowly added dropwise, followed by a reaction under stirring for 2 hours. After completion of the reaction, hydrochloric acid was added to the reaction mixture for neutralization, and the mixture was extracted with ethyl acetate. The obtained solid was recrystallized from ethanol to obtain white crystals of 10.0 g of Compound (A-4).

Synthesis Example A-5

In a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube, 31 g of 1-bromo-4-(4-n-pentylcyclohexyl)benzene, 0.23 g of palladium acetate, and 1.2 g of cis (o-tolyl) were added. Phosphine, 56 mL of triethylamine, 8.2 mL of acrylic acid and 200 mL of N,N-dimethylacetamide were stirred at 120 ° C for 3 hours. After the reaction was completed, the reaction mixture was filtered, and 1 L of ethyl acetate was added to the obtained liquid crystals, and the obtained organic layer was washed twice with diluted hydrochloric acid, washed three times with water, dried over magnesium sulfate, and then solvent was evaporated under reduced pressure. The obtained solid was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain 15 g of a crystal of Compound (A-5).

Synthesis Examples A-6 and A-7

In the above Synthesis Example A-5, except that 28 g of 1-bromo-4-(4-n-propylcyclohexyl)benzene (synthesis example A-6) and 34 g of 1-bromo-4-(4) were used, respectively. - n-heptylcyclohexyl)benzene (Synthesis Example A-7) was used in the same manner as in Synthesis Example A-5 except for 1-bromo-4-(4-n-pentylcyclohexyl)benzene, and 13 g of a compound (A) was obtained. Crystallization of -6) and crystallization of 14 g of the compound (A-7).

Synthesis Example A-8

In a 300 mL flask with a reflux tube and a nitrogen inlet tube, 21 g of 4-n-pentyl-4'-carboxybicyclohexyl, 80 mL of sulfinium chloride and 0.1 mL of N,N-dimethylformamide were added. The reaction was stirred at 80 ° C for 1 hour. After the end of the reaction, sulfinium chloride was distilled off from the reaction mixture, then 150 mL of dichloromethane was added, and the obtained organic layer was washed three times with water. The organic layer was dried over magnesium sulfate, and then the solvent was evaporated under reduced pressure, and 400 ml of tetrahydrofuran was added to the obtained solid.

On the other hand, 16 g of p-hydroxycinnamic acid, 24 g of potassium carbonate, 0.87 g of tetrabutylammonium bromide, 200 mL of water and 100 mL of tetrahydrofuran were placed in a 1 L three-necked flask having a dropping funnel and a thermometer, and ice-cooled to 5 ° C or lower. The above tetrahydrofuran solution was added dropwise over 3 hours, and the reaction was further carried out for 1 hour while stirring. After completion of the reaction, dilute hydrochloric acid was added to the reaction mixture to adjust the pH to 4 or less, and then 3 L of toluene and 1 L of tetrahydrofuran were added, and the obtained organic layer was washed three times with water. After the organic layer was dried over magnesium sulfate, the solvent was evaporated under reduced pressure, and the obtained solid was recrystallized from a solvent mixture of ethanol and tetrahydrofuran to obtain 21 g of compound (A-8).

<Synthesis of polyorganosiloxane (A)>

Synthesis Example S-1

Into a 200 mL three-necked flask, 5.0 g of the polyoxyorganooxane (EPS-1) having an epoxy group obtained in the above Synthesis Example E-1, 46.4 g of methyl isobutyl ketone, and 1.34 g of a carboxylic acid as a carboxylic acid were added. The compound (A-1) obtained in the above Synthesis Example A-1 of the acid (A1) (corresponding to an epoxy group of EPS-1, corresponding to 25 mol%) and 0.13 g of tetrabutylammonium bromide at 80 ° C The reaction was carried out under stirring for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. After washing the solution three times, the solvent was distilled off to obtain 2.3 g of polyorganopolyorganosiloxane (A). A white powder of decane (S-1).

Synthesis Example S-2~S-33

In the above Synthesis Example S-1, the polyorganosiloxane (S-) shown in Table 1 was synthesized in the same manner as in Synthesis Example S-1, except that the type and amount of the carboxylic acid used were as described in Table 1, respectively. 2)~(S-33).

Among them, in Synthesis Examples S-3 to S-7, S-17 and S-21, as the carboxylic acid, the carboxylic acid (A1) and the other carboxylic acid (1) and other carboxylic acids of the types and amounts described in Table 1 were used. Acid (2) is used in combination. In Synthesis Examples S-31 to S-33, as the carboxylic acid (A1), two acids were used in combination.

The amount of the carboxylic acid described in Table 1 is mol% relative to the epoxy group having EPS-1.

