TWI554550B - Liquid crystal alignment agent, method for manufacturing liquid crystal display device, liquid crystal alignment film, liquid crystal display device, polymer and carboxylic acid - Google Patents

Description

Liquid crystal alignment agent, method for producing liquid crystal display element, liquid crystal alignment Membrane, liquid crystal display element, polymer and carboxylic acid

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, and a method for producing a liquid crystal display element, and more particularly to a liquid crystal alignment agent which can be suitably used for the production of a vertical alignment type liquid crystal display element.

Conventionally, as the liquid crystal display element, various driving methods have been developed in which the electrode structure or the physical properties of the liquid crystal molecules used are different. For example, a twisted nematic (TN) type or a super twisted nematic (Super Twisted Nematic) is known. Various types of liquid crystal display elements such as a Vertical Alignment (VA) type and an In-Plane Switching (IPS) type. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. As a material of the liquid crystal alignment film, for example, polylysine or polyimine, polyester, polyorganosiloxane or the like is known.

Further, in recent years, in liquid crystal display elements, as a new technique for controlling the alignment of liquid crystal molecules, a polymer stable alignment has been proposed (Polymer Sustained). Alignment (PSA) technology (for example, refer to Patent Document 1). The PSA technique is a technique in which a polymerizable component which is polymerized by irradiation with light is mixed into a liquid crystal layer of a liquid crystal cell, and the liquid crystal cell is irradiated with light by applying a voltage to tilt the liquid crystal molecules. The polymerizable component is polymerized to control the molecular alignment of the liquid crystal molecules.

However, when the alignment of liquid crystal molecules is controlled by the PSA technique, it is necessary to perform light irradiation with a relatively high irradiation amount. Therefore, defects such as decomposition of liquid crystal molecules or deterioration of performance of the liquid crystal alignment film occur, and as a result, display unevenness of the liquid crystal display element or poor long-term reliability of the panel occurs. On the other hand, when the amount of light irradiation is reduced, there is a problem that the response speed of the liquid crystal molecules to the voltage change becomes slow in the liquid crystal display element formed. In view of such a situation, it has been previously proposed to impart a desired pretilt angle characteristic to a coating film formed using a liquid crystal alignment agent with as little amount of light irradiation as possible, and to obtain a response of a liquid crystal molecule to a voltage change. A technique of a liquid crystal display element having a sufficiently fast speed (for example, refer to Patent Document 2). Patent Document 2 discloses the use of a liquid crystal alignment agent comprising a polyorganosiloxane having a (meth)acryl fluorenyl group and a polyamid acid or a polyimine as a polymer component to form a liquid crystal on a substrate. The alignment film is used, and the liquid crystal cell is formed using the substrate, and the liquid crystal cell is irradiated with light in a state where a voltage is applied between the substrates, thereby manufacturing a liquid crystal display element.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-149647

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-118358

However, in recent years, liquid crystal display elements have not only been used for personal calculations as before. A display terminal such as a computer, and is used for various purposes such as a liquid crystal television or a car navigation system, a mobile phone, a smart phone, a message display, and the like. With such versatility, there is a demand for higher performance of liquid crystal display elements, and as a liquid crystal alignment agent, a liquid crystal alignment agent which can further improve the display quality of a liquid crystal display element is required. For example, in the technique described in Patent Document 2, in the technique of controlling the alignment of liquid crystal molecules by light irradiation, it is possible to impart pretilt characteristics to a coating film which is a liquid crystal alignment film with a small amount of light irradiation. And a liquid crystal display element in which the response speed of the liquid crystal molecules to the voltage change is sufficiently fast can be manufactured.

The present invention has been made in view of the above problems, and a main object of the invention is to provide a liquid crystal alignment agent which transmits light to a liquid crystal cell while a voltage is applied between the substrates after the liquid crystal cell is formed. When a liquid crystal display element is manufactured, a liquid crystal alignment film which can exhibit good pretilt characteristics with as little light irradiation amount as possible can be formed, and a liquid crystal display element in which liquid crystal molecules are sufficiently fast in response to voltage changes can be obtained.

In order to achieve the above-described problems of the prior art, the inventors of the present invention have found that the liquid crystal alignment agent contains a polymer having a specific structure, and the above problems can be solved, and the present invention has been completed. Specifically, the present invention provides the following liquid crystal alignment agents, liquid crystal alignment films, liquid crystal display elements, and methods for producing liquid crystal display elements.

In one aspect, the present invention provides a liquid crystal alignment agent comprising a polymer (P) having a group represented by the following formula (1).

[Chemical 1]

(In the formula (1), A ¹ is a divalent group represented by the following formula (1a), an anthranyl group, a tetrahydronaphthalenediyl group, or a decahydronaphthalenediyl group.

(In the formula (1a), A ² is 1,4-phenylene, 1,4-cyclohexylene, piperidine-1,4-diyl, Piperidine-2,5-diyl, piperazine-1,4-diyl, piperazine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, pyridyl Pyrazine-2,5-diyl, or pyridine-2,5-diyl, X ⁴ is a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) ₂ - or -C≡C- m is an integer of 0 to 2. When m is 1 or 2, a plurality of A ^{2 's} may be the same or different, and when m is 2, a plurality of X ⁴ may be the same or different. "* ¹ " indicates a bonding hand)

Y is a single bond, -O-, * ² -COO-, * ² -OCO-, -OCOO-, -CO-, * ² -CONH-, * ² -NHCO-, -NH-, -N(CH _{3 ) -, - N (C 2} H 5) -, - Si (CH 3) 2 -, - S -, * 2 -COS -, * 2 -SCO- , or -C≡C- (wherein, "* ^2" Indicates the bond key with A ¹ ). A divalent group in which L is a single bond, an alkanediyl having 1 to 20 carbon atoms, or an alkyldiyl group having 1 to 20 carbon atoms, which is substituted with a halogen atom, At least one of -O-, -S-, and -NH- may be contained between the carbon-carbon bonds in the middle, and a part of the carbon-carbon bond may be a double bond or a triple bond. a and b are independently 0 or 1. Among them, there is no case where a=b=0. When a=b=1, a plurality of Y and L may be the same or different from each other. Z is a group represented by the following formula (2a) or the following formula (2b). "*" means the key button)

(In the formula (2a), the formula (2b), X ¹ is a hydrogen atom or a methyl group. "* ³ " represents a bond bond)

The liquid crystal alignment agent includes a polymer having a group represented by the formula (1) as a polymer component. When the liquid crystal cell is formed by using a substrate on which a coating film is formed by using the liquid crystal alignment agent, and the liquid crystal cell is irradiated with light while applying a voltage between the substrates, the liquid crystal display element is produced. It is possible to impart good pretilt characteristics to a coating film which is a liquid crystal alignment film with a relatively small amount of light irradiation (for example, a light irradiation amount of about 5,000 J/m ² ), and to obtain a liquid crystal having a sufficiently fast response speed of liquid crystal molecules. Display component.

According to another aspect of the invention, a method of manufacturing a liquid crystal display device, comprising: a first step of applying a liquid crystal alignment agent of the present invention to the conductive film of a pair of substrates having a conductive film, respectively And heating the film to form a coating film; and in the second step, the liquid crystal cell is constructed by arranging the pair of substrates on which the coating film is formed so as to face each other with the layer of the liquid crystal molecules facing each other; In the third step, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.

Moreover, in another aspect, the present invention provides a liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention and a liquid crystal display element including the liquid crystal alignment film. Furthermore, in another aspect, the present invention provides a polymer (P) having a group represented by the formula (1) and a carboxylic acid having a group represented by the formula (1).

A, B‧‧‧ substrate

1 is a plan view showing a pattern of a transparent electrode patterned into a slit shape.

Hereinafter, each component contained in the liquid crystal alignment agent of the present invention and other components optionally arbitrarily prepared will be described.

<Polymer (P)>

The liquid crystal alignment agent of the present invention contains a polymer component and contains at least a polymer (P) having a group represented by the following formula (1) as the polymer component.

In the formula (1), A ¹ is a divalent group represented by the following formula (1a), an anthranyl group, a tetrahydronaphthalenyl group, or a decalinyl group.

(In the formula (1a), A ² is 1,4-phenylene, 1,4-cyclohexylene, piperidine-1,4-diyl, piperidine-2,5-diyl, piperazine-1 , 4-diyl, piperazine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, pyrazine-2,5-diyl, or pyridine-2, 5-diyl, X ⁴ is a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) ₂ - or -C≡C-, m is an integer from 0 to 2. wherein, m is When 1 or 2, a plurality of A ^{2 's} may be the same or different from each other. When m is 2, a plurality of X ^{4 's} may be the same or different from each other. 2 "* ¹ " means a bond key)

Examples of the divalent group represented by the formula (1a) include, for example, one to three selected from the group consisting of 1,4-phenylene, 1,4-cyclohexylene, and piperidine-1. 4-diyl, piperidine-2,5-diyl, piperazine-1,4-diyl, piperazine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6 a divalent group in which at least one of the group consisting of a diyl group, a pyrazine-2,5-diyl group, and a pyridine-2,5-diyl group is bonded, or in the A ² and A ² The bond between the bond groups contains -O-, -COO-, -OCO-, -(CH ₂ ) ₂ - or -C≡C-.

m is preferably 1 or 2. Further, when m is 1 or 2, X ^{4 is} preferably a single bond. The two "* ¹ " in the formula (1a) may be bonded to any of the two Ys in the formula (1a).

A ^{2 is} preferably a 1,4-phenylene group or a 1,4-cyclohexylene group. Specific examples of the divalent group represented by the above (1a) include a stretched biphenyl group, a bicyclohexylene group, and a terphenylene group (-C ₆ H ₄ -C ₆ H). ₄ - C ₆ H ₄ -) and a group represented by each formula of the following formula (1a-1) to formula (1a-6).

Y is a single bond, -O-, * ² -COO-, * ² -OCO-, -OCOO-, -CO-, * ² -CONH-, * ² -NHCO-, -NH-, -N(CH _{3 ) -, - N (C 2} H 5) -, - Si (CH 3) 2 -, - S -, * 2 -COS -, * 2 -SCO- , or -C≡C- (wherein, "* ^2" Indicates the bond key with A ¹ ). Among these, a single bond, -O-, * ² -COO-, * ² -OCO-, -OCOO- or -C≡C- is preferred, and -O-, * ² -COO-, * is more preferred. ² -OCO- or -C≡C-.

a divalent group in which L is a single bond, an alkanediyl group having 1 to 20 carbon atoms, or an alkyldiyl group having 1 to 20 carbon atoms, which is substituted with a halogen atom, and carbon in these groups - at least one of -O-, -S-, and -NH- may be included between the carbon bonds, and a part of the carbon-carbon bond may be a double bond or a triple bond. Here, examples of the alkanediyl group having 1 to 20 carbon atoms in L include a methylene group, an ethyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, and a butane-1. 2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1, 8-diyl, decane-1,9-diyl, decane-1,10-diyl, dodecyl-1,12-diyl, tetradecyl-1,14-diyl, ten Hexaalkyl-1,16-diyl, octadecyl-1,18-diyl, eicosane-1,20-diyl, etc., these groups may be linear or branched. However, from the viewpoint of liquid crystal alignment, it is preferably linear. Further, when L is a group in which the hydrogen atom of the exemplified alkanediyl group is substituted by a halogen atom, the halogen atom is preferably a chlorine atom or a fluorine atom, more preferably a fluorine atom.

L may be a group containing at least one of -O-, -S-, and -NH- between the carbon-carbon bonds of the alkanediyl group, and examples thereof include "-(CH ₂ ). _s -X ³ -(CH ₂ ) _t -" (wherein X ³ is -O-, -S- or -NH-, s, t are integers of 1 or more satisfying s+t≦20), "-( CH ₂ ) _c -X ³ -(CH ₂ ) _d -X ³ -(CH ₂ ) _e -" (wherein X ^{3 is} independently -O-, -S- or -NH-, and c, d, e are A group represented by an integer of 1 or more satisfying c + d + e ≦ 20). Further, L may be a group in which a part of the carbon-carbon bond of the alkanediyl group is a double bond or a triple bond, and for example, prop-1-en-1,3-diyl (prop-1-en-) 1,3-diyl), pent-1-ene-1,5-diyl (pent-1-en-1,5-diyl), hex-1-ene-1,6-diyl (hex-1- En-1,6-diyl), etc.

As L, from the viewpoint of further increasing the response speed of the liquid crystal molecules, the carbon number is preferably 2 to 20, and more preferably the carbon number is 3 to 20. Further, from the viewpoint that L can form the pretilt stability more favorably, the carbon number is preferably from 2 to 8, more preferably The carbon number is 2~4.

a and b are each independently 0 or 1, and there is no case where a=b=0. Furthermore, when a=b=1, a plurality of Y and L may be the same or different. A combination of a=1 and b=0, or a combination of a=0 and b=1 is more preferable, and a combination of a=0 and b=1 is more preferable. Further, when a=1 and b=0, or a=0 and b=1, the permeated polymer (P) has a relatively short chain having a carbon number of 2 to 4, and the carbon number of L is As the group represented by the above formula (1), a group having a relatively long chain of 8 to 20 can further improve the stability of the pretilt angle, and is preferable.