The abbreviations of the carboxylic acids in the above Table 1 have the following meanings, respectively.

[carboxylic acid (A1)]

A-1: Compound (A-1) obtained in the above Synthesis Example A-1

A-2: Compound (A-2) obtained in the above Synthesis Example A-2

A-3: Compound (A-3) obtained in the above Synthesis Example A-3

A-4: Compound (A-4) obtained in the above Synthesis Example A-4

A-5: Compound (A-5) obtained in the above Synthesis Example A-5

A-6: Compound (A-6) obtained in the above Synthesis Example A-6

A-7: Compound (A-7) obtained in the above Synthesis Example A-7

A-8: Compound (A-8) obtained in the above Synthesis Example A-8

[Other carboxylic acids (1)]

B-1: Stearic acid

B-2: 1,4-succinic acid mono(3-cholestyl) ester

B-3: 4-(4,4,4-trifluorobutoxy)benzoic acid

[Other carboxylic acids (2)]

C-1: 3,5-dinitrobenzoic acid

<Synthesis of Polyimine (B)>

Synthesis Example P-1~P-29

In these synthesis examples, each polymer as the polyimine (B) was synthesized by the following procedure.

As the monomer, tetracarboxylic dianhydride and diamine of the kind and amount shown in Table 2 were used, respectively. The amount of each monomer used in Table 2 is shown in units of mol% in the case where the amount of the tetracarboxylic dianhydride used is 100 mol%.

The monomer mixture composed of the tetracarboxylic dianhydride and the diamine was dissolved in N-methyl-2-pyrrolidone to form a solution having a monomer concentration of 20% by weight, and reacted at 60 ° C for 4 hours, respectively. A solution containing 20% by weight of polyamic acid was obtained. The solution viscosity of each polyaminic acid solution is shown in Table 2.

Then, N-methyl-2-pyrrolidone is added to each of the obtained polyaminic acid solutions, the concentration of polyproline is diluted to 10% by weight, and pyridine and acetic anhydride are further added to make them relative to 1 mol, respectively. The methionine unit of polylysine was a mole ratio described in Table 2, and then dehydrated and closed at 100 ° C for 4 hours. Then, the solvent in the reaction system was replaced with a new N-methyl-2-pyrrolidone solvent to obtain about 20% by weight of polyimine (PI) as a polyimine (B). 1)~(PI-29). The oxime imidization rates of the respective polyfluorenes contained in these solutions are shown in Table 2 together.

<Synthesis of other polylysine>

Synthesis example p-1~p-5

In the synthesis of the above polyimine (B), in addition to the use of the kinds and amounts of the tetracarboxylic dianhydride and the diamine shown in Table 2, the same as in the synthesis of the polyimine (B), respectively, 20 was obtained. % by weight of polylysine (pa-1) to (pa-5) as other polyaminic acid. The solution viscosity of each polyamine was shown in Table 2.

These polyaminic acid solutions can be directly used for the preparation of liquid crystal alignment agents without dilution and dehydration ring closure reaction by N-methyl-2-pyrrolidone.

<Synthesis of other polylysine>

Synthesis example p-6~p-8

In the synthesis of the above polyimine (B), in addition to the use of the kinds and amounts of the tetracarboxylic dianhydride and the diamine shown in Table 2, the same as in the synthesis of the polyimine (B), respectively, 20 was obtained. % by weight of each polyamine. The solution viscosity of each polyamine was shown in Table 2.

Then, using each polyaminic acid solution, as in the synthesis of the polyimine (B), 20% by weight of polyimine (pi-1) to (pi-3) as another polyimine was obtained. ). The oxime imidization ratio of each of the polyimine contained in these solutions is shown together in Table 2.

The abbreviations of the monomers in Table 2 above are respectively the following meanings.

[tetracarboxylic dianhydride]

T1: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

T2: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

T3: trimellitic acid dianhydride

[diamine]

-diamine (b1)-

a: a compound represented by the above formula (b1-1-4)

b: a compound represented by the above formula (b1-1-7)

c: 3,5-diaminobenzoic acid-3-cholesteryl ester

d: 2,4-diamino-3-cholestyloxybenzene

-diamine (b2)-

e: 3,5-diaminobenzoic acid

f: 3,3'-dicarboxy-4.4'-diaminobiphenyl

g: bis(4-aminophenyl)bis(2-carboxyethyl)methane

-diamine (b3)-

h:N-(2,4-diaminophenyl)perazine

i: 4,4'-diaminodiphenylmethane

j: p-phenylenediamine

k: 1-(4-Aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-5-amine

l: N, N'-bis(4-aminophenyl) piperidine

m: 2,2'-dimethyl-4,4'-diaminobiphenyl

n: 4,4'-diaminodiphenyl ether

<Preparation and evaluation of liquid crystal alignment agent> Example 1

[Preparation of Liquid Crystal Aligning Agent]

In the solution containing the polyimine (PI-1) obtained in the above Synthesis Example P-1, 10 parts by weight of the above synthesis example is added to 100 parts by weight of the polyimine contained in the polyhydrazine salt solution. The polyorganosiloxane (S-1) obtained in S-1, and then N-methyl-2-pyrrolidone and butyl cyanidin are added to make the solvent N-methyl-2-pyrrolidone: Butyl cyanohydrazide = 40:60 (weight ratio) to form a solution having a solid concentration of 6.5% by weight. This solution was filtered through a screening procedure having a pore size of 0.2 μm to prepare a liquid crystal alignment agent for evaluation of printability.

Further, a liquid crystal alignment agent for producing a liquid crystal display element was prepared in the same manner as above except that the solid content concentration was 3.5% by weight.

[Printability evaluation]

On a 6-inch tantalum wafer, a resin gasket (manufactured by Sekisui Chemical Co., Ltd., "Micro Pearl EX-0041-AC4") having a diameter of about 4.1 μm was dispersed and heat-treated on a hot plate set at 120 ° C for 10 minutes. Prepare a tantalum wafer with attached spacers. Using a liquid crystal alignment agent for printability evaluation prepared as described above, a liquid crystal alignment film printing machine (manufactured by Japan Photo Printing Co., Ltd.) was applied on the above-mentioned wafer sheet with an attached spacer, and a heating plate at 80 ° C was used. Heated for 1 minute (pre-bake), then heated on a 200 ° C hot plate for 10 minutes (post-baking) to form an average film thickness of 800 Coating film. The coating film was observed under a microscope at a magnification of 20 times, and the printability was evaluated. Evaluation was made by the unevenness of the printing and the presence or absence of the depression in the adhesion pad, and it was evaluated that the printing unevenness and the unevenness of the adhesion pad were not observed at all, and the printing property was "excellent", and little coating was observed to be poor, but In the case where it was judged that the above-mentioned coating was not excellent, it was evaluated that the printing property was "good", and that the printing unevenness and the unevenness of the adhesion of the gasket were observed in a large amount, and the printing property was "poor".

[Manufacture of liquid crystal display elements]

The liquid crystal alignment agent for liquid crystal display element preparation prepared above was applied by spin coating on a transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film, and prebaked on a hot plate at 80 ° C for 1 minute. Then, the chamber was replaced with a nitrogen gas oven, and heated at 200 ° C for 1 hour to form a coating film having a film thickness of 0.08 μm. Then, on the surface of the coating film, an Hg-Xe lamp and a Glan-Taylor prism were used, and the substrate was used. A polarized ultraviolet ray having a bright line of 313 nm was irradiated at 500 J/m ^{2 in} a direction in which the normal line was inclined by 40° to form a liquid crystal alignment film. The same operation was repeated to obtain a pair of (two) substrates having a liquid crystal alignment film.

On one of the pair of substrates, the outer circumference of the surface of the liquid crystal alignment film is coated by a screen to coat an epoxy resin bonded with alumina balls having a diameter of 5.5 μm, and then a liquid crystal of a pair of substrates is applied. The alignment film was placed facing each other and pressure-bonded so that the projection direction of the ultraviolet light axis of each substrate on the substrate surface was antiparallel, and the adhesive was thermally cured at 150 ° C for 1 hour. Then, a negative liquid crystal (manufactured by Merck, MLC-6608) was filled into the space between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow alignment at the time of liquid crystal injection, it may be 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 perpendicular to each other, and the ultraviolet light axis of the liquid crystal alignment film was formed at an angle of 45° on the projection direction of the substrate surface, thereby manufacturing a liquid crystal display element.

The liquid crystal display element was evaluated in the following manner. The composition and evaluation results of the liquid crystal alignment agent are shown in Table 3.

[Evaluation of liquid crystal display elements]

(1) Evaluation of pretilt angle

The liquid crystal display element manufactured as described above can be used according to the method described in Non-Patent Document 1 (TJ Scheffer et. al. J. Appl. Phys. vol. 19, p2013 (1980)) by using He-Ne laser. The pretilt angle was measured by a crystal rotation method.

(2) Evaluation of voltage retention rate

The liquid crystal display element manufactured as described above was applied at an application temperature of 60 ° C at an application temperature of 60 μ C and then applied with a span of 167 msec, and then, the voltage holding ratio from the release of application to 167 msec was measured. The measuring device was manufactured by TOYO Corporation, and the model number was "VHR-1".