Z is a group represented by the following formula (2a) or the following formula (2b).

(In the formula (2a), the formula (2b), X ¹ is a hydrogen atom or a methyl group. "* ³ " represents a bond bond)

Among them, a group represented by the formula (2a) is preferred as Z.

When A ¹ is an anthranyl group, a tetrahydronaphthalenediyl group or a decahydronaphthalenediyl group, the group "Z-(LY) _a -" bonded to A ¹ and the group "-(YL) _b -" The bonding position is not particularly limited, and examples thereof include a 1,3-position, a 1,4-position, a 1,5-position, a 1,6-position, a 1,7-position, a 2,6-position, and a 2,7- A bit or the like, wherein the 1,5-position or the 2,6-position is preferred.

Preferable specific examples of the group represented by the formula (1) include the following groups.

(where "*" means the keying key)

When the liquid crystal alignment agent of the present invention is used for the production of a vertical alignment type liquid crystal display element, the polymer (P) may have a vertical alignment group in order to impart a good vertical alignment property to the formed coating film. Examples of the vertical alignment group include an alkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 4 to 40 carbon atoms, an alkoxy group having 4 to 40 carbon atoms, and a carbon number of 17 to 51. a group having a steroid skeleton, a group having a polycyclic structure, and the like.

Here, examples of the alkyl group include n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, n-octadecyl group and the like; Examples of the fluoroalkyl group include a trifluoromethylpropyl group, a trifluoromethylbutyl group, a trifluoromethylhexyl group, a trifluoromethylsulfonyl group, a pentafluoroethylpropyl group, and a pentafluoroethylbutyl group. And a pentafluoroethyloctyl group; and the alkoxy group may, for example, be a butoxy group, a pentyloxy group, a hexyloxy group, a hexyloxy group, an octyloxy group or the like; and as a group having a steroid skeleton, for example, Cholestanyl, cholestenyl, lanostanyl, etc.; as a group having a polycyclic structure, for example, 4,4'-extended biphenyl, 4, 4'-bicyclohexyl group and a group having at least one selected from the group consisting of groups represented by the formulas of the formula (1a-1) to the formula (1a-6).

Further, unlike the group represented by the above formula (1), the polymer (P) may also contain a group having a polymerizable unsaturated bond. By containing this group, the pretilt stability of the liquid crystal display element can be improved. Such a group having a polymerizable unsaturated bond is preferably a group containing a (meth)acryl fluorenyl group, and specific examples thereof include (meth) propylene decyloxy group and (meth) propylene fluorenyloxy group. Propyl and the like. Further, in the present specification, the (meth)acrylonitrile group means an acryloyl group and a methacryloyl group.

The main chain skeleton of the polymer (P) is not particularly limited, and examples thereof include a polyorganosiloxane skeleton, a polyester skeleton, a polyamine skeleton, and a polyimine skeleton. Among these skeletons, a polyorganosiloxane skeleton is preferred. In other words, the liquid crystal alignment agent of the present invention preferably contains a polyorganosiloxane (hereinafter, also referred to as "specific polyorganosiloxane") having a group represented by the above formula (1) as a polymer component. .

<Specific polyorganosiloxanes>

The specific polyorganosiloxane can be produced by a suitable combination of conventional methods of organic chemistry. For example, the method of (I) a hydrolyzable decane compound (a1) having a group represented by the above formula (1) in an alcohol solvent and under an oxalic acid catalyst, or the like a method of heating a mixture of a decane compound (a1) and another decane compound; (II) a method of reacting a polymer having a carboxylic acid (AC) having a group represented by the formula (1), The polymer obtained by hydrolyzing and condensing a hydrolyzable decane compound (a2) having an epoxy group or a mixture of the decane compound (a2) and another decane compound (hereinafter, also referred to as "containing a ring" a polyorganosiloxane having an oxy group"); (III) a hydrolyzable decane compound (a1) having a group represented by the formula (1), or a decane compound (a1) and another decane compound The mixture is subjected to hydrolysis and condensation.

[About method (I)]

[decane compound (a1)]

The decane compound (a1) has at least one group represented by the above formula (1), and examples thereof include a compound represented by the following formula (a-1).

[11]

(In the formula (a-1), X is independently a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. Among them, 2 of the 3 Xs present in the molecule More than one X is a halogen atom or an alkoxy group having a carbon number of 1 to 4. W ¹ is a single bond, an oxygen atom, -OR ⁵ -* or -C≡CR ⁵ -* (wherein R ⁵ is a phenylene group) Or a divalent group substituted with at least one hydrogen atom of a phenyl group and substituted by an alkyl group having 1 to 5 carbon atoms. "*" represents a bond with a ruthenium atom). A ¹ , Y, L, The meanings of Z, a and b are the same as those of the above formula (1))

For the halogen of the formula (a-1), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; and examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group. And an ethoxy group, a propoxy group, a butoxy group, etc., and an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, etc. . As X, from the viewpoint of reactivity, it is preferred that all three X are alkoxy groups having a carbon number of 1 to 4, more preferably a methoxy group or an ethoxy group.

The pendant phenyl group of W ¹ and R ⁵ is preferably a 1,4-phenylene group.

Regarding A ¹ , Y, L, Z, a and b in the formula (a1), the description in the group represented by the formula (1) can be applied, respectively.

A preferred example of the decane compound (a1) is a compound represented by each of the following formulas (a1-1) to (a1-33). Such a decane compound (a1) can be synthesized by a suitable combination of conventional methods of organic chemistry.

(wherein Me represents a methyl group and Et represents an ethyl group)

In addition, the compounds represented by the formulas (a1-1) to (a1-33) are also referred to as decane compounds (a1-1) to decane compounds (a1-33), respectively.

[Other decane compounds]

In the synthesis of the specific polyorganosiloxane using the method (I), the decane compound (a1) may be used alone, but other decane compounds other than the decane compound (a1) may be used in combination. Examples of the other decane compound include tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, and phenyl triethoxy group. Decane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, dimethyldimethoxydecane, two Methyl diethoxy decane, a hydrolyzable decane compound having the above-mentioned vertical alignment group (hereinafter also referred to as a decane compound containing an alignment group), and a decaneization having a polymerizable unsaturated bond The compound (except for the compound of the decane compound (a1)), a hydrolyzable decane compound having an epoxy group (hereinafter also referred to as an epoxy group-containing decane compound), and the like.

Here, examples of the decane compound containing an alignment group include hexyltriethoxydecane, octyltriethoxydecane, decyltriethoxydecane, and dodecyltriethoxydecane. And octadecyltrimethoxydecane, octadecyltriethoxydecane, trifluoromethylhexyltriethoxydecane, octyloxytrimethoxydecane, and the like. When a specific polyorganosiloxane is synthesized, by using these decane compounds containing an alignment group, a polyorganosiloxane having a group represented by the above formula (1) and a vertical alignment group can be produced.

Further, by using a decane compound having a polymerizable unsaturated bond as another decane compound, the pretilt stability can be improved. As the decane compound, 3-(meth)acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, 8-(methyl group) can be preferably used. a decane compound having a (meth) acrylonitrile group such as acryloxyoctyltrimethoxydecane.

In addition, as a preferable specific example of the epoxy group-containing decane compound, a decane compound having a group represented by the following formula (a2-1) or formula (a2-2) is exemplified.

(In the formula (a2-1), Z ¹ is a single bond or an oxygen atom, h is an integer of 1 to 3, and i is an integer of 0 to 6. Here, when i is 0, Z ¹ is a single bond. In a2-2), j is an integer from 1 to 6. "*" indicates a bond with a ruthenium atom)

Preferable specific examples of the epoxy group-containing decane compound include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3- Glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 3-glycidol Oxypropyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy decane Wait. Among these decane compounds, at least one of 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane and 3-glycidoxypropyltrimethoxydecane can be particularly preferably used.

Further, the other decane compound may be used alone or in combination of two or more.

When a specific polyorganosiloxane is synthesized, the use ratio of the decane compound (a1) is preferably set to 5 mol% or more, more preferably 10 mol%, based on the total amount of the decane compound used for the synthesis. ~70% by mole, and more preferably set to 20% by mole to 60% by mole.

In the method (I), an oxalic acid alcohol solution may be prepared by previously adding oxalic acid to an alcohol, and then the solution is mixed with a decane compound and heated, thereby obtaining a solution containing the target polyorganosiloxane.

Here, examples of the alcohol used for the reaction include methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether and the like.

The proportion of the alcohol used in the reaction is preferably from 10 parts by weight to 10,000 parts by weight, more preferably 50%, based on 100 parts by weight of all the decane compound used for the reaction. Parts by weight to 1,000 parts by weight. The amount of oxalic acid used for the reaction is preferably set to 0.2 mol to 2 mol with respect to 1 mol of all alkoxy groups possessed by the decane compound. Further, the heating temperature is preferably from 50 ° C to 180 ° C, and the heating time can be, for example, from several tens of minutes to several ten hours.

Thus, a reaction solution containing a specific polyorganosiloxane can be obtained. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, and if necessary, after the reaction solution is concentrated or diluted, it can be supplied to the preparation of the liquid crystal alignment agent. Further, when the specific polyorganosiloxane having a reaction obtained by the reaction has an epoxy group, the specific polyorganosiloxane (having an epoxy group having a group represented by the formula (1)) may be further The polyorganosiloxane of the group is reacted with a carboxylic acid having the vertical alignment group. Through this reaction, a vertical alignment group can be introduced to a specific polyorganosiloxane.

Specific examples of the carboxylic acid having a vertical alignment group include long-chain fatty acids such as caproic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, n-hexadecanoic acid, and stearic acid; N-hexylbenzoic acid, 4-n-octylbenzoic acid, 4-n-decylbenzoic acid, 4-n-dodecylbenzoic acid, 4-n-hexadecylbenzoic acid, 4-stearylbenzoic acid, etc. Long-chain alkyl benzoic acid; 4-n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid, 4-n-dodecyloxybenzoic acid, 4-positive Benzoic acid having a long-chain alkoxy group such as alkoxybenzoic acid or 4-stearyloxybenzoic acid; cholestyloxybenzoic acid, cholestyloxybenzoic acid, lanostatinoxybenzoic acid, cholesteric甾 alkoxycarbonylbenzoic acid, cholestyloxycarbonylbenzoic acid, lanostatinoxycarbonylbenzoic acid, succinic acid-5ξ-cholest-3-yl, succinic acid-5ξ-cholestene- Benzoic acid having a steroid skeleton such as 3-yl, succinic acid-5ξ-lanostan-3-yl; 4-(4-pentyl-cyclohexyl)benzoic acid, 4-(4-hexyl-cyclohexyl)benzene Formic acid, 4-(4-heptyl-cyclohexyl)benzoic acid, 4'-pentyl-bicyclic Hexyl-4-carboxylic acid, 4'-hexyl-dicyclohexyl-4-carboxylic acid, 4'-heptyl-bicyclohexyl 4-carboxylic acid, 4'-pentyl-biphenyl-4-carboxylic acid, 4'-hexyl-biphenyl-4-carboxylic acid, 4'-heptyl-biphenyl-4-carboxylic acid, 4- (4-pentyl-dicyclohexyl-4-yl)benzoic acid, 4-(4-hexyl-dicyclohexyl-4-yl)benzoic acid, 4-(4-heptyl-dicyclohexyl-4-yl)benzoic acid a polycyclic structure of benzoic acid such as 6-(4'-cyanobiphenyl-4-yloxy)hexanoic acid; 6,6,6-trifluorohexanoic acid, 4-(4,4,4-tri A fluoroalkyl group-containing carboxylic acid or the like such as fluorobutyl)benzoic acid. Further, the carboxylic acid having a vertical alignment group may be used alone or in combination of two or more.

In the reaction of the specific polyorganosiloxane and the carboxylic acid, the carboxylic acid having a vertical alignment group may be used alone, but other carboxylic acids other than the carboxylic acid may be used in combination. Specific examples of such other carboxylic acid include formic acid, acetic acid, propionic acid, benzoic acid, and methylbenzoic acid.

Further, the details of the reaction of the specific polyorganosiloxane having an epoxy group with a carboxylic acid will be collectively described in the following method (II).

[About method (II)]

In the method (II), the decane compound (a2) used for the synthesis of the polyorganosiloxane containing an epoxy group may, for example, be an epoxy group in the description of the method (I). a compound exemplified by a decane compound.

When the polyorganosiloxane containing an epoxy group is synthesized, the decane compound (a2) may be used singly, or other decane compound other than the decane compound (a2) may be used in combination. Examples of the other decane compound include a compound exemplified as the "other decane compound" in the description of the method (I). As the other decane compound, a decane compound having a polymerizable unsaturated bond is preferably used from the viewpoint of improving the stability of the pretilt angle, and examples thereof include the decane compound (a1) and 3-(meth) propylene.醯oxypropyltrimethoxydecane, 3-(methyl)propene oxime Propyl triethoxy decane, 8-(meth) propylene decyloxy octyl trimethoxy decane, and the like. Among them, a decane compound having a (meth) acrylonitrile group is preferably used.

[Hydrolysis condensation reaction of decane compounds]

Hydrolysis of decane compounds. The condensation reaction can be carried out by reacting one or two or more kinds of the above-described decane compounds with water in the presence of a suitable catalyst and an organic solvent. Here, the ratio of the decane compound (a2) used for the synthesis is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably set to the total amount of the decane compound. 90% or more. Also, in hydrolysis. In the condensation reaction, the use ratio of water is preferably from 0.5 mol to 100 mol, more preferably from 1 mol to 30 mol, based on 1 mol of the decane compound (total amount).

Examples of the catalyst include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound. Specific examples of the catalyst include hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, and various Lewis acids. Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide. Examples of the organic base include ethylamine, diethylamine, piperazine, and piperidine. , pyrrolidine, pyrrole-like primary organic amine ~ secondary organic amine; such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene A tertiary organic amine; a tetra-organic amine such as tetramethylammonium hydroxide. As the organic base, among these, a tertiary organic amine or a tertiary organic amine is preferred.

As the catalyst, the side reaction such as ring opening of an epoxy group can be suppressed. Among these catalysts, an alkali metal compound or an organic base is preferred, and an organic base is particularly preferred as a viewpoint of improving the hydrolytic condensation rate and the viewpoint of excellent storage stability.

The amount of the organic base to be used varies depending on the type of the organic base, the reaction conditions such as the temperature, and the like, and should be appropriately set. For example, it is preferably 0.01 to 3 moles, more preferably 0.05 times, based on all the decane compound. Ear ~ 1 times Mo.

Examples of the organic solvent which can be used in the hydrolysis condensation reaction include a hydrocarbon, a ketone, an ester, an ether, and an alcohol. Specific examples of the hydrocarbon include toluene and xylene. Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, and cyclohexane. Examples of the ester include ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, and the like; as the ether, for example, Examples thereof include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, and the like; examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, and B. Glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Among these organic solvents, it is preferred to use a water-insoluble organic solvent. In addition, these organic solvents may be used alone or in combination of two or more.

The proportion of the organic solvent used in the hydrolysis condensation reaction is preferably from 10 parts by weight to 10,000 parts by weight, more preferably from 50 parts by weight to 1,000 parts by weight, based on 100 parts by weight of all the decane compounds used for the reaction.

hydrolysis. The condensation reaction is preferably carried out by dissolving the above-described decane compound in an organic solvent, mixing the solution with an organic base and water, and then heating it by, for example, an oil bath. In hydrolysis. When the condensation reaction is carried out, it is preferred to add The heat temperature is set to 130 ° C or lower, more preferably 40 ° C to 100 ° C. The heating time is preferably set to 0.5 hours to 12 hours, more preferably 1 hour to 8 hours. The mixture may be stirred during heating or placed under reflux. After completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction liquid by water. At the time of the washing, it is preferred to use a water containing a small amount of salt (for example, an aqueous solution of ammonium nitrate of about 0.2 wt%) to facilitate the washing operation. The cleaning is carried out until the water layer after the cleaning becomes neutral. Thereafter, the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve, and the solvent is removed, whereby the desired polyorganosiloxane can be obtained. An alkane (polyorganosiloxane containing an epoxy group).

[carboxylic acid (AC)]

The carboxylic acid (AC) to be used in the reaction with the polyorganosiloxane having an epoxy group may have a group represented by the formula (1) and a carboxyl group, and examples thereof include the following formula (AC1). ) a compound or the like represented.

(In the formula (AC1), the meanings of A ¹ , Y, L, Z, a, b, and W ¹ are the same as those of the above formula (a-1))

Regarding A ¹ , Y, L, Z, a and b in the formula (AC1), the description in the group represented by the formula (1) can be applied, respectively. Further, regarding W ¹ , the description in the group represented by the formula (a-1) can be applied.

Preferable specific examples of the compound represented by the formula (AC1) include, for example, the following formula (AC-1) to formula (AC-30) and formula (AC-33) to formula (AC-). 41) A compound represented by each formula.

Further, the compounds represented by the formulas (AC-1) to (AC-30) and (AC-33) to (AC-41) are also referred to as carboxylic acids (AC-), respectively. 1) ~carboxylic acid (AC-30), carboxylic acid (AC-33) ~ carboxylic acid (AC-41).

As the carboxylic acid which reacts with the polyorganosiloxane containing an epoxy group, a carboxylic acid (AC) may be used alone, or a carboxylic acid (AC) may be used in combination with another carboxylic acid. Examples of the other carboxylic acid include formic acid, acetic acid, propionic acid, benzoic acid, methylbenzoic acid, and a carboxylic acid having a polymerizable unsaturated bond (except for a compound corresponding to the carboxylic acid (AC)). The carboxylic acid or the like having a vertical alignment group described in the above method (I). From the viewpoint of improving the pretilt stability of the obtained liquid crystal display element, as the other carboxylic acid, a carboxylic acid having a polymerizable unsaturated bond other than the carboxylic acid (AC) is preferably used. As such a carboxylic acid, a carboxylic acid having a (meth)acryl fluorenyl group is preferred, and examples thereof include acrylic acid, methacrylic acid, and 2-propenyloxyethyl-2-hydroxyethyl-phthalic acid. And 2-(meth)acryloxyethyl hexahydrophthalic acid.

[Synthesis of carboxylic acid]

The carboxylic acid (AC) can be produced by a suitable combination of conventional methods of organic chemistry. As an example, it can be synthesized by first synthesizing a carboxylic acid ester in which a carboxyl group is protected by a t-butyl group or the like in the compound represented by the formula (AC1), and then subjecting the obtained carboxylic acid ester to deprotection treatment.

Here, when the carboxylic acid ester of a=0 and b=1 is exemplified as an example, when “Y” is “* ^2- CO-O-”, for example, it can be synthesized as follows: In the presence of a suitable catalyst, a compound represented by "ZA ¹ -COOH" and a halide represented by "X ^h -L-COO-R ^p " (wherein X ^h is a halogen atom, and R ^p is The protecting group is subjected to a reaction, followed by deprotection of the conjugate obtained by the reaction.

When "Y" is "* ^2- O-CO-", it can be synthesized, for example, by reacting a compound represented by "ZA ¹ -OH" with "X ^h - in the presence of a suitable catalyst. The halide represented by CO-L-COO-R ^p " (wherein, X ^h is a halogen atom and R ^p is a protecting group) is reacted, and then the deprotection of the coupled body obtained by the reaction is carried out.

When "Y" is "-O-", it can be synthesized, for example, by reacting a compound represented by "ZA ¹ -OH" with "X ^h -L-COO- in the presence of a suitable catalyst. The halide represented by R ^p " (wherein, X ^h is a halogen atom and R ^p is a protecting group) is reacted, and then the deprotection of the coupled body obtained by the reaction is carried out. However, the method of synthesizing the carboxylic acid (AC) is not limited to the method.

[Reaction of an epoxy group-containing polyorganosiloxane with a carboxylic acid]

The reaction of the epoxy group-containing polyorganosiloxane with the carboxylic acid can preferably be carried out in the presence of a catalyst and an organic solvent.

In the reaction, the ratio of the carboxylic acid (total amount) to the epoxy group of the epoxy group-containing polyorganosiloxane is preferably 5 mol% or more, more preferably 10 mol%. ~90% by mole, and more preferably 15% by mole to 80% by mole. Further, in the method (I), the use ratio of the carboxylic acid having a vertical alignment group is preferably 50 mol% or more, more preferably 70 mol% or more, based on the total amount of the carboxylic acid used for the reaction. On the other hand, in the method (II), the use ratio of the carboxylic acid (AC) is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total amount of the carboxylic acid used for the reaction.

As the catalyst to be used for the reaction, for example, an organic base or a known compound which is a so-called hardening accelerator for promoting the reaction of the epoxy compound can be used.

Here, as the organic base, for example, a primary organic amine to a secondary organic amine such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine or pyrrole; for example, triethylamine or tri-n-propylamine can be mentioned. a tertiary organic amine such as tri-n-butylamine, pyridine, 4-dimethylaminopyridine or diazabicycloundecene; a quaternary organic amine such as tetramethylammonium hydroxide. As the organic base, among these, a tertiary organic amine or a quaternary organic amine is preferred.

Moreover, as the hardening accelerator, for example, a tertiary amine such as benzyldimethylamine or 2,4,6-tris(dimethylaminomethyl)phenol; for example, 2-methylimidazole, 2 - n-heptyl imidazole, 2-n-undecylimidazole, 2-phenylimidazole-like imidazole compound; organophosphorus compound such as diphenylphosphine or triphenylphosphine; such as benzyltriphenylphosphonium chloride a quaternary phosphonium salt such as tetra-n-butyl bromide, methyltriphenylphosphonium bromide or ethyltriphenylphosphonium bromide; such as 1,8-diazabicyclo[5.4.0] eleven Alkenyl-7 or its organic acid salt-like diazabicycloalene; such as zinc octoate, tin octoate, aluminum acetoacetate complex gold a compound; such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride-like quaternary ammonium salt; such as boron trifluoride, boric acid a phenyl ester-like boron compound; a metal halogen compound such as zinc chloride or tin chloride; an amine-forming accelerator such as dicyandiamide or an amine and an epoxy resin; Promoter; microcapsule latent hardening accelerator formed by coating a surface of a hardening accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt with a polymer; an amine salt type latent hardening accelerator; a Lewis acid A latent curing accelerator such as a high temperature dissociating type thermal cationic polymerization type latent curing accelerator such as a Lewis acid salt or a Bronsted acid salt. Among these hardening accelerators, a quaternary ammonium salt is preferred.

The catalyst is preferably 100 parts by weight or less, more preferably 0.01 parts by weight to 100 parts by weight, even more preferably 0.1 parts by weight to 20 parts by weight per 100 parts by weight of the epoxy group-containing polyorganosiloxane. The proportion to use.

Examples of the organic solvent which can be used for the reaction of the polyorganosiloxane containing an epoxy group 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 these organic solvents, 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. Specific examples of the solvent which is particularly preferred are exemplified. : 2-butanone, 2-hexanone, methyl isobutyl ketone, and butyl acetate. The organic solvent is preferably used in a ratio of a solid content concentration (a ratio of a total weight of components other than the solvent in the reaction solution to the total weight of the solution) of 0.1 wt% or more, more preferably a solid content concentration. It is used in a ratio of 5 wt% to 50 wt%.

The reaction temperature is preferably from 0 ° C to 200 ° C, more preferably from 50 ° C to 150 ° C. anti- The time should preferably be from 0.1 hours to 50 hours, more preferably from 0.5 hours to 20 hours. Further, after completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction liquid by water. After washing with water, the organic solvent layer is dried with an appropriate desiccant as necessary, and then the solvent is removed, whereby a target polyorganosiloxane (specific polyorganosiloxane) can be obtained.

[About method (III)]

The decane compound (a) used in the method (III) may, for example, be the same compound as the compound exemplified in the above method (I), and examples of the other decane compound include the epoxy group-containing decane. a compound, the above-described decane compound containing an alignment group, the above-described decane compound having a polymerizable unsaturated bond, and the like. Regarding the hydrolysis in the method (III). For the details of the condensation reaction, the description of the method (II) can be applied.

The specific polyorganosiloxane used in the liquid crystal alignment agent of the present invention preferably has a polystyrene-equivalent weight average molecular weight of 500 to 100,000 as measured by Gel Permeation Chromatography (GPC), more preferably The weight average molecular weight is 1,000 to 30,000.

In the manufacturing step of the liquid crystal display device, even when the amount of light irradiation is relatively small (for example, when it is about 5,000 J/m ² ), good pretilt characteristics can be obtained and the speed can be sufficiently accelerated. From the viewpoint of the response speed of the liquid crystal molecules, the content of the polymer (P) in the liquid crystal alignment agent of the present invention is preferably 1 wt% or more, more preferably the total amount of the polymer component contained in the liquid crystal alignment agent. Good is 5 wt% or more.

<Polymer (Q)>

When the liquid crystal alignment agent of the present invention contains a specific polyorganosiloxane When the polymer (P) is contained, it may contain a specific polyorganosiloxane and at least one polymer (Q) selected from the group consisting of polyglycolic acid, polyphthalate and polyimine. The polymer (Q) may have a group represented by the formula (1) or may not have a group represented by the formula (1). It is preferred that the polymer (Q) does not have a form of a group represented by the formula (1).

When a specific polyorganosiloxane and a polymer (Q) are contained as a polymer component, the content of the polymer (Q) is preferably 1 wt% with respect to the total amount of the polymer component contained in the liquid crystal alignment agent. 99 wt%, more preferably 10 wt% to 95 wt%. By setting the content of the polymer (Q) to 1 wt% or more, the heat resistance or mechanical strength of the liquid crystal alignment film can be improved, and the content of the polymer (Q) can be suitably obtained by setting the content of the polymer (Q) to 99 wt% or less. The effect of improving the response speed or pretilt characteristics of liquid crystal molecules by a specific polyorganosiloxane.

<polylysine>

The polyglycine contained in the liquid crystal alignment agent of the present invention can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine.