(3) Evaluation of the imprinting characteristics according to the difference in brightness

Two liquid crystal display elements were prepared in the same manner as above, and an alternating voltage of 10 V was applied to one (element A) at 60 ° C, and an alternating voltage of 1 V was applied to the other (element B) for 20 hours. Then, when the applied voltage is switched to a DC voltage of 2.5 V, when the difference in luminance between the observed element A and the element B is 256 levels, the difference in luminance is 10 or less, and the burn-in characteristic is "good", which exceeds 10 The situation is evaluated as "bad"

Examples 2 to 129 and Comparative Examples 1 to 7

In the above-mentioned Example 1, the liquid crystal alignment agent for liquid crystal display element production and the liquid crystal alignment agent for printability evaluation were prepared and evaluated in the same manner as in Example 1 except that the type and amount of the polymer to be used were as described in Table 3.

The evaluation results are shown in Table 3.

Further, in Examples 31, 32, 41, 42, 84, 85, 86, 91 and 101, two kinds of polyorganosiloxanes (A) may be used, respectively, and in Comparative Examples 2 and 3, two types are respectively used. Other polymers.

The abbreviations in the solvent composition column have the following meanings.

NMP: N-methyl-2-pyrrolidone

BC: Butyl cypress

In the above Table 3, it was confirmed that the liquid crystal alignment agents of the present invention of Examples 1 to 129 can exhibit excellent printability on the surface of the substrate having fine unevenness. Further, the liquid crystal alignment film formed of these liquid crystal alignment agents of the present invention exhibits a good pretilt angle and a high voltage holding ratio, and has excellent branding characteristics. Thus, the liquid crystal display element having the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is excellent in display quality and excellent in long-term reliability, which can be easily estimated by those skilled in the art.

On the other hand, the liquid crystal alignment agent belonging to the prior art prepared in the comparative example cannot satisfy all of the above characteristics at the same time.

Claims (7)

A liquid crystal alignment agent comprising: (A) a polyorganosiloxane having a structure represented by the following formula (A1), In the formula (A1), R is a fluorine atom or a cyano group, a is an integer of 0 to 4, "*" represents a linkage; and (B) is obtained by polyhydrazide and dehydration of the polyamine. At least one polymer selected from the group consisting of polyimine, wherein the polyamine is obtained by reacting a tetracarboxylic dianhydride with a diamine comprising (b2) a diamine having a carboxyl group. The liquid crystal alignment agent of claim 1, wherein the diamine further comprises (b1) a diamine having an alkyl group having 4 to 20 carbon atoms and an alkoxy group having 4 to 20 carbon atoms; A group having two or more 6 membered ring structures or a group having a steroid structure. The liquid crystal alignment agent according to claim 1 or 2, wherein the (A) polyorganosiloxane is a polyorganosiloxane having an epoxy group and a carboxylic acid having a structure represented by the above formula (A1). reaction product. The liquid crystal alignment agent of the third aspect of the invention, wherein the (b2) diamine is a compound represented by the following formula (b2-1), In the formula (b2-1), y is an integer of 0 to 2; x is an integer of 0 to 4, wherein, when there are a plurality of x, each x may be the same or different; each of R ^I is a single bond a methylene group, an alkylene group having 2 to 6 carbon atoms or a cyclohexyl group, wherein the above alkylene group may also be interrupted by an ether bond or an ester bond in the chain; X ^I is: a single bond, a methylene group , fluorinated methylene, alkylene group having 2 to 4 carbon atoms, fluorinated alkyl group having 2 to 4 carbon atoms, oxygen atom, carbonyl group, *-COO-, *-OCO-, *- NH-, *-CONH-, *-NHCO-, wherein "*" indicates that the linking chain imparted thereto is oriented to the left of (b2-1); or a group represented by the following formula (X ^I -1), In the formula (X ^I -1), R ^II is a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms or a cycloalkyl group, wherein the above alkyl group may also be ether in the chain. The bond or the ester bond is interrupted; R ^III is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a group -R ^IV COOH, wherein R ^IV is a single bond, a methylene group, and a carbon number of 2 to 6 An alkyl group or a cyclohexyl group, wherein the above alkyl group may be interrupted by an ether bond or an ester bond in the chain; and the total number of carboxyl groups in the formula (b2-1) is an integer of from 1 to 4. The liquid crystal alignment agent of claim 3, wherein the (b1) diamine is a diamine containing a group having a steroid structure. A method for forming a liquid crystal alignment film, comprising applying a liquid crystal alignment agent according to any one of claims 1 to 5 to form a coating film, and irradiating the coating film with radiation. A liquid crystal display element comprising a liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 5.