[tetracarboxylic dianhydride]

Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid in the present invention include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the tetracarboxylic dianhydride include, as the aliphatic tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and the like; as the alicyclic tetracarboxylic dianhydride, For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro- 5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b- Hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxa Bicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3) -furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6- Dihydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ] The undecane-3,5,8,10-tetraketone, cyclohexanetetracarboxylic dianhydride, and the like; examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like; The tetracarboxylic dianhydride or the like described in JP-A-2010-97188 is used. In addition, the tetracarboxylic dianhydride may be used alone or in combination of two or more.

As the tetracarboxylic dianhydride for synthesizing polyamic acid, it is preferred to use an alicyclic tetracarboxylic dianhydride alone or a mixture of an alicyclic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride. In the latter case, it is preferred to contain 20 mol% or more of alicyclic tetracarboxylic dianhydride, more preferably 40 mol% or more, based on the total amount of the tetracarboxylic dianhydride used for the synthesis. Alicyclic tetracarboxylic dianhydride.

[diamine]

Examples of the diamine used for the synthesis of the polyamic acid in the present invention include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, and a diamine organic decane. Specific examples of the diamine include, as the aliphatic diamine, 1,1-m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and six. Methylenediamine or the like; as the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(amine) Methyl)cyclohexane or the like; examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl sulfide. , 5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diamine linkage Benzene, 2,7-diaminoguanidine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-double (4-Aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane , 4,4'-(p-phenylenediisopropylidene)diphenylamine, 4,4'-(meta-phenyldiisopropylidene)diphenylamine, 1,4-bis(4-aminobenzene) Oxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminopurine , 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-amine Phenyl)-piperazine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-5-amine, 1-(4-amine Phenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indol-6-amine, 3,5-diaminobenzoic acid, cholestyloxy-3,5- Diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestyloxy-2,4-diaminobenzene, Cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, lanostino 3,5-diaminobenzoic acid, 3,6-double (4-aminobenzimidyloxy)cholesterol, 3-(3,5-diaminobenzylideneoxy)cholestane, 3,6-bis(4-aminophenoxy)cholate Decane, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzylideneoxy) Cyclohexyl-3,5-diaminobenzoic acid ester, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1- Bis(4-((aminophenyl)methyl)phenyl -4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-( (aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2,4-diamino-N,N-diallylaniline, 4-aminobenzyl An amine, 3-aminobenzylamine, a compound represented by the following formula (D-1), and the like;

(In the formula (D-1), X ^I and X ^II are each independently a single bond, -O-, -COO- or OCO-, and R ^I is an alkanediyl group having a carbon number of 1 to 3, and a is 0 or 1 , b is an integer from 0 to 2, c is an integer from 1 to 20, and n is 0 or 1. Where a and b are different at 0)

For example, 1,3-bis(3-aminopropyl)-tetramethyldioxane or the like can be exemplified as the diamine-based organic decane, and the Japanese Patent Laid-Open No. 2010-97188 can be used. The diamine described in the publication. As the diamine, one type of the above diamine may be used alone or two or more types may be used in combination.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _n -" in the formula (D-1) is preferably an alkanediyl group having 1 to 3 carbon atoms, *-O-, *-COO- or *-OC ₂ H ₄ -O- (wherein the bond with "*" is bonded to the diaminophenyl group). Specific examples of the group "-C _c H _2c+1 " include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and anthracene group. Base, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-ten N-alkyl, n-icosyl and the like. The two amine groups in the diaminophenyl group are preferably at the 2,4-position or the 3,5-position relative to the other groups.

Specific examples of the compound represented by the formula (D-1) include a compound represented by each formula of the following formula (D-1-1) to formula (D-1-3).

In addition, from the viewpoint of improving the properties such as heat resistance and mechanical strength of the liquid crystal alignment film, the polycarboxylic acid contained in the liquid crystal alignment agent can be obtained, and these tetracarboxylic dianhydrides and diamines are For those with the same role. Therefore, even if it is not described in the following examples, it can be used in the present invention.

[Molecular weight regulator]

When the polyamic acid is synthesized, the tetracarboxylic dianhydride and the diamine as described above may be used together with a suitable molecular weight modifier to synthesize the terminal-modified polymer. By forming the terminal-modified polymer, the coating property (printability) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention.

Examples of the molecular weight modifier include an acid monoanhydride, a monoamine compound, and a monoisocyanate compound. As specific examples thereof, examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, and n-tetradecyl amber. An acid anhydride, n-hexadecyl succinic anhydride or the like; examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, and the like; as a monoisocyanate compound, For example, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned.

The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably set to 100 parts by weight based on the total of the tetracarboxylic dianhydride and the diamine to be used. 10 parts by weight or less.

<Synthesis of polylysine>

The ratio of the tetracarboxylic dianhydride to the diamine used in the synthesis reaction of the polyproline in the present invention is preferably 1 equivalent to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride becomes 0.2 equivalent. More preferably, the ratio of the equivalent amount of the acid anhydride group of the tetracarboxylic dianhydride becomes 0.3 equivalent to 1.2 equivalent.

The synthesis reaction of polylysine is preferably carried out in an organic solvent. The reaction temperature at this time is preferably from -20 ° C to 150 ° C, more preferably from 0 ° C to 100 ° C. Further, the reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

Here, examples of the organic solvent used for the reaction include an aprotic polar solvent, a phenol solvent, 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, 1,3-dimethyl-2-imidazolidinone, and N-ethyl-2- Pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylhydrazine, γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine, etc.; Examples of the phenol-based solvent include phenol, m-cresol, xylenol, and halogenated phenol. Examples of the alcohol include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, and propylene glycol. 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc., and examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like; Examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, isoamyl propionate, and the like. Isoamyl butyrate, diethyl oxalate, diethyl malonate, etc.; examples of the ether include diethyl ether, ethylene glycol methyl ether, and ethylene glycol. Ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethyl Glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisoamyl ether, tetrahydrofuran, etc.; Examples of the halogenated hydrocarbon include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, and the like. Hexane, heptane, octane, benzene, toluene, xylene, and the like.

Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenol solvent (the organic solvent of the first group) or an organic solvent selected from the first group is preferably used. One or more kinds of the mixture of one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (organic solvents of the second group). In the latter case, the ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40%, based on the total amount of the organic solvent of the first group and the organic solvent of the second group. % or less, and more preferably 30 wt% or less.

The amount (a) of the organic solvent to be used is preferably such an amount that the total amount (b) of the tetracarboxylic dianhydride and the diamine becomes 0.1 wt% with respect to the total amount (a+b) of the reaction solution. 50 wt%.

A reaction solution obtained by dissolving polylysine was obtained in the manner described. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or may be used for the preparation of the liquid crystal alignment agent after the polyamic acid contained in the reaction solution is isolated, or may be subjected to the isolated polyamic acid. After purification, it is supplied to the preparation of the liquid crystal alignment agent. In addition, when polypyridic acid is subjected to dehydration ring closure to form a polyimine, the reaction solution may be directly supplied to a dehydration ring closure reaction, or may be a polyamine contained in the reaction solution. After the acid is isolated, it may be subjected to a dehydration ring closure reaction, or may be subjected to a dehydration ring closure reaction after purifying the isolated polyamic acid. The isolation and purification of polylysine can be carried out according to a known method.

<polyimine]

The polyimine contained in the liquid crystal alignment agent of the present invention can be obtained, for example, by subjecting polylysine synthesized as described above to dehydration ring closure to carry out hydrazine imidization.

The polyimine may be a fully ruthenium imide formed by dehydration ring closure of all of the proline structure of the polyglycolic acid as its precursor, or may be only a part of the structure of the proline. A part of the quinone imide compound which has a dehydration ring closure and a valeric acid structure and a quinone ring structure. The ruthenium imidization ratio of the polyimine in the present invention is preferably 30% or more, more preferably 40% to 99%, and still more preferably 45% to 99%. The ruthenium imidization ratio is a ratio of the number of quinone ring structures to the total number of guanidine structures and the number of quinone ring structures of the polyimine. Here, a part of the quinone ring may also be an isoindole ring.

The dehydration ring closure of polylysine is preferably carried out by a method of heating polylysine; or dissolving polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution; The method of heating as needed. Among them, the latter method is preferably used.

In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of the polyamic acid, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The dehydrating agent is preferably used in an amount of from 0.01 mol to 20 mol based on 1 mol of the proline structure of the poly-proline. As a dehydration ring-closing catalyst, for example For example, a tertiary amine such as pyridine, collidine, lutidine or triethylamine can be used. The amount of the dehydration ring-closure catalyst to be used is preferably from 0.01 mol 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 organic solvent used in the synthesis of polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 ° C to 180 ° C, more preferably from 10 ° C to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

A reaction solution containing polyienimine was obtained in the manner described. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or may be prepared for the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or may be supplied to the liquid crystal alignment after segregation of the polyimine. The preparation of the agent or the preparation of the liquid crystal alignment agent may also be carried out after refining the isolated polyimine. These refining operations can be carried out according to a known method.

<Polyurethane>

The synthesis of the polyphthalate contained in the liquid crystal alignment agent of the present invention is, for example, [i] opening a tetracarboxylic dianhydride to form a dicarboxylic acid diester, and then using a dehydration catalyst. a method for reacting a dicarboxylic acid diester obtained with a diamine; [ii] a method for reacting the obtained diester dimethyl hydrazine chloride with a diamine after obtaining a diester dimethyl hydrazine chloride using a tetracarboxylic dianhydride [iii] A method of esterifying the carboxyl group of the polyproline to be used. Examples of the tetracarboxylic dianhydride and the diamine which can be used for the synthesis of the polyphthalate include the compounds exemplified in the description of the polyamic acid.

<Solid viscosity of polymer>

The polylysine, polyphthalate and polyimine obtained in the above manner preferably have a concentration of 10 m% when it is made into a solution having a concentration of 10 wt%. s~800 mPa. The solution viscosity of s is more preferably 15 mPa. s~500 mPa. s solution viscosity. Further, the solution viscosity (mPa.s) of the polymer is a concentration of 10% by mass prepared for a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer. The polymer solution was measured using an E-type rotational viscometer at 25 °C.

<weight average molecular weight of polymer>

The polyamic acid, polyphthalate, and polyimine are preferably a polystyrene-equivalent weight average molecular weight of 500 to 300,000 as measured by gel permeation chromatography (GPC), more preferably The weight average molecular weight is 1,000 to 200,000.

<Other ingredients>

The liquid crystal alignment agent of the present invention may contain other components as needed. Examples of the other component include a polymer other than the above, a compound having at least one epoxy group in the molecule (hereinafter referred to as "a compound containing an epoxy group"), a functional decane compound, and the like.

[Other polymers]

The other polymers can be used to improve solution properties or electrical properties. Examples of the other polymer include polyorganosiloxanes other than the specific polyorganosiloxane, polyesters, polyamines, cellulose derivatives, polyacetals, polystyrene derivatives, and poly (Styrene-phenyl butylmaleimide) derivative, poly(meth) acrylate, and the like.

When other polymers are added to the liquid crystal alignment agent, the compounding ratio is preferably 50% by weight or less, more preferably 0.1% by weight to 40% by weight, and even more preferably, relative to the total amount of the polymer in the composition. 0.1 wt% to 30 wt%.

[Epoxy group-containing compound]

An epoxy group-containing compound can be used to lift a liquid crystal alignment film and a substrate The bonding or electrical properties of the surface. Here, examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol condensate Glycerol ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N , N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethyl As a preferred example, cyclohexane, N,N-diglycidyl-cyclohexylamine and the like are mentioned. Further, as the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane having the disclosure of WO 2009/096598 can be used.

When these epoxy compounds are added to the liquid crystal alignment agent, the compounding ratio is preferably 40 parts by weight or less, more preferably 0.1 parts by weight to 30 parts by weight based on 100 parts by weight of the total of the polymers contained in the liquid crystal alignment agent. Parts by weight.

[functional decane compound]

The functional decane compound can be used for the purpose of improving the printability of the liquid crystal alignment agent. Examples of such a functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-amino group. Propyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldi Methoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-triethyl Oxymethalylpropyltrisethyltriamine, 10-trimethoxycarboxamido-1,4,7-triazadecane, 9-trimethoxyformamidin-3,6-diaza Heteroyl acetate, 9-trimethoxyformamidin-3,6-diazepine Methyl ester, N-benzyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, glycidoxymethyltrimethoxydecane, 2-glycidol Oxyethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, and the like.

When these functional decane compounds are added to the liquid crystal alignment agent, the compounding ratio is preferably 2 parts by weight or less, more preferably 0.02 parts by weight to 0.2 parts by weight, based on 100 parts by weight of the total of the polymer.

Further, as the other component, in addition to the above-exemplified compounds, a compound having at least one oxetanyl group in the molecule, an antioxidant, or the like can be used.

<solvent>

The liquid crystal alignment agent of the present invention is preferably formed by dissolving a polymer component or, if necessary, other components arbitrarily dissolved in an organic solvent.

Here, examples of the solvent used in the preparation of the liquid crystal alignment agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butylide, and N,N-dimethyl Mercaptoamine, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxypropionic acid Methyl ester, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve) , ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol single Methyl ether acetate, diethylene glycol monoethyl ether acetate, Dipropylene Glycol Monomethyl Ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl Ether, ethylene carbonate, propylene carbonate, and the like. These solvents may be used singly or in combination of two or more.

The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferable. The range is from 1 wt% to 10 wt%. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described later, and is preferably heated to form a coating film as a liquid crystal alignment film or a coating film to be a liquid crystal alignment film. When the concentration is less than 1 wt%, the film thickness of the coating film becomes too small, and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes 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 deteriorates.

The range of the solid component concentration which is particularly preferable differs depending on the method used when the liquid crystal alignment agent is applied onto the substrate. For example, in the case of using the rotator method, it is particularly preferable to set the solid content concentration to a range of 1.5 wt% to 4.5 wt%. In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3 wt% to 9 wt%, thereby making the solution viscosity 12 mPa. s~50 mPa. The scope of s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1 wt% to 5 wt%, thereby making the solution viscosity 3 mPa. s~15 mPa. The scope of s.

The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 10 ° C to 50 ° C, more preferably from 20 ° C to 30 ° C.

<Liquid alignment film and liquid crystal display element>

The liquid crystal alignment film of the present invention is formed of a liquid crystal alignment agent prepared as described above. Further, the liquid crystal display element of the present invention comprises a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal display element is not particularly limited, but is preferably applied to a vertical alignment type.

The liquid crystal display element of the present invention can be manufactured by the following method. The method includes the first step of applying the liquid crystal alignment agent of the present invention to the conductive film of a pair of substrates having a conductive film, followed by heating to form a coating film; and the second step, interposing liquid crystal molecules The liquid crystal cell is formed by arranging a pair of substrates on which the coating film is formed to face each other so that the coating film faces each other, and the third step is to apply a voltage between the conductive films of the pair of substrates. The liquid crystal cell performs light irradiation.

[Step 1: Formation of coating film]

In this step, two sheets of the substrate on which the patterned transparent conductive film is provided are formed as a pair, and on the surface on which the transparent conductive film is formed on the substrate, offset printing or spin coating is preferably used. The liquid crystal alignment agent of the present invention is applied by a method, a roll coater method or an inkjet printing method, respectively. Here, as the substrate, for example, glass such as float glass or soda glass may be used; including polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly (aliphatic) A transparent substrate of plastic such as olefin). As the transparent conductive film provided on one side of the substrate, a NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA) and an oxidation containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) can be used. Indium Tin Oxide (ITO) film or the like. When a patterned transparent conductive film is to be obtained, for example, a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern, and a desired method for forming a transparent conductive film are used. The method of masking the pattern. When the liquid crystal alignment agent is applied, in order to make the adhesion between the surface of the substrate and the transparent conductive film and the coating film better, the surface of the substrate on which the coating film is to be formed may be coated with a functional decane compound or a functional group. Pretreatment of a titanium compound or the like.

After the liquid crystal alignment agent is applied, preheating (prebaking) is preferably performed in order to prevent sag of the applied liquid crystal alignment agent. The prebaking temperature is preferably 30 ° C~ 200 ° C, more preferably 40 ° C ~ 150 ° C, particularly preferably 40 ° C ~ 100 ° C. The prebaking time is preferably from 0.25 minutes to 10 minutes, more preferably from 0.5 minutes to 5 minutes. Thereafter, the solvent is completely removed, and if necessary, a calcination (post-baking) step is carried out for the purpose of thermally imidating the proline structure present in the polymer. The post-baking temperature is preferably from 80 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C. The post-baking time is preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 100 minutes. The film thickness of the film formed in the above manner is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

The organic solvent is removed by heating after coating the liquid crystal alignment agent to form a coating film to be an alignment film. In this case, in the case where the polymer contained in the liquid crystal alignment agent of the present invention is a polyaminic acid or a ruthenium iodide polymer having a quinone ring structure and a phthalic acid structure, the coating may be formed. After the film is further heated, a dehydration ring-closure reaction is carried out to prepare a coating film which is further imidized. The coating film formed in the above manner can be directly used as a liquid crystal alignment film, but may be subjected to a rubbing treatment as needed.

[Step 2: Construction of liquid crystal cell]

In this step, two substrates in which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal was placed between the two substrates arranged in the opposite direction to manufacture a liquid crystal cell. Here, when the coating film is subjected to the rubbing treatment, the two substrates are arranged to face each other such that the rubbing directions of the respective coating films are at a predetermined angle, for example, orthogonal or antiparallel.

When manufacturing a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a method known from the prior (vacuum injection method). First, the two substrates are opposed to each other with a gap (cell gap) interposed therebetween, and the peripheral portions of the two substrates are bonded together using a sealant. The liquid crystal cell is manufactured by injecting into the cell gap defined by the surface of the substrate and the sealant to fill the liquid crystal, and then sealing the injection hole.

The second method is a method called the One Drop Fill (ODF) method. Applying, for example, an ultraviolet curable sealing material to a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed, and further adding the liquid crystal to a predetermined number of portions on the liquid crystal alignment film surface, The other substrate is bonded in such a manner that the liquid crystal alignment film faces each other, and the liquid crystal is diffused to the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, thereby manufacturing a liquid crystal cell.

When any of the methods is used, the liquid crystal cell produced in the above manner can be further heated until the liquid crystal used reaches the temperature of the isotropic phase, and then slowly cooled to room temperature, thereby removing the filled liquid crystal. The flow alignment at the time.

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

The liquid crystal may, for example, be a nematic liquid crystal or a smectic liquid crystal. Among them, a nematic liquid crystal is preferably used, for example, a Schiff base liquid crystal, an azoxy liquid crystal, or a biphenyl system. Liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cetane liquid crystal, or the like. Further, for example, the following compounds may be added to these liquid crystals: cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate; as the trade names "C-15" and "CB-15" (a chiral agent sold by Merck); a ferroelectric liquid crystal such as p-oxybenzylidene-p-amino-2-methylbutyl cinnamate or the like. The thickness of the layer of the liquid crystal molecules is preferably set to 1 μm to 5 μm.

[Step 3: Light irradiation step]

After the construction of the liquid crystal cell, the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates. The voltage applied here can be, for example, a direct current or an alternating current of 5 V to 50 V. Further, as the light to be irradiated, for example, ultraviolet light and visible light having a wavelength of 150 nm to 800 nm can be used, but ultraviolet light having a wavelength of 300 nm to 400 nm is preferable. As the light source of the irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. Further, the ultraviolet light in the preferred wavelength region can be obtained by a method of using a light source in combination with, for example, a filter, a diffraction grating, or the like.

The irradiation amount of light is preferably 1,000 J/m ² or more, less than 100,000 J/m ² , and more preferably 1,000 J/m ² to 50,000 J/m 2 . For example, in the manufacture of a liquid crystal display element of a PSA mode which is known in the prior art, it is necessary to irradiate light of about 100,000 J/m ² , but in the method of manufacturing a liquid crystal display element of the present invention, even when the amount of light irradiation is set to 10,000 J / m ² or less, and further to the case of 5,000 J / m ² or less, can be obtained a liquid crystal pretilt angle has the desired characteristics of the display element, contributes to reduce the manufacturing cost of the liquid crystal display element. Further, it is possible to suppress a decrease in electrical characteristics caused by irradiation of strong light or a decrease in responsiveness of liquid crystal molecules.

Then, the polarizing plate is attached to the outer surface of the liquid crystal cell, whereby the liquid crystal display element of the present invention can be obtained. Examples of the polarizing plate include a polarizing plate in which a polarizing film called “H film” is sandwiched between a cellulose acetate protective film, or a polarizing plate including an H film itself, which is made of polyvinyl alcohol on one side. A polarizing film that absorbs iodine while extending.

The liquid crystal display element of the present invention can be effectively applied to various devices, such as a clock, a portable game machine, a word processor, a notebook personal computer, Various display devices such as car navigation systems, camcorders, personal digital assistants (PDAs), digital cameras, mobile phones, smart phones, various monitors, LCD TVs, and message displays.

[Examples]

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

The weight average molecular weight, the epoxy equivalent of each polymer in the examples and the synthesis examples, the solution viscosity of each polymer solution, and the oxime imidization ratio of polyimine were measured by the following methods.

[weight average molecular weight]

The weight average molecular weight Mw of the polymer is measured by gel permeation chromatography (GPC) under the following conditions by using the following apparatus, and monodisperse polystyrene is used as a standard substance as a polystyrene equivalent value. Find out.

. Measuring device: manufactured by Tosoh (share), model "8120-GPC"

. Pipe column: manufactured by Tosoh (share), "TSKgelGRCXLII"

. Solvent: tetrahydrofuran

. Sample concentration: 5 wt%, sample injection amount: 100 μL

. Column temperature: 40 ° C, column pressure: 68 kgf / cm ²

[醯Iminization rate of polyimine]

The solution of the polyimine is put into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl hydrazine, and tetramethyl decane is used as a reference substance in the room. ¹ H-NMR was measured at a temperature. From the ¹ H-NMR spectrum obtained, the oxime imidization ratio [%] was determined by the formula represented by the following formula (1x).

醯imination rate [%]=(1-A ¹ /A ² ×α)×100...(1x)

(In the formula (1x), A ¹ is the peak area of the proton derived from the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of other protons to the polymer (proportion of the number of protons of the NH group in (polyproline))

<Synthesis of Polymer (P) (1)>

[Example P1]

Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 3.2 g of oxalic acid and 39.6 g of ethanol were placed and stirred to prepare an ethanol solution of oxalic acid. Then, after heating the solution to 70 ° C in a nitrogen atmosphere, a compound represented by the above formula (a1-1) as a raw material, that is, a decane compound (a1) is added thereto (wherein the group "-C ₆ H ₁₂ -" is hexane-1,6-diyl) 5.1 g, and further, tetraethoxy decane (TEOS) 2.2 g as another decane compound was added dropwise. After completion of the dropwise addition, the temperature at 70 ° C was maintained for 6 hours, and then cooled to 25 ° C, followed by the addition of 40.0 g of butyl cellosolve to prepare a polyorganosiloxane (A-1) as a polymer (P). Solution. The polyorganosiloxane (A-1) contained in the solution had a weight average molecular weight Mw of 12,000.

[Example P2 to Example P33, Synthesis Example 1]

The polyorganoindole was separately prepared in the same manner as in the above Example P1 except that the type and amount of the decane compound used as the raw material and the amounts of oxalic acid and ethanol used were as described in the following Table 1, respectively. A solution of oxane (A-2) ~ polyorganosiloxane (A-33) and polyorganosiloxane (c-1). Further, as the decane compound (a1), a group "-C _n H _2n -" is used as a linear one. The weight average molecular weight Mw of each polyorganosiloxane contained in each solution is shown together in Table 1 below.

In Table 1, the abbreviations of the respective compounds have the following meanings.

ODES: octadecyltriethoxydecane

MPTMS: 3-methacryloxypropyltrimethoxydecane

Further, "-" in Table 1 indicates that the raw materials in accordance with the column are not used (the same is true in the following table).

<Synthesis of Carboxylic Acid (AC)>

[Example AC-1]

The carboxylic acid (AC-1) was synthesized by the following Scheme 1.

Process 1

22.3 g (77.5 mmol) of 4-(4-methylpropenyloxy-cyclohexyl)benzoic acid, 320 ml of dimethylformamide, and 17.1 g (81.4 mmol) of tert-butyl 6-bromo-n-heptanoate, 21.9 mg of dibutylhydroxytoluene and 21.4 g (155 mmol) of potassium carbonate were mixed and stirred at 70 ° C for 7 hours. Then, 700 ml of ethyl acetate and 700 ml of cyclohexane were added, and extraction washing was performed five times with 500 ml of distilled water. The organic layer was concentrated to obtain 28 g of a coupling body.

Then, 28 g of the obtained coupled body, 98 ml of dichloromethane, 28 mg of dibutylhydroxytoluene, and 24.5 ml of trifluoroacetic acid were mixed, and stirred at room temperature for 2 days. After concentration to remove trifluoroacetic acid, add 500 ml of ethyl acetate and use distilled water. Two extraction rinses were performed in 250 ml. 250 ml of ethanol was added to the organic layer, and the mixture was concentrated to precipitate, and then filtered, washed with ethanol, and dried to obtain 23 g of a carboxylic acid (AC-1) as a target.

[Embodiment AC-9]

The carboxylic acid (AC-9) was synthesized by the following Scheme 2.

Process 2

Add 42.8 g (0.2 mol) of 4-(4-hydroxyphenyl)benzoic acid, 16 g (0.4 mol) of sodium hydroxide, 1 L of water and make them uniform to a 2 L three-necked flask equipped with a dropping funnel and a thermometer. After dissolving in the ground, it is cooled to below 5 °C. Then, 23.4 mL (0.24 mol) of methacrylonitrile chloride and 300 mL of dichloromethane were added to the dropping funnel, and the mixture was added dropwise at 5 ° C for 2 hours, and the mixture was returned to room temperature for further 3 hours. After completion of the reaction, the white precipitate recovered by filtration was dissolved in 1 L of ethyl acetate and 2 L of tetrahydrofuran, and washed once with 1 L of 1 M aqueous hydrochloric acid, and then washed three times with 500 mL of water. Then, the organic layer is dried with magnesium sulfate, and the white crystal obtained by concentrating to about 500 mL is collected and dried to obtain a compound represented by the above formula (AC2-1) (hereinafter, also referred to as " The white crystal of the compound (AC2-1)") was 56.5 g.

Then, to a 500 mL three-burner with a thermometer and a nitrogen introduction tube. The compound (AC2-1) obtained in the manner described above was added 13.59 g (48.1 mmol), DMF 200 mL, 11-bromo-n-undecanoic acid-tert-butyl ester 16.24 g (50.5 mmol), potassium carbonate 13.31 g and The reaction was carried out at 70 ° C for 8 hours. After completion of the reaction, 500 mL of cyclohexane and 500 mL of ethyl acetate were added, and the mixture was washed three times with 400 mL of water, dried with magnesium sulfate, and then concentrated to obtain a liquid form (AC2-2). The compound represented (hereinafter, also referred to as "compound (AC2-2)")) was 28.62 g.

Then, to a 500 mL eggplant type flask, 28.62 g of the compound (AC2-2) obtained in the above manner, 100 mL of dichloromethane, and 25 mL of trifluoroacetic acid were added and reacted at room temperature for 5 hours. After completion of the reaction, 100 mL of ethanol was added and concentrated, and 100 mL of ethanol was added thereto and concentrated. Then, the crystals which were allowed to stand overnight were filtered, washed with ethanol, and dried to obtain a carboxylic acid (AC). -9) White crystal 12.51 g.

[Example AC-14]

The carboxylic acid (AC-14) was synthesized by the following Scheme 3.

Process 3

Add 5.00 g (36.22 mmol) of hydroxybenzoic acid, 150 mL of tetrahydrofuran, 100 mL of tert-butanol and 0.17 g of N,N-dimethylaminopyridine to a 1 L three-necked flask equipped with a dropping funnel, a thermometer and a nitrogen inlet. (1.45 mmol). Then, 8.22 g (39.84 mmol) of dicyclohexylcarbodiimide was dissolved in a dropping funnel. The mixture was added dropwise in 50 mL of tetrahydrofuran for 30 minutes and directly reacted for 15 hours. After completion of the reaction, the filtrate obtained by filtration of diatomaceous earth was concentrated, and 300 mL of ethyl acetate was added thereto, and the mixture was washed twice with a sodium hydrogencarbonate aqueous solution, and separated by water for 3 times, followed by concentration and vacuum. Drying, thereby obtaining an orange viscous liquid. The viscous liquid was subjected to a cerium oxide column purification (developing solvent: hexane/ethyl acetate = 80/20 (weight ratio)), whereby a compound represented by the above formula (AC3-1) was obtained (hereinafter, Also known as "compound (AC3-1)"), white crystals were 3.6 g.

Then, a compound (AC3-1) 12.25 g (63.1 mmol), 11-bromo-n-undecyl alcohol 16.64 g (66.2 mmol), N,N-dimethyl was added to a 500 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube. 180 mL of acetamide, 9.58 g (69.4 mmol) of potassium carbonate and 2.09 g (12.6 mmol) of potassium iodide were reacted at 100 ° C for 2 hours. After completion of the reaction, 500 mL of ethyl acetate was added, and the mixture was washed once with dilute hydrochloric acid, and then washed three times with water. Thereafter, it is dried with magnesium sulfate, concentrated, and dried and solidified to obtain a white solid of a compound represented by the above formula (AC3-2) (hereinafter, also referred to as "compound (AC3-2)"). 21.3 g.

Then, a compound (AC2-1) 16.48 g (58.4 mmol), a compound (AC3-2) 21.3 g (58.4 mmol), and 440 mL of dichloromethane were added to a 1 L three-necked flask equipped with a thermometer and a nitrogen gas introduction tube. They are suspended and then cooled in an ice bath. Then, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride 13.47 g (70.3 mmol) and N,N-dimethylaminopyridine 1.43 g (11.7 mmol) were added. After stirring for 2 hours under ice-cooling, it was returned to room temperature and reacted for 16 hours. After completion of the reaction, 2 L of ethyl acetate was added and the mixture was washed three times with water, and then dried with magnesium sulfate. Then, the white precipitate produced by concentration is filtered, After drying, 26.0 g of a white crystal of the compound represented by the above formula (AC3-3) (hereinafter, also referred to as "compound (AC3-3)") was obtained.

Then, a compound (AC3-3) 26.0 g (41.3 mmol), trifluoroacetic acid 55 mL, and dichloromethane 110 mL were added to a 500 mL eggplant flask and reacted at room temperature for 5 hours. After completion of the reaction, the solvent was removed by an aspirator, and then 2 L of ethyl acetate and 2 L of tetrahydrofuran were added and washed with water three times, followed by drying with magnesium sulfate. Then, the precipitate produced by concentration was filtered and dried to obtain 20.64 g of a white crystal of a carboxylic acid (AC-14).

[Embodiment AC-33]

A carboxylic acid (AC-33) was synthesized in the same manner as in the above Example AC-14 except that 6-bromo-n-hexanol was used instead of 11-bromo-n-decyl alcohol.

[Embodiment AC-34]

The carboxylic acid (AC-34) was synthesized in the same manner as in the above Example AC-14 except that 3-bromo-n-propanol was used instead of 11-bromo-n-decyl alcohol.

[Embodiment AC-35]

The carboxylic acid (AC-35) was synthesized by the following Scheme 4.

Process 4

Add to a 300 mL eggplant flask with a nitrogen inlet and return tube Potassium hydroxide 8.1 g (144 mmol), water 24 mL, potassium iodide 0.51 g (3 mmol), 4-(4-hydroxyphenyl)benzoic acid 11.58 g (54 mmol) and ethanol 36 mL, and dissolve them evenly . Then, 12.9 g (60 mmol) of 12-bromo-n-dodecyl alcohol was added and refluxed for 2 hours. After completion of the reaction, the precipitate obtained by filtration was washed with water, suspended in 300 mL of 1 M hydrochloric acid water, and then recovered by filtration, and washed with acetone. Then, recrystallization was carried out using 150 mL of methoxyethanol to obtain 15.6 g of a white powder of the compound represented by the above formula (AC6-1) (hereinafter, also referred to as "compound (AC6-1)").

Then, a compound (AC6-1) obtained in the manner described above (3.96 g (10 mmol)) was added to a 100 mL three-necked flask equipped with a Dean-Stark tube, a thermometer, and a nitrogen introduction tube. Resorcinol 0.74 g (6.7 mmol), toluene 100 mL, p-toluenesulfonic acid 0.57 g (3.3 mmol) and methacrylic acid 8.61 g (100 mmol) were refluxed for 11 hours. After completion of the reaction, 100 mL of tetrahydrofuran was added and the mixture was separated three times with 50 mL of water, and then dried with magnesium sulfate, and then further concentrated, dried and solidified. The obtained solid was recrystallized with 65 mL of ethanol, whereby 2.15 g of a pale brown solid of carboxylic acid (AC-35) was obtained.

[Embodiment AC-36]

The carboxylic acid (AC-36) was synthesized in the same manner as in the above Example AC-35 except that 4-hydroxybenzoic acid was used instead of 4-(4-hydroxyphenyl)benzoic acid.

[Embodiment AC-37]

The carboxylic acid (AC-37) was synthesized by the following Scheme 5.

Process 5

To a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen inlet tube, 12.4 g (50 mmol) of 4-iodobenzoic acid, 1.85 g (7.5 mmol) of N,N-dimethylaminopyridine, and 200 mL of tetrahydrofuran and Di-tert-butyl dicarbonate 16.35 g (75 mmol) was reacted at 50 ° C for 5 hours. After completion of the reaction, the mixture was concentrated to about 50 mL, and then 100 mL of hexane was added thereto for filtration. Then, the filtrate was washed three times with 50 mL of a saturated aqueous solution of sodium carbonate, and the filtrate was subjected to liquid separation for 10 times with 50 mL of water, dried with magnesium sulfate, concentrated, and dried under vacuum, thereby obtaining 7.51 g of a pale yellow oil of the compound represented by the formula (AC8-1) (hereinafter, also referred to as "compound (AC8-1)").

Then, a compound (AC8-1) obtained in the manner described above (7.5 g (24.7 mmol), dichlorobistriphenylphosphine palladium 0.433 g (0.62 mmol)) was added to a 100 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube. After 0.236 g (1.24 mmol) of copper iodide and 24.7 mL of triethylamine, 2.66 g (27.1 mmol) of 5-hexyn-1-ol was added and reacted at room temperature for 4 hours. After completion of the reaction, ethyl acetate was added to the filtrate obtained by the filtration, and the mixture was washed with water for 8 times. Then, after drying with magnesium sulfate, it concentrated, and the brown oil was obtained. Then use dioxane The oil was purified by a hydrazine tubing column (developing solvent: hexane/ethyl acetate = 2:1 (weight ratio)), followed by concentration and vacuum drying, thereby obtaining the formula (AC8-2) The light yellow oil of the compound (hereinafter, also referred to as "compound (AC8-2)") was 3.44 g.

Then, a compound (AC2-1) 0.55 g (1.93 mmol), a compound (AC8-2) 0.53 g (1.93 mmol), and 10 mL of dichloromethane were added to a 100 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube. They were suspended and then cooled to 0 ° C in an ice bath. Then, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride 0.445 g (2.32 mmol), N,N-dimethyl-4-aminopyridine 0.047 g (0.386 mmol) and reacted for 16 hours under ice-cooling. After completion of the reaction, ethyl acetate was added thereto, and the mixture was washed three times with water, and then dried with magnesium sulfate and concentrated, and then the white precipitate obtained by adding ethanol was filtered and dried to obtain the above-mentioned The white crystal of the compound represented by the formula (AC8-3) (hereinafter, also referred to as "compound (AC8-3)") was 0.54 g.

Then, 3.8 g (7.05 mmol) of the compound (AC8-3) was added to a 100 mL eggplant type flask equipped with a nitrogen introduction tube, and then 20 mL of dichloromethane and 10 mL of trifluoroacetic acid were added and reacted at room temperature for 1 hour. After completion of the reaction, 150 mL of ethyl acetate and 150 mL of tetrahydrofuran were added and washed with water for 8 times, and then dried with magnesium sulfate and concentrated, and then the crystals precipitated by adding ethanol were filtered and dried. A white crystal of the carboxylic acid (AC-37) was obtained.

[Embodiment AC-38]

The carboxylic acid (AC-38) was synthesized in the same manner as in the above Example AC-37 except that 9-decyn-1-ol was used instead of 5-hexyn-1-ol.

[Embodiment AC-39]

The carboxylic acid (AC-39) was synthesized by the following Scheme 6.

Process 6

Add 4-hydroxybenzoic acid-tert-butyl ester 19.4 g (0.1 mol), potassium carbonate 15.2 g (0.11 mol), potassium iodide 3.22 g (0.02 mol) to a 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen inlet tube. After 200 mL of N,N-dimethylacetamide and 12.2 g (0.105 mol) of 5-chlorohexyne, the reaction was carried out at 100 ° C for 4 hours. After completion of the reaction, 400 mL of ethyl acetate was added and the mixture was washed three times with water, and then dried with magnesium sulfate, filtered, and concentrated. The obtained solution was purified by a ruthenium dioxide column (developing solvent: hexane: ethyl acetate = 20:1 (weight ratio)), thereby obtaining a compound represented by the formula (AC10-1) ( Hereinafter, it is also referred to as "compound (AC10-1)") 21.9 g.

Then, a 100 mL three-necked flask equipped with a thermometer, a dropping funnel, and a nitrogen introduction tube was charged with 4-iodophenol 11.0 g (50 mmol), tetrahydrofuran 25 mL, and tetraethylamine 6.1 g (60 mmol), and cooled in an ice bath. . On the other hand, 5.75 g (55 mmol) of methacrylium fluorene chloride and 10 mL of tetrahydrofuran were added to the dropping funnel, and the mixture was added dropwise over 30 minutes, and then returned to room temperature and reacted for 1 hour. After the reaction is completed, 50 mL of ethyl acetate is added and the mixture is washed once with dilute hydrochloric acid, and then utilized. The sodium carbonate aqueous solution was subjected to liquid separation washing once, and then subjected to liquid separation washing three times with water, followed by drying with magnesium sulfate, followed by concentration and drying, thereby obtaining a compound represented by the above formula (AC10-2) ( Hereinafter, 10.3 g of a pale yellow oil, also referred to as "compound (AC10-2)").

Then, 8.4 g of a compound (AC10-2), 0.52 g of dichlorobistriphenylphosphine palladium, 0.28 g of copper iodide, and 29 mL of triethylamine were added to a 200 mL three-necked flask equipped with a thermometer and a nitrogen introduction tube. Compound (AC10-1) 8.8 g was added and reacted at room temperature for 4 hours. After the completion of the reaction, 200 mL of ethyl acetate was added to the filtrate obtained by filtration of the diatomaceous earth, and the mixture was washed three times with water, and then dried with magnesium sulfate, concentrated, and then a column of cerium oxide was used. The solvent: hexane: ethyl acetate = 20:1 (weight ratio)) is purified, thereby obtaining a compound represented by the above formula (AC10-3) (hereinafter, also referred to as "compound (AC10-3)" ) oil 7.5 g.

Then, 7.5 g of a compound (AC10-3), 40 mL of dichloromethane, and 20 mL of trifluoroacetic acid were added to a 200 mL eggplant type flask equipped with a nitrogen introduction tube, and reacted at room temperature for 4 hours. After completion of the reaction, dichloromethane and trifluoroacetic acid were distilled off, and then 100 mL of ethyl acetate and 100 mL of tetrahydrofuran were added and washed with water 10 times. Then, it dried by magnesium sulfate, filtered, concentrated, dried and solidified, and recrystallized by ethanol, and 4.7 g of white crystal of carboxylic acid (AC-39) was obtained.

<Synthesis of Polymer (P) (2)>

[Synthesis Example S1]

8.4 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECETS) as a decane compound (a2) was added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube. The solvent was 42 g of methyl isobutyl ketone and 0.85 g of triethylamine as a catalyst, and mixed at room temperature. Then, 8.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was stirred under reflux at 80 ° C for 6 hours. After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% aqueous solution of ammonium nitrate until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain an epoxy having a viscous transparent liquid. A polyorganosiloxane (hereinafter also referred to as "polyoxyalkylene (S-1)"). The polystyrene-equivalent weight average molecular weight Mw measured by the GPC to the polyoxyalkylene (S-1) was 2,200. Further, as a result of ¹ H-NMR analysis of polyoxyalkylene (S-1), an epoxy group-based peak was obtained as the theoretical intensity near the chemical shift (δ) = 3.2 ppm, and it was confirmed that no reaction occurred in the reaction. A side reaction of an epoxy group.

[Example P34]

To a 200 mL three-necked flask, 6 g of polyoxyalkylene (S-1) obtained in the above manner, 85 g of methyl isobutyl ketone as a solvent, and 4-(4-n-pentyl) as a carboxylic acid were added. -cyclohexyl)benzoic acid (PCHBA) 1.9 g (corresponding to the epoxy group of polyoxyalkylene (S-1), equivalent to 20 mol%), and carboxylic acid (AC-1) 7.1 g (relative Epoxy compound produced by polyoxyalkylene (S-1), equivalent to 50 mol%), and UCAT 18X (trade name, San-Apro) The hardening accelerator) was 0.10 g, and the reaction was carried out at 90 ° C for 48 hours with stirring. Further, as the carboxylic acid (AC-1), a hexanediyl group is used as a linear one. After completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed with water three times, dried with magnesium sulfate, and then the solvent was distilled off to obtain a polyorganosiloxane as a polymer (P). (A-34). The polystyrene-equivalent weight average molecular weight Mw measured by GPC on the polyorganosiloxane (A-34) It is 9,200.

[Example P35 to Example P67, Synthesis Example 2]

The polyorganoindole was obtained in the same manner as in the above Example P34 except that the type and amount of the decane compound used as the raw material and the type and amount of the carboxylic acid to be used were as described in the following Table 2, respectively. Oxane (A-35) ~ polyorganosiloxane (A-67) and polyorganosiloxane (c-2). Further, in Example P65, Example P66 and Synthesis Example 2, two kinds of decane compounds were used, and in Example P66, two other carboxylic acids were used. Further, two kinds of carboxylic acids (AC) were used in Example P67. As the carboxylic acid (AC), a compound in which the group "-C _n H _2n -" is linear is used. The polystyrene-equivalent weight average molecular weight Mw measured by GPC for these polyorganosiloxanes is shown in Table 2.

In Table 2, the abbreviations of the respective compounds have the following meanings.

GPTMS: 3-glycidoxypropyltrimethoxydecane

OCTBA: 4-n-octyloxybenzoic acid

PCHBA: 4-(4-n-pentyl-cyclohexyl)benzoic acid

[Synthesis Example S2]

To a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, EECTS 6.3 g as a decane compound (a2) and 2.1 g of methacryloxypropyltrimethoxydecane as a solvent were added as a solvent. 42 g of butyl ketone and 0.85 g of triethylamine as a catalyst were mixed at room temperature. Then, 8.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was stirred under reflux at 80 ° C for 6 hours. After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% aqueous solution of ammonium nitrate until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain an epoxy having a viscous transparent liquid. A polyorganosiloxane (hereinafter also referred to as "polyoxane (S-2)"). The polystyrene-equivalent weight average molecular weight Mw measured by the GPC to the polyoxyalkylene (S-2) was 2,100.

[Synthesis Example S3]

To a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, EECTS 5.9 g as a decane compound (a2) and 2.8 g of methacryloxyoctyltrimethoxydecane as a solvent, cyclopentanone as a solvent were added. 42 g, and 0.85 g of triethylamine as a catalyst, were mixed at room temperature. Then, 8.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was stirred under reflux at 80 ° C for 6 hours. After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% aqueous solution of ammonium nitrate until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain an epoxy having a viscous transparent liquid. A polyorganosiloxane (hereinafter also referred to as "polyoxane (S-3)"). The polyoxyalkylene (S-3) by GPC The measured polystyrene-equivalent weight average molecular weight Mw was 2,400.

[Example S4]

2.9 g of ECETS as a decane compound (a2), 5.7 g of a decane compound (a1-33) as a decane compound (a1), and a solvent as a solvent were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube. 42 g of isobutyl ketone and 0.85 g of triethylamine as a catalyst were mixed at room temperature. Then, 8.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was stirred under reflux at 80 ° C for 6 hours. After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% aqueous solution of ammonium nitrate until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain an epoxy having a viscous transparent liquid. A polyorganosiloxane (hereinafter also referred to as "polyoxyalkylene (S-4)") having a group represented by the above formula (1). The polystyrene-equivalent weight average molecular weight Mw measured by the GPC to the polyoxyalkylene (S-4) was 2,800.

[Example P77 to Example P93]

The type and amount of the epoxy group-containing polyorganosiloxane used as a raw material, and the type and amount of the carboxylic acid to be used were changed as described in Table 3 below, respectively. The same method was used to synthesize polyorganosiloxane (A-77) ~ polyorganosiloxane (A-93). As the carboxylic acid (AC), a compound in which the group "-C _n H _2n -" is linear is used. The polystyrene-equivalent weight average molecular weight Mw measured by GPC for these polyorganosiloxanes is shown in Table 3.

<Synthesis of Polymer (P) (3)>

[Example P68]

5.6 g of oxalic acid and 106 g of ethanol were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, and stirred to prepare an ethanol solution of oxalic acid. Then, after heating the solution to 70 ° C in a nitrogen atmosphere, a mixture of 9.9 g of the compound represented by the formula (a1-1) and EECTS 4.9 g as a raw material, that is, a decane compound, was added thereto, and The temperature of 70 ° C was maintained for 6 hours. Thereafter, the mixture was cooled to 25 ° C, and then 100 g of butyl cellosolve was added to prepare a solution containing polyorganosiloxane (A-68). The polyorganosiloxane (A-68) contained in the solution had a weight average molecular weight Mw of 9,200.

[Example P69 to Example P71]

The polyorganoindole was separately prepared in the same manner as in the above Example P1 except that the type and amount of the decane compound used as the raw material and the amounts of oxalic acid and ethanol used were as described in the following Table 4, respectively. A solution of oxane (A-69) ~ polyorganosiloxane (A-71). The weight average molecular weight Mw of each polyorganosiloxane contained in each solution is shown in Table 4 together.

[Example P72]

To a 200 mL three-necked flask, 12.7 g of polyorganooxane (A-68) obtained in Example P68, 85 g of methyl isobutyl ketone as a solvent, and 2.3 g of PCHBA as a carboxylic acid were added (relative to The polyorganooxynonane (A-68) had an epoxy group corresponding to 20 mol%) and 0.10 g of "UCAT 18X" as a catalyst, and was reacted at 90 ° C for 48 hours under stirring. After completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed with water three times, dried with magnesium sulfate, and then the solvent was distilled off to obtain a polyorganosiloxane as a polymer (P). (A-72). The polystyrene-equivalent weight average molecular weight Mw measured by the GPC of the polyorganosiloxane (A-72) was 11,200.

[Example P73 to Example P75]

The type and amount of the polyorganosiloxane used as a raw material, and the type and amount of the carboxylic acid to be used were respectively obtained in the same manner as in the above-described Example P72 except that the types and amounts of the carboxylic acid to be used were as described in the following Table 5. As the polymer (P), polyorganosiloxane (A-73) to polyorganosiloxane (A-75). The polystyrene-equivalent weight average molecular weight Mw measured by GPC for these polyorganosiloxanes is shown in Table 5.

<Synthesis of Polymer (Q)>

[Synthesis Example 3]

2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride 110 g (0.50 mol), and p-phenylenediamine as a diamine 11 g (0.10 mol), 3, 5 -diaminobenzoic acid 15 g (0.10 mol), 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-5-amine 53 g (0.20 mol) and 3-(3,5-diaminobenzylideneoxy)cholestane 52 g (0.10 mol) were dissolved in N-methyl-2-pyrrolidone (NMP) 830 g, The reaction was carried out at 60 ° C for 6 hours. A small amount of the obtained polyaminic acid solution was separated and extracted, and NMP was added to prepare a solution having a polyglycine concentration of 10 wt%, and the solution viscosity measured at 25 ° C using an E-type rotational viscometer was 52 mPa. s. Further, the polystyrene-equivalent weight average molecular weight Mw measured by GPC for the obtained polylysine was 160,500.

Then, 1,900 g of NMP was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were added, followed by dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement using a new NMP, thereby obtaining a solution containing about 15% by weight of polyamidolimine (PI-1) having a ruthenium iodide ratio of about 50%. A small amount of the obtained polyaminic acid solution was separated and extracted, and NMP was added to prepare a solution having a polyglycine concentration of 10 wt%, and the measurement was carried out using E type. The viscosity of the solution measured by a rotary viscometer at 25 ° C is 35 mPa. s. Further, the polystyrene-equivalent weight average molecular weight Mw measured by the GPC on the obtained polyimine was 135,000.

[Example 1]

<Preparation of liquid crystal alignment agent>

To the solution containing the polyorganosiloxane (A-1) obtained in the above Example P1 as a polymer, butyl cellosolve was added to prepare a solution having a solid concentration of 5 wt%. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent.

<Manufacture and evaluation of VA type liquid crystal display element>

A total of six liquid crystal display elements were produced by using the liquid crystal alignment agent prepared as described above and changing the pattern of the transparent electrode and the amount of ultraviolet irradiation (three levels). Further, various characteristics of these manufactured liquid crystal display elements were evaluated.

[Manufacture of liquid crystal display element having a transparent electrode without pattern]

Each of the liquid crystal alignment agents prepared in the manner described above was applied onto a transparent electrode surface of a glass substrate having a transparent electrode including an ITO film using a liquid crystal alignment film printer (manufactured by Nissha Co., Ltd.). The mixture was heated (prebaked) on a hot plate at 80 ° C for 1 minute to remove the solvent, and then heated on a hot plate at 150 ° C for 10 minutes (post-baking) to form a coating film having an average film thickness of 600 Å. The coating film was subjected to a rubbing treatment using a friction machine having a roller wound with a rayon cloth at a roll rotation speed of 400 rpm, a table moving speed of 3 cm/sec, and a press-in length of 0.1 mm. Thereafter, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a clean oven at 100 ° C for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of (two sheets) substrates having a liquid crystal alignment film.

Next, after coating the outer edges of the pair of substrates having the liquid crystal alignment film, an epoxy resin binder having an alumina ball having a diameter of 5.5 μm is applied, and then the liquid crystal alignment film faces are superposed. The crimping is performed and the bonding agent is hardened. Then, a nematic liquid crystal (manufactured by Merck, MLC-6608) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. These operations were repeated to manufacture three liquid crystal display elements having transparent electrodes without patterns. One of them is directly used for the evaluation of the pretilt angle to be described later. The remaining two liquid crystal display elements were subjected to light irradiation in a state where a voltage was applied between the conductive films by the following method, and then the initial pretilt angle, the pretilt angle stability, and the heat resistance were evaluated.

For two of the liquid crystal display elements obtained in the above manner, an alternating current 10 V having a frequency of 60 Hz was applied between the electrodes, and an ultraviolet irradiation device using a metal halide lamp for the light source was used in a state where the liquid crystal was driven. The ultraviolet ray is irradiated at an irradiation dose of 5,000 J/m ² or 10,000 J/m ² . Further, the irradiation amount is a value measured using a photometer measured with a wavelength of 365 nm.

[Evaluation of initial pretilt angle]

For each liquid crystal cell manufactured in the manner described above, according to Non-Patent Document 1 (TJ Scheffer et al., J. Appl. Phys. vo. 48, p. 1783 (1977) And the method described in Non-Patent Document 2 (F. Nakano et al., "JP. J. Appl. Phys." vo. 19, p. 2013 (1980)), The tilt angle of the liquid crystal molecules from the substrate surface was measured by a crystal rotation method using a He-Ne laser, and the measured value was defined as an initial pretilt angle. The measurement results of the initial pretilt angles of the liquid crystal display elements which are not irradiated with light, the liquid crystal display element having an irradiation amount of 5,000 J/m ² , and the liquid crystal display element having an irradiation amount of 10,000 J/m ² are shown in Table 8 below. .

[Evaluation of pretilt stability]

Under the condition of fluorescent lamp illumination, a liquid crystal display element having an irradiation amount of 10,000 J/m ² among the liquid crystal display elements after the initial pretilt angle measurement was applied under the condition of applying an AC voltage of 20 Vp-p at 60 °C. Aging was performed for 20 hours, and the method was used to determine the pretilt angle after aging. Further, the amount of change in the pretilt angle before and after aging was determined, and the pretilt angle stability was evaluated based on the amount of change. The evaluation was performed in such a manner that the pretilt angle change amount was 2° or less, the pretilt angle stability was “good”, and the pretilt angle change amount was more than 2°, and the pretilt angle stability “bad” was used. The results are shown in Table 8 below.

[Evaluation of heat resistance (evaluation of thermal stability of voltage holding ratio)]

Among the liquid crystal display elements manufactured as described above, a liquid crystal display element which was irradiated with ultraviolet light was applied with a voltage of 5 V at an application time of 60 μsec and a span of 167 msec at 23 ° C, and then the measurement was released after the application was released. Voltage holding ratio (initial value) after 167 ms. VHR-1 manufactured by Toyo Corporation (Stock) was used as a measuring device. Then, the liquid crystal display elements after the measurement of the initial VHR were allowed to stand in an oven set to a temperature of 120 ° C for 5,000 hours. Thereafter, the voltage holding ratio was measured in the same manner as described above. The measurement results of the respective voltage holding ratios of these liquid crystal display elements are shown in Table 8 below.

[Manufacture of liquid crystal display element having patterned transparent electrode]

A liquid crystal alignment film printer (Japanese photo printing (Japanese photo printing) is used on each of the electrode surfaces of the glass substrate A and the substrate B each having an ITO electrode which is patterned into a slit shape as shown in FIG. 1 and divided into a plurality of regions. (manufacturing) coating the liquid crystal alignment agent prepared in the manner described above, heating on a hot plate at 80 ° C for 1 minute (pre After baking, the solvent was removed, and heating was performed on a hot plate at 150 ° C for 10 minutes (post-baking) to form a coating film having an average film thickness of 600 Å. The coating film was ultrasonically washed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of (two sheets) substrates having a liquid crystal alignment film. Furthermore, the pattern of the electrodes used is the same type of pattern as the electrode pattern in the PSA mode.

Next, after coating the outer edges of the pair of substrates having the liquid crystal alignment film, an epoxy resin binder having an alumina ball having a diameter of 5.5 μm is applied, and then the liquid crystal alignment film faces are superposed. The crimping is performed and the bonding agent is hardened. Then, a nematic liquid crystal (manufactured by Merck, MLC-6608) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell.

The above operation was repeated to fabricate three liquid crystal cells having patterned transparent electrodes. One of them is directly used for evaluation of the response speed of liquid crystal molecules to be described later. For the remaining two liquid crystal cells, in the same manner as in the case of manufacturing a liquid crystal display element having a transparent electrode having no pattern, 5,000 J/m ² or 10,000 J/m is applied in a state where a voltage is applied between the conductive films. The amount of irradiation of ² was evaluated by the response speed of the liquid crystal molecules after light irradiation.

[Evaluation of response speed of liquid crystal molecules]

With respect to each liquid crystal display element manufactured as described above, first, a visible light lamp was irradiated without applying a voltage, and the luminance of light transmitted through the liquid crystal display element was measured with a light multimeter, and the value was set to a relative transmittance of 0%. Next, the transmittance at which an AC voltage of 60 V was applied between the electrodes of the liquid crystal display device for 5 seconds was measured in the same manner as described above, and the value was set to be 100% relative transmittance. When applying to each liquid crystal display element When an AC voltage of 60 V was applied, the time until the relative transmittance was changed from 10% to 90% was measured, and this time was defined as the response speed, and the responsiveness of the liquid crystal molecules to the change from the voltage to the voltage-on was evaluated. .

The measurement results of the respective response speeds of the liquid crystal display element which is not irradiated with light, the liquid crystal display element having an irradiation amount of 5,000 J/m ² , and the liquid crystal display element having an irradiation amount of 10,000 J/m ² are shown in Table 8 below. .

[Example 2 to Example 71, Comparative Example 1, Comparative Example 2]

A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the types and amounts of the polyorganosiloxane used for the preparation of the liquid crystal alignment agent were changed as described in the following Tables 6 and 7. Further, using these liquid crystal alignment agents, liquid crystal display elements were produced in the same manner as in Example 1, and the manufactured liquid crystal display elements were evaluated. The evaluation results of these are shown in Tables 8 and 9 below.

[Example 72]

In the solution containing the polyorganosiloxane (A-34) obtained in the above Example P34, the synthesis was added with respect to 10 parts by weight of the polyorganosiloxane (A-34) in the solution. 90 parts by weight of polyimine (PI-1) obtained in Example 3, further adding NMP and butyl cellosolve (BC) to prepare NMP: BC = 50: 50 (wt%), solid concentration 5 Wt% solution. This solution was filtered using a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent. Further, using this liquid crystal alignment agent, a liquid crystal display element was produced and evaluated in the same manner as in the above-described Example 1. The evaluation results are shown in Table 11 below.

[Example 73 to Example 109, Comparative Example 3, Comparative Example 4]

A liquid crystal alignment agent was prepared in the same manner as in Example 72 except that the type and amount of the polymer to be used were changed as described in the following Table 10, and then a liquid crystal display element was produced and evaluated. The evaluation results are shown in Table 11 below.

[Embodiment 110, Example 111]

The types and amounts of the components other than the polymer (P) and the polymer (Q) were changed as described above, except that the type and amount of the polymer to be used were changed as described in Table 10, respectively. A liquid crystal alignment agent was prepared in the same manner as in the above Example 72, and then a liquid crystal display element was produced and evaluated. The evaluation results are shown in Table 11. Further, the abbreviations of the other components in Table 10 are as follows.

GA-80: Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.)

MBOMA: 4,4'-methylenebis[N,N-bis(oxiranylmethyl)aniline]

[Example 112 to Example 128]

A liquid crystal alignment agent was prepared in the same manner as in the above Example 72 except that the type and amount of the polymer to be used were changed as described in the following Table 12, and then a liquid crystal display element was produced and evaluated. The evaluation results are shown in Table 13 below.

As shown in Table 8, Table 9, Table 11, and Table 13, in Examples 1 to 128, the initial pretilt angle was good at a low ultraviolet irradiation amount of about 5,000 J/m ² . Further, even with such a low ultraviolet irradiation amount, the response speed of the liquid crystal molecules to the voltage change is sufficiently fast. Further, in Examples 1 to 128, voltage holding characteristics and heat resistance were also excellent. On the other hand, in the comparative example, when the ultraviolet irradiation amount is 5,000 J/m ² and 10,000 J/m ² , the initial pretilt angle is not good, and the response speed of the liquid crystal molecules to the voltage change is also slow.

A, B‧‧‧ substrate

Claims (9)

A liquid crystal alignment agent comprising a polymer (P) having a group represented by the following formula (1), In the formula (1), A ¹ is a divalent group represented by the following formula (1a), an anthranyl group, a tetrahydronaphthalenediyl group, or a decahydronaphthalenediyl group; In the formula (1a), A ² is 1,4-phenylene, 1,4-cyclohexylene, piperidine-1,4-diyl, piperidin-2,5-diyl, piperazine-1, 4-diyl, piperazine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, pyrazine-2,5-diyl, or pyridine-2,5 -diyl, X ⁴ is a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) ₂ - or -C≡C-, m is an integer from 0 to 2; wherein, when m is 1 Or 2, a plurality of A ² may be the same or different from each other. When m is 2, a plurality of X ⁴ may be the same or different from each other; 2 "* ¹ " represents a bonding key; Y is -O- , * ² -COO-, * ² -OCO-, -OCOO-, -CO-, * ² -CONH-, * ² -NHCO-, -NH-, -N(CH ₃ )-, -N (C ₂ H ₅ )-, -Si(CH ₃ ) ₂ -, -S-, * ² -COS- or * ² -SCO-; wherein "* ² " represents a bonding bond with A ¹ ; L is a single bond, a divalent group in which at least one hydrogen atom having 1 to 20 carbon atoms or at least one hydrogen atom having 1 to 20 carbon atoms is substituted by a halogen atom, and a carbon-carbon bond in these groups may be Including at least one of -O-, -S-, and -NH-, a part of the carbon-carbon bond may be a double bond or a triple bond; a is 0, b is 1; and Z is represented by the following formula (2a) or a group represented by the following formula (2b); * "Denotes a bond bond; In the formula (2a) and the formula (2b), X ¹ is a hydrogen atom or a methyl group; "* ³ " represents a bond bond. The liquid crystal alignment agent according to claim 1, wherein the L has a carbon number of 2 to 20. The liquid crystal alignment agent according to claim 1 or 2, wherein the polymer (P) has a polyorganosiloxane skeleton. The liquid crystal alignment agent according to claim 3, further comprising at least one polymer (Q) selected from the group consisting of polyglycolic acid, polyphthalate, and polyimine. A method of producing a liquid crystal display device, comprising: a first step of applying a liquid crystal alignment agent according to any one of claims 1 to 4 to a pair of substrates having a conductive film The conductive film is then heated to form a coating film, and in the second step, the pair of substrates on which the coating film is formed are opposed to each other with the layer of liquid crystal molecules interposed therebetween In the third step, the liquid crystal cell is light-irradiated while a voltage is applied between the conductive films of the pair of substrates. A liquid crystal alignment film formed by using the liquid crystal alignment agent according to any one of claims 1 to 4. A liquid crystal display element characterized by comprising: The liquid crystal alignment film according to item 6. A polymer comprising a group represented by the following formula (1), In the formula (1), A ¹ is a divalent group represented by the following formula (1a), an anthranyl group, a tetrahydronaphthalenyl group, or a decahydronaphthalene group; In the formula (1a), A ² is 1,4-phenylene, 1,4-cyclohexylene, piperidine-1,4-diyl, piperidin-2,5-diyl, piperazine-1, 4-diyl, piperazine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, pyrazine-2,5-diyl, or pyridine-2,5 -diyl, X ⁴ is a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) ₂ - or -C≡C-, m is an integer from 0 to 2; wherein, when m is 1 Or 2, a plurality of A ² may be the same or different from each other. When m is 2, a plurality of X ⁴ may be the same or different from each other; 2 "* ¹ " represents a bonding key; Y is -O- , * ² -COO-, * ² -OCO-, -OCOO-, -CO-, * ² -CONH-, * ² -NHCO-, -NH-, -N(CH ₃ )-, -N (C ₂ H ₅ )-, -Si(CH ₃ ) ₂ -, -S-, * ² -COS- or * ² -SCO-; wherein "* ² " represents a bonding bond with A ¹ ; L is a single bond, a divalent group in which at least one hydrogen atom having 1 to 20 carbon atoms or at least one hydrogen atom having 1 to 20 carbon atoms is substituted by a halogen atom, and a carbon-carbon bond in these groups may be Including at least one of -O-, -S-, and -NH-, a part of the carbon-carbon bond may be a double bond or a triple bond; a is 0, b is 1; and Z is represented by the following formula (2a) or a group represented by the following formula (2b); * "Denotes a bond bond; In the formula (2a) and the formula (2b), X ¹ is a hydrogen atom or a methyl group; "* ³ " represents a bond bond. A carboxylic acid characterized by comprising a group represented by the following formula (1), In the formula (1), A ¹ is a divalent group represented by the following formula (1a), an anthranyl group, a tetrahydronaphthalenyl group, or a decahydronaphthalene group; In the formula (1a), A ² is 1,4-phenylene, 1,4-cyclohexylene, piperidine-1,4-diyl, piperidin-2,5-diyl, piperazine-1, 4-diyl, piperazine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, pyrazine-2,5-diyl, or pyridine-2,5 -diyl, X ⁴ is a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) ₂ - or -C≡C-, m is an integer from 0 to 2; wherein, when m is 1 Or 2, a plurality of A ² may be the same or different from each other. When m is 2, a plurality of X ⁴ may be the same or different from each other; 2 "* ¹ " represents a bonding key; Y is -O- , * ² -COO-, * ² -OCO-, -OCOO-, -CO-, * ² -CONH-, * ² -NHCO-, -NH-, -N(CH ₃ )-, -N (C ₂ H ₅ )-, -Si(CH ₃ ) ₂ -, -S-, * ² -COS- or * ² -SCO-; wherein "* ² " represents a bonding bond with A ¹ ; L is a single bond, a divalent group in which at least one hydrogen atom having 1 to 20 carbon atoms or at least one hydrogen atom having 1 to 20 carbon atoms is substituted by a halogen atom, and a carbon-carbon bond in these groups may be Including at least one of -O-, -S-, and -NH-, a part of the carbon-carbon bond may be a double bond or a triple bond; a is 0, b is 1; and Z is represented by the following formula (2a) or a group represented by the following formula (2b); * "Denotes a bond bond; In the formula (2a) and the formula (2b), X ¹ is a hydrogen atom or a methyl group; "* ³ " represents a bond bond.